Energy Reports 8 (2022) 12853–12870

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Energy Reports
journal homepage: www.elsevier.com/locate/egyr

Review article

Review of emerging materials for PVDF-based energy harvesting

∗
Albert Veved a,b , , Geh Wilson Ejuh c,d , Noël Djongyang a
a
University of Maroua, National Advanced School of Engineering of Maroua, Department of Renewable Energy, P.O. Box 46, Maroua, Cameroon
b
University of Ngaoundéré, School of Chemical Engineering and Mineral Industries, Department of Basic and Technical Engineering Sciences, P.O.
Box 455, Ngaoundéré, Cameroon
c
University of Bamenda, National Higher Polytechnic Institute, Department of Electrical and Electronic Engineering, P.O. Box 39, Bambili, Cameroon
d
University of Dschang, IUT-FV Bandjoun, Department of General and Scientific Studies, P.O. Box 134, Bandjoun, Cameroon

article info a b s t r a c t

Article history: The purpose of this study is to review the literature on the techniques for improving the physico-
Received 19 May 2022 chemical properties of Polyvinyl Difluoride (PVDF) and its application. It has been proven that the
Received in revised form 2 September 2022 piezoelectric and dielectric properties, polar phase, thermal stability, flexibility and adaptability of
Accepted 18 September 2022
PVDF can be improved by modifying its matrix with suitable nanofillers and using a good manufactured
Available online xxxx
method like electrospinning. The article first briefly presents the fundamental properties of PVDF
Keywords: and then the potential nanofillers as well as the approaches used in the literature. As regards
PVDF the second phases, the additives Al(NO3 )3.9H2 O, SiO2 , MoS2 ; ZnO, TiO2 , BaTiO3 , RGO, TiO2 /BaTiO3 ,
Nanocharges CdS; BiFeO3 ; MgO; HfO2 ; ZrO2 ; (Na,K)NbO3 and Au showed efficient improvements in PVDF films.
Composite polymers Their contributions to the piezoelectric response of electrospun PVDF are highly competitive. The
Improve properties
concentration of nanofibers must be properly taken into account. As for the method, electrospinning
is an efficient, economical and relatively simple method for the preparation of PVDF.
© 2022 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND
license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Contents

1. Introduction................................................................................................................................................................................................................... 12853
2. Energy harvesting ......................................................................................................................................................................................................... 12854
2.1. Piezoelectric effects ......................................................................................................................................................................................... 12854
2.2. Energy harvesting mechanism ...................................................................................................................................................................... 12854
2.3. Piezoelectric modes and categories ............................................................................................................................................................... 12855
2.3.1. Piezoelectric modes ......................................................................................................................................................................... 12855
2.3.2. Piezoelectric categories .................................................................................................................................................................. 12855
2.3.3. Centrosymmetric character of piezoelectric materials ............................................................................................................... 12856
2.3.4. Crystallinity and microscopy dipole ............................................................................................................................................. 12857
3. Piezoelectric polymers and its copolymers (virgin and modified)......................................................................................................................... 12857
3.1. Different phases of PVDF and P(VDF-TrFE) .................................................................................................................................................. 12857
3.2. Improvement of piezoelectric properties of PVDF and P(VDF-TrFE) ......................................................................................................... 12859
3.2.1. Methods for improving piezoelectric properties .......................................................................................................................... 12859
3.2.2. Improvement of piezoelectric and optoelectronic properties, and the thermal stability of PVDF by adding nanofillers .. 12859
3.2.3. Morphotropic Phase Boundary (MPB) in piezoelectric polymers ............................................................................................. 12866
4. Synthesis, expectation and future development of composite piezoelectric ........................................................................................................ 12866
5. Conclusion ..................................................................................................................................................................................................................... 12867
Declaration of competing interest.............................................................................................................................................................................. 12867
Data availability ............................................................................................................................................................................................................ 12867
Acknowledgments ........................................................................................................................................................................................................ 12867
References ..................................................................................................................................................................................................................... 12868

