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v1

Review

Composites, Fabrication and Application of

Polyvinylidene Fluoride for Flexible
Electromechanical Devices: A Review
Shuaibing Guo 1, Xuexin Duan 1, Mengying Xie 1, Kean Chin Aw 2 and Qiannan Xue 1,*
1 State Key Laboratory of Precision Measuring Technology & Instruments, College of Precision Instrument
and Opto-electronics Engineering, Tianjin University, China
2 Department Mechanical Engineering, University of Auckland, New Zealand

* Correspondence: [email protected]

Abstract: The technological development of piezoelectric materials is crucial for developing

wearable and flexible electromechanical devices. There are many inorganic materials with
piezoelectric effects, such as piezoelectric ceramics, aluminum nitride, and zinc oxide. They all have
very high piezoelectric coefficients and large piezoelectric response ranges. The characteristics of
high hardness and low tenacity make inorganic piezoelectric materials unsuitable for flexible
devices that require frequent bending. Polyvinylidene fluoride (PVDF) and its derivatives are the
most popular materials used in flexible electromechanical devices in recent years and have high
flexibility, high sensitivity, high ductility, and a certain piezoelectric coefficient. Owing to increasing
the piezoelectric coefficient of PVDF, researchers are committed to optimizing PVDF materials and
enhancing their polarity by a series of means to further improve their mechanical–electrical
conversion efficiency. This paper reviews the latest PVDF-related optimization materials, related
processing and polarization methods, and the applications of these materials such as those in
wearable functional devices, chemical sensors, biosensors, and flexible actuator devices for flexible
micro-electromechanical devices. We also discuss the challenges of wearable devices based on
flexible piezoelectric polymer, consider where further practical applications could be.

Keywords: PVDF; piezoelectric polymer; wearable device; flexible sensor; electromechanical.

1. Introduction
Piezoelectric materials have been in development for 140 years[1]. These materials are widely
used in electromechanical devices because they can convert mechanical energy to electrical energy
under pressure or generate mechanical motion by electricity[2,3]. The use of piezoelectric materials
for the preparation of micro-electromechanical devices makes it possible to develop miniature
resonators[4-8], frequency meters[9] and micro energy supply chips[10-14]. Piezoelectric crystals
have a single crystal structure and natural piezoelectricity, such as α-quartz[15,16]. In addition to
natural piezoelectric materials that can adapt to different application scenarios, researchers have also
manufactured many high-performance artificial piezoelectric materials. Typical piezoelectric-crystal
materials include aluminum nitride (AlN) and zinc oxide (ZnO)[17,18], which have a variety of
advantages, such as very high strength, large piezoelectric coefficients, and good applicability to
micro devices[19,20]. Piezoelectric ceramics consist of many small crystals and the crystals are
randomly oriented. The crystal orientation can be changed through a polarization process to exhibit
piezoelectricity. The polarization process is usually performed by applying a high electric field. PZT-
series materials such as PMN-PZT and PMMPT are typical representatives of piezoelectric ceramics;
they not only have high piezoelectric coefficients but also good ductilities. However, the bending
property of PZT-series materials is still poor, and they pollute the environment because of their lead
content. Generally, these inorganic piezoelectric materials have the features of high hardness and
brittleness, which are not suitable for flexible devices that require high material flexibility.

© 2020 by the author(s). Distributed under a Creative Commons CC BY license.

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With the rapid development of wearable devices, there is an increasing demand for device
flexibility. Compared with inorganic and ceramic materials, piezoelectric polymers have more
remarkable bending and tensile properties. Polymer piezoelectric materials have a carbon chain as
the backbone, and their flexibility is higher than those of single crystals and ceramics[21-23]. This
high flexibility allows them to withstand a greater amount of strain, thus making them more suitable
for application scenarios with large bending and twisting requirements. Some suitable piezoelectric
polymers, such as polyvinylidene fluoride (PVDF), polyvinylidene fluoride-trifluoro ethylene
(P(VDF-TrFE)), cellulose and its derivatives, polyamides, and polylactic acids, are widely used in
ultrasonic sensors, audio sensors, medical sensors, display equipment, vibrometers, impact sensors,
pressure sensors, and many other applications[24]. Among flexible piezoelectric materials, PVDF has
a high piezoelectric coefficient, good flexibility, and excellent biocompatibility; therefore, PVDF is
widely used to develop flexible electromechanical devices.
However, improvement of the polarization characteristics of flexible piezoelectric materials
continues to be challenging. The piezoelectric coefficient of PVDF can be effectively improved by
doping with inorganic piezoelectric materials, such as PZT and piezoelectric ceramics. In addition,
nano-clay, BTO, Ag, graphene, and other nanomaterials can change the crystal structure of PVDF and
increase the β phase proportion. Moreover, some new fabrication methods can also improve the
polarity of flexible piezoelectric materials. In this paper, the recent progress in material science of
PVDF and PVDF composites, aiming for micro fabrication techniques, is reviewed. We discuss the
latest technological scheme and processing methods and compare their merits and demerits. The
improvement in the performance of flexible piezoelectric materials has overcome the limitations of
wearable electromechanical devices. The applications of these materials in electromechanical devices
are discussed in detail. Finally, the development trend of flexible electromechanical devices based on
PVDF is prospected in the future, such as using the help of piezoelectric properties of biocrystals,
improving the biocompatibility and for the development of bionic devices.

2. Polyvinylidene fluoride-based-series piezoelectric material

2.1. The piezoelectric effect principle of PVDF

The piezoelectric effect[25,26] refers to the polarization of certain dielectrics in a specific
direction under the action of an external force. A dielectric material has positive and negative charges
on two opposite surfaces. When the external force is eliminated, the material returns to a neutral state.
This phenomenon is called the positive piezoelectric effect. As the direction of the force changes, the
polarity of the charge also changes. Conversely, when an electric field is applied in the polarization
direction of the dielectric, the material will deform. When the electric field is removed, the
deformation disappears. This phenomenon is called the reverse piezoelectric effect. The fundamental
reason for the piezoelectric effect is that the mechanical deformation caused by the polarization
intensity is linear with respect to the electric field strength in crystal materials without a symmetry
center.
Piezoelectric materials have unique mechanical and electrical coupling characteristics, including
the direct piezoelectric effect of charge generated under the action of external mechanical stress and
the reverse piezoelectric effect of mechanical strain caused by an external electric field. The direct and
converse piezoelectric effects obey several equations[27-31] such as eq. (1).
𝛿 𝜎
= 𝑠 𝑑 , (1)
𝐷 𝑑 𝜀 𝐸

