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Nanoparticle-Enhanced β‑Phase Formation in Electroactive PVDF

Composites: A Review of Systems for Applications in Energy
Harvesting, EMI Shielding, and Membrane Technology
Amanuel Gebrekrstos, Tanyaradzwa S. Muzata, and Suprakas Sinha Ray*

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ABSTRACT: With the continuous advancement of electronic devices, lightweight, flexible, and easily processable materials have
gained substantial techno-commercial importance. Most electronic devices must possess a lightweight, high conductivity, high
dielectric permittivity, low dielectric loss, and high breakdown strength. Hence, polymer-based piezoelectric materials are in great
demand for design and development in energy storage, electromagnetic interference (EMI) shielding, and ultrafiltration applications.
Among the piezoelectric polymers, poly(vinylidene fluoride) (PVDF) with a predominantly polar β-phase is the most important.
However, the main drawbacks of the PVDF matrix are its relatively low electrical conductivity and dielectric permittivity, and poor
energy harvesting and EMI shielding performance. In this context, the incorporation of conductive nanofillers such as reduced
graphene oxides, graphene quantum dots, and carbon nanotubes in the PVDF matrix has attracted considerable interest owing to
their extraordinary properties. The final properties of these piezoelectric composites depend on the preparation methods, structural
conformation, processing conditions, dispersion of nanofillers in the matrix, surface modification of fillers, and specific or nonspecific
interaction of the fillers with the PVDF matrix. Herein, we have critically reviewed the formation mechanism of the electroactive β-
phase in PVDF, the effects of nanofillers on the phase transformation of PVDF (dispersion and specific interaction), and the
correlation of β-phase PVDF piezoelectric and dielectric properties with energy harvesting, EMI shielding, and membrane
applications.
KEYWORDS: β-phase PVDF, nanoparticles, formation mechanism, energy storage, EMI shielding, membrane applications

1. INTRODUCTION where vector Di is the dielectric displacement in N/mV or C/m2,

Polymer-based piezoelectric materials have garnered consid-
erable interest from the electronics and membrane industries
because of their lightweight, excellent processability, chemical
resistance, and superior mechanical and electrical properties.1
Piezoelectricity is the ability of certain materials to generate an
electric field when subjected to mechanical stress, or vice versa.2
The coupled electromechanical behavior of piezoelectric
materials can be modeled using two linearized constitutive
equations.
Direct piezoelectric effect:
d Received: May 18, 2022
Di = eijδEj + dim δm
and converse piezoelectric effect:
εk is the strain vector, Ej is the applied electric field vector in V/
m, and δm is the stress vector in N/m2. The piezoelectric
constants are the piezoelectric coefficients ddim and dcjk in m/V or
C/N, eδij is the dielectric permittivity in N/V2 or F/m, and SEkm is
the elastic compliance matrix in m2/N. The superscripts c and d
refer to the converse and direct effects, respectively, and the
superscripts δ and E indicate that the quantity is measured at
constant stress and constant electric field, respectively.3−5 The
three most common piezoelectric materials are ceramics
(barium titanate, lead zirconate titanate, potassium niobate),
(1) Accepted: May 31, 2022
Published: June 10, 2022

εk = djkcEj + Skm
E
δm (2)

© 2022 American Chemical Society https://doi.org/10.1021/acsanm.2c02183

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ACS Applied Nano Materials www.acsanm.org Review

Figure 1. Simplified schematic outlining the nanomaterial-induced polarization locking mechanism in PVDF-TrFE as an alternative to the
conventional electrical poling method. (a) The β phase PVDF-TrFE chains, obtained directly following film deposition, exhibit a randomized dipolar
orientation (green arrows), resulting in a negligible net polarization (P). (b) In the electrical poling method, electrodes are attached to the surfaces
perpendicular to the desired polarization direction and an electric field (E) is applied, significantly higher than the coercive field (Ec) to orient the
individual dipole moment vectors and maximize the P to the spontaneous polarization (Ps). (c) Following the removal of the E, the PVDF-TrFE chains
undergo partial relaxation from Ps to the remnant polarization (Pr). (d) Conversely, adding the Ti3C2Tx (Tx ≈ OH) nanosheets to the PVDF-TrFE in
the solution enables the P to align, without an applied electric field, perpendicular to the basal plane of the Ti3C2Tx nanosheets via electrostatic
interactions at the interface. (e) Following deposition, the Ti3C2Tx nanosheets are generally aligned parallel to the substrate, and the subsequent
evaporation of the solvent locks the P at Ps with no relaxation. Reproduced from ref 9. Copyright 2021 Springer.

polymers (nylons, poly(vinylidene fluoride) (PVDF) and its On the contrary, the β- and γ- phases are polar with parallel
copolymers, polypropylene, polystyrene), and polymer− dipole orientation. Because of the net dipole moment present in
ceramic composites.6−8 The nature of the piezoelectric response both phases, they are electroactive.18−20 The summary of the
is closely related to the presence of electric dipole moments. different properties of the three phases in PVDF is presented in
Usually, the dipoles are randomly oriented; however, they can be Figure 2.21
aligned by poling. For example, as depicted in the schematic
shown in Figure 1a, poly(vinylidene fluoride−co-trifluoro-
ethylene) (PVDF-TrFE) without poling the dipoles are
randomly oriented. With the application of electric field or
poling, the dipoles in PVDF-TrFE are oriented, as shown in
Figure 1b. As poling is energy-intensive, incorporating Ti3C2Tx
(Tx ≈ OH) in PVDF-TrFE promotes orientation without poling
due to electrostatic interactions (Figure 1d). Hence, dipoles can
orient by applying voltage or by electrostatic interactions
between the polymer and nanoparticles.9
The piezoelectric response of piezoelectric materials depends
on the number of possible orientations and alignment of dipoles
and the ability to sustain a large strain under mechanical stress.10
Hence, the best piezoelectric performance is obtained when all
the dipoles of the polymer are aligned in the same direction or
field direction. Currently, a large number of piezoelectric Figure 2. Different phases of PVDF and their properties.
polymers, such as nylons, polypropylene, polystyrene, PVDF,
and PVDF copolymers, are used in electronic devices.11−14 The β-phase, due to its highest electrical dipole moment and
Among them, PVDF with predominantly polar phases is the piezoelectric characteristics, is the most desirable phase as
most important. It is well determined that PVDF is a compared to α- and γ-phases.22
semicrystalline polymer that exists in four crystalline phases, On the basis of the aforementioned discussion, obtaining and
namely α-, β-, γ-, and δ-phases.15−17 The α-phase is trans− maximizing the β-phase has always been of immense interest in
gauche conformation, nonpolar and thermodynamically un- this area of ongoing research. PVDF exhibits excellent dielectric
stable. As PVDF chains crystallize in antiparallel dipole and piezoelectric performances owing to the electroactive β-
orientation, the net dipole moment is zero resulting in α- phase. On the basis of the advantage of the piezoelectric
phase. Because of this, the α-phase is nonelectroactive. response of the β-phase, PVDF-based piezoelectric materials
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ACS Applied Nano Materials
Figure 3. Synopsis of main experimental features of the different experimental techniques for correct identification of the PVDF phase: (a) XRD (Kα1,
λ = 1.5405600 Å), (b) FTIR, and (c) DSC. Reproduced with permission from ref 34. Copyright 2014, Elsevier Science Ltd.
have gained interest in the field of energy harvesting.23,24 The
key requirements for this application are high electrical
conductivity, dielectric permittivity, low dielectric loss, and
high breakdown strength.25 These materials are normally
introduced to operate various devices, such as sensors, actuators,
medical implants, and wearable electric devices. Owing to the
rapid development of electronic devices, it is of paramount
importance to develop enclosures capable of shielding them
from undesirable electromagnetic interference. Electromagnetic
interference (EMI) shielding refers to the shielding of
microwave radiations so that the radiations cannot penetrate
the shield, which serves as a radiation barrier. EM emissions can
be blocked by either reflecting the incoming waves using
conducting materials or completely absorbing them using
magnetically or dielectrically lossy materials.26 The critical
properties of a material for shielding electromagnetic pollution
include high electrical conductivity, high dielectric permittivity,
and lossy nature.27 It is well reported that increasing the β-phase
content in PVDF increases the dielectric permittivity and
electrical conductivity. Thus, a proper sequence of highly
conductive magnetic nanoparticles and the large permittivity of
β-phase-enriched PVDF-based composites are very effective in
interacting with microwave radiations and consequently
reducing EM pollution.28 Hence, polymer-matrix composites
containing conductive and magnetic fillers exhibit excellent
potential for shielding applications. Aside from energy harvest-
ing and EMI shielding applications, PVDF-based piezoelectric
materials have been widely used in membrane technologies,
such as ultrafiltration (UF), microfiltration (MF), and
membrane bioreactors (MBRs), owing to their high piezo-
electric response.29−31 However, these membranes have a
limited lifetime owing to membrane fouling. The basic
requirements of membranes prepared from polymers are high
porosity, the desired thermal stability, hydrophobicity, and
chemical resistance.32
With the rapid development and ubiquitous nature of
piezoelectric devices, several reviews have been published on
PVDF-based piezoelectric materials for various applications. For
example, Wan et al.,33 Martins et al.,34 and Ruan et al.35 reviewed
the formation mechanism of the β-phase in PVDF and its
application in sensors, actuators, and energy harvesting. Prateek
et al.36 and Pusty et al.37 reviewed PVDF-based composites for
energy harvesting applications. Most applications related to the
β-phase in PVDF rely on the amount and orientation of the polar
phases. By taking a step further, Amanuel et al.38 reviewed the
orientation mechanism of the β-phase in PVDF and its energy
harvesting application. Another review by Cui et al.39 reviewed
the formation mechanism of different crystalline structures in
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PVDF and their application in membrane technology. As
mentioned above, despite several reviews on PVDF-based
piezoelectric materials for various applications, there are still
major gaps in the literature, which are identified as follows:
(a) There are no comprehensive reports focusing on the
degree of orientation of β-phase PVDF with respect to the
dielectric and piezoelectric responses and its correlation
with energy harvesting, EMI shielding, and membrane
applications.
(b) The effects of specific interactions and states of dispersion
of nanofillers in the PVDF matrix on the β-phase
formation and their correlation with dielectric and
piezoelectric properties that lead to key applications and
shielding mechanisms are not clear.
(c) There is no review correlating the β-phase in PVDF and
its piezoelectric response in the membrane for antifouling
applications.
This review comprehensively reports on the formation
mechanism of the electroactive β-phase in PVDF, effects of
nanofillers in phase transformation PVDF (dispersion and
specific interaction), and correlation of β-phase PVDF piezo-
electric and dielectric properties with energy harvesting, EMI
shielding, and membrane applications.
2. QUANTIFICATION AND DETERMINATION OF
β-PHASE IN PVDF
The change in anisotropy, degree of crystallinity, crystalline
phase, and other morphological changes that occur during
transformation can be identified using various characterization
techniques such as X-ray diffraction (XRD), Fourier transform
infrared spectroscopy (FTIR), and differential scanning
calorimetry (DSC).40 The analysis of phase transformations in
the PVDF film is discussed below.
2.1. X-ray Diffraction. The XRD peaks essentially
correspond to the different phases of PVDF are depicted in
Figure 3a. The confirmation of the γ-phase is an intermediate
between the α- and β-phases, and it is difficult to obtain the
details of the existence of the γ-phase in the sample. The peaks
corresponding to the 2θ values of 17.7°, 18.4°, and 19.9°
correspond to the diffraction in the (100), (020), and (021)
planes, respectively, and are assigned to the α-phase. The peak at
20.4° is due to the sum of the diffraction in the (110) and (200)
planes, which is a characteristic of the β-phase.41
2.2. Fourier Transform Infrared Spectroscopy. FTIR
spectroscopy provides valuable information about the crystal
phases of PVDF. The crystal phases are clearly identified on the
basis of the characteristic bands related to a particular phase, as
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 Table 1. Formation Mechanism of β-Phase in PVDF via Various Processing Techniques
β-phase
content %
sample processing techniques (Fβ) mechanism for the formation of β-phase ref
PVDF Stretched at 90 °C stretching ratios between 4.5 and 5 74 Polymer chain alignment due to applied stress. 18
PVDF Shearing at 220 °C and crystallizing at 155 °C 84.4 The distance between shear temperature and crystallization temperature favored preordering 44
of PVDF chains.
PVDF Melt extrusion calendaring technique at rotating speed 3 rpm, 82 High calendaring force led to high deformation facilitated β-phase formation. 53
temperature 100 °C and gap between the rollers 0.1 mm.
PVDF Electrospinning from dimethylacetamide: acetone (1:1 by volume) 72.4 Slower evaporation rate of dimethylacetamide allows fibers to stretch and stimulate β-phase 54
solutions at applied voltage of 25 kV and flow rate of 0.5 mL h−1. formation.
ACS Applied Nano Materials

