MINI REVIEW

Received: Apr. 16, 2021 | Accepted: July 1, 2021 | Published: Aug. 27, 2021

Recent Advances in
Polyaniline-Based Thermoelectric
Composites
Siqi Liu1, Hui Li2*, Pengcheng Li2, Yalong Liu2 & Chaobin He1,3*
1
Department of Materials Science and Engineering, National University of Singapore, Singapore 117574, 2Hubei Key
Laboratory of Plasma Chemistry and Advanced Materials, Hubei Engineering Technology Research Center of
Optoelectronic and New Energy Materials, School of Materials Science and Engineering, Wuhan Institute of Technolo-
gy, Wuhan 430205, 3Institute of Materials Research and Engineering, A*STAR (Agency for Science, Technology and
Research), Singapore 138634

*Corresponding authors: mselh@wit.edu.cn; msehc@nus.edu.sg; cb-he@imre.a-star.edu.sg

Cite this: CCS Chem. 2021, 3, 2547–2560

Polyaniline (PANI)-based thermoelectric (TE) materi-

als have attracted considerable attention for flexible
electronic energy harvesting devices because of prop-
erties such as solution processibility, excellent environ-
mental stability, and low cost. However, the typical
opposite dependence between electrical conductivity
and Seebeck coefficient impedes their development,
and tremendous efforts have been devoted to increas-
ing their TE efficiency. This mini review focuses on
key strategies in developing high-performance
PANI-based TE materials, including doping engineer-
ing (fine-tuning of doping level), modulation of molec-
ular orientation, inorganic nanoparticles incorporation
to combine the merits of their components, interface
engineering that introduces interfacial interactions and
an energy-filtering effect, and other strategies. With
properly optimized components, microstructure,
and fabrication processing, which aid in the carrier
transport properties, the overall performance of
PANI-based TE composites has been greatly enhanced, Keywords: polyaniline, composites, thermoelectric
promoting the improvement of PANI-based compo- properties, microstructure, carrier transport
sites for sustainable energy utilization.

technologies are urgently required to alleviate the current

Introduction issues and fulfill the growing energy demand. Energy
Due to the depletion of fossil fuels and heightened environ- harvesting from environmental waste heat, such as solar
mental pollution, advanced green energy resources or energy and dissipated energy from power consuming