where 𝛿 and 𝐷 represent the strain component and electric displacement component, respectively;
𝑠 and 𝑒 represent the elastic compliance and constant under a constant electric field, respectively;
𝑑 represents the piezoelectric coefficient; 𝑡 represents the transposition; 𝜀 and 𝑇 represent the
dielectric constant and constant stress, respectively; 𝜎 and 𝐸 represent the stress and electric field
components, respectively. The direct piezoelectric effect is very important for the sensing and energy
collection of surface charge generated by applied stress on piezoelectric materials.
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Many piezoelectric materials have a very clear polar axis. Energy harvesting performance is
related to the angle between the stress and polar axis. The direction of the polar axis is “3” directions,
and the direction perpendicular to the polar axis is “1” direction. The direction of stress application
can be along either direction “1” or “3” directions, thus forming 31-mode and 33-mode[32].
The piezoelectric properties of PVDF are directly related to its structure[33]. PVDF is a semi-
crystalline polymer polymerized by H2C =CF2 monomer, whose properties depend on the phase due
to the alignment of crystals (Figure 1a). When two CF2 or CH2 groups are connected, a defect occurs
in the connected polymer chain. Defects in the polymeric chain influence the polarity of the PVDF
film, thereby increasing the piezoelectric response. The polymer has α, β, γ, б, and ε phases, which
are five semi-crystalline polymorphs. The α and β phases are the most common phases. The γ phase,
which is not common, is a transitional state between α and β. б and ε are difficult to isolate. The α
phase of PVDF is non-polar[34], because it contains two molecular chains and the dipole moments
are reversed, forming a trans-gauche conformation (TGTG′) (Figure 1b). The β phase of PVDF has an
all-trans conformation (TTTT) (Figure 1c). Most hydrogen atoms and fluorine atoms are separated;
therefore, it has a dipole moment perpendicular to the polymer chain, which shows the highest net
dipole moment. The γ phase of PVDF is a transitional state between α and β (Figure 1d), it has a
smaller dipole moment than the β phase[35]. It is necessary to increase the proportion of β phase in
PVDF to maximize its electromechanical conversion efficiency[36].

Figure 1. (a) Structure of PVDF; (b) Space structure of α-phase PVDF; (c) Space structure of β-phase
PVDF; (d) Space structure of γ-phase PVDF.

2.2. Piezoelectric materials based on PVDF and its derivatives

Polymer piezoelectric material is a material with a carbon chain as the basic skeleton, and its
flexibility is higher than that of single crystals and ceramics[21,22]. This high flexibility allows it to
withstand a greater amount of strain, thereby making it more suitable for application scenarios with
large bending and twisting requirements. Some good piezoelectric polymers such as PVDF,
polyvinylidene fluoride-trifluoro ethylene (P(VDF-TrFE)) (Figure 2a), cellulose and its derivatives,
polyamides, and polylactic acids are widely used in ultrasonic sensors, audio sensors, medical
sensors, display equipment, vibrometers, impact sensors, pressure sensors, and many other
applications[24].
Piezoelectric polymer PVDF and its copolymers have the advantages of natural flexibility, easy
processing, and sufficient mechanical strength, which make them more suitable for flexible sensors
than inorganic piezoelectric materials[37-43].
So far, PVDF has been found to exist as five semi-crystalline polymorphs: α, β, γ, б, and ε.
Among these, α-phase (TGTG0 conformation) is not electroactive, and β-phase has the strongest
piezoelectricity. PVDF with a low component of β-phase has a d33 value of approximately 20-30
pC/N[44-51]. Therefore, increasing the β-phase PVDF composition is vital to enlarge the mechanical–
electrical energy conversion performance of PVDF. Therefore, the piezoelectric coefficient of PVDF
is lower than that of common inorganic piezoelectric materials. Chang et al.[43] prepared PVDF
nanofibers with a high β-phase PVDF component by near-field electrospinning (Figure 2a). The fiber-
based generator could provide a maximum output power with 5–30 mV and 0.5–3 nA voltage and
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current, respectively (Figure 2c). It has a much higher energy conversion efficiency than generators
made of PVDF thin films[43].

Figure 2. (a) Structure of P(VDF-TrFE) [41]; (b) PVDF nanofibers with the high component of β-phase
PVDF by near-field electrospinning[43]; (c) The generator based on fiber could provide a maximum
output power is 5-30 mV and 0.5-3 nA with different feature sizes[43]; (d) A free-standing film's
photograph and SEM image [44]; (e) The output power of the generators based on textile[44]; (f) The
“3D spacer” cross-sectional SEM image[52]; (g) 2D and 3D piezoelectric textile's output power[52].

The P(VDF-TrFE) copolymer has high crystallinity and piezoelectric properties, so it has a high
piezoelectric response[53-55]. Persano et al.[44] proposed a piezoelectric textile based on highly
aligned electrospun P(VDF-TrFE) fibers. The proposed piezoelectric textile has a large area, and it is
flexible and freestanding (Figure 2d)[44]. The maximum open-circuit voltage of the generators based
on textiles can reach 1.5 V (Figure 2e)[44], thus showing excellent flexibility and mechanical strength.
Many new designs have emerged in the practice field to produce all-fiber piezoelectric textiles. A “3D
spacer” based on all-fiber piezoelectric textiles was reported[52], consisting of top and bottom
electrodes and a spacer yarn. The spacer yarn is composed of high concentration of β-phase PVDF
monofilaments. The top and bottom electrodes are composed of silver-coated polyamide
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multifilament yarn layers (Figure 2f)[52]. The new type of 3D textile-based PVDF generator had a
much larger output power density than the traditional 2D piezoelectric textile, up to 5.07 lW/cm2 [56-
60] (Figure 2g)[52].