PVDF/Poly(methyl
methacrylate) (PMMA) blends
80/20 wt %
PVDF/PMMA blends 90/10 wt %
PVDF/Gold nanoparticles (Au)
(0.1 wt %)
PVDF/Zinc oxide nanorods
(ZnO) (15 wt %)
PVDF/barium titanate (BaTiO3)
PVDF/BaTiO3
PVDF/GO (1.0 wt %)
PVDF/rGO (0.3 wt %)
Quenched at above 40 °C and subsequently annealed at 120 °C. 98 High rate of quenching favors a low-temperature nucleation process, in which case the β-phase 55
is predominantly generated.
Rolled at 100 °C and at a strain of 80%. 95 High strain due to rolling resulted in low relaxation and α to β phase transformation. 56
Solution casting from dimethylformamide solution. 66 The electrostatic interactions between surface charge Au nanoparticles and CF dipoles in the 57
PVDF chain.
Solution casting from dimethylformamide solution. 76.1 The surface charge interaction between ZnO nanoparticles and PVDF dipoles responsible for 58
the enhancement of β phase.
3D printing and in situ poling. 55.91 Due to nucleating effect of BaTiO3. 59
Electrospinning from dimethylformamide solution at applied voltage of 91 The elongation forces, stretching, and simultaneous local poling during the electrospinning 60
10 kV and flow rate of 2 mL h−1. processes are responsible for the transformation of the α-phase into the polar β-phase.
Electrospinning from dimethylacetamide and acetone (4:6 by volume/ 88.5 Due to electrostatic interaction between PVDF and the oxygen group of GO. 61
volume) solution at 30 kV applied voltage and 0.2 mL h−1 flow rate.
Solution casting method from dimethylformamide solution. 100 The specific interaction between CF2 groups of PVDF and the carbonyl groups of rGO. 62

