ACADEMIA Letters

Electroactive Polymer Composites: Future of Clean

Energy Applications
Pradip Thakur, Department of Physics, Netaji Nagar College for Women, Kolkata:
700092, India

Electroactive polymer nanocomposites (NCs) with improved dielectric properties have drawn
tremendous interest due to their diverse applications including high energy density arrays of
capacitors, light switches or displays, piezoelectric or pyroelectric sensors and in development
of diverse film based energy storage devices, high performance electromechanical devices,
piezoelectric nanogenerator, thin film transistors, non-volatile memories and most recently in
biomedical and electronic fields.[1-5]
Studies on spontaneously polarized or ferroelectric polymers are increasingly gaining im-
portance due to their excellent dielectric, piezoelectric, pyroelectric, ferroelectric and electro-
optic properties. The basic key element of electrical and electromechanical responses of these
electroactive polymers is the storage and movement of electrical charges in the polymer ma-
trix. Hence, the development of electroactive polymer NCs with enhanced electric energy
densities, which are dependent on dielectric constant and applied electric field has gained
tremendous interest worldwide.[10-13]
Electroactive polymers (EAPs) are a new class of polymers that change their size or shape
in response to applied electrical stimulus. Recently, EAPs are used as smart materials in di-
verse applications like energy harvesting, nanogenerators, sensors, actuators, stimuli respon-
sive biomaterials etc.[2-7]
EAPs are mainly classified into two types depending on the actuation mechanism: Ionic
and electronic. In ionic EAPs the deformation or shape change occur by the movement or
diffusion of ions and their conjugated substances within a polymer under a low driving voltage
which is nearly equal to 1-5V required for the actuation process. Whereas in electronic EAPs
the shape or size changes are driven by coulombic forces and applied electric stimulus and it

Academia Letters, August 2021 ©2021 by the author — Open Access — Distributed under CC BY 4.0

Corresponding Author: Pradip Thakur, pradipthakurju@gmail.com

Citation: Thakur, P. (2021). Electroactive Polymer Composites: Future of Clean Energy Applications.
Academia Letters, Article 2857. https://doi.org/10.20935/AL2857.

1
requires generally high activation fields (>150V/μm) which are very close to the breakdown
strength of the polymer.[1-10] A list of main EAPs:

1 Ionic EAPs
Ionic polymer gels, Conducting polymers, Ionic polymer metal composite, Carbon nanotubes
etc.

2 Electronic EAPs
Dielectric EAPs, Ferroelectric polymers, Electrostrictive graft elastomers, Electro-viscoelastic
elastomers, Electrostrictive paper, Liquid crystal elastomers etc.
Ferroelectric polymers (Electronic EAPs) mainly poly(vinylidene fluoride) (PVDF) and
its copolymers have drawn great interest to researchers in this decade due to their versatile
application possibilities in electronic and biomedical fields.
PVDF is a semicrystalline, highly non-reactive, light weighted and pure thermoplastic
fluoro-polymer with glass transition temperature (Tg) of about -35 °C and is synthesized
directly from the polymerization of vinylidene difluoride (VDF) monomer. PVDF chains
consist of many elementary repeating unit i.e. monomer vinylidene Difluoride (VDF) (CH2-
CF2) which are chemically linked together during polymerization process. Thus, the repeated
molecular formula of PVDF is [(CH2-CF2)n]. Semi-crystalline PVDF has five crystalline
polymorphs α, β, γ, δ and ε. Among these the most common and thermodynamically sta-
ble polymorph of PVDF is the nonpolar α-phase which have a monoclinic unit cell with
TGTG฀ (T-trans, G-gauche+, G฀-gauche) dihedral conformation. The electroactive or polar
polymorph β-phase and γ have an orthorhombic unit cell with all-trans (TTTT) conformation
(μ = 7 x 10-30 C-m per repeat) and TTTGTTG฀ conformation respectively. The β phase shows
highest ferroelectric, piezoelectric, pyroelectric and dielectric property than other phases. The
δ and ε polymorphs are the polar and anti-polar equivalent of α and γ phase respectively.[1-3,
11-13]
Previously PVDF is commonly used as insulation kits on electrical wires, because of good
flexibility, low weight, low thermal conductivity, high chemical corrosion resistance, and heat
resistance. But after the invention of the piezoelectricity of the polymer the versatile areas of
application have been opened. Electroactive β-PVDF and high dielectric as well as piezo-
electric PVDF based nanocomposite thin films has been suitably used in the fields of sensors
and actuators, energy storage devices (like capacitors, fuel cells, lithium ion batteries etc.),

Academia Letters, August 2021 ©2021 by the author — Open Access — Distributed under CC BY 4.0

Corresponding Author: Pradip Thakur, pradipthakurju@gmail.com

Citation: Thakur, P. (2021). Electroactive Polymer Composites: Future of Clean Energy Applications.
Academia Letters, Article 2857. https://doi.org/10.20935/AL2857.