1. Introduction
∗ Corresponding author at: University of Ngaoundéré, School of Chemical En-
gineering and Mineral Industries, Department of Basic and Technical Engineering For more than twenty years, countless researchers have stud-
Sciences, P.O. Box 455, Ngaoundéré, Cameroon. ied ambient energy recovery technologies as the most convincing
E-mail address: veved.albert@yahoo.fr (A. Veved).
https://doi.org/10.1016/j.egyr.2022.09.076
2352-4847/© 2022 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
A. Veved, G.W. Ejuh and N. Djongyang
choice compared to conventional energy sources, namely batter-
ies (Safaei et al., 2019). The ambient energy sources can supply
electrical power to nomadic devices, namely the telephone, ra-
dios, torches, agricultural sprayers, etc. Limited life and the need
to periodically recharge or replace batteries are major prob-
lems for nomadic devices reported in literature (Safaei et al.,
2019; Chalasani and Conrad, 2008). In addition, ambient energy
resources are available and come in several forms. The most
recurrent of which are: vibrating energy, thermal energy and
radiant energy. Among these energy sources, vibrating energy
is the most dominant in nature and in structures according to
literature (Chakhchaoui et al., 2020; Safaei et al., 2019; Tiwari
et al., 2019; Wang et al., 2018a,b; Tran et al., 2018). Various
transduction pathways (piezoelectric, electromagnetic and elec-
trostatic generators) are often used to convert vibrational energy
into helpful electrical energy. In accordance with the literature
(Safaei et al., 2019; Chalasani and Conrad, 2008), piezoelectric
conversion technique is the most used because they have a high
electro-mechanical coupling coefficient and power density com-
pared to those of electromagnetic and electrostatic transduction
pathway. The main role of piezoelectric transducers is to generate
electrical energy from the human activities and movements of
the structure, and vice versa (Chakhchaoui et al., 2020). Recently,
new transduction techniques, improved electrical circuits and
reliable analytical models have been established to upgrade the
energy conversion and recovery devices reported in the literature
(Harne and Wang, 2013; Gibson, 2010). Piezoelectric materials
developed in industries and marketed are ceramics, polymers, ce-
ramics/polymers, composites and polymers/nanocharges (Valiya-
neerilakkal et al., 2017; Bhavanasi et al., 2016). Today, the main
common objectives focus much more on polymers (PVDF) and its
copolymers P(VDF-TrFE), because of their smoothness, flexibility,
lightness, availability, resilience to fatigue and above all their
adaptability to all forms of portable electronic devices (Bhavanasi
et al., 2016; Yaqoob et al., 2016; Maity et al., 2018; Pascariu et al.,
2018). In view of these compelling properties of piezoelectric
polymers, how to further improve them remains a major concern
for researchers around the world. One of the major alterna-
tives presented by the literature is to introduce, in the PVDF
matrix, materials capable to improve the β -phase of the com-
posite (Cho et al., 2022; Ahmed et al., 2022; Akash et al., 2021).
This mechanism makes it possible to promote the alignment
of the microscopic dipoles within the composite (Chakhchaoui
et al., 2020; Habibur et al., 2018; Hu et al., 2018; Yousry et al.,
2018; Badali et al., 2019; Roy and Mandal, 2018; Dash et al.,
2017; Biswas et al., 2017). According to Pan et al. to improve
the properties of the PVDF composite sensor and actuator, a
dopant/filler must be added (Pan et al., 2016). For this pur-
pose, Lakshmi et al. have successfully increased the permittivity
of polymer nanoparticles (NP) using PolyVinylPyrrolidone (PVP)
nanocharges (Lakshmi et al., 2017). If we stick to the literature
(Chakhchaoui et al., 2020; Pascariu et al., 2018; Surmenev et al.,
2019; Arshad et al., 2019; Veved et al., 2019, 2020a), the doping
materials most used are metal oxides such as zinc oxide (ZnO),
magnesium oxide (MgO), titanium dioxide (TiO2 ), hafnia (HfO2 ),
zirconia (ZrO2 ), graphene oxide (GO), reduced graphene oxide
(rGO), nanoparticle such as barium titanate (BaTiO3 ), salts such
as Lanthanum(III) chloride (LaCl3 ), erbium(III) chloride (ErCl3 ),
Gadolinium(III) chloride (GdCl3 ), potassium and sodium niobate
(KNaNbO3 ), carbon nanotubes (CNTs), metallic NP such as silver
(Ag), and platinum (Pt), etc. In addition to that, PVDF modi-
fied with stable nanocharges has good chemical flexibility, good
chemical stability and improved chemical hardness (Veved et al.,
2020b). It also has a privileged docility compared to virgin PVDF
(Veved et al., 2020b). Interestingly, the addition of ferroelectric
materials as a second phase contributes to the improvement of
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Energy Reports 8 (2022) 12853–12870
β -phase of the composite (Chakhchaoui et al., 2020). It also pools
to the increases of dielectric, piezoelectric and optoelectronic
properties (Veved et al., 2019, 2020a). To our knowledge, the
precise understanding of the behavior of piezoelectric materials
as well as their structure is far from being reached to date.
The method widely employed in the literature to characterize
piezoelectric materials is XRD (X-ray diffraction) (Habibur et al.,
2018; Gaur and Rana, 2019; El-Metwally et al., 2019; Balpande
et al., 2016). This method makes it possible to analyze the mor-
phology and the crystalline structure of the material. In addition,
recent published studies use the DFT (Density Functional Theory)
method implemented in Gaussian to understand, at the atomic
scale, the behavior of the molecule with respect to external
stresses (Veved et al., 2019, 2020a; Sarkar and Kundu, 2018; Fu
et al., 2018; Buensuceso et al., 2016). The DFT method essentially
assesses the physicochemical parameters once the positions of
the atoms in space and in time within the solid are known
(Veved et al., 2019, 2020a). In this review, we briefly present
the notion and different categories of piezoelectric materials and
their frequent applications. The fundamental properties which
characterize them are also presented. The state of the art as well
as the recent publications devoted to piezoelectric composites
based on PVDF main for the improvement of optoelectronic, di-
electric, piezoelectric and electromechanical coupling properties
is exposed. The improvement of β -phase and the output voltage
by introducing NP into the PVDF matrix is also reviewed. In
addition, the main characterization methods recently reported in
the literature are also examined.
2. Energy harvesting
2.1. Piezoelectric effects
For more than a century, following the discovery of piezo-
electricity by the brothers Jacques and Marie Curie in 1880, an
intense research and application activity is dedicated to materi-
als with piezoelectric properties, namely ferroelectric materials
and pyroelectric materials. A piezoelectric material is a material
capable of converting mechanical energy into electricity and vice
versa (Veved et al., 2019; Tran et al., 2018; Arnau and Soares,
2009). In other words, the piezoelectric materials exhibit the
power of transforming vibrational energy into electricity, that
is to say an acoustic wave into an electric wave or vice versa.
Curiously two effects exist: the direct piezoelectric effect defined
as the appearance of electric charges due to the application of
a pressure and the indirect piezoelectric effect characterized by
the appearance of a deformation following an application of an
electric field. Fig. 1 shows us the situation of piezoelectric effect.
The direct piezoelectric effect (Fig. 1b) is used in the sensors,
while the indirect piezoelectric effect (Fig. 1c) is at the base of
the actuators. These combined effects make piezoelectric mate-
rials prime candidates for the development of ‘‘smart’’ systems.
These smart materials are used in different applications such as
injection mechanisms, piezoelectric motors, sonars and ultrasonic
cleaning tanks as presented in Table 1.
2.2. Energy harvesting mechanism
Piezoelectric materials have the different behavior and the
different energy conversion capacity. According to the literature,
the mechanical energy (respectively electrical energy) available
is not completely transformed into electrical energy (respectively
mechanical energy) (Wang et al., 2022; Anand, 2022). The trans-
formed energy is a function of the electromechanical coupling
coefficient (Wang et al., 2022; Anand, 2022; Yu et al., 2019). For
this reason, it is necessary to start from the overall efficiency of
A. Veved, G.W. Ejuh and N. Djongyang
Fig. 1. The two piezoelectric effects: (a) piezoelectric material without deformation; (b) direct effect (appearance of electric charges due to the application of a
pressure); (c) indirect effect (appearance of a deformation following an application of an electric field).
Fig. 2. Energy harvesting mechanism via piezoelectric material.
an energy recovery device presented in Fig. 2. The main objective
is therefore to make the yield optimal. In piezoelectricity, this
efficiency is seen as the electromechanical coupling coefficient
(Kem ). The closer the coefficient is to one, the better the material
converts electricity into vibrational energy and vice versa. These
coefficients are therefore an important characteristic of piezo-
electric materials (Veved et al., 2020a; Leung et al., 2022). They
may vary depending on the specific properties of the materials,
the geometry (asymmetry) of the materials and their mode of
vibration.
Depending on the physicochemical properties of the material
and the conditions of use, the proportion of the dielectric loss
during conversion and electrical loss during storage cannot be
precise. These arrows in Fig. 2 succinctly indicate the different
energy leaks due to the internal behavior of the material related
to the microscopic dipoles. In addition, not all materials have the
same performance. Studies are therefore carried out to reduce
these losses either by modifying the internal structure of the
material (Xie et al., 2021) or by using an efficient design method
(Feng et al., 2021). The lower these losses, the higher the stored
energy according to the literature (Patel et al., 2021; Khatua and
Karan, 2016; Yousry et al., 2018; Wang et al., 2022; Anand, 2022).
The conversion yields of vibrational energy into electricity are
presented as follows (Mistral, 2008):
ea
ηa = (1)
em
er
ηc = (2)
ea
where, ea is the energy absorbed by the polymer, em is the
mechanical energy supplied to the polymer, er is the recovered
electrical energy, ηa is the mechanical absorption coefficient and
ηc is the electromechanical conversion efficiency. Therefore, Kem
can be expressed by Eq. (3):
(Kem )2 = ηc ηa
Kem is the electromechanical and dimensionless coupling coeffi-
cient whose value is between 0 and 1 which is usually expressed
Energy Reports 8 (2022) 12853–12870
as a percentage (Khanbareh et al., 2022; Wang et al., 2022; Anand,
2022). For this, a good piezoelectric material must have this
coefficient tending towards 1 (Khanbareh et al., 2022). This is
the case of Chen et al. which introduced less than 2 mol% of
fluorinated alkyne monomers into the P(VDF-TrFE) matrix and
markedly improved the electromechanical coupling coefficient by
88% (Chen et al., 2022).
2.3. Piezoelectric modes and categories
2.3.1. Piezoelectric modes
For a piezoelectric material to optimally perform a required
function, the mechanical or electrical actions must be well ori-
ented (Khanbareh et al., 2022; Wang et al., 2022). Due to their
particular crystallographic structure, piezoelectric materials are
anisotropic reported in literature (Wang et al., 2022), which
means that the properties vary depending on the orientation of
the crystal. The calculation of the piezoelectric coefficients of an
anisotropic material strongly depends on the orientation of the
microscopic dipoles (Veved et al., 2020a; Wang et al., 2018a,b).
In literature, there are a dozen piezoelectric modes which define
these orientations. Among all these modes, modes 33 and 31 are
the fundamental modes which make it possible to write all the
other modes. These two lateral modes are represented according
to Fig. 3.
2.3.2. Piezoelectric categories
There are essentially four main categories of piezoelectric
materials presented in literature and in the piezoelectric industry.
We have crystals, ceramics, polymers and piezoelectric compos-
ites (Akdogan et al., 2005). The crystals are natural piezoelec-
tric materials. We have quartz (SiO2 ), lithium niobate (LiNbO3 ),
gallium orthophosphate (GaPO3 ) and lithium tantalate (LiTaO3 ).
Crystals are widely used in a range of applications, from oscil-
(3)
lators to microbalances. The resonant frequency of crystals is
independent of the temperature of the first order (Akdogan et al.,
2005). This is desirable in mass detection and synchronization
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A. Veved, G.W. Ejuh and N. Djongyang Energy Reports 8 (2022) 12853–12870

Fig. 3. The two most recurrent piezoelectric modes in the description and analysis of the orientations of microscopic dipoles.