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systems, is considered as a promising strategy for sustain-
1
able energy utilization. Thermoelectric (TE) materials,
which effectively utilize the surrounding waste thermal
energy with direct conversion into useful electrical energy
and enable reversible conversion as a cooler without any
moving parts and noise pollution, have attracted significant
attention and exhibited extensive applications in aero-
2
space, cogeneration, and microsensors. Most commercial
TE materials are inorganic TE materials, such as Bi2Te3 and
PbTe. However, toxic components, manufacturing difficul-
ties, and brittleness impede their widespread applicability,
especially for wearable and portable electronic devices.3
In contrast, organic TE materials are now attracting
ever-increasing interest, due to their versatile advantages,
such as low thermal conductivity, light weight, solution
processibility, and excellent flexibility.4,5 So far, numerous
efforts have been devoted to pursuing better TE properties
of organic TE materials, fulfilling the increasing demands of
flexible energy harvesting devices.
Generally, the performance of a TE material is quanti-
fied by the dimensionless figure of merit, ZT = S2σT/κ,
where σ, S, T, and κ represent electrical conductivity,
Seebeck coefficient, absolute temperature, and thermal
conductivity, respectively. In addition, power factor
(PF =S2σ) is also commonly adopted to evaluate the
TE efficiency of organic materials.6 Therefore, from the
definition of the ZT value, large S and σ, but low κ are
favorable for high TE efficiency. However, these para-
meters are strongly interdependent, and the opposite
dependence of S and σ greatly restricts the optimization
of TE properties.7 The electrical conductivity (σ = nqμ,
where n is the carrier concentration, q is the elementary
charge, and μ is the charge carrier mobility) is propor-
tional to n, which is closely related to doping level, and μ
which is affected by chemical structure and morphology.8
In contrast, S is defined as:
Z
k B E−E F σðEÞ
S= dE
q kBT σ
where kB is the Boltzmann constant, E is the carrier-
occupied energy level, and EF is Femi energy level, which
represents the average transported entropy per charge
carrier.9 When the Fermi level is close to the conduction
band gap, n increases, which subsequently causes a reduc-
tion in transported energy of charge carriers, and thereby
the reduction of S.10,11 This competing trend of S and σ
complicates the improvement of TE materials and it is
therefore crucial to optimize S and σ simultaneously,
leading to enhanced TE efficiency.
Polyaniline-Based Composites
Among the abundant organic TE materials, conducting
polymers are regarded as the most high potential candi-
dates for TE applications,12 including polypyrrole (PPy),
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polyaniline (PANI), polythiophene (PTh), and poly(3,4-
ethylenedioxythiophene) (PEDOT). Until now, poly(3-hex-
ylthiophene) (P3HT) has been reported to reach a PF of
20 μW m−1 K−2 via immerse-doping with the ferric salt
of triflimide [Fe(TFSI)3],13 while the vapor phase-doped
P3HT with 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodi-
methane (F4TCNQ) approached a high PF of 27 μW m−1
K−2, accompanied with a larger S over 85 μV K−1.14 Meanwhile,
PEDOT with various counter-ions were intensively studied,
where PEDOT:poly(styrene sulfonate) (PSS) recorded a
high PF over 334 μW m−1 K−2 via sequential treatment
of common acid and base solution,15 and the tosyl
anion-doped PEDOT (PEDOT:Tos) films demonstrated a
maximum PF approaching 324 μW m−1 K−2.16 In comparison
with these other conducting polymers, PANI has received
significant attention because of the merits of low cost,
easy synthesis, and excellent chemical stability. In the early
years, PANI was primarily used after chemical oxidative
polymerization with HCl doping, which possessed a rather
low σ of several S cm−1.17,18 Even combined with highly
conductive nanofillers, the σ values of the resulting compo-
sites were still undesirable and showed an inferior PF of
less than 20 μW m−1 K−2, greatly impeding its application for
TE devices.19 Aimed at improving σ and TE performance
of PANI-based materials, secondary doping engineering
was conducted to optimize the microstructural ordering
in polymers, leading to greatly increased σ of 280 S cm−1 and
PF of 11 μW m−1 K−2, respectively, for pure PANI film.20–24 After
that, a variety of PANI-based composites with nanomater-
ials possessing high σ or S, such as inorganic TE materials,
Figure 1 | TE PFs of PANI-based composites from 2010 to
now. (The inset images have been reproduced with per-
mission from ref 25. Copyright 2010 American Chemical
Society; ref 26. Copyright 2015 American Chemical Soci-
ety; ref 27. Copyright 2018 American Chemical Society;
ref 28. Copyright 2019 American Chemical Society; ref 29.
Copyright 2021 American Chemical Society.)
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carbon nanomaterials [mainly carbon nanotubes (CNTs)
and graphene (GN)], and other conducting polymers, have
been extensively investigated, and great progress has been
achieved using various techniques (Figure 1). By properly
optimizing the components, microstructure, and fabrica-
tion process, the majority of the reported PANI-based TE
composites has steadily improved to higher PF above
200 μW m−1 K−2 in recent years, and a more attractive
PF up to 2710 μW m−1 K−2 has been approached with a
PANI/GN-PEDOT:PSS/PANI/double-walled carbon nano-
tube (DWCNT)-PEDOT:PSS multilayer film at room tem-
perature (RT), comparable with the TE performance of
commercial inorganic materials.30
To date, huge efforts have been devoted to pursuing
high-performance PANI-based TE composites, and many
effective processing methods have been applied to en-
hance TE efficiency including doping engineering, modu-
lation of molecular orientation, inorganic nanoparticles
incorporation, interface engineering, and other strategies
(Figure 2). Specifically, upon properly tuning the doping
parameters, such as dopant, solvent, and doping level, the
consequently modulated morphology and energy level of
PANI, which are strongly correlated to carrier concentra-
tion and carrier mobility, result in optimized σ and S,
thus high TE efficiency.21,24 Moreover, the σ and PF of the
PANI-based TE composites can also be significantly im-
proved by constructing ordered polymer chain micro-
structure, which effectively decreases the interchain
hopping activation energy and contributes to enhanced
carrier mobility without sacrificing S.1,37 Besides the opti-
mization of polymer microstructure, incorporating inor-
ganic nanoparticles to fabricate hybrid composites is
another straightforward route to pursuing high TE prop-
erties by combining the unique properties of inorganic TE
nanoparticles that possess a high S and a highly conduc-
tive PANI polymer. Besides, strong interchain π–π interac-
tions which lead to better charge transport properties and
effective energy-filtering effects that restrict low-energy
carriers are introduced by properly engineering PANI-filler
interfaces, contributing to simultaneously enhanced σ
and S.38 Furthermore, other novel techniques such as the
modification of nanofillers and ionic TE effects have also

Figure 2 | Schematic illustration of key strategies to enhance the performance of PANI-based TE composite materials.
(The inset images have been reproduced with permission from ref 31. Copyright 2021 Elsevier; ref 32. Copyright 2019
Elsevier; ref 25. Copyright 2010 American Chemical Society; ref 33. Copyright 2021 American Chemical Society; ref 34.
Copyright 2021 MDPI; ref 35. Copyright 2018 American Chemical Society; ref 29. Copyright 2021 American Chemical
Society; ref 36. Copyright 2018 Royal Society of Chemistry.)

