Applications and Future Scope - Energy Harvesting Applications

REVIEW
Piezoelectric www.mme-journal.de
Advances in Piezoelectric Polymer Composites for Energy

Harvesting Applications: A Systematic Review
Suvrajyoti Mishra, Lakshmi Unnikrishnan,* Sanjay Kumar Nayak, and Smita Mohanty
is a simplified technology which converts

Polymeric piezoelectric composites for energy harvesting applications are waste energy into viable electricity and
considered a significant research field which provides the convenience of supplies power to low electronic devices
mechanical flexibility, suitable voltage with sufficient power output, lower efficiently. Extensive research is being
carried out to establish self-powered elec-
manufacturing cost, and rapid processing compared to ceramic-based tronic devices like micro-electro-mechan-
composites. This review focuses majorly on the basic theory and principles ical systems (MEMS) as a productive
behind piezoelectric energy harvesting (PEH) devices, followed by specified alternative to weird battery-based systems.
materials used for the different devices. Different structural configurations A number of energy sources such as solar,
associated with fabrication of PEH devices are discussed in detail along with wind, nuclear power, thermal energy,
mechanical vibration are responsible for
their major advantages and drawbacks. Numerous classes of piezoelectric
producing electricity in these devices.
polymers such as polyvinylidene fluoride, polylactic acid, cellulose, poly Among them, mechanical vibration-based
amides, polyurea, polyurethanes, and their composites used for energy har- energy harvester has been manifested to
vesting applications as a productive alternative of lead-based piezo-ceramics, provide greater potential, better lifespan,
are extensively addressed and explored. Additionally, current global and and comparatively high power density.[2]
Indian scenarios associated with PEH devices, major challenges associated Several methods are available for the
transformation of mechanical vibrations
with them, and the future perspective of such devices are also reported in
into electrical energy viz., electromagnetic,
this review. electrostatic, and piezoelectric effect.
Piezoelectric energy harvesting (PEH)
systems have attracted increased attention
owing to their simple configuration, maximum conversion pro-
1. Introduction
ficiency along with the capacity of being integrated into more
Fossil fuels have been considered as the primary source of complex systems.[3] PEH system is mainly associated with three
energy since the nineteenth century and the world’s growing vital phases (Figure 1) named as: a) mechanical–mechanical
population is moving toward these sources without considering energy conversion comprising mechanical strength of the
their harmful effects on the environment. Also, over-consump- PEH under huge stresses and matching of mechanical imped-
tion of fossil fuels makes it super challenging to supply enough ance, b) mechanical–electrical energy conversion, associated
power for the future generation as a consequence of the over- with electromechanical coupling factor of the PEH structure
growing population. However, renewable energies could be an and piezoelectric coefficients, and c) electrical-electrical energy
option to overcome these issues but are not completely suf- transfer involving electrical impedance matching.[4]
ficient to support energy crisis in the coming decades. Con- There exist about 200 piezoelectric materials for energy har-
sidering these factors, scientists and engineers have started vesting applications[5] out of which piezo-ceramics (mainly PZT
developing advanced energy harvesting technologies from and BaTiO3) have attracted major attention due to their better
wasted energy sources as an alternative to the abovementioned piezoelectric properties as compared to other piezoelectric
issues.[1] materials.[6] A wide range of piezoelectric ceramics (PZT-based
The last few decades in the field of energy harvesting has thin films and lead-free ceramic films) and their applicability
been tremendously challenging as the use of portable smart toward transducers and energy harvesting areas have been
electronic devices with expanded durability has become the first elucidated by Khan et al.[7] Irrespective of better piezoelectric
choice for every human being. Energy harvesting technology properties associated with piezoelectric ceramics, some of their
disadvantages such as rigidity, brittleness, toxicity, high den-
sity, lower voltage coefficient, and lack of design flexibility limit
S. Mishra, Dr. L. Unnikrishnan, Prof. S. K. Nayak, Dr. S. Mohanty their energy-related application to some extent.[8] The choice of
Laboratory for Advanced Research in Polymeric Materials a particular piezoelectric material for a specific energy-based
School for Advanced Research in Polymers application is not only limited to their piezoelectric perfor-
Central Institute of Plastics Engineering and Technology mance but also depends on other parameters like design flex-
B-25, CNI Complex, Bhubaneswar 751024, Odisha, India
E-mail: lakshmi@larpm.in, lakshmipvallath@gmail.com
ibility, application frequency, available volume. Piezoelectric
polymers serve as a better candidate for concerned applications
DOI: 10.1002/mame.201800463 satisfying most of the abovementioned criteria. The mechanical
Macromol. Mater. Eng. 2019, 304, 1800463 1800463 (1 of 25) © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com www.mme-journal.de
flexibility, faster processing, lower fabrication cost, and biocom-

patibility of piezo-polymers like polyvinylidene fluoride (PVDF) Suvrajyoti Mishra received
and its copolymers, cellulose and their derivatives, polylactic her M.Sc. degree in polymer
acids (PLA), polyurethanes (PU), polyimides (PI) outspread science and technology from
their applications to several, energy-related systems.[8] Polymers CIPET, Utkal University,
usually show higher dielectric breakdown behavior and pos- Odisha, India in 2015.