applications. According to the literature (Akdogan et al., 2005),

the crystals present a very high Curie temperature and have
a low piezoelectric coefficient. They are very fragile and their
Synthesis is very expensive. Piezoelectric ceramics are inorganic
polycrystalline materials, with a complex structure. They have
an essential characteristic compared to other piezoelectric ma-
terials: the atoms of their crystal lattice are in general very
strongly linked between them by strong bonds (ionic and co-
valent). Ceramics currently plays an important role, profiling its
electrical, electromechanical, insulating and optical properties.
Indeed, there are many different kinds of ceramic compositions
whose dielectric and mechanical properties vary considerably,
so that there is always a ceramic suitable for a particular ap-
plication. We cite among others: BaTiO3 (BT), PZT, PbTiO3 and
Pb(NbO3 )Z. Discovered in 1969, piezoelectric polymers are more
and more very promising candidates in the miniaturization of
systems. Certain polymers such as PVDF and copolymers such as
PolyVinyliDeneFluoride ThreeFluorideEthylene (PVDF-TrFE) can Fig. 4. Schematic illustrative showing the difference between centrosymmetric
and no centrosymmetric materials.
acquire important piezoelectric properties. They are character-
ized by low acoustic impedance and are therefore important from
this point of view according to the literature (Tong, 2018). Finally, Table 1
the piezoelectric composites result from the association of at least Piezoelectric materials categories and their performances (Kem electromechanical
one piezoelectric material with one or more non-piezoelectric coupling coefficient; d piezoelectric coefficient; Tc Curie temperature).
phases. They appeared in the early 1980s and represent the Category Typical materials Advantages Disadvantages
major advance in the field of piezoelectric materials and are now Natural SiO2 , AlPO4 , Very high T c Very weak d,
reaching the stage of industrialization. Their origin come from crystals tourmaline, fragile, high
the observation that no existing material had both an acous- sucrose, Topaz, . . . cost
tic impedance low enough to properly transmit its energy to Synthetic GaPO4 , Very high T c Very weak d,
biological tissues and a high electromechanical coupling coeffi- crystals La3 Ga5 SiO14 fragile, high
cost
cient. Indeed, some researchers have shown that ceramics suffer
from very high acoustic impedance while polymers suffer from Piezo- (K,Na)NbO3 , High d, High K em , Heavy, fragile
ceramics BiFeO3 , Bi4 Ti3 O12 , High T c ,
very low electromechanical coupling coefficient. The idea was Na0.5 Bi0.5 TiO3
therefore born that it was necessary to use both a ceramic of
Synthetic BaTiO3 , PbTiO3 , High d, High T c Heavy, fragile,
high coupling coefficient, associated with a passive material of ceramics PZT, KNbO3 , Toxicity
low acoustic impedance so that the resulting material has lower LiNbO3 , LiTaO3 ,
acoustic impedance while keeping a coefficient of coupling com- Na2 WO3 , ZnO, . . .
parable to that of a ceramic. However, the use of higher frequency Polymers PVDF, P(VDF-TrFE) Flexibility, Low d, low T c
by piezoelectric composites is currently limited by the presence Lightness,
of undesirable resonance modes linked to the internal structure of Adaptability
these materials. Each category of piezoelectric material presents Organic PNTs Flexibility, Low d
some advantages and disadvantages. The Table 1 summarizes the Nano- Adaptability
structure
performance of the different piezoelectric materials developed
and presented in literature (Akdogan et al., 2005; Tong, 2018). Piezo- PZT/BaTiO3 , Improved Partial com-
composites PTFE/PDMS, properties, prehension
PVDF/nanocharges, improved β -phase
2.3.3. Centrosymmetric character of piezoelectric materials PZT/PVDF,
The properties of piezo-materials are directly related to their PVDF/metals
symmetry and more precisely to their point group symmetry. The
symmetry properties of crystals have a fundamental relevance for
their existence as piezoelectric material or not as piezoelectric
material. Any material with a center of symmetry cannot be The piezoelectric effect in a piezo-material results essentially
piezoelectric while those with no center of symmetry as pre- from the existence of internal electric dipoles. These dipoles are
sented in Fig. 4 according to the literature can be piezoelectric created by the separation at the scale of the mesh of the center of
(Dorbakov et al., 2019). gravity of the positive charges from that of the negative charges
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A. Veved, G.W. Ejuh and N. Djongyang
Fig. 5. Hysteresis curve highlighting the behavior of microscopic dipoles within
a piezoelectric material during polarization (Harada et al., 2019).
under the effect of an external constraint as reported in literature
by Yan et al. (2019).
2.3.4. Crystallinity and microscopy dipole
In general, we have 32 classes of crystalline materials found
in literature (Costa et al., 2019; Cornfeld and Chapman, 2019).
Among the 32 existing crystalline classes, 20 have the piezo-
electric effect and all have absence a center of symmetry (Costa
et al., 2019). 10 of the 20 piezoelectric crystalline classes ex-
hibit a spontaneous electrical polarization or permanent dipole
moment in absence of stress or external field; they are called
polar. Crystals belonging to these classes are referred to as py-
roelectric because of the variation in spontaneous polarization
with temperature (Cornfeld and Chapman, 2019). The so-called
ferroelectric materials have a zero-field remnant polarization,
responsible for their anisotropy and conversion properties such as
HfO2 reported in literature (Veved et al., 2019). This macroscopic
polarization is likely to vary when the material is subjected to
strong electrical, mechanical and thermal stresses, which can
induce a highly non-linear and hysterical behavior and a decrease
in the conversion efficiency (Veved et al., 2020a). The application
of an external stress can have two effects: an intrinsic effect, at
the scale of the mesh, which results in a variation of the dipole
moment associated with the relative displacement of the ions,
and an extrinsic effect on the scale of domains, which results
in a switchover of the polarization in the different directions
allowed by the crystallographic structure (Harada et al., 2019;
You et al., 2019; Tan et al., 2018). In Fig. 5, we present the
Hysteresis curve highlighting the behavior of microscopic dipoles
during the polarization within a piezoelectric material found in
literature (Harada et al., 2019; You et al., 2019).
For piezoelectric behavior to be possible in a material, cer-
tain conditions must be made (Costa et al., 2019; Cornfeld and
Chapman, 2019). Firstly, it is necessary for the material to contain
permanent dipoles capable of changing the orientation under
the clout of an outer electric field. Secondly, it is necessary that
the already oriented dipoles can maintain this direction even
if relatively large deformations are applied according to Fig. 6.
The compound should not be easily depolarized permanently
because of the applied stresses. From the microscopic point of
view, several phenomena occur under the effect of an electric
field: the electronic polarization due to the displacement and the
deformation of the electronic cloud, the atomic or ionic polar-
ization due to displacements of atoms or ions, the orientation
polarization, for materials initially polarized, but whose elements
do not necessarily have the same orientation and the macro-
scopic polarization due to displacement of charges throughout
the material.
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Energy Reports 8 (2022) 12853–12870
The constituent equations of piezo-materials which arise from
the behavior of microscopic dipoles are presented below. The
application of an alternating electric field of amplitude E >
Ec across a piezoelectric material produces a hysteresis cycle
between the electric displacement vector Di (C m2 ) and the ap-
plied field E i (Volt) (Ejuh et al., 2018; Veved et al., 2020a, 2019;
Tchangnwa Nya et al., 2017; Ejuh et al., 2017).
Di = ε0 ε Ei + Pi (4)
With, 1 < i < 3, relative to the direction of polarization, ε the
dielectric permittivity of the material, Di is electric displacement
vector, P i is polarization vector.
Under the effect of certain constraints (thermal or mechan-
ical), the remnant polarization (Pr ) varies. These materials are
called pyroelectric material if Pr varies with temperature and
piezoelectric material during variation of Pr with mechanical
stress. The piezoelectric bill is manifested by a variation in the
macroscopic polarization ∆P during the application of a stress
∆σ on the sample (Veved et al., 2020a, 2019).
∆Pi = dij ∆σj (5)
where, i = 1–3 and j = 1–6 corresponding to the axis of
polarization and application of the constrained respectively. The
piezoelectric coefficient dij represents the coefficient measured by
applying a stress in the polarization direction of the sample.
The general expression of the piezoelectric coefficient accord-
ing to the literature (Veved et al., 2020a, 2019) is given by the
relation in Eq. (6) below:
δ Pi
dij = (6)
δσj
The piezoelectric coefficient is made up of two terms. The first
effect is called the primary piezoelectric effect. This is the direct
variation of the dipole moment with the constraint at constant
volume. The piezoelectric coefficient linked to the primary effect
is of positive sign. The second term, called secondary piezoelec-
tric, links the variation in polarization with the expansion or
contraction of the polymer under stress. The sign of d associated
with the secondary piezoelectric effect is negative. Similarly, the
pyroelectric coefficient p corresponds to a change in remnant po-
larization under the effect of a change in temperature reported in
literature (Veved et al., 2020a, 2019). It is obtained by association
of a primary effect (p > 0) and a secondary bill (p < 0).
δP
p= (7)
δT
The primary effect representing the variation ∆P under the effect
of temperature and the secondary effect represents the thermal
expansion of the material.
3. Piezoelectric polymers and its copolymers (virgin and mod-
ified)
3.1. Different phases of PVDF and P(VDF-TrFE)
Piezoelectric polymers particularly hold our attention in this
document in the context where the need for intelligent mi-
crosystems is clearly felt. Polymers such as PVDF and its copoly-
mers P(VDF-TrFE) exhibit remarkable piezoelectric properties.
Polymers in general are characterized by their good flexibil-
ity, lightness, adaptability and low acoustic impedance reported
in the literature (Cho et al., 2022; Maity et al., 2018; Khalifa
et al., 2018). These characteristics encourage polymers to be good
candidates for nomadic devices according to literature (Veved
et al., 2020b). However, until recently, their electromechanical
coupling coefficients were much lower than those of ceramics.
A. Veved, G.W. Ejuh and N. Djongyang Energy Reports 8 (2022) 12853–12870