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been developed to fabricate flexible PANI-based compo-
sites with enhanced TE performance. In this mini review,
we will give a brief summary of the primary reports of
PANI composites with enhanced TE properties. In each
section, the specific strategy and rational design in
approaching high TE performance of PANI-based com-
posite materials will be described. Finally, we will highlight
the current challenges and perspectives for the improved
TE performance and efficiency enhancement of
PANI-based composite materials.
Strategies to Optimize the
Performance of PANI-Based TE
Composites
Doping engineering
Since acid doping can greatly increase carriers through
protonation of the imine nitrogen sites to increase σ
several S cm−1, abundant dopants, such as boric acid,39
5-sulfosalicylic acid (SSA),40–42 PSS,28 methane sulfonic
acid,43 HCl,44–49 and especially camphorsulfonic acid (CSA)
with m-cresol as the solvent, have been utilized to develop
various PANI-based TE materials. Although great progress
has been achieved for PANI-based composites, their TE
efficiency is still far less than commercial organic materials,
which greatly impedes their widespread applications in
energy harvesting.17 Since the microstructures and energy
band of PANI are greatly dependent on doping level, the
tuning of the doping degree is expected to be a quite
effective strategy in optimizing TE efficiency of PANI
composites.
Doping level manipulation has been proven to greatly
affect the PANI chain conformation and σ. Typically, with
increasing doping level, polarons tend to be increased and
Figure 3 | (a) Schematic images and (b) TE properties of SWCNTs/PANI composite films with varying molar ratios of
PANI/CSA. Reproduced with permission from ref 31. Copyright 2021 Elsevier. (c) Schematic representation of carrier
transport and (d) TE properties of SWCNTs/PANI composites after dedoping. Reproduced with permission from
ref 32. Copyright 2019 Elsevier.
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transferred from localization to delocalization with expand-
ed chain conformation, resultinginrapidly increasedσ atthe
beginning of the doping process. Further increasing the
dopant cannot effectively protonate PANI chains or even
cause undesirable screening effect to contract the chain
with more compact coil conformation, resulting in un-
changed or decreased σ with higher doping.17,50–52 However,
increasing carrier density leads to deteriorated S as doping
level increases. Therefore, maximum σ and TE performance
of PANI is mainly achieved with a protonation degree of
50% (mole ratio of PANI:CSA = 2:1), which has been widely
applied for the fabrication of PANI-based materials.53 Con-
trasting with previous reports, Li et al.31,32,54,55 demonstrated
the significantly enhanced TE performance of CNTs/PANI
compositesat low dopinglevels. As shown in Figures3a–3d,
they investigated the effect of doping level, which had been
fine-tuned by decreasing the amount of CSA, on the TE
properties of single-walled CNTs (SWCNTs)/PANI com-
posite films.31,54 Ascribed to the strong π–π interactions
promoting the formation of a unique PANI interface layer
and the existence of a CNT-interconnected network which
provides conductive pathways to enable efficient carrier
transportation, σ was decreased less and accompanied
with a greatly increased S as doping level decreased, lead-
ing to a high PF value of 321 μW m−1 K−2 at a PANI/CSA mole
ratios of 3:1 with CNTs loading of 69 wt %. Furthermore,
amine-functionalized CNT (A-CNTs)/PANI composites
also exhibited greatly enhanced PF of 401 μW m−1 K−2 with
a properly reduced doping level. Subsequently, they
reported greatly enhanced TE efficiency of typically un-
modified SWCNTs/PANI films by immersing in ammonium
hydroxide and ethanol, subsequently, to partially remove
CSA and control doping level.32,55 With the dedoping pro-
cess, conductive, ordered, and protonated PANI chains
were transferred to an insulating, disordered PANI
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emeraldine base (PANIeb) that reduced carrier density,
while the interconnected SWCNTs networks would com-
pensate the deteriorating effects of PANI chains on carrier
transport, leading to greatly enhanced S accompanied with
a slightly decreased σ. Based on these investigations, the TE
efficiency of PANI-based composites is expected to be
further enhanced by properly modulating the doping level,
as most of them were prepared with a traditional doping
level of 50%.
Molecular self-assembly
Along with doping engineering, molecular self-assembly
is another important route to enhance TE efficiency of
PANI composites, which efficiently improves the carrier
mobility and σ without deteriorating S. So far, several
strategies have been explored to enhance molecular
orientation of PANI, such as the secondary doping of
PANI, the introduction of strong interactions between
PANI and fillers, electrospinning process, mechanical
stretching, and so on.
Many studies have focused on secondary doping engi-
neering to promote electron delocalization along the
chains and enable good dissolution and processing of
PANI in a variety of common organic solvents, contrib-
uting to improved TE efficiency and enhanced process-
ibility.56 Since Cao et al.20,57,58 reported that functionalized
protonic acid, especially CSA, can effectively protonate
PANIeb to give doped PANI solutions in weakly or non-