sess maximum functional field strength, signifying that they Currently she is pursuing
can resist much higher driving fields as compared to ceramics. her Ph.D. in polymer science
They provide potential to pattern electrodes on the surface of and technology at SARP-
the film, and pole only specified regions as required. Based on LARPM, Utkal University,
these characteristics, piezoelectric polymers exhibit their own under the guidance of Prof.
potential and effectiveness for technical applications and func- S. K. Nayak and Dr. Lakshmi
tional device configurations.[9] Unnikrishnan. Her Ph.D. work
This review mainly aims at exploring the applications of dif- is majorly associated with different piezoelectric
ferent piezoelectric polymers and composites in energy har- polymers suited for energy harvesting applications in a
vesting systems for delivering maximum voltage and power more reliable and convenient way.
outputs. The effects of incorporation of inorganic and organic
nano-fillers for improving the piezo-responsiveness of the pie- Lakshmi Unnikrishnan works
zoelectric polymers are discussed. Current global scenario and as a scientist at SARP-LARPM.
future perspective of polymer-based PEH devices are discussed She obtained her Ph.D.
here along with major issues and challenges. Major applica- degree from Biju Patnaik
tions of these polymeric PEHs in different sectors including University of Technology,
sensor and actuators, biomedical field, wearable and implant- Rourkela, India in 2016. Her
able devices, ultrasonics are also discussed in this review. research interests include
polymeric composites/
nanocomposites, gas separa-
tion membranes, proton
2. Theory and Principles Involved in Piezoelectricity exchange membranes for
and Energy Harvesting Technology fuel cells, and piezoelectric
The unusual characteristics of certain materials that are capable materials for energy related applications.
of converting mechanical energy into electric energy without
the application of any external input and vice versa (deforma- Sanjay Kumar Nayak is the
tion due to the application of electric field) have been termed director general of CIPET,
as “piezoelectricity” and materials possessing this property are Department of Chemicals and
called as piezoelectric materials. Conversion of mechanical Petrochemicals, Government
energy into electrical energy is known as “direct piezoelectric of India. He has extensive
effect” and the reverse is referred to as “converse piezoelectric teaching and research experi-
effect” (Figure 2). Most of the energy transducer and sensor ence over a period of more
devices are based on direct effect while the converse effect is than 30 years in material
associated with actuators.[10] (polymer) science and tech-
This phenomenon is attributed to the elemental structure nology, and holds member-
associated with certain crystal lattices. In these crystalline struc- ship in different professional
tures, there exists a balanced equilibrium between the positive societies. He is a chief
and negative charges, which remains neutralized across the researcher at SARP-LARPM, India, and works in the field of
virtual polar axis. This equilibrium within the crystal structure different aspects of polymers, focused toward composites
gets disturbed causing an irregular arrangement of the dipoles and biopolymers, membrane science and technology, and
when subjected to a mechanical stress or vibrations and pro- sustainable and renewable energy resources.
duces an electrical charge.[11,12] The effect of mechanical stress
on the molecular structure of a piezoelectric crystal is clearly
shown in Figure 3. Here, application of mechanical stress (ten- and polycrystalline configuration of the material. Piezoelectric
sion or compression) resulted in disruption of charge balance effect is commonly exhibited by non-centrosymmetric crystals.