Fig. 6. Schematic illustrative of microscopic dipoles within a piezoelectric material: (a) random orientation of the microscopic dipoles before polarization;
(b) polarization phase under a continuous electric field E; (c) remnant polarization P0 after suppressing the electric field E.

Fig. 7. Illustration of the three phases of piezoelectric materials existing in the virgin PVDF industry: β -phase, α -phase and γ -phase; and copolymers P(VDF-TrFE).

Fig. 8. Diagram illustrating the polarization of the β -phase under the effect of traction or compression.

Improved manufacturing techniques for PVDF as well as copoly- When the material is stressed in tension or in compression, an
mers have led to more enhanced values of piezoelectric and electric field appears as shown in Fig. 8. The electric field created
dielectric properties (Xiong et al., 2017). PVDF exhibit 5 most
and the stress undergone are linked by the constitutive equation
common crystalline phases: α , β , γ , δ and ε phase reported in
literature (Hu et al., 2018; Sarkar and Kundu, 2018; Ruan et al., of piezoelectricity (Wang et al., 2022; Veved et al., 2020a; Tong,
2018; Zhu et al., 2015). The β -phase is the most polar and show 2018).
ferroelectric and piezoelectric properties according to literature
D = ε T E + dT
{
(Ahmed et al., 2022; Sarkar and Kundu, 2018; Ruan et al., 2018;
(8)
Zhu et al., 2015) (see Fig. 7). S = dE + S E T
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A. Veved, G.W. Ejuh and N. Djongyang
With T , S, S E , D, E and ε T express respectively stress, strain,
compliance, electric displacement, the electric field and the per-
mittivity and d, the piezoelectric constant describe in Eq. (8).
3.2. Improvement of piezoelectric properties of PVDF and P(VDF-
TrFE)
3.2.1. Methods for improving piezoelectric properties
Recent studies have shown that researchers have a common
goal to improve the physicochemical properties of piezoelectric
polymers so that they are more competitive. There are several
techniques and methods used in the literature to improve these
properties. The technique that seems to be the most convenient
consists in modifying the PVDF matrix with nanofillers to im-
prove either the dielectric properties (Liu et al., 2022; Celebi
et al., 2022; Ma et al., 2018; Veved et al., 2020a,b), or the po-
lar phase (Cho et al., 2022; Ahmed et al., 2022; Akash et al.,
2021), or thermal stability (Sagar et al., 2022; Faust and Lakes,
2015; Veved et al., 2020a,b; Begum et al., 2021), or the flex-
ibility and adaptability of the material (Veved et al., 2020a,b),
or the piezoelectric coefficient (Chen et al., 2022; Sagar et al.,
2022; Ma et al., 2018; Cho et al., 2022; Begum et al., 2021;
Veved et al., 2020a,b). Recently and widely used second phases
are: Salt Al(NO3 )3 .9H2 O (Yousry et al., 2018); SiO2 (Zhu et al.,
2015); MoS2 (Arunguvai and Lakshmi, 2021) ; Zinc oxide and
(3-Aminopropyl) trimethoxysilane (Akash et al., 2021); TiO2 (Pas-
cariu et al., 2018; Chakhchaoui et al., 2020); BaTiO3 (Cho et al.,
2022; Valiyaneerilakkal et al., 2017); reduce Graphene Oxide
(Habibur et al., 2018; Roy and Mandal, 2018); TiO2/BaTiO3 (Hu
et al., 2018); CdS (Thakur et al., 2018); BiFeO3 (Dash et al., 2017);
PolyVinylPyrrolidone (Lakshmi et al., 2017); Magnesium Oxide
(Arshad et al., 2019); HfO2 (Liu et al., 2022; Veved et al., 2019);
ZrO2 (Veved et al., 2020a); Li4 Ti5 O12 (El-Metwally et al., 2019);
(Na,K)NbO3 (Kim et al., 2020); Au (Mahanty et al., 2019).
According to the literature, the physicochemical properties
of piezoelectric materials can be improved by taking into ac-
count the manufacturing method and environmental parame-
ters such as temperature and humidity (Valadorou et al., 2022).
For example, Fig. 9 illustrate the robust super hydrophobic sur-
face based on PVDF membrane via the caging effect of confined
micro/nanostructure (Xiong et al., 2017)
3.2.2. Improvement of piezoelectric and optoelectronic properties,
and the thermal stability of PVDF by adding nanofillers
In order to improve the piezoelectric properties, several re-
searches have been undertaken. Yousry et al. (2018) conducted
a study on the mechanism to improve the polarization and
piezoelectric parameters of PVDF. Indeed, PVDF is considered as
an excellent piezoelectric material with regard to its flexibility,
strength and ability to adapt to any shape and to be integrated
into portable devices. Nevertheless, the piezoelectric properties of
the PVDF, namely K em , dij , quality factor and acoustic impedance,
are not appealing compared to ceramics (Yousry et al., 2018). The
objective of their study was therefore to improve the piezoelectric
properties by reinforcing the polarization and intrinsic parame-
ters of the PVDF by modifying its matrix with salt Al(NO3 )3 .9H2 O
according to Fig. 10. The work consisted of introducing 0%, 8%,
10%, 12%, 14% and 16% salt into the PVDF matrix.
We note in Fig. 11 that the piezoelectric coefficient, the dielec-
tric constant and the dielectric loss of virgin PVDF are respectively
23 µm/V; 10, 15 and 3.10−3 . These results corroborate those of
Satyabati et al. (2017) who believe that the piezoelectric coeffi-
cient of virgin PVDF is between 12 and 23 pm/V, taken up by
Veved et al. (2020a). At 8% of the introduced salt, there is a
reduction in the diameter of the PVDF fibers and the elimination
of the formation of drops. Optimization at 10% of the salt content
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Fig. 9. Diagram illustrative of robust super hydrophobic surface based on PVDF
membrane via the caging effect of confined micro/nanostructure (Xiong et al.,
2017).
maintains the high dielectric constant and relatively low dielec-
tric loss as possible. In brief, hydration of PVDF with salt promotes
formation of the polar phase and improves the piezoelectric con-
stant and the voltage coefficient (d33 = −116 pm/V, g 33 = −1180
Vm/N).
This piezoelectric coefficient in absolute value is much higher
compared to the results obtained by Veved et al. d = 25.635
pC/N, when they modify the PVDF matrix with hafnia (Veved
et al., 2019) and d = 17 pC/N when the latter is modified with
zirconia (Veved et al., 2020a). By introducing less than 2 mole
% fluorinated alkyne monomers into the PVDF-TrFE matrix, Chen
et al. were able to increase the piezoelectric coefficient d33 above
1000 pm/V, an all-time high (Chen et al., 2022).
It should also be noted that the dielectric constant varies
according to the frequency as reported in the literature (Celebi
et al., 2022). The Fig. 12 show that the dielectric constants of
virgin PVDF at 102 Hz and 106 Hz are respectively 10.9 and 7.1.
The introduction of BaTiO3 (BT) and/or SiO2 into the PVDF matrix
significantly improves the dielectric constants. Thus, at 102 Hz,
the dielectric constants of BT/PVDF are 14.2 and 18.7 respectively
for the volume concentrations of BT 5% and 15%. These results
show that the dielectric constant of PVDF varies not only as a
function of frequency (Celebi et al., 2022) but also and above all
as a function of the concentration of nanocharges introduced into
its matrix (Celebi et al., 2022; Yousry et al., 2018).
In the same line, Kachroudi et al. (2016) published an arti-
cle entitled: ‘‘Study of the piezoelectric properties of a polymer
piezoelectric material for micro mechanical vibration sensors’’.
Their work consisted of optimizing the piezoelectric response
and the dynamic piezoelectric coefficient of an electroactive poly-
mer (PDMS) followed by the presentation of the low cost man-
ufacturing process. The piezoelectric response of these meta-
materials has been theoretically processed through a simplified