2.3. Piezoelectric materials doped in PVDF

To balance the contradiction between flexibility and higher voltage coefficient, researchers have tried to
mix polymer piezoelectric materials with inorganic piezoelectric materials. Because of the good piezoelectric
properties and relatively soft properties of PZT and the tensile and flexural properties of PVDF, the combination
of the two will make sense. According to the above ideas, Tiwari et al.[61] prepared PZT and PVDF piezoelectric
composite films using solution casting technology. This method can achieve both electric field polarization and
mechanical stretching during the electrospinning process, making it very suitable for manufacturing
piezoelectric nanofibers. Similarly, the dielectric properties of PZT/P (VDF-TrFE) composite films[62] were also
studied. In 2020, Pal et al.[63] used lanthanum-doped lead zirconate titanate (PLZT), PVDF, and multi-walled
carbon nanotubes (MWCNTs) as supplementary fillers to create a three-phase hybrid piezoelectric
nanogenerator. Figure 3a shows the variation of stored power with time and SEM of PLZT particles dispersed
in the PVDF matrix. Raad et al.[64] fabricated nanogenerator devices on the basis of composite structure of
PVDF, ZnO, nanorods, and BaTiO3. The voltage output of these composite structures are up to 12 V under the
force of 1.5 N(Figure 3b).
Considering the compatibility with the human body, lead-free materials are more popular. Titanate or
bismuth[65] are mixed with PVDF to develop lead-free piezoelectric nanofiber composites. The piezoelectric
properties of PVDF can be changed by adding calcined BaTiO3 ceramic powder[66,67].

Figure 3. (a) Variation of stored power with time and SEM of PLZT particles dispersed in the PVDF
matrix[63]; (b) The relationship between output voltage and applied forces with different
frequencies[64]; (c) Relationship between output frequency and voltage of PVDF nanofiber composite
containing BNT-ST[9]; (d) Optical diagram PVDF/BTZO hybrid film[68]; (e) SEM of PVDF/BTZO
hybrid film[68].

Researchers at Kyungnam University have synthesized an excellent lead-free piezoelectric material[9],

which is a kind of flexible lead-free piezoelectric nanofiber composite of BNT-ST((1-x)Bi0.5Na0.5TiO3- xSrTiO)
ceramics and PVDF polymer,
which were fabricated by electrospinning. By measuring the functional relationship between the output
frequency and voltage of the PVDF nanofiber composite containing BNT-ST (Figure 3c)[9], the piezoelectric
properties of the composite and the sensitivity of the piezoelectric output to frequency are substantially
improved. This is because BNT-series materials can overcome large coercive field defects and exhibit strong
piezoelectric properties[69-73].
In 2015, Alluri et al.[68] developed a flexible hybrid film of PVDF doped with highly crystalline BaTi(1-
ZrxO3 (x = 0, 0.05, 0.1, 0.15, and 0.2) nanocomposites (BTZO). During preparation, the PVDF matrix solution
x)

was embedded in BTZO using a molten-salt process under ultrasonication (Figure 3d)[68]. The SEM images of
the PVDF/BTZO hybrid film are shown in Figure 3e. It can be concluded that by the molten salt method,
replacing the Ti4+ (0.605 Å) site with a Zr4+ atom (0.72 Å) can modify the high-purity bulk BaTiO3
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nanocomposites and enhance the piezoelectric coefficient (d33) from 100 pC/N (BaTiO3)[74-78] to 174-236 pC/N
(BaTi(1-x)ZrxO3)[79-83]. The properties of BTZO/PVDF hybrid films have been substantially improved compared
to those of pure piezoelectric films and have great potential in manufacturing environmental protection devices,
active sensors, and flexible nanogenerators.

2.4. Conductive nanomaterials doped in PVDF

Although polymer materials have the advantages of high flexibility and high mechanical strength
compared to inorganic materials, the piezoelectric coefficient of piezoelectric materials is relatively small;
moreover, their piezoelectric conversion efficiency is low, and they do not easily conduct electricity. The
introduction of nanomaterials may change the crystal structure of polymer piezoelectric polymers and improve
the piezoelectric properties[84-89]. Zirconate titanate, barium titanate, and zinc oxide have high piezoelectric
constants; therefore, polymer piezoelectric matrices usually use them as piezoelectric fillers [90-95]. Compared
with those of the pure piezoelectric polymer, the piezoelectric properties of the nanocomposites are improved,
dielectric constant is significantly increased, crystallinity of the phase is increased, and local stress is increased.
Adding nanoclay[96] to PVDF can prompt the formation of the β-phase in the spinning process, which is an
ideal method to prepare piezoelectric nanofibers. BTO nanoparticles were used to improve the P(VDF-TrFE)
nanofibers’ piezoelectric sensing properties (Figure 4a)[97]. BTO/P(VDF-TrFE) nanofibers doped with BTO
nanoparticles have the largest β-phase crystallinity and the best piezoelectric properties.
Wu et al.[98] studied the piezoelectric properties, crystal structure, and sound absorption properties of
PVDF nanofibers doped with carbon nanotubes prepared by electrospinning.. The results show that adding
CNTs further improves the piezoelectric properties and the ability to absorb sound waves at low frequencies.
Hosseini et al.[99] studied the potential synergistic effect of OMMT and MWCNT nanofillers on PVDF crystal
structure and piezoelectric device performance. They evaluated PVDF fiber mats' sound-absorbing and
piezoelectric properties, and the results showed that compared with OMMT, the MWCNT could decrease PVDF
impedance and increase the dielectric constant. MWCNT/OMMT hybrid nanocomposites have good sound
absorption properties, which might be caused by the enhanced interaction at the polymer-filled interface
between the acoustic wave and OMMT plates and MWCNT nanotubes [100-104]. They found that the sound
absorption efficiency of PVDF/MWCNT/OMMT hybrid nanocomposites was higher than that of pure PVDF
fibers and film. Negar et al.[11] fabricated PVDF nanocomposites by doping with PZT particles. The PVDF-PZT
nanocomposite fiber, the crystallization mechanism, and β-phase formation based on the addition of PZT are
shown in Figure 4b.
PVDF and graphene-silver (GAg) nanocomposites have plasma-coupled piezoelectric properties, and the
piezoelectric energy conversion efficiency reaches 15%[105]. Using the unique interface structure of silver
nanoparticles, silver-doped oriented PVDF nanofibers with a high content of β phase were prepared by
electrospinning[106], and the crystallinity of the β phase was 44.5%. Silver nanoparticles in graphene dispersion
form n-type doping on graphene owing to electrostatic effects [107-111]. The self-polarization of silver
nanoparticles in PVDF is beneficial to the nucleation of the electroactive β phase. PVDF nanocomposites are
environmentally friendly and low-cost nanocomposites, having high piezoelectric coefficients and different
piezoelectric coefficients under different light conditions ( Figure 4c)[105].
Gan et al.[112] developed composite materials using TiO2 nanoparticles and PVDF. The increase in
conductivity makes the polarization process easier, and the required electric field is smaller (260-120 mV/m). In
2017, Al-Saygh et al.[113] proposed a flexible pressure sensor based on PVDF doped with rGO and TiO2
nanolayers (TNL). The hybrid PVF/rGO-TNL film had a higher β-phase content (75.68%) than PVDF (70.37%),
PVDF/rGO (72.73%), and PVDF/TNL (73.5%) films. Similarly, Pusty et al.[114] combined iron with carbon
nanotubes and graphene nanomaterials and proposed that adding CNT and Fe-RGO to PVDF can increase the
conductivity of nanocomposite membranes. Mishra et al.[115] developed a flexible piezoelectric polymer
nanocomposite film to collect mechanical energy, which is based on PVDF doped with gallium ferrite
nanoparticles (GFO). Under mechanical pressure and release conditions, the output voltage and current are 3.5
V and 4 nA, respectively (Figure 4d)). As a type of piezoelectric ceramic, nano ZnO is also used as a piezoelectric
filler[116]. Dodds et al.[117] prepared PVDF TrFE/ZnO nanoparticle films by spin coating and studied their
piezoelectric response. The prepared films not only maintain their mechanical flexibility but also improve their
piezoelectric properties. Zinc oxide-PVDF composite membrane[118] can also be prepared by sol-gel
technology. The latest report is on the preparation of metal ZnO PVDF composite films by doping ZnO
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nanoparticles into metals, which shows the potential for mechanical energy generation and motion sensing.
Figure 4e shows the fabrication process of the device. They respectively studied and compared the voltage
output of pure ZnO-PVDF samples and ZnO-PVDF composites doped with sodium (Na), cobalt (Co), silver
(Ag), ferric oxide (Fe3O4), and lithium (Li)[119].