while deforming the internal structure of the crystal. Conse- In case of a mono-crystalline structure, as shown in Figure 4a,
quently, both the positive and negative charges get separated by the polar axes of all of the charge carriers show one-way orienta-
destroying the neutrality of the molecule and create a surface tion characteristics. Here all the polar axes remain unidirectional
charge density to be collected via electrodes.[13] throughout the crystal even if that crystal was broken into several
The behavior and performance of piezoelectric materials are pieces, which signifies symmetry. Alternatively, a polycrystalline
closely related to the number of electric dipoles present within structure, Figure 4b is defined by the presence of different polar
these materials. Crystal symmetry plays an important role in axes in different segments along the material structure causing
evaluating the piezoelectric property in terms of monocrystalline irregular alignment of dipoles. It is unsymmetrical due to the
Figure 1. Three vital phases associated with piezoelectric energy harvesting.
unavailability of any point where the crystal would show similar the electric dipoles in one single orientation corresponding to the
resultant polar axes when split into pieces. Subsequently, the direction of the applied electric field as presented in Figure 4c,d.
material does not show any polarization and exhibits no piezo- Afterward, while the temperature is brought down to room tem-
electric effect. In order to acquire piezoelectricity, an important perature and the electric field is removed, the dipoles still retain
operation known as “poling” has to be done to these materials, closely aligned polarization with a permanently locked configu-
which comprises the application of a strong electric field, com- ration thereby exhibiting piezoelectric behavior. However, poly-
monly at a temperature nearly to the Curie temperature. Poling crystalline materials offer the flexibility of change in polarization
treatment results in the development of an instinctive polariza- as and when required. Also, their degree of polarization can be
tion by allowing the molecules to move more freely and aligning tailored easily by varying the poling conditions.[11,14]
Figure 2. Direct and converse piezoelectric effect.
Figure 3. Disruption of charges in neutral molecule under applied mechanical stress. Adapted with permission.[158] Copyright 2016, AKGEC.
The two piezoelectric effects, that is, direct and converse electric field, respectively. Three different axes termed as 1, 2,
effects are well explained by two piezoelectric constitutive equa- and 3 (Figure 5) which are identical to Cartesian coordinate
tions as shown below.[15] axes x, y, and z are used to define the three directions (i, j, and
Direct piezoelectric effect k) in piezoelectric elements. Direction along z-axis, that is,
direction “3” signifies the direction of polarization (which may
Di = eij σ E j + dim dσ m (1) be the effect of poling). Subscript “m” specifies the rotational
motion/shear motion around the three axes (1, 2, and 3) and
Converse piezoelectric effect termed as 4, 5, and 6, respectively, for which it is designated
from number 1 to 6. These indices also help in determining
ε k = d jk c E j + Skm E σ m (2) the mode of operation, that is, directions of electric field cor-
responding to an applied mechanical strain of a piezoelectric
where Di, dielectric displacement; εk, mechanical strain vector; energy harvesting device.[16,17]
Ej, applied electric field vector; σm, mechanical stress vector;
dimd and djkc, piezoelectric coefficients; eijσ, dielectric permit-
tivity; SkmE, elastic compliance matrix. Considering the fact that 2.1. Structural Configuration and Performance of PEH Devices
direct piezoelectric effect has been utilized by energy harvesting
devices and the converse effect is associated with actuators, There are many structural configurations available for PEH
the importance of subscripts and superscripts used in Equa- devices, wherein cantilever beam type is the most widely used
tions (1) and (2) are described in more detail below. structure owing to its simple structural geometry and genera-
The superscripts “d” and “c” are used as a symbolic represen- tion of the maximum amount of strain for a given amount of
tations for direct and converse piezoelectric equations, respec- mechanical vibration. This type of configuration can be con-
tively. The different directions inside the coordinate system of structed by bonding a thin layer of piezoelectric material to a
the material are represented by the subscripts i, j, and k while non-piezoelectric layer (generally a conductive metallic layer)
the superscript “σ” and “E” symbolizes the dielectric constant and by fixing it at one end to achieve a structure operating in
measurement under constant mechanical stress and constant its flexural mode as shown in Figure 6a,b. When mechanical
Figure 4. Dipole arrangement in a) mono-crystalline and b) poly-crystalline material. c,d) Polarization of polycrystalline material in presence of electric
field to generate piezoelectricity.
such as cymbal and stack type configuration have been also

explored for PEH systems to harvest energy through mechan-
ical vibrations.