model based on alternating massive layers and micro-structured
layers of polymers. The main objective of their work was to
introduce microcavities into a host matrix of polymer that do not
only reduces the overall mass of structure but the air held in the
microcavities is likely to be ionized following the application of
a high electric field on these materials. The ionization of the air
thus generates charges of opposite signs which are implanted at
A. Veved, G.W. Ejuh and N. Djongyang
Fig. 10. PVDF matrix modified by salt in order to enhance β -phase; (a) Interaction between PVDF and salt; (b) Formation of the pore at the surface polarized;
(c) Appearance of charged voids at the surface (Yousry et al., 2018).
Fig. 11. Diagram presenting the piezoelectric coefficient, the dielectric constant and the dielectric loss of salt doped-PVDF as a function of salt concentration, measured
at 25 ◦ C and 1 kHz reported in literature (Yousry et al., 2018).
the air/polymer separation surfaces. Each microcavity is similar
to a micro-dipole. The optimization of the piezoelectric polymers
allowed having the piezoelectric coefficient up to 34 pC/N largely
above that of PVDF which is 20 pC/N according to the authors.
These values remain lower than the record results obtained by
Yousry et al. (2018) and Chen et al. (2022).
Zhu et al. (2015), on their part, conducted a study on Zwit-
terionic (SiO2 ) NP as new additives to improve the antifouling
properties of PVDF membranes (Zhu et al., 2015). Indeed, in
their study, Zwitterionic NP was mixed with PVDF to prepare
hybrid ultrafiltration membranes of PVDF. The distribution of
Zwitterionic NP was extremely uniform in PVDF hybrid ultra-
filtration membranes, indicating that agglomeration of the NP
was effectively inhibited. The Zwitterionic NP has significantly
enhanced the antifouling performance of the PVDF membranes.
In addition to the excellent antifouling performance of PVDF/SiO2 ,
the authors indicate that hybrid modification with a Zwitterionic
material is a powerful and practical method for enhancing the
fouling resistance of PVDF (Zhu et al., 2015).
The permittivity of a material quantifies the Coulomb force
between two point charges within the material. The higher,
the permittivity and the β -phase, the more significant are the
applications such as in energy harvesting, spin valve devices,
biomedicine, sensors and intelligent scaffolds. The increase of
the β -phase of the PVDF consists in favoring the free alignment
of the microscopic dipoles state in a promoted direction by
injecting certain NP into its matrix. This technique is based on a
principle as schematized in Fig. 13. Some authors have introduced
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different types of second-phase materials to contribute to the
improvement of the beta-phase of mixing (Biswas et al., 2017;
Kim et al., 2020; Zhang et al., 2014; Thakur et al., 2016; Mahanty
et al., 2019; Fu et al., 2018; Hu et al., 2018; Alluri et al., 2017).
In addition, Arunguvai et al. have combined PVDF-TrFE and
MoS2 in order to boost the dielectric constant (Arunguvai and
Lakshmi, 2021). The Fig. 14 shows the natural resonance fre-
quency of the virgin PVDF-TrFE and MoS2 doped- PVDF-TrFE, with
or without substrate.
Their results show that MoS2 doped- PVDF-TrFE with substrate
is much better than the others. From these result, it can be
concluded that nanoparticles have a particular power to align
microscopic dipoles within the material reported in literature
(Veved et al., 2019, 2020a). Therefore, some nanofillers are dipole
alignment promoters which can promote the improvement of the
piezoelectric properties of material.
In the same line, Akash et al. (2021) modified the PVDF matrix
with Zinc oxide and (3-Aminopropyl) trimethoxysilane (APTES) in
order to improve the polar phase of the composite thus formed.
The dielectric, piezoelectric and ferroelectric has been consider-
ably enhanced by the addition of nanoparticles reported by the
authors (Akash et al., 2021). The Fig. 16a presents the variation
of the polar phase of virgin and modified PVDF. The assessment
of the polar phase is done using Eq. (9):
Aβ
βfraction = (9)
1, 26Aα + Aβ
A. Veved, G.W. Ejuh and N. Djongyang
Fig. 12. Dielectric constant and dielectric loss of virgin and modified PVDF: (a) BT/PVDF, (b) BT@SiO2-L/PVDF, (c) BT@SiO2-H/PVDF, (d) Experimental and theoretical
dielectric constant of PVDF and composites at 1 kHz (Celebi et al., 2022).
Fig. 13. Diagram illustrating the approach used in the literature (Alluri et al.,
2017) to improve the electroactive β -phase of virgin PVDF.
where Aβ and Aα are the areas under the absorbance bands at
762 and 840 cm−1 which are previously obtained by Fourier
Transform-Infrared (FTIR) as shown in Fig. 15b. The value of 1.26
is the ratio of the absorption coefficient K α = 6.1 × 104 cm2
mol−1 to K β = 7.7 × 104 cm2 mol−1 . The observation of Fig. 15b
confirms the significant increase in the polar phase as functions
of the nanoparticles ZnO while on the other hand the α -phase
decrease according to the authors (Patel et al., 2021).
Finally, the authors noted that the voltage is markedly im-
proved by the addition of nanoparticles Fig. 16.
Some researchers (Arunguvai and Lakshmi, 2021; Akash et al.,
2021; Dang et al., 2005; Patsidis and Psarras, 2008; Chanmal and
Jog, 2008; Upadhay and Deshmukh, 2013), in order to improve
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the performance of PVDF, have inserted BaTiO3 NP into the PVDF
matrix. Based on these studies and with the advancement of
improved technology, Upadhay and Deshmukh (2013), Zhang
et al. (2014), Fu et al. (2018) and Hu et al. (2018) investigated
the dielectric, optoelectronic and morphological properties of
LV-modified PVDFs as discussed in the following paragraphs.
Upadhay and Deshmukh (2013) use BT as nanofibers to enhance
phase formation in a PVDF matrix. The PVDF molecule is modi-
fied by BT NP. Their work reveals an average dielectric constant
of about 7 and an average dissipation factor of about 0.03 in
the temperature range of 25 ◦ C to 50 ◦ C, which is appreciable
from the point of view of the application for electrical charge
storage devices. Zhang et al. in 2014 (Zhang et al., 2014) in-
vented a new strategy shown in Fig. 17 for the treatment of
PVDF doped BT. In this work, the nanofibers were synthesized by
electrospinning and the surfaces were modified with 1H, 1H, 2H,
2H-perfluorooctyl trimethoxysilane as shown in Fig. 17. Finally,
the PVDF/BT NC were treated using a solution mixture, in which
the dielectric properties of the final composites were improved.
In summary, this technique has an advantage over the grafting
method for the treatment of NC because of its low cost and simple
procedure according to the authors (Zhang et al., 2014).
A study on PVDF/BT has also been carried out by Fu et al.
(2018) in order to characterize the dielectric properties of the
composite. In their work, their results showed that the permit-
tivity of the composites increased extensively compared to pure
PVDF (Fu et al., 2018). Equally, they showed that PVP/BT/PVDF
functional composites have good electrical properties which are
very attractive for use in high technological fields. Hu et al.
(2018) examined the permittivity and energy density induced by
the TiO2 (TO) buffer layer in a PVDF NC contained in TO NP,
structured BT. In their work, they analyzed the effect of TO buffer
layer coated with BT on physico-chemical properties of PVDF
A. Veved, G.W. Ejuh and N. Djongyang Energy Reports 8 (2022) 12853–12870

Fig. 14. Diagram illustrating the natural resonance frequency (Arunguvai and Lakshmi, 2021).