2
photovoltaically self-charging cell, non-volatile memory, piezoelectric nanogenerator, energy
harvester and more recently in the biomedical field as artificial muscles and smart skins.[8-13]
My previous research deals with the synthesis and characterization of electroactive PVDF
composite thin films having large dielectric constants by incorporating clays (kaolinite and
halloysite), metal oxide nanoparticle (Fe2O3, Co3O4), Ni(OH)2 nanoparticle, WO3.H2O
nanoparticle and hydrated rare earth salt (Ce(NO3)3·6H2O and Y(NO3)3·6H2O). Simple so-
lution casting method has been developed to achieve β phase and large dielectric properties
by doping clay minerals, WO3.H2O nanoparticle and hydrated rare earth salt in PVDF ma-
trix. Whereas Fe2O3, Co3O4 and Ni(OH)2 nanoparticles are formed in the polymer matrix
via simple in situ process. It has been found that the composite thin films exhibited more
than 80% electroactive β crystalline polymorphs after incorporating 10.7 volume% Ni(OH)2
NBs, 10 mass% Ce(NO3)3·6H2O and 5 mass% of Y(NO3)3·6H2O in the polymer matrix
respectively.[6-9] The electroactive β phase nucleation mechanism are explained in terms of
electrostatic or ion-dipole interaction and formation of hydrogen bonds. The origin of β phase
nucleation for clay minerals (kaolinite and halloysite), Fe2O3, Co3O4 and WO3.H2O NPs
incorporated PVDF thin films have been suitably discussed in terms of strong electrostatic
or ion dipole interactions between the positive -CH2 charge density of polymer chains and
negatively charged nanoparticle surfaces of the fillers. Whereas for Ni(OH)2 NBs and rare
earth salt doped PVDF thin films, formation and stabilization of β polymorph occurred due
to strong interaction via hydrogen bonding between the F atoms of the polymer chains and
–OH groups of Ni(OH)2 or water molecules of the salts. This interaction drives the polymer
chains in longer TTTT conformation on the surfaces of the fillers resulting nucleation of large
piezoelectric β phase in the composite samples.[6=7, 11, 13]
The dielectric properties have also been shown to improve due to the addition of the fillers
in the polymer matrix. Polymer thin film with huge dielectric value (ε 3.1 x 106 at 20 Hz) has
been achieved by incorporating 23.1 volume% Ni(OH)2 NBs in PVDF matrix. The incorpora-
tion of Fe2O3 and Co3O4 in polymer matrix also resulted in high dielectric percolative com-
posites. Impregnations of salts (Ce(NO3)3·6H2O and Y(NO3)3·6H2O) also lead to remark-
able improvement in dielectric properties. The other fillers like clay minerals and WO3.H2O
NPs improved the dielectric properties only moderately. [6=11] This large enhancement of di-
electric properties is mainly due to occurrence of the large interfacial polarization in between
the interfaces of the fillers and polymer chains.
Thus, novel electroactive PVDF based high dielectric composite thin films have been pre-
pared via facile in situ and solution casting method for development of sensors, actuators,
piezoelectric nanogenerators, energy storage devices like super-capacitors and Li ion battery,
energy harvesters and biomedical applications.

Academia Letters, August 2021 ©2021 by the author — Open Access — Distributed under CC BY 4.0

Corresponding Author: Pradip Thakur, pradipthakurju@gmail.com

Citation: Thakur, P. (2021). Electroactive Polymer Composites: Future of Clean Energy Applications.
Academia Letters, Article 2857. https://doi.org/10.20935/AL2857.

3
 Currently, a large part of the scientific community is involved in polymer based research
especially that addresses problems of energy and healthcare. Therefore tremendous attention
has been drawn towards the investigation and development of electroactive and high dielec-
tric polymer NCs because of their versatile applications in the areas of electronics, energy
and more recently in biomedical applications. However, there still exists some missing dots
that would join the gap between the excellent physico-chemical properties of these devel-
oped polymer NC thin films and practical applications in the proposed areas. Some studies
focusing to investigate the P-E loops, break down strengths, piezoelectric coefficient (d33)
of the newly developed polymer composite thin films and fabrication of energy harvesting
devices will be devoted in future. Finally, it is accepted by scientific communities that the
electroactive PVDF NCs with high dielectric properties are ready for practical applications
in capacitive sensors, nanogenerators, actuators due to their unique piezoelectric, pyroelec-
tric and ferroelectric response. Though there are some protocols reported by some scientific
groups to fabricate polymer based devices, much works still remain for developing devices
for practical use in modern society.

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Academia Letters, August 2021 ©2021 by the author — Open Access — Distributed under CC BY 4.0

Corresponding Author: Pradip Thakur, pradipthakurju@gmail.com

Citation: Thakur, P. (2021). Electroactive Polymer Composites: Future of Clean Energy Applications.
Academia Letters, Article 2857. https://doi.org/10.20935/AL2857.

4
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Academia Letters, August 2021 ©2021 by the author — Open Access — Distributed under CC BY 4.0

Corresponding Author: Pradip Thakur, pradipthakurju@gmail.com

Citation: Thakur, P. (2021). Electroactive Polymer Composites: Future of Clean Energy Applications.
Academia Letters, Article 2857. https://doi.org/10.20935/AL2857.