polar organic solvents, and induce significant enhance-
ment in σ within the range of 100–400 S cm−1, secondary
doping engineering has received great attention for the
processing of PANI composites. MacDiarmid et al.22,50,59
studied the viscosity, electronic spectra, and σ of PANI
doped with CSA in varied solutions of m-cresol and
chloroform. It was shown that PANI chain conformation
changed from compact to expanded coil with enhanced
electron delocalization along the polymer chains and σ
approaching 200 S cm−1 was achieved as the m-cresol
proportion increased, ascribed to strong interactions
between polymer chains and m-cresol and hydrogen
bonding with the carbonyl group from CSA and hydroxyl
group in m-cresol. Furthermore, vapor exposure of
m-cresol also introduced an effective secondary doping
effect on PANI.23 Recently, Yao et al.24,60 revealed in-
creased carrier mobility and a decreased hopping barrier,
accompanying the increased PANI-ordered regions as
the m-cresol proportion increased. This led to remark-
ably improved σ from 4.7 to 220 S cm−1 with a slight
increase of S when m-cresol increased from 0% to 100%,
and thereby a high PF of 11 μW m−1 K−2 was achieved,
60 times higher than that from chloroform.
In recent years, with the merits of solution processing
and enhanced σ via secondary doping engineering, PANI
hybrid composites have experienced rapid develop-
ment and promising results have been reported.61–63
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Yao et al.64 prepared SWCNTs/PANI hybrid films by
solution mixing the two components. Chemical interac-
tions between PANI and m-cresol induce PANI chain
transition of compact-to-expand in the solution pro-
cess, which was then further oriented to form a highly
ordered PANI interface layer on the surface of SWCNTs
ascribing to strong π–π interactions between PANI and
CNTs. The enhanced and ordered polymer chains bene-
fit increased carrier mobility, resulting in improved σ and
S. Consequently, the σ of SWCNTs/PANI hybrid compo-
sites was gradually increased with the increment
of SWCNTs content, reaching a maximum PF of
176 μW m−1 K−2 with 64 wt % SWCNTs. Similar behavior
has also been observed for SWCNTs/PANI composites
prepared by in situ polymerization which induced stron-
ger interactions between the two constituents.63 In ad-
dition, Wang et al.26 reported a series of DWCNTs/PANI
composite films by mixing the CNTs dispersion with
PANIeb or PANI-CSA (Figures 4a and 4b). The conduct-
ing polymer can effectively bridge nanotubes and de-
crease electrical contact resistance between CNTs,
enabling good charge transport at CNTs junctions and
leading to superior σ. Moreover, with the addition of
DWCNTs, largely increased carrier mobility and de-
creased carrier concentration was observed, contribut-
ing to the simultaneous improvement in σ (610 S cm−1)
and S (61 μV K−1). Thus, PF reached 220 μW m−1 K−2 with
CNTs amount of 30 wt %, one of the highest values
among previously reported PANI composites.
Yao et al.25 prepared HCl-doped SWCNTs/PANI via in
situ polymerization with dispersed CNTs and aniline
monomers, in which the PANI chains were grown along
the outer surface of SWCNTs to form ordered chain
packing because of π–π interactions between conjugated
SWCNTs and PANI, leading to enhanced σ of 125 S cm−1, S
of 40 μV K−1, and a resultant PF over 20 μW m−1 K−2 with
SWCNTs content of 41.4 wt % (Figures 4c and 4d). Abad
et al.66 prepared GN nanoplatelet (GNPs)/PANI compos-
ite pellets by mechanical blending and cold pressing
techniques. Due to the addition of highly conductive
GNPs and the strong interactions between PANI and
GNPs, which promotes the increment of PANI quinoid
rings structure and facilitates charge transport, σ was
increased with the addition of GNPs, in accordance with
the percolation law from 0.48 S cm−1 of raw PANI to 123 S
cm−1 of 50 wt % GNPs/PANI composite. Combined with
the increased S, a maximum PF reaching 14 μW m−1 K−2
was obtained. Recently, Wang et al.65 proposed an effi-
cient strategy by solution mixing of PANI and PPy/GNs
composite to fabricate a PPy/GNs/PANI ternary nano-
composite with improved TE efficiency (Figures 4e
and 4f). With strong π–π interaction and hydrogen bond-
ing between PANI and PPy, PANI molecules tend to be
more expanded and ordered stacking, which can effi-
ciently promote carrier transport and enhance carrier
mobility, while the additional barriers may generate
energy-filtering and quantum-confinement effects,
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Figure 4 | (a) σ, S, and (b) PF of DWCNTs/PANI composite films with varied CNTs content, where the inset presents the
crucial role of PANI-CSA to connect CNTs junctions. Reproduced with permission from ref 26. Copyright 2015
American Chemical Society. (c) TEM images of 25 wt % SWNT/PANI composites. (d) TE properties of SWNT/PANI
composites with varying SWNT content. Reproduced with permission from ref 25. Copyright 2010 American Chemical
Society. (e) Schematic illustration of the synthesis process of PPy/GNs/PANI composites. (f) PF of PPy/GNs/PANI
composites with 32 wt % GNs loading at different temperatures. Reproduced with permission from ref 65. Copyright
2017 American Chemical Society. (g) Schematic illustration of DMSO-induced, greatly enhanced, and ordered PANI
nanostructures along SWCNT interfaces by electrochemical polymerization methods. Reproduced with permission
from ref 33. Copyright 2021 American Chemical Society.