Fig. 15. Diagram illustrating the percentage of the β -fraction (a); FTIR (b) of the pure PVDF, PVDF/ZnO and PVDF/ZnO-APTES respectively (Akash et al., 2021).

The results obtained reveal that the introduction of TO layer

on the BT induces a two-charge interface and captures more
charge carriers in the inter-facial region to improve inter-racial
polarization. The interposed layer of moderate dielectric constant
weakens the permittivity contract between NP and PVDF matrix.
Consequently, it causes a homogenization of the local electric
field and the space charge at the interface as well as an increase
in the breaking strength. According to the authors, the energy
density is considerably improved thanks to the optimized struc-
ture of the TO/BT NP. It should therefore be established that the
process of modulating the inter-facial buffer layer represents a
new technic for increasing the energy density in polymer NC.
From Gr, GO and then rGO can be obtained according to the
literature (Szostak et al., 2018) as illustrated in Fig. 18. Many
Fig. 16. Peak voltage of the PVDF, PVDF/ZnO and PVDF/ZnO-APTES respectively
(Akash et al., 2021).
researchers have proven the effectiveness of these additives el-
ements in the improvement of piezoelectric and dielectric prop-
erties of PVDF, the most recent of which are those of Badali et al.
(2019) and Roy and Mandal (2018).
molecule. Energy density, dielectric properties and polarizability Literature (Wang et al., 2018a,b; Lou et al., 2016) explains
of the doped- PVDF were examined. the mechanism for the formation of PVDF fibers coated by the
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A. Veved, G.W. Ejuh and N. Djongyang
Fig. 17. PVDF/FluoroSilane modified by BT, in order to enhance inter-racial polarization (Zhang et al., 2014; Upadhay and Deshmukh, 2013).
Fig. 18. Illustrative diagram of the synthesis of rGO from Gr found in literature (Szostak et al., 2018).
rGO Nano sheets, followed by electrostatic interaction shown in
Fig. 19. Lou et al. (2016), Badali et al. (2019) and Roy and Mandal
(2018), on the basis of the electrostatic interaction between PVDF
and the NP of Gr and rGO, have developed a strategy for the
manufacture of PVDF fibers covered with these NP. This technic
makes it possible to acquire a composite of which the permittivity
and the β -phase are enhanced.
Badali et al. (2019) examined Gr-doped PVDF stabilized with
boron and rare earth elements. The authors showed that an
increase in the amount of Gr causes an increase in the amounts
of α and β -phases. This result presents that the crystallinity of
the NP increases with enhancing amount of Gr. In addition, the
authors reveal that the β -phase gives an elevated peak when
PVDF is doped with Gr. On the other hand, by doping it with
boron and rare earths, the value of the α -phase of the PVDF
became dominant according to the authors (Badali et al., 2019).
Therefore, we ascertained that the dopants make it possible to
enhance the mechanical strength, but attenuate the piezoelectric
and permittivity due to this phase change. In addition, their
results revealed that the insertion of Gr in PVDF matrix improves
the dielectric properties and the piezoelectric charge constant,
but when the Gr velocity exceeds a certain value, the permittivity
begins to decrease due to the increase in electrical conductivity.
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Energy Reports 8 (2022) 12853–12870
In addition, the addition of boron and rare earths resulted in a
decrease in capacitance and dielectric constant. Likewise, their
results showed that these materials could be an alternative to
lead-based piezoelectric materials.
Roy and Mandal (2018) have developed an efficient PVDF/rGO
hybrid film piezoelectric energy sensor. In this study, the rGO
sheets are homogeneously dispersed in the PVDF matrix. This
reveals that PVDF and rGO have good miscibility. In addition,
the authors showed that the surface charge interaction between
the rGO sheet and different dipoles (-CH2 -/-CF2 ) of PVDF makes
it possible to align the dipoles in a particular direction and to
stabilize the electroactive phase of the composite. This makes the
composite very attractive because of its interesting polarization.
Gaur et al. in 2019 have described the in situ synthesis and
characterization of composite PVDF films doped with a different
weight percentage of CC/BC (Gaur and Rana, 2019). The authors
used the solution casting process for the production of compos-
ite films. As regards the analysis of the surface morphology of
composite films of PVDF, X-ray Diffraction and Semi empirical
method were used. The PVDF is doped with CC/BC and a different
weight content ranging from 3 to 12%. The graph obtained in
Fig. 20 indicates the presence of the crystalline phase as well as
the amorphous phase. According to Fig. 20, the diffraction peak
A. Veved, G.W. Ejuh and N. Djongyang Energy Reports 8 (2022) 12853–12870

Fig. 19. Illustrative diagram of introduction of rGO into the PVDF matrix: (a) Formation of PVDF fibers incorporated into rGO nanofillers. (b) PVDF fibers modified
with rGO nanofillers. (c) Production of a flexible pressure sensor. (d) Typical pressure sensor. (e) Variation of the responses as a function of the charge and the
discharge (Wang et al., 2018a,b; Lou et al., 2016).