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PVDF/ionic liquid (IL) modified Melt mixing 100 The specific interactions between MWCNTs surface wrapped by imidazolium ring and > CF2 63
MWCNTs PVDF chains promoted β phase formation.
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depicted in Figure 3b. The FTIR spectra of PVDF appear for the
α-phase at the vibration bands of 763 cm−1 (CF2 bending and
skeletal bending), 795 cm−1 (CH2 rocking), and 975 cm−1 (CH2
twisting) and for the β-phases at 510 cm−1 (CF2 bending) and
840 cm−1 (CH2 rocking).18
2.3. Differential Scanning Calorimetry. It is well
established that the presence of α-, β-, and γ-phases can be
depicted by the presence of different melting endotherms in the
DSC curve. The thermodynamic melting points of the individual
crystal phases are shown in Figure 3c.
3. FORMATION MECHANISM OF β-PHASE IN PVDF
As we mentioned in the previous section, PVDF has three main
crystalline phases, namely α-, β-, and γ-phases. Among them, the
β- phase is most desirable as it provides the highest piezoelectric
response. Specifically on the amount and orientation of β-phase.
As a result, when used in an electronic device, it exhibits
outstanding piezoelectric performance. The higher the amount
of β-phase and better orientation in the field direction play an
important role in the energy storage device, EMI shielding, and
piezoelectric membrane for antifouling application, as discussed
in the applications chapter. Therefore, over the past few years,
many efforts have been made to obtain β-phase in PVDF via
various processing methods such as mechanical rolling at
optimizing temperature, blending with other polymers, shearing
and stretching, cooling from the melt, grafting and the addition
of nanoparticles, and electrospinning techniques.19,42−48 Details
can be found in Table 1, where various processing methods and
their influence on β-phase formation are summarized. For
example, the incorporation of iron oxide (Fe2O3) and cobalt
oxide (Co3O4) in PVDF facilitated the formation of β-phase due
to the ion-dipole interaction between the polymer and
nanoparticles.49 The maximum amount of β-phase was found
to be 71% at 2.6 vol % Fe2O3 and 75% at 6.6 vol % Co3O4
loadings. Another study showed that the incorporation of gold
nanoparticles and gold nanoshells in PVDF resulted in α- to β-
phase transformation due to the dipole interaction between the
gold nanoparticles and PVDF chain.50 It was also reported that
doping of palladium nanoparticles (Pd-NPs) in PVDF facilitated
the formation of β-phase due to the electrostatic interaction
between the PVDF chain dipoles and the surface charge of the
Pd-NPs.51 In addition to nanoparticles, the β-phase in PVDF
can be enhanced by using the electrospinning process. The
electrospinning method uses high electric potential resulting in
the uniaxial stretching of polymer solution and allows to orient
along the fiber axis to generate a large amount of β-phase. For
instant, Hernández-Navarro et al.52 prepared electrospun PVDF
fibers via bubble-electrospinning technique.52 The fraction of
the β-phase calculated was 95.9% at applied voltage of 20 kV.
Summary of the formation mechanism of β-phase in PVDF via
various processing techniques presented in Table 1.
In the case of nanoparticle-containing PVDF composites, the
formation mechanism of β-phase are either due to good
dispersion of nanoparticles or due to specific interaction
between the nanoparticles with PVDF chain and then correlates
with different applications. The higher the amount of β-phase
and better orientation in the field direction play an important
role in the energy storage device, EMI shielding, and
piezoelectric membrane for antifouling application, as described
below.
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4. APPLICATION OF PVDF-BASED PIEZOELECTRIC
MATERIALS IN ENERGY HARVESTING, EMI, AND
MEMBRANE TECHNOLOGY
PVDF-based piezoelectric materials are essential for designing
electronic devices in various areas such as sensors, actuators,
transducers, dielectrics, energy harvesting, EMI shielding, and
membrane technology.64−66 Here, we focus only on applications
related to energy harvesting, EMI shielding, and membrane, which are
important research areas when considering environmental pollution
and energy depletion.
4.1. Energy Harvesting Application. Fossil fuels have been
hailed as the primary source of energy since the 19th century, without
considering their harmful effects on the environment. As a consequence
of the overgrowing population, energy resources derived from fossil
fuels are continuously depleting, thereby threatening human existence.
Operation of basic tools to lead a life is exclusively dependent on fossil
fuels; they need to be replaced with sustainable and renewable energy
resources. Therefore, materials that can directly convert or store
renewable energy have been extensively studied.67 In this regard,
polymer-based piezoelectric materials offer a great opportunity to solve
this problem. Ideally, the energy storage performance of piezoelectric
materials depends on breakdown strength, piezoelectric coefficient,
dielectric constant, and dielectric loss.68 Liu et al.69 prepared self-
polarized β-PVDF piezoelectric devices based on PVDF/ionic liquid
(1-ethyl-3-methylimidazolium tetrafluoroborate (IL-[C2mim] [BF4]))
composites with different ionic liquid (IL) concentrations (0, 5, 10, 15,
and 20 wt %) via fused deposition modeling (FDM). The fabricated
piezoelectric device showed a maximum β-phase content of 98.3%, an
output voltage of 4.7 V, and an area current density of 17.5 nA cm−2.
The synergistic effect of the ion−dipole interaction and shearing force
determined by FDM promoted the formation of the β-phase. Using the
same approach, Song et al.70 prepared a PVDF-based piezoelectric
device via FDM. The fabricated device showed a maximum β-phase
content of 86.7%, an output voltage of 13 V, and a maximum current
density of ∼0.27 μA/cm2. The morphology developed during FDM and
the enhanced β-phase content were responsible for the increase in
energy performance. Renjun et al.71 prepared piezoelectric PVDF films
via solution casting followed by vacuum baking and corona poling.
They determined 86% β-phase content and obtained ∼2.1 V and ∼240
nA·cm−2 output voltage and current density, respectively, at 10.5 kV
poling voltage and 50 °C baking temperature.
Recently, Wang et al.72 fabricated silk fibroin (SF)/PVDF piezo-
electric nanofibers (NFs) via electrospinning. An increased β-phase
content of 66% and a voltage output of 16.5 V at 14 wt % of SF were
observed. The hydrogen bonding between the PVDF shell and SF core
and the electrostatic interaction are responsible for the increase in the β-
phase content. Li et al.73 fabricated PVDF/dopamine (DA) core−shell
NFs via electrospinning and studied their piezoelectric performance.
The NFs showed high β-phase content and excellent piezoelectric
performance. The hydrogen bond (between the −NH2 of DA and
−CF2 of PVDF) and the dipole interactions are responsible for the
increase in the electroactive β-phase. The core−shell NFs were
successfully demonstrated as biomedical sensors to electrically detect
diaphragm motions and blood pulsation. To improve the β-phase
content, Amith et al.74 prepared PVDF/Cloisite30B (C30B) composite
fibers with different concentrations of C30B via electrospinning
techniques. A maximum β-phase content (89.7%) and a voltage output
of 4.74 V were observed at 3 wt % C30B concentration and 22 kV
applied voltage. Other studies have shown that the incorporation of
two-dimensional materials such as graphene oxide (GO) and MXene in
PVDF promotes the formation of β-phase owing to high surface-to-
volume ratios and abundant surface functional groups. For example,
Kim et al.75 demonstrated a piezoelectric skin sensor based on MXene
(Ti3C2Tx)/PVDF 3D porous structures, fabricated via vapor-induced
phase separation (VIPS). The amount of β-phase for neat PVDF was
60%, which drastically increased to 99% after incorporating 10 wt %
MXene. The surface functional groups of MXene interact with the CH2
group of PVDF, leading to enhanced β-phase formation, as shown in
Figure 4. Further, the piezoelectric material exhibits piezoelectric
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Figure 4. (a) Schematic illustration of porous MXene/PVDF e-skin and molecular structures of MXene and PVDF. (b) Schematic illustration of
interior structure formed by intermolecular hydrogen-bonding between PVDF and MXene and significantly enhanced formation of polar β-phase. (c)
Output current of porous MXene/PVDF piezoelectric e-skin. (d) SEM image of porous MXene/PVDF e-skin. (e) Photograph of highly flexible
porous MXene/PVDF e-skin. (f) Finite-element analysis (FEA) of planar and porous structures and stress distribution under 100 kPa. (g)
Compression analysis of porous and planar structures with a constant speed (0.01 mm/s) of indentation load of up to 5.0 N. Reproduced with
permission from ref 75. Copyright 2021, Elsevier Science Ltd.

sensitivities of 11.9 and 1.4 nA kPa−1 in low (<2.5 kPa) and high (2.5−
100 kPa) pressure ranges, respectively.
To understand the impact of GO on β-phase formation, Shuai et al.76
prepared PVDF/GO composite scaffolds with various concentrations
of GO (0.1, 03, and 0.5 wt %) via selective laser sintering (SLS). The
observed maximum amount of β-phase, open-circuit voltage, and short-
circuit current were 49.1%, 8.2 V, and 101.6 nA, respectively, at 0.3 wt %
of GO. They explained that the interface bonding between GO and
PVDF and the formation of the β-phase are responsible for the
enhanced output performance. In the same direction, Yang et al.77
prepared PVDF/GO, and PVDF/reduced GO (rGO) composite NFs
via electrospinning and studied their effects on the piezoelectric
response. They determined the maximum amount of the β-phase by
incorporating 2 wt % of GO and rGO in PVDF matrix. Furthermore, the
short-circuit currents and open-circuit voltages were determined to be
200 nA (PVDF/GO) and 700 nA (PVDF/rGO) and 1.5 V (PVDF/
GO) and 16 V (PVDF/rGO), respectively. They reasoned that the
functional groups attached to PVDF/rGO are responsible for the
increase in electrical properties; rGO-PVDF has a higher electron speed
than GO-PVDF. To find out the effects of incorporation of fillers (GO
and rGO) characteristics on the β-phase content and dielectric behavior
in stretched and unstretched PVDF-GO/rGO composite films, Mishra
et al.78 prepared PVDF-GO/rGO composite films with a wide range of
compositions (0.1, 0.5, 1, and 2 wt %) via solvent casting. The results
showed that the films stretched with the stretch ratio of 2 showed the
maximum β-phase fraction (86% for PVDF-GO and 84% for PVDF-
rGO) with improved dielectric properties (dielectric constant: 28.5 for
PVDF-GO and 27.5 for PVDF-rGO; dielectric loss: 0.025 for PVDF-
GO and 0.015 for PVDF-rGO). In the same direction, Gebrekrstos et
al.79 prepared PVDF, PVDF/GO, PVDF/carboxylated GO (GO-
COOH), and PVDF/fluorinated GO (GOF) composite fibers via
electrospinning. The authors observed that the amount of β-phase
increased with the incorporation of nanoparticles. The β-phase
fractions of pristine PVDF, PVDF/GO, PVDF/GOCOOH, and
PVDF/GOF were 38, 69, 79, and 89%, respectively. Further, the
highest dielectric, piezoelectric, and energy storage values were
observed for the PVDF composite doped with fluorine (PVDF/
GOF). The results revealed that incorporating fluorinated GO
significantly enhanced the dielectric constant of the PVDF composites.
We believe this can be due to the fluorine group in GOF, which can trap
electrons and lead to large charge accumulation at the interface. To find
out the impact of specific or nonspecific interaction between the filler
and PVDF matrix on β-phase formation, Anand et al.80 fabricated
PVDF/rGO, PVDF/Bi2Al4O9, and PVDF/Bi2Al4O9/rGO piezoelectric
nanocomposite films via solution casting. They revealed that the
PVDF/Bi2Al4O9/rGO-based nanocomposite showed the highest β-
phase content (76%), output voltage (5.92 V), and current (0.76 μA) as
compared to the neat and other nanocomposites. According to the
authors, the specific interactions between the Bi3+/Al3+ nanorods with
CF2− dipoles of PVDF and the O2− nanorods of Bi2Al4O9 with CH2−
dipoles of PVDF are responsible for the increase in piezoelectric
response, as shown in Figure 5.
On the same topic, Rashed et al.81 prepared different PVDF, PVDF−
ZnO, PVDF−rGO, and PVDF−ZnO−rGO composite films using
spin-coating and drop-casting. The fabricated piezoelectric device
exhibited maximum output voltage, current density, and power density
of 44 V, 1000 nA cm−2, and 193.6 μW cm−2, respectively, as shown in
Figure 6. The increase in local strain caused by ZnO and the presence of
oxygen groups in rGO are responsible for the enhancement in the
piezoelectric performance.