which can reduce carrier concentration in the compo-
sites. Consequently, optimized σ, S, and PF values of
500 S cm−1, 32.4 μV K−1, and 52.5 μW m−1 K−2, respectively,
were achieved with 32 wt % GNs at 90 °C, higher than
GNs/PANI and GNs/PPy. Similar enhancement was also
found in in situ-polymerized PANI/GN composite films,
where the π–π interactions between in situ-synthesized
PANI and GN led to the PANI conformation changing
from coil to a more expanded structure. Meanwhile, the
improved σ was also aided by the greatly improved
dispersion homogeneity of GNPs inside the PANI matrix
during the in situ polymerization process.67
Furthermore, with the assistance of the electrospinning
process, Wang et al.68 reported electrospun CNT/PANI
nanofibers with more oriented PANI chains along the
CNTs axis. The ordered molecule alignment contributed
to the 80% higher σ in the parallel orientation direction
compared to the perpendicular direction, whereas S was
independent. Recently, Yin et al.33 reported that with the
presence of dimethyl sulfoxide (DMSO) in the electrolyte
during the electrochemical polymerization of PANI, great-
ly enhanced ordered molecular structures of PANI were
introduced (Figure 4g). Therefore, higher σ and a mini-
mum impact on S of PANI/DMSO/SWCNT composites
were obtained at the same SWCNT loadings compared
with the PANI/SWCNT composites, leading to an en-
hanced PF over 236.4 μW m−1 K−2. Moreover, more ordered
structures can be realized by mechanical stretching, which
induces polymer chain alignment parallel to the drawing
direction, leading to dramatically enhanced σ.52,69 As for
PANI films, a high σ of 820 S cm−1 could be achieved by
stretching to 100% extension at 150 °C.18 The more ex-
tended and ordered polymer chains by spinning were also
found by Lee et al.70 in the spin-coated multilayer PANI-
CSA/PEDOT:PSS composite films. Raman results showed
that as the coating repetition cycles increase, the coiled
PANI and PEDOT chains tend to be stretched by spin
coating on a 20 nm thick PANI-CSA layer. Thus, the
interactions between the layers were strengthened, which
facilitates the carrier transport and leads to increased σ
with insignificant variation in S.
Inorganic nanoparticle incorporation
Another approach to enhancing the PF of PANI-based
composites is by hybridizing inorganic nanoparticles that
possess intrinsic high σ or S while retaining the merits of
organic PANI polymers. Various inorganic materials have
been chosen as TE-enhancing fillers into the PANI matrix,
including metal nanoparticles,71,72 metal sulfides,73–76 metal
oxides,77–80 metal selenides,35,81 and metal tellurides,40,82 and
so on. On the one hand, to obtain an enhanced σ, Roussel
et al.83 blended metallic silver (Ag) particles into the PANI
matrix. With Ag particle loading over 16.2 vol %, the σ of the