Cymbal type PEH is required for applications withstanding
higher impact forces. This configuration composed of a piezoe-
lectric layer placed between two metal end caps on both sides is
shown in Figure 6d. When axial stress is applied on the metal
end caps, it amplifies the axial stress and converts them into
radial stress in the piezoelectric layer, thus providing higher
piezoelectric coefficients which lead to higher charge genera-
tion from the PEH.[12]
Stack configuration for PEHs consists of multiple piezoelec-
tric layers stacked over each other (Figure 6e) in such a way
that the poling direction of the layers aligns with the applied
pressure. This configuration utilizes the d33 mode, as it has a
higher coefficient than d31 mode and suitable for applications
demanding high pressure. However, it utilizes the d33 mode,
the higher stiffness of the structural configuration lowers the
mechanical energy evolved from the applied pressure, for
which they need to be coupled with mechanical amplifiers for
Figure 5. Three co-ordinate axes direction system in piezoelectric better output.[17]
materials. A comparative analysis of the major advantages and disad-
vantages of different types of PEH structural configurations are
shown in Table 1. From Table 1 it is clear that, cantilever beam
vibrations are applied to the mass system of the cantilever, type configuration in the simplest type structure could deliver
it results in the oscillation of the structure producing an AC maximum strain depending upon the proof mass. Moreover,
voltage by the piezoelectric layer. Depending on the number of the design of PEH devices for a particular operation could
piezoelectric layers bonded to the metallic layer, cantilever beam always be specified depending upon the application perspective
structure is categorized into two configurations namely “uni- and mode of operation.
morph” as only one active piezoelectric layer exists (Figure 6a)
and “bimorph” as two thin layers of active piezoelectric mate-
rial are used (Figure 6b). Since bimorph structure improves 2.2. Frequency Response of PEHs
the electrical energy output twice, without making any remark-
able changes in the device volume as compared to unimorph The performance and efficiency of an energy harvesting device
structure it has received significant attention in PEH devices. is greatly influenced by several factors like resonance frequency,
The operation mode, calculation of resonance frequency as a structural configuration, resonance voltage.[18] Frequency
function of the proof mass of the cantilever beam and the dis- serves as one of the major characteristics in PEHs over other
tribution of strain throughout the piezoelectric structure were parameters as maximum power is generated at their resonant
effectively discussed by Huidong Li et al.[12,17] frequency. Most efficient conversion from vibrational to elec-
Another structure employed for PEH device is the circular trical energy occurs while there is a close resemblance between
diaphragm. In this kind of configuration, a thin disk-shaped applied vibrational frequency and natural frequency owned by
layer of piezoelectric material is attached to a metal shim and the device.[5] Erturk[19] also explained that performance of PEHs
the whole arrangement is fixed on the edges of the clamping is dependent on the linear resonance nature of the harvester
ring (Figure 6c). In order to enhance its performance under and maximum power can be achieved only when there is a per-
low-frequency operation and to improve the power output, fect match between the excitation frequency of ambient sources
pre-stress is supplied to the piezoelectric material by affixing and resonance frequency. Otherwise, a little mismatch could
a proof mass at the core of the circular diaphragm. Pre-stress result in a significant reduction in voltage and power output.
can also be induced during the fabrication stage of the piezoe- For this reason, the size and shape of the piezoelectric layers
lectric-metal composite. The superiority of diaphragm type over are determined depending upon the natural frequency of the
cantilever type configuration involves its affinity to operate in energy harvester. There exist several kinds of piezoelectric
pressure mode as it is capable of converting different type of materials that are suitable to operate under various frequen-
pressure fields to an AC signal by a piezoelectric transformer. cies mode ranging from 1–100 Hz or higher. Applications
Diaphragm type configuration assists in harvesting energy from demanding higher vibration frequencies (100 Hz or higher),
slowly varying, periodic pressure fields, or periodic acoustic choose piezoelectric ceramics as a better option because of
waves, as well as mechanical vibrations. As compared to a can- their higher stiffness along with superior piezoelectric prop-
tilever, this structure is substantially stiffer which leads to the erties whereas applications requiring lower vibration frequen-
greater resonance frequency in vibration mode operation.[12,17] cies (1–30 Hz), piezoelectric polymer, and composites serve as
Rather than cantilever and circular diaphragm type config- most favorable material. Considering the fact suggested by Li
uration, two more different types of structural configurations et al., the output power of PEH device is inversely proportional
Figure 6. Different structural configurations of PEH.