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Figure 5. Working mechanism of (a) PVDF, (b) PVDF/rGO, (c) PVDF/Bi2Al4O9, and (d) PVDF/Bi2Al4O9/rGO nanocomposite films. Reproduced
with permission from ref 80. Copyright 2020, Elsevier Science Ltd.

Figure 6. (a) Output voltage and (b) output current measurements of PVDF−rGO−ZnO at different applied forces. (c) XRD patterns of the as-
synthesized PVDF and PVDF−rGO films. (d) Investigation of variations in piezoelectric results using various materials. Reproduced with permission
from ref 81. Copyright 2020, American Chemical Society.

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To study the effect of incorporating different GO derivatives in the
PVDF matrix on the crystalline structure, and hence, β-phase
formation, Li et al.82 synthesized PVDF composites with different
GOs, such as GO, rGO, carboxyl-riched perylene derivative (Py)
modified GO (PyrGO), electrochemically exfoliated graphene (EG),
and Py modified EG (PyEG). They determined 97% β-phase content at
a low volume fraction of 0.74% PyEG. A plausible reason for the
enhancement was the interfacial interactions between the PVDF chains
and carboxyl groups on PyEG nanosheets. Further, at 0.74 vol% PyEG
loading, the composite displayed a high dielectric constant (480) and a
lower dielectric loss (0.27). In the same vein, Abbasipour et al.83 studied
the effect of incorporating different fillers (GO, graphene, and halloysite
nanotubes) with different concentrations in a PVDF matrix on the
piezoelectric and pyroelectric properties. They found that the highest
output voltage was for PVDF/GO. The output voltage for 1.6 wt % Gr
was 1.3, 1.6 wt % HNT was 1.5, and 1.6 wt % GO was two times greater
than that of pristine PVDF (1 V) in response to bending (5 mm
deflection) due to the enhancement in the electroactive β-phase.
Ongun et al.84 showed that adding different concentrations of GO and
rGO (0.4 and 0.8 wt %) to the PVDF matrix increased the dielectric and
output voltages. The fabricated piezoelectric nanogenerator showed a
maximum dielectric constant of 35 and an output voltage of 4.38 V at
0.8 wt %.
It has been reported that the incorporation of functionalized
graphene derivatives into the PVDF matrix promotes the formation of
an electroactive β-phase. For instance, Choi et al.85 prepared PVDF/
graphene quantum dot (GQD) NF composites via electrospinning for
triboelectric nanogenerator device (TENG) application. An increase in
the amount of β/α-phase ratio from 0.66 to 1.12 at 0 to 5 vol% of GQD
was observed. Further, an enhancement in output power from 35 to 97
μW is shown in Figure 7. The increased β-phase content and the
conductive nature of the GQDs are responsible for the increased power
Figure 7. (a) Load resistance-dependent output power of the TENGs
with the various GQD contents and the equivalent electrical circuit of
the measurement system. (b) Output power of the TENGs with the
variation of the GQD contents at an external load resistance of 20 MΩ.
The inset is a snapshot of the commercial LED bulbs in serial-
connection directly driven by the TENG with GQD contents of 5%.
Reproduced with permission from ref 85. Copyright 2019, Elsevier
Science Ltd.
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output. The presence of functional groups in carbon quantum dots
(CQDs) enables CQDs to disperse well and promotes the formation of
the β-phase in PVDF and its copolymers.86 For example, Ma et al.87
prepared PVDF with different concentrations of CQDs (0, 1, 2, and 3
wt %) photoluminescent composites via solution casting followed by a
high-pressure crystallization process. The maximum amount of β-phase
was found at 1 wt % of CQD loading. Further, the piezoelectric devices
showed a maximum open-circuit voltage and a current output of 19.2 V
cm−2 and 550 nA cm−2, respectively.
Li et al.88 prepared PVDF/carbon-coated zinc oxide via electro-
spinning. They found that incorporating carbon-coated zinc oxide
nanoparticles (ZnO@C NPs) in PVDF increased the amount of β-
phase from 81% for neat electrospun PVDF to 88% for electrospun
PVDF/ZnO@C NPs at 5 wt % of ZnO@C NPs. This is due to the
interfacial attraction between CH2 in the PVDF segment and the
carbon surface. Further, the piezoelectric coefficient (d33) increased
from 26.30 pC/N for the neat PVDF to 39.50 pC/N for PVDF/ZnO@
C at 5 wt % of ZnO@C loading. In another report, Dutta et al.89 studied
the effects of incorporating different concentrations of silica-coated
nickel oxide (NiO@SiO2) nanoparticles in PVDF on the mechanical,
electrical, and thermal properties of NiO@SiO2/PVDF composite
films. The authors reported the maximum amount of β-phase (80%) at
15 wt % NiO@SiO2 nanoparticle loading. The electrostatic interaction
between the positive − CH2 group of PVDF and the negatively charged
surface of the NiO@SiO2 nanoparticles were responsible for the
enhancement in the β-phase content. This led to an enhanced dielectric
constant of 83 at 100 Hz and an output voltage up to ∼53 V. Therefore,
the enhancement in the dielectric constant value was due to the increase
in the β-phase content in the composite. Mohanty et al.90 prepared
0.94Na0.5Bi0.5TiO3−0.06BaTiO3/PVDF composites via solution cast-
ing. For pure PVDF, the β-phase fraction was 29%, whereas, for 35 wt%,
it was 74%. The increase in the β-phase is explained by the ion−dipole
interaction between the ferroelectric ceramic and the polymer matrix.
Therefore, the maximum dielectric and ferroelectric properties were
observed. In general, the incorporation of ceramics into a PVDF matrix
enhances β-phase formation and leads to an increase in dielectric and
piezoelectric properties owing to dipole−dipole interactions.91 The
effects of incorporating polydopamine functionalized BaTiO3 (p-BT)
in PVDF on the formation of different phases and piezoelectric and
mechanical properties were investigated by Shuai et al.92 The authors
prepared a PVDF/p-BT scaffold via SLS. An increase in the β-phase
content from 46% for neat PVDF to 59% for PVDF/p-BT at 1 vol% was
observed. Further, the output voltage and current of scaffolds at this
composition increased from 1.8 to 7.0 V and from 18 nA to 90.4 nA,
respectively. They concluded that the specific interaction between the
amino groups present in polydopamine and the C−F group present in
PVDF led to better dispersion of the nanoparticles in the PVDF matrix,
resulting in enhanced β-phase and piezoelectric performance. In the
same direction, Yang et al.93 also prepared PVDF/BaTiO3/CNT bionic
balsa wood structures via SLS and supercritical carbon dioxide foaming.
The prepared foam produced an output voltage and current of 19.3 V
and 415 nA, respectively. Singh et al.94 fabricated gold (Au) coated BT
modified by 2,3,4,5,6-pentafluorothiophenol (PFTP) in PVDF and
studied the dielectric and energy storage performance. The dielectric
and energy density of PFTP-Au-BT/PVDF composites were 11.9 and
2.04 J cm−3 at ∼2100 kV cm−1, respectively. PFTP improves the
dispersion and compatibility of the nanoparticles in the PVDF matrix
resulted in enhanced dielectric performance.
On the other hand, Mokhtari et al.95 used melt spinning to fabricate
PVDF/rGO/barium−titanium oxide (BT) piezoelectric fibers for
application in wearable energy generators and sensors. The obtained
results revealed that the fabricated coiled PVDF/rGO/BT fibers
showed the maximum β-phase (84%) and generated an output voltage
of 1.3 V and a power density of 3 W/kg during longitudinal extension at
1 Hz. In a recent work, Cho et al.96 coated BaTiO3 (BT) nanoparticles
on a PVDF-trifluoroethylene (TrFE) matrix to facilitate better
dispersion in the polymer matrix. Owing to better interaction or
dispersion of the nanoparticles, the BT@PVDF−TrFE nanocompo-
sites exhibited a high β-phase fraction. The nanocomposites generated
an output voltage of 59.5 V and an output current of 6.52 μA under 100
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Table 2. Correlation between β-Phase Content in PVDF-Based Composites with Energy Generation
β-phase current/ output
content % current voltage
sample preparation methods (Fβ) density (V) ref
PVDF/1-ethyl-3-methylimidazolium Fused deposition modeling (FDM) 98.3 17.5 nA cm−2 4.7 69
tetrafluoroborate (IL-[C2mim] [BF4]) 15 wt %
PVDF Solution casting followed by corona poling at 10.5 kV 86.1 240 nA cm−2 2.1 71
poling voltage and 50 °C baking temperature.
PVDF/silk fibroin (SF) 14 wt % Electrospinning 66 290 nA 16.5 72
PVDF/GO (0.3 wt %) Selective laser sintering 49.1 101.6 nA 8.2 76
PVDF/rGO (2 wt %) Electrospinning 87 700 nA 16 77
PVDF/Bi2Al4O9/rGO Solution casting 76 0.76 μA 5.92 80
PVDF/CQD (1 wt %) Solution casting followed by a high-pressure crystallization 83.67 550 nA cm−2 87
PVDF/p-BT Selective laser sintering 59 90.04 nA 7 92
PVDF/rGO/BT Melt spinning 84 1.3 95
BT@PVDF−TrFE Phase separation nanocoating 56.9 6.52 μA 59.5 96
PVDF/MWCNTs (0.01 wt %) Electrospinning 75 0.71 102
PVDF/MWCNTs (0.05 wt %) Electrospinning 65 0.6 104
PVDF/CNT Solution casting 65 30 nA cm−2 12 106