Figure 4. (a) The SEM of BTO/P(VDF-TrFE) nanocomposite fiber[97]; (b) PVDF-PZT nanocomposite
fiber, the crystallization mechanism, and β-phase formation based on adding PZT[11]; (c) Change of
piezoelectric coefficient in the form of output voltage under different light conditions[105]; (d)
Output voltage and current signal of GFO-PVDF composite films[115]; (e) Schematic of the
manufacturing process of the device[119].

2.5. Biomaterials functional PVDF

Some biomaterials have certain piezoelectric properties naturally. In 2017, Nuraeva et al.[120] investigated
(S)-glutamine and ortho-carboranyl derivatives of (S)-asparagine films and bulk crystal piezoelectric properties,
demonstrating a very high piezoelectric response. The high local transverse piezoelectric coefficients of these
biocrystals indicate that they are promising materials for various piezoelectric applications. Stapleton et al.[121]
provided experimental evidence of the globulin and lysozyme's direct piezoelectric effect. They measured the
direct piezoelectric effect of the lysozyme crystal aggregation film and found that the average piezoelectric
coefficients of the monoclinic and tetragonal lysozyme films were 0.94 pC/N and 3.16 pC/N, respectively (Figure
5a). Nguyen et al.[122] reported that diphenylalanine (FF) is a short peptide composed of two natural amino
acids, with special piezoelectric properties and excellent mechanical properties(Figure 5b). Doping with a
piezoelectric polymer can stimulate the piezoelectric properties. Recently, Yang et al.[123] modified barium
titanate (BTO) with polydopamine (PDA). Then, the mixing ratio was adjusted between it and the PVDF matrix,
and finally formed a uniform and homogeneous PDA @ BTO / PVDF composite material. The facial solution-
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casting method was used to make the flexible piezoelectric pressure sensor shown in Figure 5c. PDA can
improve the dispersion of BTO in the PVDF matrix, reduce interface void defects and cracks between the two
components. The output voltage is about 2 times higher than the unmodified one, and 13.3 times higher than
the original PVDF. Tamang et al.[124] reported that DNA was used as a nucleating agent to produce a self-
polarized PVDF membrane with higher piezoelectric properties (Figure 5d). This nucleating agent can achieve
the molecular dipole arrangement and the nucleation of the electroactive β phase in PVDF. Phosphate ions
interact with hydrogen bonds on the single-strand deoxyribonucleic acid (ss-DNA) backbone to form a stable
polar β phase, accounting for more than 80% of polar β-phase in the PVDF matrix (Figure 5e).

Figure 5. (a) Piezoelectric voltage generated increases with increasing applied force[121]; (b) Open-
circuit voltage of the FF-generator[122]; (c) The fabrication process of PDA@BTO/PVDF composite
membrane on the basis of flexible pressure sensor[123]; (d) DNA was used as a nucleating miagent
to produce a self-polarized PVDF membrane to fabricate nanogenerator[124]; (e) Denaturation of
DNA and the forming process of ß-enriched DNA-PVDF membrane[124].

3. Fabrication and polarization of PVDF

There are many methods to convert PVDF into the β phase, including electrospinning, spin
coating, solvent casting, and 3D printing. PVDF processed by the two spin coating and solvent casting
methods mainly forms the α phase; therefore, a subsequent polarization method is needed to increase
the β phase state of PVDF[125,126]. Polarization can be achieved with a set of widely used techniques
that can be used to reorient polymers to increase the net polarization vector in 3 directions, which is
an important step during the fabrication process. For the processing methods of electrospinning and
3D printing, the polarization process can be completed directly in situ under the action of an electric
field and temperature, and no subsequent polarization process is required. The following sections
mainly discuss the preparation and polarization methods of PVDF films, including the piezoelectric
effect principle.

3.1. Fabrication of PVDF by spin coating and solvent casting

Spin coating and solvent casting mainly form the α phase of PVDF; therefore, a subsequent
polarization process is required. In the spin coating method, the surface stress is increased during the
spinning process, and the addition of some compounds helps induce and contribute to the formation
of the β phase state of PVDF, and sometimes it can be formed with a certain piezoelectric coefficient
without subsequent polarization. A schematic diagram of the spin coating and solvent casting is
shown in Figure 7a, b.
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Figure 6. (a) Schematic of electrode poling method and (b) corona poling method.