at 2θ = 20.3, manifests the presence of β -phase in samples of

composite film thus obtained. According to the authors (Gaur
and Rana, 2019), the peaks observed at 2θ = 18.2, 26.8, 28.7
and 36.25 indicates the presence of α and γ -phases as shown
in Fig. 20. When the dopant concentration increases to 12% by
weight, the intensity of the peak corresponds to the decrease of
the β -phase, which indicates the transformation of the crystalline
structure of the PVDF. In addition, it has been shown that the
reduction in the intensity of certain peaks provides informa-
tion on the transformation of the crystal structure into a more
amorphous phase as reported in literature (Fakhri et al., 2016;
Bhunia et al., 2015). So, the predominant formation of the β
and α -phase is observed in Fig. 20. The XRD spectra confirm
the reduction of the intensity of certain peaks associated with
the α -phase and β -phase which are mainly during the insertion
of dopants. The permittivity and conductivity of the modified
PVDF were evaluated at high temperature. The authors (Gaur
and Rana, 2019) affirm that the permittivity and conductivity of
PVDF/CC/BC depend on the frequency and different percentages
by weight of CC/BC charges. In summary, the addition of CC/BC
to the PVDF polymer matrix affects the dielectric permittivity
and conductivity of the PVDF composite. In addition, annealing Fig. 20. Illustrative intensity curve as a function of 2θ of CC/BC doped-PVDF
obtained by X-ray diffraction (Gaur and Rana, 2019).
influences the overall crystallization process and the different
phases of the doped PVDF composite, which can in turn affect the
piezoelectric behavior according to the authors (Gaur and Rana,
2019). distribution of these nanofillers in the PVDF matrix results in
Thakur et al. (2016) doped PVDF with NP (NiO) and NC (C-NiO) significant polarization. In addition, the authors obtained the ele-
via a simple solution casting method to develop electroactive vated permittivity (317.4) at 20 Hz, adding 20 percent by mass of
polymers with high dielectric density. The results obtained in this NC in the PVDF matrix. This result shows that the permittivity is
work indicate that the electroactive β -phase transformation for 35 times greater than that of pure PVDF. It is therefore important
the two nanofiber-modified PVDF thin particles (Thakur et al., to note the composite thus synthesized with low dielectric loss
2016). In fact, 82 percent of the nucleation of the electroactive and high dielectric constant may be the attractive candidate to
β -phase is obtained by introducing 10 percent by weight of NP develop sensors, actuators, protectors or UV detectors, energy
and 80 percent by adding 5 percent by weight of NC reported storage devices, a piezoelectric nanogenerator and energy recu-
in literature. The nucleation of the β -phase produced in the C- perator according to some authors (Thakur et al., 2016; Bispo-Jr
NiO samples is due to the strong electrostatic attraction between et al., 2019). Mahanty et al. (2019) modified the PVDF with Gold
the negatively charged nanofiber surfaces and the -CH2 dipoles (Au) structure to improve the polar phase and promote elec-
of the polymer chains according to the authors. The uniform tromechanical coupling of the composite. Their results showed
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A. Veved, G.W. Ejuh and N. Djongyang
Fig. 21. Analysis of infrared spectroscopy of PVDF-HFP doped with different TiO2 nanoparticles content (Chakhchaoui et al., 2020).
that the resulting composite has a higher percentage of polar
phases compared to virgin PVDF. In addition, the piezoelectric
nanogenerator electrospinning Au-PVDF thus synthesized gave
a better output response in their work. According to the au-
thors (Mahanty et al., 2019), the NC PVDF/Au can be used for a
wide range of applications, including surveillance of biomedical
health care and consumer portable electronic gadgets. Biswas
et al. in 2017 (Biswas et al., 2017) doped PVDF with bismuth
oxide (Bi2 O3 ) nanostructures to enhance energy conversion. The
results obtained make it possible to observe 99.6 percent of the
electroactive phase in the PVDF matrix. In addition, the output
voltage and current using PVDF containing Bi2 O3 nanostructures
are improved over those of virgin PVDF and 3.6 V and 2.4 µA
respectively. This improvement is due to the more polar β -phase
in the favored PVDF of the electrostatic interactions between -
CH2 -/-CF2 - dipoles and the surface charge of Bi2 O3 nanostructures
according to the authors.
Chakhchaoui et al. (2020) have introduced the TiO2 nanopar-
ticle into the PVDF-HFP matrix in order to enhance the β -phase
and the flexibility of the composite thus formed. These authors
have introduced different weight fraction of TiO2 including 0,1
wt%; 0,3 wt%; 0,5 wt%; 0,8 wt%; 1 wt%; 1,5 wt%. The results
obtained were very relevant according to the authors as the
nanoparticles improved the β -phase and the flexibility of the
composite. It emerges that from a fraction of 1wt%, the β -phase
of the composite become dominant as describe in the Fig. 21.
Dash et al. (2017) used the multiferriocs as a dopant to im-
prove the dielectric constant of the PVDF-based composite. The
authors showed that the inclusion of ceramic particles in a poly-
mer increases the crystalline phase in composites. Using X-ray
Diffraction analyzes, they also confirmed the presence of α , β and
γ polymorphs in the PVDF matrix with less porosity. In addition,
the dopants improved the dipole–dipole interaction as well as
the effective dielectric constant of the composite. There is also
a higher polarization of Bismuth Ferrite (BiFeO3 )-50 compared
to that of pure PVDF, which is related to the low porosity and
the stronger dipole–dipole interaction according to the authors.
The advantage of these PVDF/BiFeO3 composites lies in its easy
processing, flexibility, adaptability and good dielectric behav-
ior which can make them competitive for practical applications
(Dash et al., 2017). In addition, the high dielectric permittivity and
relatively low dielectric loss make these PVDF/BiFeO3 composites
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Energy Reports 8 (2022) 12853–12870
suitable candidates for the application of integrated capacitors
according to literature (Dash et al., 2017; Wang et al., 2017).
The study by Wang et al. (2017) uses Fe3 O4 /MWNT (multiwall
carbon nanotube) as filler to obtain a PVDF composite material for
capacitor applications. The authors showed that the incorporation
of a small amount of Fe3 O4 into the MWNT/PVDF matrix improves
the dispersion of multiwall carbon nanotube and optimizes the
conductive network. This contributed to the improvement of
the dielectric constant of the composite reported in literature
(Wang et al., 2017). These low dielectric concentrations offer
many potential applications for integrated capacitors.
Da Silva et al. (2014) have compared the electronic parameters
such as dielectric properties of MWNT/PVDF and CNW (copper
nanowire)/PVDF composites at room temperature. The results
showed that the copper nanowire/PVDF composites had a higher
dielectric permittivity and relatively lower dielectric loss and
therefore a much lower dissipation factor than the multiwall
carbon nanotube/PVDF composites. An elevated dielectric permit-
tivity of the CNW/PVDF NC has been attributed to a raiser intrinsic
conductivity of the CNW core compared to the MWNT (Da Silva
et al., 2014). This allows the NC of the more free charges to
favor interfacial polarization according to the authors. The lower
dielectric losses in the CNW/PVDF were attributed to the presence
of an oxide layer on the surface of these NW, which made it
possible to avoid the direct contact between the CNW and the
PVDF. Da Silva et al. (2014) were able to claim that the high
conductivity of CuNW’s fresh core, combined with the presence
of oxide layers on the surface of the latter, gave rise to new
composites with high dielectric properties.
In order to enhance the optical properties of PVDF,
El-Metwally et al. (2019) use the casting technique to prepare
PVDF-based NC films doped at different concentrations (0 to 2
percent by step 0.5 by weight) of Li4 Ti5 O12 nanocharges. In their
study, the structure of the doped-PVDF was scrupulously exam-
ined by X-ray diffraction and by infrared. The crystalline charac-
teristics shown by the X-ray Diffraction spectra are attributed to
the PVDF matrix according to authors (El-Metwally et al., 2019).
The results indicate that Li4 Ti5 O12 is completely dispersed in the
PVDF matrix for a low concentration of nanocharges. In addition,
a strong interaction between the PVDF matrix and nanocharges
was observed in their study (El-Metwally et al., 2019). In addition,
it has been observed that the optical band gap of pure PVDF
A. Veved, G.W. Ejuh and N. Djongyang
decreased from 3.625 eV to 1.005 eV for indirect transitions
and from 5567 eV to 4.858 eV for direct transitions when the
weight content of nanocharges ranged from 0 to 2 percent. The
results also showed that the refractive index n, the dielectric
constant of the extinction coefficient and the dielectric loss are
improved compared with those of pure PVDF. This study could
be an alternative to improve the optical properties of PVDF.
To optimize the performance of PVDF, it is necessary to intro-
duce the means of luminescent particles in his matrix. It is why;
Bispo-Jr et al. (2019) modified the PVDF matrix by means of lumi-
nescent particles to evaluate the structural and optical properties
of the composite. The authors synthesized a novel luminescent
composite polymer by combining particles of PVDF with NP Buriti
oil and Eu2 O3 . The influence of the Eu2 O3 and Buriti oil NP on
the structural, thermal, morphological and optical properties of
the polymer was then evaluated. Their results showed that the
band gap composite membranes between 5.60 and 5.90 eV were
obtained as a γ -PVDF phase after drying at 100 ◦ C. In addition, it
was found that the modified PVDF membranes are very stable up
to temperatures up to 370 ◦ C. On the other hand, the addition of
Eu2 O3 particles into PVDF matrix increases the thermal stability
of the membrane according to authors. Contrary, the Buriti oil
decreases the stability of PVDF. Due to this sensitivity to temper-
ature, the system has potential for temperature sensing platforms
according to the authors (Bispo-Jr et al., 2019).
Thakur et al. (2018) have modified PVDF membrane by CdS