N compression pressure and 2.5 Hz frequency. They also determined
the maximum output power to be 165.8 μW. It was reported that the
incorporation of MXene in PVDF and its copolymer increased the β-
phase formation and led to a higher energy density. For example, Wang
et al.97 prepared PVDF−TrFE/MXene nanofibrous films via electro-
spinning. The composite film generated a peak-to-peak output voltage
of 1.58 V at a sinusoidal force of 20 N and a frequency of 1 Hz. Overall,
the output voltage generated by the composite was three times greater
than that generated by the pure PVDF−TrFE fibrous membrane (0.5
V) at the same applied force. Han et al.98 designed core−shell
piezoelectric NF-based poly(3,4-ethylenedioxythiophene) polystyrene
sulfonate (PEDOT:PSS) via electrospinning. They measured the
output voltage and current to be 8.76 V and 547 nA, respectively. They
concluded that extra space charge polarization and the content of the β-
phase were responsible for the increased energy harvesting.
Aside from graphene derivatives, the incorporation of multiwalled
carbon nanotubes (MWCNTs) in the PVDF matrix has received
significant attention in energy harvesting applications. The addition of
MWCNTs to PVDF renders superior electrical properties and a greater
β-phase formation with a very low percolation threshold.99 The
piezoelectric properties and formation of the polar β-phase in PVDF/
CNTs depend on the processing conditions, dispersion of nanotubes in
the matrix, and surface modification of CNTs.38,63,100,101 For example,
Eun et al.102 fabricated PVDF fibers with different MWCNT contents.
The effects of MWCNT content and PVDF fiber orientation on the
mechanical and piezoelectric responses were investigated. The
maximum amount of β-phase (75%) and piezoelectric output voltage
0.71 V were obtained at 0.01 wt % of MWCNT. They concluded that
the samples with higher β-phase content showed a maximum
piezoelectric response. To further improve the dielectric response of
PVDF composites, Chen et al.103 incorporated polypyrrole (PPy)/
MWCNTs nanocomposite in the PVDF matrix by melt blending to
obtain PPy/MWCNT/PVDF nanocomposites. The reported results
showed that an increase in the PPy/MWCNT content increased the
formation of the β-phase. Further, the maximum dielectric response
(83) was obtained at 12 wt % PPy/MWCNTs, which was ten times that
of pure PVDF.
The effects of the content of MWCNTs on the β-phase formation
and electrical properties in PVDF/MWCNTs thin films were
investigated by Zhu et al.104 The PVDF/MWCNTs thin films with
different content of MWCNTs (0.01, 0.02, 0.03,0.04, and 0.05 wt %)
were prepared via electroprinting. They found out that the amount of β-
phase and the output voltage were 63% and 0.6 V, respectively, at 0.05
wt % of MWCNT loading. Mahanty et al.105 also use electrospinning in
fabricating a pyro- and piezo-electric nanogenerator (PPNG) based on
PVDF/MWCNTs. The PPNG showed an enhancement in polar β-
phase from 67% for neat PVDF fibers to 87% for PVDF/MWCNT
fibers. This was due to the electrospinning process and interfacial
interaction between the π cloud of MWCNTS and the − CH2− dipoles
of the PVDF chain. Further, the fabricated PPNG showed a maximum
output voltage and power density of 35 V and 34 mW/cm2, respectively.
Badatya et al.106 prepared PVDF/CNT foam via solution casting. The
fabricated PVDF−CNT foam showed a high fraction of β-phase (65%)
and a piezoelectric coefficient of 9.4 pC/N. Further, a high output
voltage and current density of 12 V and 30 nA/cm2, respectively, were
achieved. Huang et al.107 studied the effects of processing and
localization of MWCNTs in PVDF/acrylonitrile butadiene styrene
(ABS) blends on the dielectric behavior. They determined the
maximum dielectric constant (165) and low dielectric loss (0.20) by
localizing the MWCNTs at both interfaces. The effects of incorporating
three-dimensional nanofillers composed of CNTs, graphene, and
MnO2 in PVDF on the electrical properties were studied by Yang et
al.108 They obtained a maximum output voltage of 11 V and energy
density of 72 μW/cm3 at a strain of 729 με and a frequency of 14 Hz. Pal
et al.109 reported on a PVDF−Pb0.93La0.07Zr0.52Ti0.48O3 (PLZT)−
MWCNT composite film, fabricated using the tape casting technique.
The PVDF−PLZT films exhibited 74% polar phases at 50 vol%
MWCNT. They reasoned that the enhancement in polar phases after
adding MWCNTs in PVDF−PLZT is due to the increase in interfacial
interaction between the filler PLZT and the PVDF matrix. The 50 vol%
PLZT−PVDF−MWCNT composite films displayed an energy density
of 29.1 mJ/cm3 and a piezoelectric coefficient of 30 pC/N. A summary
of the correlation between the β-phase content in PVDF-based
composites with energy generation is presented in Table 2.
In summary, better interfacial interactions between the nanoparticles
and PVDF matrix and better dispersion of the nanoparticles in the
PVDF matrix result in higher values of β-phase content and lead to
higher values of the output voltage, output current, power density, and
energy density.
4.2. Electromagnetic Interference Shielding Application. As
previously mentioned, another area where PVDF-based piezoelectric
materials can be used is electromagnetic interference (EMI) shielding.
EMI has emerged as one of the perils of modern electronic devices. EM
radiations can be blocked by one or a combination of the three
mechanisms: reflection (due to impedance mismatching), absorption
(due to the interaction of electric dipoles or magnetic dipoles), and
multiple internal reflections.26 The key parameters for a material to
have excellent EMI shielding effectiveness (SE) are high electrical
conductivity (σ), high dielectric constant (ε), high dielectric loss (ε″),
and high magnetic permeability (μ). Furthermore, it should be
lightweight, flexible, and easily processable.27 Considering all these
important factors, PVDF-based piezoelectric materials have been
extensively studied in great depth.
It is well reported that the presence of β-phase in PVDF and PVDF-
based composites can improve the EMI shielding performance. For
example, Sutradhar et al.28 prepared PVDF/BaFe12O9 composite films