Electrode poling and corona poling are the two most common methods of polarization.
Electrode poling has the advantages of high d33 coefficient and reproducibility. Electrode poling is a
relatively simple method among these two methods. The PVDF film is sandwiched between two
electrodes and then wrapped by a shell (Figure 6a). To prevent the PVDF film from being broken
down by the arc between the electrodes, the air in the shell needs to be evacuated or an insulating
liquid needs to be injected into the shell[127,128]. To polarize the PVDF film, we need to apply an
electric field between 5 and 100 MV/m. Corona poling needs to keep the gas in the shell dry. We can
circulate dry or inert gas. The PVDF film is only in contact with one of the electrodes. The corona tip
is placed on the top and connected to a 10 kV voltage. The voltage connected to the grid is much
lower (10 kV), ionizing the gas between the corona tip and the grid and accelerating the movement
to the PVDF film, thereby polarizing the PVDF film (Figure 6b). The electron beam poling method
uses a focused electron beam and irradiates the PVDF film to reorient into the β phase. In addition to
the above polarization methods, mechanical drawing and additive manufacturing can polarize
PVDF. As for additive manufacturing, we can induce the formation of the β phase using composite
systems. Table 1 shows the advantages of various polarization methods. The method of solvent
casting mainly relies on the addition of some compounds and application of high temperature and
external electric field, to promote the formation of the β phase state of PVDF. Chien et al.[129] spin-
coated PVDF–TrFE dissolved in MEK and hot embossed the silicon mold on the film under DC poling
(Figure 7c). The electric voltage varied from 30 to 60 V, and the temperature was 90 or 110 °C.

Figure 7. (a) Schematic diagram of the spin coating and (b) Solvent casting; (c) Spin coated PVDF-
TrFE was dissolved in MEK and the silicon mold was hot pressed on the film [129]; (d) SEM of PVDF–
TrFE copolymer thin films fabricated by spin coating[130]; (e) Preparing the PVDF-BaTiO3
nanocomposite films by spin coating[131].
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Table 1. The advantages of various polarization methods.

Polarization methods Advantages

Electrode poling High d33 coefficient and reproducibility

High d33 coefficient and No requirement

Corona poling
for one end structure of the material

Increased the design scope of the three-

Additive manufacturing dimensional structure of the material and
low temperature

Mechanical drawing High d33 coefficient and reproducibility

Increased the design scope of the three-

Electron beam poling
dimensional structure of the material

The piezoelectricity of thin films reaches as high as 14.0 pm/V, with a d33 value of 72.2 pC/N.
Tushar et al.[130] spin-coated PVDF–TrFE copolymer into thin films to induce the formation of the β
phase with a d33 value varying from 38 pC/N to 74 pC/N (Figure 7d). Schulze et al.[132] prepared
P(VDF-TrFE) films for 20 µm thickness by solvent casting under the effect of electrode poling and an
electric field of 75 MV/m. The d33 coefficients were measured to be about 20 pC/N. The spin-coating
technique[131] was used to prepare the PVDF-BaTiO 3 nanocomposite films on an interdigital ITO
electrode(Figure 7e). Vineet et al.[61] fabricated PVDF/PZT piezoelectric composite films by a
solution cast technique. The d33 value varied from 60 pC/ N to 84 pC/ N. The higher the content of
PZT ceramic, the greater the proportion of the β phase of PVDF.

3.2. Fabrication of PVDF by electrospinning

Electrospinning is a very promising processing technology. The needle tube containing the
PVDF solution sprays the PVDF solution onto a drum through a nozzle, the substrate wraps around
the drum, and a voltage between 10 and 20 kV is usually added between the nozzle and the
substrate[133]. Nano- to micro-scale PVDF fibers are randomly deposited on the substrate, forming
a low-density PVDF film. The electrospinning technique completes the PVDF deposition and
polarization process in one step. The rotation of the drum increases the stress between PVDF and the
substrate, which in turn promotes the formation of the β-phase state of PVDF. A schematic diagram
of the electrospinning technique is shown in Figure 8a. Gong et al.[134] combined the PVDF nanofiber
membrane by electrospinning with PDMS-Ag NWS and PET/ITO electrodes to fabricate sensors. Lu
et al.[106] made a flexible bend sensor to monitor human respiration by electrospinning PVDF and a
silver mixed solution (Figure 8b).
Xiaohe et al.[97] fabricated (BTO)/P(VDF-TrFE) composite nanofibers by electrospinning and
were able to distinguish and sense the movement of walking ants and the energy of a free-falling ball
as low as 0.6 µJ (Figure 8c). Sang et al.[9] fabricated flexible lead-free piezoelectric nanofibers
composed of PVDF and BNT-ST ceramic by electrospinning. The output voltage measurement
system is a frequency function for the BNT-ST/PVDF nanofiber composite module (Figure 8d). Rahul
et al.[135] fabricated PVDF nanofibers with a high β phase state to develop a PVDF strain sensor to
measure the string force (Figure 8e). Kunming et al.[136] fabricated nanocomposite fiber mats by
electrospinning graphene nanosheets, barium titanate, and PVDF, obtaining as high as 11 V of open-
circuit voltage (Figure 8f,g)).
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Figure 8. (a) Schematic diagram of the Electrospinning technique; (b) Flexible bend sensor to monitor
human respiration[106]; (c) Optical photo and SEM of (BTO)/P(VDF-TrFE) composite nanofibers[97];
(d) Optical photo and SEM of BNT-ST/PVDF nanofiber composite[9]; (e) PVDF strain sensor for
measuring the force of the string[135]; (f) Mechanical movement in the primitive phase and the
bending phase[136]; (g) Optical image and output voltage generated by human movement[136].

3.3. Fabrication of PVDF devices by 3D print

The 3D print can deposit PVDF or PVDF compounds on the bottom heating plate under heating
and nozzle extrusion (Figure 9a). Based on the 3D printing principles, we can incorporate polarizing
processes, including heat press, electric field poling, and mechanical stretching simultaneously. The
polarization process is shown in Figure 9b.
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Figure 9. (a) Schematic of 3D printing of PVDF layer; (b) Corona poling process; (c) Simultaneous 3D
printing and in-situ polarization; (d) 3D printing process and fabricated PVDF film[137]; (e) 3D
cylindrical sensor's piezoelectric voltage output when five finger taps[138]; (f) Optical diagram of 3D
printing technique and corona poling process[139].