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Figure 5 | (a) High-resolution transmission electron microscopy (HR-TEM) image of 70%-Sb2Se3/30%-β-Cu2Se/PANI

composites. (b) Seebeck coefficient and (c) electrical conductivity of Sb2Se3/β-Cu2Se/PANI composite films as a
function of β-Cu2Se content. Reproduced with permission from ref 34. Copyright 2021 MDPI. (d) Field emission
transmission electron microscopy (FE-TEM) images of PANI-SnSeS nanosheets with single layer-coated PANI. (e) PF
of PANI-SnSeS composites at 300 K with increasing PANI coating cycles. (f) PF value of a PANI(2)-SnSeS nanosheet/
PVDF(2:1) film compared with other reported materials. Reproduced with permission from ref 35. Copyright 2018
American Chemical Society.

PANI-based composites was enhanced by several order of
magnitudes over 1 × 106 S m−1. Although the S decreased as
Ag loading increases, the optimized PF of the composites
increased by five orders of magnitudes from 10−5 μW m−1 K−2
of neat PANI to 3 μW m−1 K−2 with 26 vol % Ag loading. In
contrast, the S of pure PANI was reported to increase with
the incorporation of intrinsically high S inorganic nanopar-
ticles. Wang et al.84 reported the integration of tellurium
nanorods (Te NRs) with PANI. A thin PANI layer was ob-
served to be tightly attached to the Te NRs surface by a
mixtureofvan der Waals forces and electronic π interactions
between Te atoms and PANI conjugated structures. The
improved carrier transport properties by the well-matched
PANI/TeinterfaceandhighS of TeNRsleadstoanenhanced
PF of 105 μW m−1 K−2 at RT and 146 μW m−1 K−2 at 463 K.
Moreover, ascribed to the efficient phonon scattering be-
tween Te/PANI interfaces, the binary composite exhibited a
rather low κ of only 0.2 W·m−1·K−1, giving rise to a high ZT
reaching0.156 atRT. Apartfrom conventionalTe nanofillers,
the incorporation of other inorganic nanoparticles like
Sb2Se3 and β-Cu2Se with PANI have been reported by Kim
et al.34 PANI has also been coated on Sb2Se3/Cu2Se surfaces
(Figure 5a), and the trends in S and σ can be explained by the
parallel-connected model (Figures 5b and 5c). As a result,
after the incorporation of high S nanoparticles, the 70%-
Sb2Se3/30%-Cu2Se/PANI film exhibited a maximum PF of
181.61 μW m−1 K−2 at 473 K. Besides, Ju et al.35 successfully
fabricated dodecylbenzenesulfonic acid (DBSA)-doped
PANI-coated SnSe0.8S0.2 nanosheets (PANI-SnSeS NSs) for
flexible TE applications (Figures 5d and 5e), where different
cycles of polymerized PANI coatings on the surface of
SnSeS NS affected the TE properties of the composites. A
maximum PF was reported to approach 252 μW m−1 K−2 with
two layers of PANI coating (Figure 5f), as the increased
content of DBSA-doped PANI led to a higher σ outweighing
the lowered S. To ensure good durability for flexible TE
applications, polyvinylidene fluoride (PVDF) was added
into the PANI/SnSeS matrix and the PANI(2)-SnSeS
nanosheet/PVDF(2:1) film exhibited a high PF of 134 μW
m−1 K−2 at 400 K. Moreover, n-type inorganic TE fillers have

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also been used to blend with p-type PANI. Wang et al.75
fabricated PANI/bismuth sulfide nanorods (Bi2S3 NRs)
composite films exhibiting n-type TE behavior. The hybrid
films showed a p-to-n type transition as the heat treatment
temperature increased to 483 K, ascribed to the rapid
reduction in the concentration of hole carriers from PANI
after heat treatment and the electronic carriers from Bi2S3
NRs gradually taking their place. The transition temperature
is correlated to the Bi2S3 NRs/PANI ratio, and a higher Bi2S3
NRs concentration leads to a lower transition temperature.
By varying the heat treatment temperature and Bi2S3 NRs
content, a negative S of −42.8 μV K−1 with a corresponding
PF of 0.07 μW m−1 K−2 was achieved at RT.
Interface engineering
Aimed at high TE efficiency of PANI-based composite
materials, engineering component interfaces has also
drawn extensive attention as one of the most promising
strategies. Due to the unique electronic structures of the
PANI polymer chain, strong interactions between PANI and
specific fillers can be introduced, especially widely reported
π–π interactions between the interfaces of PANI and conju-
gated carbon nanoparticles. The π–π interactions at the
interfaces promote more oriented and arranged PANI mo-
lecular chains with electron delocalization, giving rise to
high carrier mobility and σ.67 In addition, other interfacial
interactions consisting of covalent bonding, hydrogen
bonding, and Van de Waals force between the PANI/filler
interfaces were also considered to contribute to better
charge transfer and higher σ and TE performance.75,84
Apart from interfacial interactions between the compo-
nents, the energy filtering effect generated from the en-
ergy offset between the interfaces of the components has
also been extensively studied for enhancing TE properties
of conducting polymer-based TE composites.85 With the
presence of appropriately manipulated interfacial energy
barrier (ΔEb), only high-energy carriers with an average
energy above ΔEb can pass-through the interfaces, while
the low-energy carriers are selectively filtered out, leading
to an increase in S.86 Based on theoretical calculation and
experimental verification, ΔEb values around 0.05–0.1 eV
give the most effective S enhancement and slightly low-
ered σ. Therefore, properly modulating the interfacial
interactions and interface energy barrier can be an effec-
tive approach for achieving high S and σ synergistically,
either in binary or ternary hybrids.87–90 For instance, Meng
et al.19 fabricated PANI-coated multiwalled CNTs sheet
with a CNT network sheet that served as the template
for the deposition of polymer chains, forming a PANI
coating layer on the surface of CNTs. The conductive CNT
network and energy-filtering effect at interfaces which
preferentially allow the high-energy carriers to pass con-
tribute to the improved σ and S, resulting in a maximum PF
of 5 μW m−1 K−2 at 84 wt % CNT, higher than the individual
constituent. Moreover, the electron transport and TE
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MINI REVIEW
properties in CNT/PANI composite films was investigated
by Wang et al.,91 where HCl-doped PANIeb/CNT compos-
ite films exhibited much higher S than PANI-CSA/CNT
composite films. This high S value is a result of the
appropriate energy barrier and filtering effects at the
CNT/PANIeb interfaces.91 Meanwhile, HCl gas treatment
led to great improvements in σ with less affected energy
barrier heights between strongly π–π interacted PANIeb
and CNT. Moreover, theoretical studies suggested that the
optimized PF value can be achieved when ΔEb = 0.16 eV
for PANIeb/CNT composite films, proving that the
energy-filtering effect with well-manipulated ΔEb can be
a feasible approach for TE enhancement. Recently,
Abinaya et al.92 reported that the energy-filtering effect
can be also found between the interfaces of ultrathin
layered molybdenum disulfide nanosheets (MoS2 NSs)
and PANI in the hybrids, where the average energy of
carriers and the average entropy per carriers increased in
the system. The ΔEb of 0.089 eV at the interface between
MoS2 and PANI was created, leading to a significantly
enhanced S by four times to MoS2. Simultaneously, σ was
improved, owing to the facilitated charge carrier transfer
between MoS2/PANI effective interfaces. Furthermore, Li
et al.29 reported sequential dedoping–redoping treatment
on SWCNTs/PANI films to fabricate multiple interface
structures in PANI composites, which contributed to the
enhanced carrier filtering effect for relatively large S and
the retained efficient carrier transport for enhanced σ
(Figure 6a). A maximum PF of 407 μW m−1 K−2 with
enhanced S to 42.7 μV m−1 K−1 was reported. Erden et al.36
reported a method by incorporating titanium oxide (TiO2)
nanoparticles into a-CNTs/PANI composites, which con-
structed multiple energy barriers between the interfaces
of PANI, TiO2, and a-CNT, and introduced a carrier
energy-filtering effect that filtered out the low-energy
hole carriers (Figure 6b). Therefore, the S enhancement
of the a-CNT/PANI could be found with TiO2 integration
(Figure 6c). The maximum PF reached 114.5 μW m−1 K−2
with 30% TiO2–70% [a-CNT (70%)/PANI (30%)] compos-
ite films at a CSA redoping temperature of 40 °C after
water treatment (Figure 6d). Wang et al.93 investigated
the decoupling of σ and S by the multiple interface con-
struction of multi-walled carbon nanotubes (MWCNTs)/
Te NRs/PANI ternary composites. After the integration
of Te NRs, the experimental S values of the ternary com-
posites were larger than the calculated S values based
on mixture rules, indicating that there was extra contribu-
tion on S enhancement except for high S Te NRs.
This abnormal S enhancement is attributed to the
energy-filtering effect with the energy barrier of 0.22 eV
at Te/PANI interfaces and 0.05 eV at MWCNTs/PANI
interfaces created. Along with the interactions between
the well-bonded components, facilitating selected
pass-through of high-energy holes leads to the simulta-
neous enhancement in both σ and S. Consequently, a
maximized PF of 54.4 μW m−1 K−2 was achieved with
2554
 MINI REVIEW