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Figure 8. (a) Schematic representation of the procedure to obtain rolled samples, SE (total) of (b) as pressed samples and (c) rolled samples, (d) % of
absorption and reflection part of total shielding effectiveness. Reproduced with permission from ref 127. Copyright 2019, Elsevier Science Ltd.
with different contents of BaFe12O9 (10 and 20 wt %) via solution
casting. The effects of incorporating BaFe12O9 fillers in PVDF on the β-
phase formation and EMI shielding performance were investigated. The
amounts of electroactive β-phase were 26%, 32%, and 31% for neat
PVDF, PVDF/10 wt % BaFe12O9, and PVDF/20 wt % BaFe12O9,
respectively. The electrostatic interaction between the negative surface
charge of BaFe12O9 and the positive CH2 in PVDF was responsible for
the increase in the β-phase after adding BaFe12O9 fillers, leading to
enhanced dielectric permittivity values. Further, they found that SE
(total) for PVDF/BaFe12O9 composite films was −93.5 dB at 8.63 GHz
and −97.6 dB at 8.61 GHz for 10 and 20 wt % of the BaFe12O9 in PVDF,
respectively. The high dielectric losses in the polar β-phase and
magnetic losses in BaFe12O9 were responsible for the increase in SE
(total). Anand and Pauline110 fabricated PVDF/rGO/BaCo2Fe16O2
composite films with different BaCo2Fe16O2 contents (10 and 30 wt %)
and a fixed amount of rGO (10 wt %) via solution casting, and the β-
phase formation and EMI shielding effectiveness were investigated.
They achieved a maximum β-phase content of 73% at 10 wt % filler
content. They explained that the increased β-phase of the composite as
compared to neat PVDF was due to the electrostatic interaction
between the positive surface charge density of CH2 of PVDF and the
negatively charged BaCo2Fe16O27 nanofiller. This enhanced electro-
active β-phase improved the SE (total) of PVDF/rGO/BaCo2Fe16O27
composite films. For the composites with a filler content of 10 wt %
BaCo2Fe16O27, the maximum EMI SE reached 35.94 dB at 9.2 GHz
with an absorption-dominant mechanism. The improvement in the SE
(total) of PVDF/rGO/10 wt % BaCo2Fe16O27 composite films may be
due to the high dielectric losses in the electroactive β-phase improved
PVDF matrix and the high magnetic losses in BaCo2Fe16O27 NPs in the
X-band frequency range (8−12 GHz). Acharya et al.111 prepared
PVDF/rGO/strontium hexaferrite (SrFe12O19) (SF) composites via gel
casting followed by hot pressing. Lakshmi et al.112 used the
solvothermal method to synthesize graphene decorated with graphene
quantum dots (G-D-GQDs) and Ag decorated with G-D-GQDs (G-D-
GQDsAg). The incorporation of G-D-GQDs and G-D-GQDsAg in the
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PVDF matrix resulted in EMI shielding effectiveness SE (total) of 31
and 43 dB at 8 GHz, respectively. The increased EMI shielding
effectiveness after incorporating G-D-GQDsAg in PVDF is due to the
better conductivity and dispersion of G-D-GQDsAg in the PVDF
matrix. Saha et al.113 prepared PVDF/Mn−Zn−Cu−ferrite (MZCF)
nanocomposite films via solution casting. The incorporation of MZCF
in PVDF increased the β-phase content from 25% (for neat PVDF) to
31% (PVDF/MZCF) at 20 wt % loading of MZCF nanofillers. The
interaction between the MZCF nanofillers and the PVDF matrix was
responsible for the increase in the β-phase content. Further, they
reported a maximum reflection loss of 33.5 dB at 11.5 GHz for 25 wt %
MZCF nanofiller loading. A similar trend was observed by the same
group when Ni−Zn−Cu−ferrite (NZCF) was incorporated in
PVDF.114 The authors concluded that the high electromagnetic energy
at GHz frequencies was due to the high permeability of NZCF
nanoparticles and the high permittivity of the electroactive β-phase
PVDF. It was reported that the EMI shielding performance could be
increased by incorporating Ni fillers into PVDF.115 Zhang et al.116
fabricated PVDF/Ni-chain composite foams via a multistep process
and investigated the EMI shielding performance. The PVDF at 10 wt %
Ni-chain foam exhibited a high EMI shielding effectiveness of 26.8 dB
and a specific shielding effectiveness (SSE) of 127.62 dB cm2/g, with
absorption-dominated shielding in the X-band region. Similarly, Dutta
et al.117 prepared PVDF/nickel oxide (NiO) composite films with
different concentrations of NiO nanoparticles (0.25, 0.5, 0.75, and 1 wt
%) via solution casting. The maximum amount of the β-phase of 85%
was achieved at 0.75 wt % NiO nanoparticle loading. The electrostatic
interaction between the − CH2 of PVDF and the negatively charged
NiO nanoparticles resulted in the formation of the electroactive β-
phase. At this filler loading, an improved remnant polarization of 46
μC/m2 was observed. Furthermore, the SE (total) was 12 dB at 8.9
GHz for the composite film with 300 μm thickness and 15 wt %
NiONPs loading.
It was reported that incorporating functionalized graphene
derivatives in PVDF increases the EMI shielding effectiveness.118 For
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Figure 9. Fabrication of PVDF nanocomposite material with a high β-phase that can be used for EMI shielding and energy harvesting applications. The
schematic presentation explains the mechanism of shielding which is internal reflection and voltage generation for light emitting diode lighting.
Reproduced with permission from ref 128. Copyright 2018, American Chemical Society.

Table 3. Correlation between β-Phase Content in PVDF-Based Composites with EMI Shielding Performance
sample β-phase EMI shielding
thickness content % effectiveness freq shielding
sample preparation methods (μm) (Fβ) (dB) (GHz) mechanism ref
PVDF/X-type hexaferrite-C3N4 (30 wt Solution casting 129.1 40.2 −88 14 absorption 129
%) dominant
PVDF/rGO (10 wt %)/ W-type Solution casting 73.04 35.94 11.8 absorption 110
BaCo2Fe16O2 (10 wt %) dominant
PVDF/BaFe12O9 (10 wt %) Solution casting 210 32 −93.5 8.63 absorption 28
dominant
PVDF/Ni-chains (10 wt %) Solution mixing followed by 200 Not quantified 26.8 8.2−12.4 absorption 116
compression molding and heat dominant
treating
PVDF/NiO Solution casting 300 85 at 0.75 12 at 15 wt % 8.9 absorption 117
loading loading dominant
PVDF/submicron graphite platelet Solution casting 400 96 at 0.5 wt % 16 at 10 wt % 8.2 absorption 120
GPs loading loading dominant
PVDF/rGO 10 wt %/Y-type barium Solution casting 32.4 25.63 10.06 absorption 130
hexaferrite (Ba2Co2Fe12O22 10 wt %) dominant
PVDF/rGO (10 wt %)/BaZrFe11O19 Solution casting 200 48 48.59 11.1 absorption 131
(10 wt %) dominant
PVDF/NiO@SiO2 (15 wt %) Solution casting 300 80 21 8.9 absorption 132
dominant
PVDF/MWCNT@SiO2 Solution casting 400 81 at 1 wt % −20 at 5 wt % 8.2−12.4 absorption 128
loading loading dominant
PVDF/MWCNTs (2 wt %) Mechanical rolling 1000 88 −25 18 absorption 127
dominant
PVDF/polyaniline/CoFe2O4 In-situ polymerization method 1500 44.21 51 dB 8.0−12.0 absorption 133
dominant

example, Sabira et al.119 prepared PVDF/graphene nanocomposite
films via solution casting. At 15 wt % graphene loading, the 20 μm thick
composite film displayed a maximum EMI shielding effectiveness of 47
dB that was absorption-dominant. Kar et al.120 fabricated PVDF/
submicron graphite platelet (GP) composite films with different
concentrations of GPs via solution casting and studied their effects on
the β-phase formation and EMI shielding performance. They obtained
a maximum electroactive β-phase content of 96% at 0.5 wt % filler
loading. The interfacial interaction between the filler and polymer
matrix at this filler loading was responsible for the increased β-phase.
Further, the EMI shielding value for the 0.4 mm thick composite film
was 16 dB at 10 wt % GP loading. Zhao et al.121 prepared PVDF/CNT/
graphene composite films (0.1 mm thick) and investigated the EMI
property. The mean EMI shielding values were 22.41, 18.70, and 27.58
dB, for PVDF/5 wt %-CNT, PVDF/10 wt %-graphene, and PVDF/
CNT/graphene composite films, respectively. The specific shielding
values were 1310 dB cm2/g for the PVDF/5 wt %-CNT composite and
1557 dB cm2/g for the PVDF/CNT/graphene composite.
The preferred orientation or the stacking of MWCNTs in polymers
affects the shielding effectiveness.122−125 Qi et al.126 prepared PVDF/
graphene nanoplatelets (GNP)−Ni−CNT composite films using
solvent casting followed by compression molding and studied the
EMI properties. They found that the SE (total) values of the PVDF/
GNP−Ni−CNT blend, three-layered PVDF/GNP−Ni−CNT compo-
site, and six-layered PVDF/GNP-Ni-CNT composite at 0.6 mm
thickness were 20.7, 39.65, and 46.4 dB, respectively. The increase in SE
(total) for the six-layered composite was due to absorption and multiple
internal reflections. In recent work, Gebrekrstos et al.127 compared the
electrical conductivity and EMI shielding effectiveness of pressed and
rolled PVDF/MWCNT composite films. The rolled samples showed
improved shielding effectiveness as compared to the as-pressed
samples, as depicted in Figure 8. They reasoned that the alignment of