Finally, we completed the integration of 3D printed PVDF and PVDF composites with the in situ
polarized PVDF. The schematic is shown in Figure 9c. The shear force between the nozzle and PVDF,
as well as heating, nucleation on filler surfaces, and electric field, all help to promote the formation
of the β-phase state of PVDF. Hoejin et al.[140] fabricated PVDF/BaTiO3 nanocomposites using a 3D
printing technique. Then, the composite material was thermally polarized to improve the
piezoelectric response of the composite. The piezoelectric response of the PVDF/BaTiO3
nanocomposite was three times higher than that of the nanocomposites fabricated by solvent casting.
Using the 3D printing technique, we can obtain a more homogeneous dispersion of PVDF/BaTiO3
nanocomposites, in comparison with nanocomposites fabricated by solvent casting. Chen et al.[137]
fabricated electroactive PVDF thin films of bi-axially oriented using layer-by-layer 3D printing.
Carbon nanotubes were added as a nucleating agent to induce the formation of the β-phase state of
PVDF (Figure 9d).
Sampada et al.[138] fabricated flexible, lightweight, and complex-shaped piezoelectric devices
by 3D printing (Figure 9e). The d31 coefficients were measured to be about 18 pC/N. PVDF films with
enhanced β-phase percentage[139] were fabricated by 3D printing (Figure 9f).
This section reviews the common preparation methods for PVDF. The different fabrication
methods and polarization of PVDF are shown in Table 2. The electrospinning process has the
advantages of direct polarization, while spin coating and pouring methods are simpler and more
compatible with other processes. As a new technology, 3D printing has also attracted the attention of
researchers.

Table 2. Different fabrication methods and polarization of PVDF

Material Performance Fabrication method Poling conditions

peak-to-peak voltage Electrospinning
PVDF[134] Vp-p= 2.2 V （dissolve PVDF in
（PDMS / Piezoelectric performance is 1.5 mL DMF and 3.5 No Poling
Ag） not greatly affected by mL acetone）
bending cycle
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peak-to-peak voltage Electrospinning

Vp-p= 4.6 V (2000 rpm and
PVDF[106]
200 times higher than needle tip-to- No Poling
(PVDF/AG)
randomly aligned PVDF collector distance is 4
nanofiber cm）
P(VDF-
able to distinguish and sense
TrFE)[97]
the energy of a free-falling Electrospinning
(BTO)/P(VD No Poling
ball as low as 0.6 µJ and (135 °C for 2 h)
F-TrFE)
movement of walking ants

Electrospinning
(feed rate of 1.0
PVDF[9] the measurement system of
ml/hour needle tip to
(PVDF/ BNT- the output voltage as a No Poling
collector distance is
ST) function of frequency
10 cm humidity of 25
∼ 40%）
Electrospinning
peak-to-peak voltage
(feed rate of 0.5
PVDF[136] Vp-p= 11 V
ml/hour 2000 rpm
(PVDF/BT/gr nanocomposite fibers are No Poling
and needle tip to
aphene) promising for wearable
collector distance is
devices.
12 cm for 3 h）
Spin coated DC poling
d33 =72.2 pC/ N the PVDF –TrFE (Electric voltage
PVDF– the piezoelectricity of thin dissolved in MEK varied from 30 to
TrFE[129] films reaches as high as 14.0 and hot embossed 60 V and the
pm/V the silicon mold on temperature was
the film 90 or 110 ℃)
Spin-coated
PVDF- d33 =38-74 pC/ N PVDF–TrFE into thin
TrFE[130] films to Induce the No Poling
formation of β phase
Solvent Casting
PVDF–TrFE for 20
PVDF– d33 = 20 pC/ N electrode poling
µm thickness under
TrFE[132] (electric field is 75
the effect of electrode
MV /m)
poling
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No Poling
Solution Casting The higher the
PVDF/PZT to content of PZT
PVDF[61] d33 = 60-84 pC/ N
fabricate ceramic, the
(PVDF/PZT)
Piezoelectric greater the
composite films proportion of β
phase of PVDF
the piezoelectric response of
the PVDF/ BaTiO3
nanocomposite is found
three times higher than
PVDF[140] nanocomposite fabricated by
Thermal poling
(PVDF/BaTi solvent casted 3D print
(performed for 2 h)
O3) more homogeneous
dispersion’s PVDF/ BaTiO3
nanocomposites than that
fabricated by solvent casted.

No Poling
（carbon
nanotubes were
thin films became very dense added as a
PVDF[137]
with high β-phase after 3D print nucleating agent to
depositing layer-by-layer. induce the
formation of β
phase state of
PVDF）
PVDF[138] No Poling
d31 =18 pC/N 3D print

piezoelectric PVDF films

PVDF[139]
with enhanced β-phase 3D print corona poling
percentage

4. Flexible Electromechanical Device Made by PVDF

PVDF polymer material has the advantages of low weight, high flexibility, high sensitivity, good
fit and ductility, and high piezoelectric coefficient. It is suitable for flexible sensors with high
flexibility requirements and is used in physics, chemistry, and biology. These fields have a wide range
of applications.
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Figure 10. (a) Schematic of the energy harvesting device; (b) Schematic diagram of woven triboelectric
nanogenerator production process[141]; (c) Nanogenerator harvests energy from human finger
tapping, human arm movement and human footsteps[141]; (d) The phenomenon of charge
separation during the process of press nanogenerator and release pressure of nanogenerator[142].

4.1. Energy Harvesting Device

The main principle of energy harvesting device manufacturing is to use the piezoelectric
conversion effect of piezoelectric materials. Under external pressure, the piezoelectric material
deforms and generates a voltage, thereby generating energy. A schematic diagram of the energy
harvesting device is shown in Figure 10a. In 2020, Mokhtari et al.[143] fabricated a high-performance
hybrid piezofiber composed of a PVDF and barium titanate (BT) nanoparticle (mass ratio 10:1). These
fibers are knitted to fabricate a wearable energy generator with a power density of 87 µW cm-3 and a
maximum voltage output of 4 V. In 2019, Sang et al.[144] prepared a wearable piezoelectric energy
harvester based on core-shell piezoelectric yarns prepared by twining the yarns around a conductive
thread. The yarns were composed of flexible piezoelectric nanofibers of BNT-ST and PVDF-TrFE by
electrospinning. Muhammad et al.[141] fabricated a woven triboelectric nanogenerator using
commercial nylon cloth and PVDF nanofibers, which can harvest energy from human motions. A
woven triboelectric nanogenerator harvests energy from human movement; a schematic diagram of
the production process of this device is shown in Figure 10b. Figure 10c shows that the nanogenerator
harvests energy from human finger tapping, human arm movement, and human footsteps.
Satyaranjan et al.[142] fabricated a nanogenerator based on flexible PVDF/SM-KNN, which has a
current density of 5.5 mA/cm2 and a power density of 115.5 mw/cm2. Figure 10d shows the charge
separation phenomenon during the pressing process and the release pressure of the nanogenerator.