Figure 6 | (a) Schematic illustration of the sequential dedoping–redoping treatment on SWCNTs/PANI films and
enhanced TE properties with final redoped SWCNTs/PANI films. Reproduced with permission from ref 29. Copyright
2021 American Chemical Society. (b) The interfacial band diagram and energy-filtering effect at TiO2/a-CNT and
TiO2/PANI interfaces. (c) Seebeck coefficients and (d) PF of 50% a-CNT/50% PANI and 70% a-CNT/30% PANI films as
a function of TiO2 content before and after water treatment at RT. Reproduced with permission from ref 36. Copyright
2018 Royal Society of Chemistry.

Table 1 | A Summary of the TE Properties of Some Typical PANI-Based Composites at RT

σ S PF
Strategies (S·cm−1) (μV·K−1) (μW·m−1·K−2) References

Doping engineering PANI-CSA/A-CNTs 1871 46.5 401 54

PANI-CSA/SWCNTs 2025 41.3 345 32
PANI-CSA/SWCNTs 2898 33.3 321 31
Molecular self-assembly PANI-CSA/SWCNTs 769 65 176 64
PANI-CSA/DWCNTs 610 61 220 26
PANI-HCl/SWCNTs 125 40 20 25
PANI-HCl/GNPs 123 14 66
PANI/PPy/GNs 500 32.4 52.5 65
PANI/DMSO/SWCNT 842.5 53 236.4 33
PANI-CSA/PEDOT:PSS 1585 17.5 49 70
Inorganic nanoparticle PANI/Te NRs 102 102 105 84
incorporation PANI/Bi2S3 NRs ∼0.4 −42.8 ∼0.07 75
PANI/Bi2Te3 11.6 40 2 95
PANI/SnSeS 14 424 252 35
Interface engineering PANI/SWCNTs 2238 42.7 407 29
PANI/a-CNT/TiO2 2183 22.9 114.5 36
PANI/MWCNTs/TeNRs 137 63 54.4 93
PANI/SWNTs/Te 345 54 101 94
PANI/CuSbSe2/MWCNTs 21 −23.5 1.16 89
Other strategies PANI/Zr-MOFs/PSS 0.021 −17,780 664 28
PANI/PDG 14.5 604 529 27
PANI/PAAMPAS/PA 0.237 ∼8100 ∼1600 96
PANI/GN-PEDOT:PSS/PANI/ 1900 120 2710 30
DWCNT-PEDOT:PSS