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Figure 10. Air gap membrane distillation setup. Reproduced with permission from ref 147. Copyright 2019, Elsevier Science Ltd.
MWCNTs, interfacial interactions, and β-phase formation after rolling
enhanced the shielding efficiency.
Kar et al.128 prepared MWCNT@silica-incorporated PVDF
(MWCNT@SiO2/PVDF) composite films via solution casting. They
achieved 81% of the β-phase fraction just with 1 wt % loading of
MWCNT@SiO2 in the PVDF matrix. The composite showed high
output voltage, current density and power density of 45 V, 1.2 μA/cm2
and 5400 W/m3 respectively. On the account of high power density, the
material could illuminate a panel of 55 LEDs. Apart from energy
storage, the piezoelectric material also showed an EMI shielding
performance of SE (total) = −20 dB and SE (absorption) = −17.25 dB
for the 400 ± 5 μm thick film. The increase in EMI shielding was due to
the incorporation of heterogeneous MWCNT@SiO2 fillers in the
PVDF matrix, which resulted in multiple internal reflections. They
concluded that the material could be used for energy harvesting and
EMI shielding applications, as shown in Figure 9. A summary of the
correlation between β-phase content in PVDF-based composites with
EMI shielding performance is depicted in Table 3.
Overall, PVDF exhibits poor EMI shielding effectiveness perform-
ance. The addition of magnetic and dielectric nanoparticles is crucial to
achieving a maximum SE. Better dispersion and interfacial interaction
of the nanoparticles in the PVDF matrix result in high permeability and
high permittivity (owing to the electroactive β-phase), leading to
maximum EMI shielding effectiveness.
4.3. Membrane Application. 4.3.1. Membrane for Water
Remediation. Owing to the scarcity of drinkable water, researchers
have explored many methods to utilize wastewater and water from
oceanic bodies for drinking. Membrane technology is now being
considered as an efficient wastewater treatment method, and numerous
related studies have been conducted.134−137 This is mainly because of
its advantages, such as ease of operation, scalability, low energy
consumption, and nonrequirement of chemical additives.
4.3.2. Classification of Membranes. Polymers are effective materials
for developing membranes for water treatment. Membranes can be
classified into different segments depending on their pore size:
nanofiltration, ultrafiltration, microfiltration, reverse osmosis, and
particle filtration.138 Usually, microfiltration membranes have a larger
pore size ranging from approximately 0.1 to 5 μm and can reject/
remove the bacteria and suspend solids present in water. Ultrafiltration
membranes (approximate pore size of 0.001−0.1 μm) can be used in
water remediation, wastewater treatment, food processing, and beyond.
Nanofiltration membranes have a pore size of approximately 0.001 μm
and can be used to soften hard water.139 Membranes for water
treatment can be fabricated from different polymeric materials.140,141
Among the available polymers, PVDF has been widely favored as a good
candidate for water treatment because of its superior mechanical
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properties, excellent chemical resistance, and high thermal stability, just
to mention a few.142 These properties are of paramount importance in
designing highly effective membranes for water treatment applications.
4.3.3. Fabrication of Membranes. PVDF membranes can be
fabricated using different methods, including thermally induced phase
separation (TIPS), vapor-induced phase separation, nonsolvent-
induced phase separation (NIPS), sintering, and the use of inorganic
particles and track etching.142−144 NIPS is used to fabricate asym-
metrical membranes, in which a well-homogenized polymer solution is
transformed into a film and then submerged in a nonsolvent. Phase
separation is mainly induced, which results in a polymer-rich phase and
a polymer-poor phase, resulting in polymer membrane matrix and
membrane pores, respectively. TIPS can be categorized into two
processes: solid−liquid (S−L) and liquid−liquid (L−L) separation.145
In this method, a solution consisting of a particular polymer and solvent
is subjected to high temperatures, and the homogeneous solution is
then cooled, inducing demixing/phase separation. L−L demixing
occurs when the solution reaches the binodal during cooling; this phase
separation can occur via spinodal decomposition, nucleation, and the
growth demixing mechanism. S−L separation results in the
crystallization of the polymer; the diluent is then extracted, and a
membrane with a porous structure is obtained.
4.3.4. PVDF-Based Membranes for Antifouling Application. Even
though PVDF is a suitable polymeric material for fabricating
membranes for water purification, its main challenge is that it is
hydrophobic and hence experiences some serious fouling challenges.144
Many methods can be employed to make the membrane hydrophilic,
but a disadvantage is that some of their mechanisms are not sustainable
for long-term use. Simple and sustainable methods must be employed
for effective water treatment. Different carbonaceous nanomaterials can
be incorporated into the PVDF matrix to fabricate membranes and
improve their properties, such as antifouling. The antifouling
performance of PVDF-based membranes can be improved by chemical
modification or the use of the piezoelectric device (β-PVDF). Hence,
the first part of this section explains how to improve the antifouling of
membranes by chemical modification followed by the use of
piezoelectric β-PVDF.
In this direction, Saraswathi et al.146 fabricated PVDF membranes
using GO and its derivative for water treatment applications and
investigated the permeability and antifouling performance of the
membrane. The authors synthesized sulfonated GO (SGO) from GO.
The presence of SGO improved the hydrophilicity and the foulant
rejection property of the PVDF membrane. The hydration layer, which
formed owing to the interaction between the sulfonic acid groups and
water molecules, imparted a negative charge to the membrane surface.
The hydration layer improved the water permeability and foulant
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Figure 11. Schematic showing the mechanism of how the polymer units of PVDF interact with NaCl. Reproduced with permission from ref 151.
Copyright 2019, Elsevier Science Ltd.
rejection because of the electrostatic repulsion between the membrane
surface and the foulant. According to the authors, the neat PVDF
exhibited low rejection of bovine serum albumin (BSA) and humic acid
(HA), which was attributed to the hydrophobic interaction between the
membrane surface and the foulant.
rGO can be incorporated into PVDF for membrane distillation
(MD) for application in desalination. The water repellency of rGO (in
comparison to GO) makes it an exciting material for enhancing the
hydrophobicity of PVDF-based membranes. Abdel-Karim et al.147
fabricated PVDF membranes containing rGO and studied the effect of
reduction in membrane performance on distillation. GO was prepared
by the Hummers method and then reduced to obtain rGO with varying
oxygen content. The membrane performance was evaluated using an air
gap membrane distillation setup, as shown in Figure 10.
The improved distillation performance after the addition of rGO was
mainly attributed to the morphological differences; the membrane with
0.5 wt % rGO exhibited the highest porosity of 70.1%, while the neat
PVDF membranes exhibited a porosity of 54%. As explained by the
authors, the porosity increased on adding rGO because rGO imparted
thermodynamic instability. The −OH and −COOH terminal groups of
rGO have some affinity for water, resulting in demixing, which leads to
high porosity.
Gontarek-Castro et al.148 used graphene nanosheets for fabricating
PVDF/graphene nanocomposites and employed the nanocomposites
in water desalination. They varied the amount of graphene nanosheets
in the PVDF matrix and observed that the composites with 0.33 and 0.5
wt % of graphene nanosheets showed excellent water repellency. They
went a step further to study the antifungal effect of the nanocomposite
membrane and observed that the highest growth inhibition of the fungal
strain was observed in the PVDF containing 0.5 wt % graphene
nanosheets. The fungal growth inhibition was mainly attributed to the
sharp edges of graphene nanosheets, which destroyed the cell walls of
the microorganisms and the ability of graphene to accept electrons from
the membrane of the microbe, resulting in a distorted membrane
structure and oxidative stress mechanism. It is of paramount
importance to design and fabricate membranes with antifungal
properties to prevent biofouling.
Graphene has been extensively used by researchers in the past and
present; however, owing to its structure, graphene has some drawbacks
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that can limit its use in membrane technology. Structural modification
of graphene can overcome the limitations. When cut into smaller
sections, graphene usually produces GQDs. GQDs are exciting new
nanofragments of graphene that are obtained from carbon-based
sources and exhibit unique characteristics that can be exploited in
different applications. The unique properties of GQDs include tunable
fluorescence, high surface area for grafting, low toxicity, and better
solubility than other nanoparticles.149 The properties of GQDs can be
tuned by chemical doping, resulting in unexpected functionalities. In
this direction, Jafari et al.150 used GQDs in their study. They studied the
application of GQD/PVDF fibrous membranes in water desalination
using the air gap membrane distillation (AGMD) process. AGMD is a
configuration of MD that is highly capable of commercialization
because of the stagnant air layer, which allows for less heat loss owing to
the lower thermal conductivity of air. The GQDs were prepared from
citric acid via direct pyrolysis. By varying the amount of GQDs, the
authors explained that the nanofibrous membranes with 0.25 wt %
GQDs had a porosity greater than 90% and a liquid entry pressure
greater than 135 kPa. High water flux and salt rejection of 17.6 kg/m2 h
and 99.7%, respectively, were achieved by the nanofibrous membrane
with 0.25 wt % GQD in comparison to the neat PVDF nanofibrous
membrane which exhibited a water flux and salt rejection of 14.7 kg/m2
h and 94.5%, respectively, on using 3.5 wt % sodium chloride (NaCl)
filtration for an 8 h duration under a feed temperature of 60 °C and
permeate temperature of 20 °C.
Many efforts have been devoted to improving membrane antifouling,
including pretreatments such as UV irradiation and hydraulic and
chemical cleaning after fouling. The piezoelectric membrane has been
proven to be effective in decreasing membrane fouling, leading to high
permeation productivity and a long lifespan. For example, Zhang et
al.151 investigated a new method of tailoring the different polymorphs of
PVDF by using Pluronic F127 to make a blend and a NaCl coagulation
bath (CB). The authors used the NaCl CB to facilitate the formation of