4.2. Physical Sensors

In sensing applications, flexible and wearable pressure sensors are made of piezoelectric
polymer materials with flexible characteristics. High-voltage electrospinning can be used to fabricate
PVDF piezoelectric nanofiber films[51,145-149]. Gong et al.[134] combined the PVDF nanofiber
membrane by electrospinning with PDMS-Ag NWS and PET/ITO electrodes to fabricate sensors
(Figure 11a)[134]. This type of sensor has evident piezoelectric properties and performs well in
quantitative pressure measurement. In addition, because of their shape-preserving function, they can
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be used as real-time monitors of people’s activities (Figure 11b). Lee et al.[94] proposed a highly
sensitive gauge sensor based on PVDF and ZnO nanostructures on graphene electrodes (Figure
11c)[94]. It can detect pressure changes with the lowest 10 Pa value, which is 1000 times lower than
the minimum required for artificial skin. The temperature value calculation is based on the signal
recovery time (Figure 11d). The PVDF-TrFE copolymer membrane pressure sensor is manufactured
via a standard photolithography process that can be used for batch processing, thereby reducing
costs. The resulting membrane has good uniformity and high polymer pattern resolution[150]. Alluri
et al.[68] processed piezoelectric films made of PVDF and BaTi(1−x)ZrxO3, which can effectively
convert pressure signals into electrical signals, with a maximum peak power of 15.8 nW. The 3D
printed PVDF with BaTiO3 (BTO) filler[151] can also be used for pressure sensing[151]. Compared
with the single PVDF composite of TNL[152-154], the sensitivity was increased by 333.46% at 5 kPa
under the effects of the new additives shape, good interaction, and well-distributed hybrid additives
in the matrix. This confirmed that it was possible to fabricate low-cost and lightweight electronic
devices with reduced quantities of metal oxides and pressure sensing devices.

Figure 11. (a) Schematic of flexible pressure sensor used to detect pressure signal[134]; (b) device was
used as a motion sensor to monitor knuckle bends and vocal cord vibrates[134]; (c) Schematic of
sensor based on PVDF and ZnO nanostructures on graphene electrodes[94]; (d) The relationship
between temperature and recovery time[94]; (e) Generated output voltages, output currents, output
powers by Finger bending, knee and elbow movements[144]; (f) Pressure sensor embedded in the
bottom of the insole or stuck on human arm and voltage generated by jumping, walking, running and
different bending angles' elbows[123].

Sang et al.[144] manufactured a wearable piezoelectric energy harvester by electrospinning

PVDF-TrFE and BNT-ST(0.78Bi0.5Na0.5TiO3-0.22SrTiO3). The generated output voltages, output
currents, output powers by finger bending, and knee and elbow movements are shown in Figure 11e.
Ye et al.[123] fabricated flexible wearable pressure sensors that were sensitive to various human
behaviors based on piezoelectric materials. The pressure sensor was embedded in the bottom of the
insole or stuck on the human arm, and the voltage generated by jumping, walking, running, and
elbows at different bending angles is shown in Figure 11f.

4.3. Chemical sensor based on piezoelectric polymer

As a flexible piezoelectric material, the mechanical deformation state of PVDF electrically driven
is directly related to its mass load. Then, by modifying the sensitive surface with adsorbent materials,
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it can specifically adsorb gas or water vapor to form a mass sensor. For example, when the sensing
interface contacts the target gas, the physical shape and mass changes caused by the absorption of
gas will affect the resonance frequency and other physical parameters of the piezoelectric polymer-
sensitive film. To detect the hydrogen concentration, Zengwei et al.[155] applied the phase separation
method to deposit a PVDF microporous membrane on the surface of a palladium-loaded tin dioxide
(Pd-SnO2) gas-sensitive film. The stability of the sensor under high humidity was evidently improved
by the influence of the PVDF microporous membrane. Hydrogen sensor[156] can be made by sticking
the Pd film on both sides of the PVDF membrane. Because of the selective absorption of hydrogen by
the palladium membrane, expansion deformation occurs under the PVDF action, which is converted
into voltage signal output.

Figure 12. (a) Schematic of the spin coated PVDF-TiO2 on interdigital ITO electrode[157]; (b-
d) Graphical representation of the PEDOT: PSS/PVDF generator producing a stable DC
voltage.

The introduction of humidity in sensitive materials can also play a role in humidity sensing. The
spin coating technique was used to prepare the PVDF TiO2 nanocomposite films on interdigital ITO
electrode[157], and the surface morphology was modified by acetone etching. The volume
deformation of PVDF is caused by the hygroscopicity of nano-TiO2, resulting in a piezoelectric effect
(Figure 12a)[157]. Wang et al.[158] proposed a simple and low-cost method to prepare a moisture-
responsive composite membrane composed of PEDOT: PSS and PVDF by spin coating and thermal
evaporation. The bending angles of the composite film in both directions can reach 191 and 225,
respectively, showing good bidirectional bending performance. As shown in Figure 12b-d, the PVDF
film is glued together with the PEDOT: PSS film. PEDOT: PSS easily absorbs water[159-161]. In
different humidity environments, PEDOT has different bending degrees due to different water
absorption rates. PVDF films produce voltage signals under the corresponding bending degrees,
representing the specific humidity.