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 MINI REVIEW

ternary Te/MWCNTs/PANI composite films, which is al-
most two times that of binary Te/PANI hybrids. Similar
findings in single-walled carbon nanotubes (SWNTs)/
PANI/Te ternary composites were also reported by Wang
et al.,94 where the experimental S values were significantly
enhanced compared with the calculated values from
the series/parallel-connected mixture rules, ascribed to
the effective energy-filtering effect between both
SWNTs/PANI and Te/PANI interfaces. Meanwhile, the
experimental σ values were located between the two
calculated values. Therefore, the TE performance was
effectively enhanced and the maximum PF approached
over 101 μW m−1 K−2.
Other strategies
In addition to the above-mentioned strategies to pursue
high TE PANI-based composites, other novel methods
have been examined as listed in Table 1. For instance, Lin
et al.28 integrated zirconium-based metal–organic fra-
meworks (Zr-MOFs) with PANI and ionic PSS, which
leads to the improved crystallinity of PANI, and thus
higher σ (Figure 7a). Besides, the slope for the κ curve
decreased significantly with increasing Zr-MOF loading,
which was ascribed to the increased interfacial and
phonon scattering at more component interfaces
(Figure 7b). Together with the large negative S of
Zr-MOF, the maximum PF of 664 μW m−1 K−2 was
achieved when PSS (molecular weight = 1,000,000 g/
mol) and 20 wt % Zr-MOF was added. Another study
by Lin et al.27 demonstrated a novel synthesis method
of p-phenediamino-modified GN (PDG) with chemical
bonding with aniline for fabricating special semi-
interpenetrating networks (Figure 7c), which not only
provide extra pathways to facilitate carriers transporta-
tion, but also trigger optimized PF of 529 μW m−1 K−2 and
ZT of 0.74 with dramatically low content of GN (3 wt %)
(Figure 7d). Recently, PANI polymer was also reported
to be fabricated into highly stretchable and self-healing
composites with exceptional ionic S by Akbar et al.96 The
ionic composite material consisted of an anionic poly-
electrolyte (poly (2-acrylamido-2-methyl-1propanesul-
fonic acid)) (PAAMPSA), phytic acid (PA), and PANI
polymer, in which the PANI polymer participated in the
gel formation by the interchain entanglement and inter-
actions with PAAMPSA and PA. Moreover, the ultrahigh

Figure 7 | (a) Thermally-driven carrier diffusion in Zr-MOF/PANI/PSS composites. (b) TE properties of the ZB-A/
PANI/PSS1 film as a function of Zr-MOF loading. Reproduced with permission from ref 27. Copyright 2018 American
Chemical Society. (c) Schematic diagram of chemically bonded PDG and linear PANI constructed S-IPNs. (d) ZT values
of the GN or PDGx-y mixed PANI composites with various GN or PDG weight ratios. Reproduced with permission from
ref 28. Copyright 2018 American Chemical Society.

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ionic S over 8.1 mV K−1 of the ternary composites was
attributed to the Soret effect introduced by PAAMPAS,
which is over 506 times higher than the electronic S of
the reported PANI-based TE composites. As a result, it
exhibited an excellent ionic PF and ZT over 1.04 under
RT with a relative humidity of 90%, which shows great
potential for PANI-based ionic TE materials.
Summary and Outlook
In this mini review, recent progress in developing prom-
ising PANI-based TE composites have been summarized
and discussed along with the strategies to improve their
TE performance. Although rapid improvement in the TE
efficiency of the composites has been achieved over the
past few decades, the performance of most current
materials is still lower than those of commercially avail-
able inorganic materials. Therefore, further efforts on the
development of novel materials with outstanding TE
properties and highly efficient routes to improve their
TE performance are urgently required for the develop-
ment of flexible energy generators. Moreover, the under-
lying carrier transport properties and fundamental
studies of structure–property relationships are unclear,
which deserve further investigation for an in-depth un-
derstanding of the TE mechanism so as to guide the way
for efficiently improved TE performance. Finally, more
studies on device fabrications for large scale application
of a flexible TE generator are necessary to fulfill com-
mercial demands in the future.
Conflict of Interests
The authors declare no competing financial interest.
Acknowledgments
This work was supported by Ministry of Education,
Singapore (grant no. MOE2019-T2-126), the National
Natural Science Foundation of China (grant nos.
51803156 and 51903194), and Scientific Research Pro-
gram of Hubei Provincial Department of Education
(grant no. B2020055).
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DOI: 10.31635/ccschem.021.202101066
Citation: CCS Chem. 2021, 3, 2547–2560
Citation denotes calendar and volume year of first online publication.
Issue Assignment: Volume 3 (2021), Issue 10
MINI REVIEW
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