nanocharges. The authors have evaluated the thermodynamic
properties and examined the effect of temperature on the vibra-
tion properties of PVDF/CdS composite thin films. In this study,
the cadmium sulphide made possible to promote the β -phase at
room temperature. It was found that the CdS modes were moving
blue due to contraction of the low temperature network. The
thermal conductivity of the CdS doped-PVDF films was evaluated
and is about 498.5 mW/cm K (Thakur et al., 2018). This value
show that the modified PVDF by cadmium sulphide is the good
electronic materials and it can have potentials applications in
several domains.
Wang et al. (2015) published an article entitled: ‘‘piezoelectric
nanowires in energy harvesting application’’. Their work focuses
on the fundamental theory of piezoelectricity highlighting the
mechanism of conversion, configuration and modeling of the
energy of nanogenerators. The principle consists in applying dy-
namic forces on piezoelectric materials such as: Polydimethyl
siloxane and ZnO in order to evaluate the evolution of the voltage
and current generated as a function of time. Their work showed
that the efficient conversion of energy in some devices may be
due to the coupling of the model in lateral bending and the
model in lateral extension. They recommended that the scientific
community should pay particular attention to the optimization of
properties and the design of piezoelectric materials.
Veved et al. (2019, 2020a,b), using DFT, widely used in recent
years to calculate the physicochemical properties of materials
(Buensuceso et al., 2016; Shah et al., 2018; Sarkar and Kundu,
2018; Das et al., 2018), were able to assess the refractive index,
electrical susceptibility, dipole moment, polarizability, hyperpo-
larizability, phase velocity, dielectric constants, ionization poten-
tials, electron affinities, electronegativities, piezoelectric coeffi-
cient, pyroelectric coefficient, chemical potential, chemical hard-
ness, chemical flexibility and interaction energy of the Pure and
modified PVDF with hafnia and zirconia. It appears from these
studies that hafnia or zirconia has ability like any nanofiller to
improve the polar phase, the thermal stability, piezoelectric and
pyroelectric coefficients of PVDF.
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Energy Reports 8 (2022) 12853–12870
3.2.3. Morphotropic Phase Boundary (MPB) in piezoelectric polymers
The morphotropic phase boundary (MPB) refers to the phase
transition between tetragonal and rhombohedral ferroelectric
phases following a change in composition or following mechan-
ical pressure according to the literature (Ahart et al., 2008). The
piezoelectric materials commonly used for MPB applications are
generally solid solutions with complex structure such as PZT and
PbTiO3. PZT is a ferroelectric with a perovskite structure. Its MPB
is between the ferroelectric tetragonal and rhombohedral phases
reported in the literature (Lallart, 2011).
Knowledge of MPB is extremely important in the design of
specific simple structure nonlinear (NL) materials with highly
nonlinear dielectric and piezoelectric properties. It should be
noted that in the vicinity of the MPB, following the abrupt change
of the crystalline structure, the piezoelectric materials of the per-
ovskite type present a high electromechanical coupling constant
or piezoelectric constant and very remarkable dielectric proper-
ties according to the literature (Liu et al., 2018) (Fig. 22). In this
illustrative diagram of the longitudinal piezoelectric coefficient
d33 (a) and the dielectric constant (b), measured at 1 kHz and
at room temperature, as a function of the molar concentration
of VDF, we clearly observe the markedly improved piezoelectric
and dielectric responses. The peak is in the MPB area indicating
the transition region. Therefore, due to its inherent and greatly
enhanced piezoelectric effect, the morphotropic phase boundary
has become an effective concept for the development of the
competitive piezoelectric materials according to the literature
(Liu et al., 2018).
However, despite the efforts made, literature tells us that
MPB has never been observed in organic materials (Liu et al.,
2018). Furthermore, the lack of effective approaches to improve
the intrinsic piezoelectric responses of polymers considerably
hampers their application to flexible devices, adaptable to any
form of nomadic device and environmentally friendly. For this
reason (Liu et al., 2018) paid special attention to the study of
stereochemically induced behavior in ferroelectric P(VDF-TrFE)
copolymers. Based on literature, this approach is similar to that
observed for MPBs in perovskite.
But a recent paper (Park et al., 2022) succeeded in discovering
a new generation of piezoelectric polymers with practical applica-
tions. In this paper, it is reported that non-polarized MPB-based
P(VDF-TrFE) nanofibers exhibit higher efficiency than polarized
P(VDF-TrFE) nanofibers. In view of the results it presents, the
MPB mechanism opens a convincing path for the development
of ferroelectric materials with remarkably competitive dielectric
and piezoelectric properties. Although in this manuscript, this
approach is briefly described, it is not excluded to explore it in
detail in our future works.
4. Synthesis, expectation and future development of compos-
ite piezoelectric
In this part of our work, we present bravely the steal. Firstly,
our curiosity after this state-of-the-art exhibition is that the op-
timization of the intrinsic properties of the material and their
understanding are among the most common and popular recom-
mendations in as reported in literature. In view of this synthesis,
their identification and synthesis of higher performance piezo-
electric composite remains a challenge. We present in Fig. 23
below the illustrative diagram of performance of the piezoelectric
materials families.
Secondly, although much research has been devoted to low-
cost synthesis and fabrication, performance enhancement, and
the application of piezoelectric composites, several problems re-
main to be solved according to the literature (Safaei et al., 2019;
Farsa et al., 2021; Arunguvai and Lakshmi, 2021; Akash et al.,
2021):
A. Veved, G.W. Ejuh and N. Djongyang
Fig. 22. Illustration of the morphotropic phase boundary of P(VDF-TrFE) copolymers (Liu et al., 2018).
Fig. 23. Illustrative diagram of the performance of the piezoelectric materials
families.
• Improvement on the piezoelectric parameters to increase
voltage and power density at the output.
• The optimization of the efficiency of electromechanical con-
version and the recovery of mechanical energy under vari-
ous working conditions.
• Improving the chemical stability, mechanical strength and
chemical flexibility of long-term piezoelectric composites.
• Limitation and slowing of depolarization and the aging pro-
cess.
• Improving the miscibility of the constituent compounds of
the composite.
• The improvement of the structural design to ensure the
long-term stability and mechanical strength of active chem-
ical sensors.
• The improvement of the mechanical energy collection
method to generate a stable and high output voltage for
active sensors.
• The improvement of the adaptability and packaging of the
piezoelectric composite to any form of nomadic electronic
device.
• The use of piezoelectric composites over a wide temperature
range.
With regard to biomedical systems using piezoelectric materi-
als, Zheng et al. published an article on energy recovery methods
based on piezoelectric materials in biomedical systems (Zheng
et al., 2017). Biomedical systems are used under high temperature
and high frequency and must therefore be flexible, sensitive,
durable, extensible and biocompatible to fit any human body. It
was therefore necessary to find piezoelectric molecules capable
of adapting to biomedical systems. It is in this line of thought
that all works on medical devices were recorded according to the
authors. They recommended that researchers conduct in-depth
studies on performance improvement, structural integration and
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Energy Reports 8 (2022) 12853–12870
optimization, and intelligent control of their dynamic properties
reported in literature (Zheng et al., 2017).
5. Conclusion
PVDF modified with nanofillers is particularly attractive for its
excellent piezoelectric properties, its flexibility, its adaptability
to any form of device and its resistance to creep. This article
examines new energy harvesting technologies based on modi-
fied PVDF. In addition, the main characterization methods and
techniques recently reported in the literature were reviewed. In
view of this review of the literature, the common objective of
the researchers is to optimize the intrinsic properties of PVDF
by introducing nanofillers into its matrix. Appropriately chosen
nanofillers have a particular contribution to the response of the
PVDF film. Electrospinning is an efficient, economical and rel-
atively simple method of making PVDF film. It is also noted
that the characterization of the piezoelectric properties at the
atomic scale is deficient because it makes it possible to explain
the interatomic and intermolecular relations in order to adapt
any form to the request (concentration, interatomic and inter-
molecular distance, phases). It also allows the determination of
the parameters evaluating the piezoelectric efficiency in order
to best optimize the piezoelectric parameters. Finally, new MPB-
based mechanisms open a convincing way for the development
of ferroelectric materials with remarkably competitive dielectric
and piezoelectric properties.
Declaration of competing interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Data availability
No data was used for the research described in the article.
Acknowledgments
All the documentation reported in this work was carried
out in the laboratory of Renewable Energy of the National Ad-
vanced School of Engineering of Maroua-Cameroon. Thank you
to Prof. Djongyang Noël, Head of the Renewable Energies Depart-
ment for opening the doors of the laboratory to me to carry out
my research work and to the entire team of the said laboratory,
with whom we have collaborated. We have, together, share rich
experiences during our work, with a great man in the broad sense
of love and humor in the person of Prof. Djongyang Noël.
A. Veved, G.W. Ejuh and N. Djongyang
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