4.4. Biosensor and bionic actuator based on piezoelectric polymer

Piezoelectric polymers are used as biosensors mainly through biosensor surface modification.
The binding of biological target molecules on the sensing surface changes the mass of the sensing end
of the sensor, thus affecting the resonant output of the piezoelectric polymer. PVDF-TrFE films were
fabricated by electrodeposition, and piezoelectric polymer ultrasonic transceivers were developed,
which proved that they can be used for the ultra-sensitive detection of antibiotics. The diameter of
the entire ultrasonic transceiver was 680 µm. The ultrasonic transducers consist of a receiver and a
transmitter, which is patterned on a gold electrode and integrated with a microfluidic channel. The
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biosensor was successfully applied to detect the animals’ doxycycline with a detection limit of 50 ppb
(Figure 13a-c)[162]. In the field of microfluidic channels, the developed on-chip ultrasonic transducer
was performed excellently, with the potential to be used for ultra-sensitive detection of DNA,
proteins, and food antibiotics. Lin et al.[163] fabricated microporous PVDF membranes with different
surface morphologies from coagulation baths of different strengths by immersion-
precipitation. Using the dual-step procedure, ss-DNA was covalently immobilized on the
membranes. The antibody in serum can be effectively adsorbed by the immobilized DNA,
performing antibody detection. Similarly, nucleic acid sensors based on PVDF[164] have been
developed. In the experiment, they used the hybridization between the capture probe and target
analyte (Figure 13d)[164] and found that the mass load on the membrane was proportional to the
quantity of target nucleic acids (Figure 13e)[164].

Figure 13. (a) Schematic of the chip[162]; (b)The experimental setup for characterizing the ultrasonic
transceivers[162]; (c)The plastic microfluidic chip with ultrasonic transceivers[162]; (d) Schematic of
the biosensor using PVDF film as piezoelectric layer[164]; (e) Relationship between mass load and
frequency shift (Δf)[164].

In recent years, much attention has been paid to the research of artificial bionics devices. In 2019,
Wu et al.[165] reported a flexible robot based on a piezoelectric single chip bending structure (Figure
14a-b)[165]. Its relative speed is 20 times its body length per second, which is the fastest measurement
speed among the reported artificial robots on an insect scale. The soft robot uses the principle of
several kinds of animal movements, such as carrying load, the firmness of a cockroach, and climbing
slopes. Even after bearing the weight of an adult's footsteps (approximately 1 million times heavier
than the robot), the system can continue to move (Figure 14c)[165].
Piezoelectric polymers also have good performance in the manufacturing of artificial muscles.
Simaite et al.[166] prepared a hybrid membrane with hydrophilic PVDF grafted poly- (ethylene
glycol) monomethyl ether methacrylate (PEGMA) outer surface and hydrophobic main body, which
is a model human muscle composition, as shown in Figure 14d . The results are expected to be used
in artificial muscles. Xiao et al.[167] fabricated a fish-like robot to imitate fish swimming. The fish-
like robot is composed of a body and a tail. The body is made of expandable polystyrene and the tail
is made of graphene-PVDF as an actuator. The graphene-PVDF film is connected with a flexible Au
wire. When the power is turned on, the fish’s tail is bent, and when the power is turned off, the tail
returns to its original position. As the power is continuously turned on and off, the fish-shaped robot
can move forward as a speed of 5.02 mm/s. Kim et al.[168] fabricated a new IPMC actuator on the
basis of blend membrane made by PVDF/ polyvinyl pyrrolidone/ /polystyrene sulfuric acid . The
robot can support 2-, 4-, or 6-IPMC-leg models and this miniature walking robot has a size of 18 x 11
x 12 mm, a weight of 1.3g and a maximum speed of 0.58mm/s.
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Figure 14. (a) Optical photo of the fabricated robot and the SEM image of the cross-sectional view of
the prototype robot with different layers of materials[165]; (b) Images of prototype robot the
movements in a driving cycled[165]; (c) After bearing the weight of an adult's footsteps (about 1
million times heavier than the robot), the system can continue to move[165]. (d) The cross-sectional
view of the hydrophilic PVDF-graft-PEGMA[166].

5. Conclusion and perspectives

Although inorganic piezoelectric materials have the advantages of a large piezoelectric
coefficient and high strength, they are fragile and unsuitable for applications with higher flexibility
requirements. As a typical representative of flexible piezoelectric polymers, PVDF has irreplaceable
advantages in the development of piezoelectric materials. It has great flexibility and can also improve
its piezoelectric properties by doping optimization or other processes. Various doping methods for
PVDF polymer materials have been introduced, and the effects of different piezoelectric materials,
nanomaterials, and biomaterials were compared. Some preparation methods for improving the
polarization properties of piezoelectric polymers have also been introduced in detail. Based on
flexible piezoelectric polymer materials, we can obtain flexible electromechanical devices for different
purposes, such as energy harvesting devices, chemical sensor for humidity, pressure, gas, and
biomolecules.
We can prepare actuators of different sizes and functions based on flexible piezoelectric polymer
materials. However, it is still less than the conversion coefficient of the inorganic piezoelectric
material. In the follow-up work, the optimization method of the piezoelectric polymer should
continue to be studied and applied to wearable devices. 1) Piezoelectric materials based on biological
crystals are one of the materials with great potential. The modification of the unique functional
groups of biological materials can be used to improve the vertical piezoelectric coefficient of PVDF.
2) Aiming at shape retention, the method of preparing flexible electromechanical devices with high
mechanical voltage conversion efficiency should be further explored. 3) In addition, the use of
piezoelectric polymer materials for wearable flexible devices requires the piezoelectric polymer
exhibiting better skin affinity, more compatibility with other flexible materials to be suitable for the
applications of physiological index sensors and implantable devices. Biomaterials and flexible
conductive polymers can be introduced to improve its biocompatibility，antifouling ability, and the
ability of integration with hydrophilic surface. In summary, giving full play to the flexible
characteristics of piezoelectric polymers and developing wearable piezoelectric sensors and
executable devices will have very broad application prospects.
Author Contributions: Conceptualization, S.G. and X.D.; investigation, S.G. and Q.X.; writing-original draft
preparation, S.G, Q.X. and X.D.; writing-review and editing, S.G, Q.X., X.D. and M.X.; supervision, Q.X. and
K.C.A; funding acquisition, Q.X. and X.D. All authors have read and agreed to the published version of the
manuscript.

Funding: This research was funded by the National Natural Science Foundation of China, grant number
61674114, 91743110, 21861132001; by National Key R&D Program of China, grant number 2017YFF0204604,
2018YFE0118700; by Tianjin Applied Basic Research and Advanced Technology, grant number 17JCJQJC43600;
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by the 111 Project, grant number B07014; and the Initial Scientific Research Fund of State Key Laboratory of
Precision Measuring Technology and Instruments, Tianjin University, grant number Pilq1902. The authors thank
the Foundation for Talent Scientists of Nanchang Institute for Micro-technology of Tianjin University.

Conflicts of Interest: The authors declare no conflict of interest.

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