β-PVDF, as shown in Figure 11. The membranes were prepared via
phase inversion, whereby the PVDF polymer was mixed with Pluronic
F127. The resultant solution was placed in the NaCl CB, and the
residual F127 was removed using an isopropanol (IPA) solution. The
PVDF membrane prepared using distilled water showed a dominant α-
phase, while the membranes prepared via the NaCl CB exhibited an α-
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ACS Applied Nano Materials
Figure 12. Plausible gas permeation mechanism for the electrically responsive PVDF1−graphene membranes with and without an electric field. In this
work, the authors fabricated PVDF−graphene membrane (Grx) (“x” was the various weight percentage of graphene 0.4, 0.6, 0.8, and 1 wt %). For
pristine PVDF they are assigned as PVDF and for PVDF composite membranes with different graphene contents are assigned as PVDF1−graphene0.4,
PVDF1−graphene0.6, PVDF1−graphene0.8, and PVDF1−graphene1. Reproduced with permission from ref 154. Copyright 2020, American Chemical
Society.
to β-phase transition. The induced β-phase was mainly due to ion−
dipole interactions, which resulted from the PVDF−sodium ions
monomeric interactions.
By taking a step further, Zhang et al.152 studied how α-PVDF and β-
PVDF affect the antifouling behavior of the PVDF membrane. The
authors used fabricated PVDF membranes with similar pore structures
but different polymorphous structures. The membranes were prepared
via NIPS. β-PVDF was fabricated using a NaCl CB. IPA solution was
later used in the post-treatment to remove the residual copolymers that
were used during the fabrication of the membranes. To determine the
fouling behavior of the PVDF membranes, different foulants such as
BSA, dextran (DEX), HA, and synthetic surface water (SSW) were
used. The authors observed that after physically cleaning the
membranes; following DEX, HA, and SSW fouling; the β-PVDF
membrane showed enhanced flux recovery in comparison to the α-
PVDF membranes. The better antifouling performance of β-PVDF was
mainly attributed to the improved electron donor component, which
was far higher than that of α-PVDF. This study showed that the fouling
behavior of PVDF is influenced by its polymorphs.
4.3.5. PVDF-Based Membranes for Sensing and Catalysis
Applications. Besides water remediation, PVDF-based membranes
find alternative applications such as catalysis and biosensing. In this
context, Zhang et al.153 prepared β-phase PVDF decorated with
platinum nanoparticles (PtNPs) and MWCNTs via electrospinning
and studied the electrochemical and electrocatalytic performance of the
PVDF−MWCNT−PtNP nanofibrous membrane. The fabricated
PVDF−MWCNT−PtNP nanofibrous membrane can be used as a
nonenzymatic biosensor for H2O2 and glucose detection and as an
oxygen reduction reaction (ORR) catalyst. They explained that the
enhanced β-phase of PVDF, excellent dispersion of PtNP, and axial
orientation of MWCNTs were responsible for enhancing the
electrochemical and electrocatalytic performance.
4.3.6. PVDF-Based Membranes for Separation Applications.
PVDF-based nanocomposite membranes also find applications in gas
separation. In this direction, Widakdo et al.154 prepared PVDF/
graphene composite membranes for gas separation via solution casting.
The maximum amount of β-phase was 69% due to the specific
interaction of the CH2 of PVDF and conjugate π electrons of graphene.
Further, the fabricated membranes showed increased permeability and
selectivity toward CO2 upon applying a voltage, as depicted in Figure
12. The molecular vibrations produced by PVDF-based piezoelectric
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materials can be used for membrane separation. For example, Chen et
al.155 used a piezoelectric β-phase PVDF membrane for kaolin
suspension filtration. Cao et al.156 prepared β-phase PVDF membranes
for application in an anaerobic membrane bioreactor (AnMBR) and
investigated their antifouling performance. The steady-state water flux
of the piezoelectric PVDF membrane under an electrical signal was
enhanced by 72.6% as compared to that of nonpiezoelectric
membranes. They concluded that the antifouling efficiency in an
AnMBR increased with the use of piezoelectric membranes. Su et al.157
fabricated PVDF membranes with different morphologies by using
different solvents (N,N-dimethylformamide (DMF), N-methyl-
pyrrolidone (NMP), and triethylphosphate (TEP)) via nonsolvent-
induced phase separation (NIPS) and studied their dielectric and
piezoelectric performance. Among them, PVDF−DMF membranes
displayed a finger-like cross-section morphology and better dielectric
and piezoelectric behavior. Furthermore, the poled PVDF−DMF
membranes exhibited better antifouling performance. The effects of
different solvents (hexamethylphosphoramide (HMPA), trimethyl-
phosphate (TMP), DMF, and TEP) on the polymorphism of PVDF
were investigated by Tao et al.158 via phase inversion. Among the four
solvents, HMPA and TEP had the highest and lowest β-phase content,
respectively. They concluded that when PVDF was well dissolved in a
solution, α-phase formation was favored, while poorly dissolved
solutions resulted in β-phase formation.
Kim et al.159 designed a highly porous piezoelectric β-PVDF
membrane by introducing ZnO particles for lithium-ion transfer
channels. The fabricated piezoelectric membrane provides effective
lithium ion transfer channels without sacrificing piezoelectric perform-
ance. Bae et al.160 prepared piezoelectric PVDF NF membranes via
electrospinning and determined the antifouling ability under an AC
signal; flux decline was reduced by 15% while filtering a 10 ppm alginate
solution. They concluded that the piezoelectric vibrations of piezo-
electric electrospun NF membranes are very effective in preventing
membrane fouling, as shown in the schematic in Figure 13.
Self-cleaning membranes are also developed using PVDF-based
nanocomposites. For example, Pu et al.161 designed ZnO−CNT/
PVDF piezoelectric membrane and studied its antifouling performance.
The ZnO−CNT/PVDF piezoelectric membrane showed excellent
permeation recovery efficiency of 98.0% (AC, 12.5 V, 8 kHz) as
compared to ZnO−CNT/PVDF (58.5%; 0 V) and neat PVDF (53%).
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ACS Applied Nano Materials
Figure 13. Schematic presentation of a piezoelectric electrospun
nanofiber membrane (pENM) and its antifouling ability through the
vibrational inducement of fluid instability. Reproduced with permission
from ref 160. Copyright 2017, Elsevier Science Ltd.
In summary, the hydrophobic and antifouling performance of PVDF-
based membranes can be improved by incorporating chemically
modified nanoparticles. The nanoparticles facilitate the formation of a
high piezoelectric β-phase content in PVDF. The piezoelectric
vibrations generated by the β-phase PVDF were effective in preventing
membrane fouling.
5. SUMMARY AND OUTLOOK
Recent advancements in PVDF-based piezoelectric composites
have aided in the development of different applications. This
review extensively investigates the mechanism by which the
electroactive β-phase is formed in PVDF and the role of the
incorporation of various nanoparticles such as ZnO, GO, rGO,
GQDs, MWCNTs, and Mxene on PVDF β-phase formation and
its correlation with energy, EMI shielding, and membrane
applications. Furthermore, the main processing techniques such
as solution casting, melt mixing, compression molding, electro-
spinning, printing techniques, and sol−gel process and
important characterization techniques to quantify and inves-
tigate the formation of the β-phase in PVDF are addressed. The
review further reports on state-of-the-art applications, including
EMI shielding, energy harvesting, and membranes for water
remediation and gas separation of piezoelectric PVDF-based
composites. These three applications were specifically correlated
with the degree of orientation and the amount of PVDF β-phase.
As discussed in this review, the multifaceted applications of
piezoelectric β-PVDF composites can be tuned by using
different processing techniques and adding nanoparticles to
the PVDF matrix. Tremendous efforts have been made to
improve the EMI shielding, energy harvesting, and membrane
performance of PVDF-based piezoelectric materials. Among
them, specific interaction of nanofillers with PVDF and proper
dispersion of nanofillers in a PVDF matrix have been identified
as effective approaches to enhance β-phase formation, leading to
excellent energy harvesting, EMI shielding, and membrane
performance. Although the specific interaction and proper
dispersion of nanoparticles in the PVDF matrix improved these
properties, challenges still exist. Several challenges have been
discussed, and possible solutions have been proposed.
(a) A comprehensive understanding of the effects of different
polymorphisms of PVDF on antifouling and separation
effectiveness needs further clarification.
(b) A comprehensive understanding of the orientation degree
of β-phase PVDF and its piezoelectric response needs
further clarification.
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The incorporation of chemically modified nanoparticles and
grafting onto PVDF without applying an electric field will be the
focus of future research for fabricating PVDF-based piezo-
electric materials.
Overall, the higher the β-phase content, the higher the
dielectric and piezoelectric responses that lead to improved EMI
shielding, energy harvesting, and membrane performance. We
hope this comprehensive review will help researchers to
understand the fabrication methods of PVDF-based piezo-
electric composites and their multifaceted applications. Finally,
through this review, PVDF-based lightweight and flexible
materials could help to develop advanced materials to partitially
solve the global environmental pollution and energy shortage.
■
AUTHOR INFORMATION
Corresponding Author
Suprakas Sinha Ray − Department of Chemical Sciences,
University of Johannesburg, 2028 Johannesburg, South Africa;
Centre for Nanostructures and Advanced Materials, DSI-CSIR
Nanotechnology Innovation Centre, Council for Scientific and
Industrial Research, Pretoria 0001, South Africa;
orcid.org/0000-0002-0007-2595; Email: rsuprakas@
csir.co.za, ssinharay@uj.ac.za
Authors
Amanuel Gebrekrstos − Department of Chemical Sciences,
University of Johannesburg, 2028 Johannesburg, South Africa;
Centre for Nanostructures and Advanced Materials, DSI-CSIR
Nanotechnology Innovation Centre, Council for Scientific and
Industrial Research, Pretoria 0001, South Africa
Tanyaradzwa S. Muzata − Department of Polymer Technology
and Engineering, Harare Institute of Technology, Harare,
Zimbabwe
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsanm.2c02183
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors would like to acknowledge the financial support
from the Department of Science and Innovation (C6ACH77),
Council for Scientific and Industrial Research, Pretoria
(086ADMIN), and the University of Johannesburg (086310),
South Africa.
■
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