to the frequency of the fundamental vibration mode; low- device, and a storage device for storing the output energy from
frequency vibrational modes are proposed to be most favorable PEH device (Figure 7).[12]
in designing PEH devices.[12] Several studies suggest about the available different AC-DC
rectifiers which include solid state diodes, silicone-based
switches, vacuum tube diodes, and mercury arc valves.[10] How-
2.3. Electronic Circuit and Storage Diagram ever, the most common and convenient method used to rectify
AC voltage to DC voltage is rectifiers with half-wave or full wave
Estimation and storage of the harvested energy within the rel- bridge rectifier consisting two or four diodes in a bridge cir-
evant storage device is equally important as harvesting energy cuit. Full-wave rectifier is more suitable for piezoelectric energy
from piezoelectric materials. Being an essential part of the- conversion as it is capable of filtering full of the voltage output
piezoelectric device, the electronic circuit of a PEH device from piezoelectric material. Synchronous rectifiers which
comprises three major constituents: a rectifier for converting replace the diodes with metal-oxide-semiconductor field effect
alternating current (AC) to direct current (DC), a voltage reg- transistors (MOSFET) outcomes with better rectifying effi-
ulator for regulating the DC power provided to the storage ciency as compared to full- and half-wave rectifiers. The lower
Table 1. Major advantages and disadvantages of different structural configurations.[12,17]
Type of configuration Features/advantages Disadvantages

Uni-morph/bi-morph cantilever beam ▪ Simple structure ▪ Inability to resist high impact force
▪ Low fabrication cost
▪ Lower resonance frequency
▪ Power output is proportional to proof mass
▪ High mechanical quality factor
Circular diaphragm ▪ Compatible with pressure mode operation ▪ Stiffer than a cantilever of same size
▪ Higher resonance frequencies
Cymbal transducer ▪ High energy output ▪ Limited to applications demanding high-magnitude vibration sources
▪ Withstands high impact force
Stacked structures ▪ Withstands high mechanical load ▪ High stiffness
▪ Suitable for pressure mode operation
▪ Higher output from d33 mode
resistance of MOSFET in comparison to diodes causes a little The significant advancement in reliability, output, and corre-
drop in voltage amount while current passes through it and the sponding technologies associated with PEHs has enhanced its
voltage produced after rectification requires controlled regula- interest in the global market which is promoting future develop-
tion for the energy storage system. Step-down voltage regulator ment. As per the findings of IDTechEx, investment on piezoe-
is most frequently used for piezoelectric elements as they gen- lectric energy harvesting technology will expand to $145 million
erate a higher output voltage for a battery or an electronic load in 2018 so that it will succeed in creating a $667 million market
and step-down converters are very effective in regulating high by 2022.[20] Technavio[21] recently reported that the global piezoe-
input voltages to low output voltages. For accumulation of har- lectric smart materials market is supposed to surpass $42 billion
vested energy, rechargeable batteries and capacitors are consid- by 2020. As per research analysts, the major three components
ered as two vital storage mediums although both are very dif- that will contribute toward the positive growth of the worldwide
ferent in their characteristics in energy harvesting application piezoelectric market are: aerospace and defense sector due to
perspective.[12] increasing demand, construction field, and growth of efforts in
research and development sectors.[21] Another report from Tech-
navio suggested that piezo-ceramics contributed major shares
3. Current Global Scenario of PEHs to piezoelectric smart materials market throughout 2016 due to
their excellent properties.[22] From the viewpoint of geographic
and Challenges
divisions, the United States is going to be the prime revenue
Piezoelectric energy harvesting technologies suffer lim- contributor to this market throughout the forecast period
ited commercialization due to their application-dependent (2017–2021). Piezoelectric materials with enhanced functional
nature. This field has been continuously explored by scien- behaviors have found applications in aerospace and military
tists and engineers for several decades. A report published by sector involving engine vibration control, flow separation owing
Zervos[20] revealed that within a few years, the power efficiency to turbulence, ice formation on wings, high cabin noise levels
of piezoelectric harvesters has been increased from the order and control surfaces in cold climatic conditions, smart sensors
of micro-watt (µW) to the order of several milliwatts (mW). and smart nano-robotics, etc.[22]
Figure 7. Energy harvesting and storage block diagram for PEH devices.
Several research attempts are carried out for improving the actuator and sensor industry. Therefore, basic electronic devices
performance of PEHs as well as their application toward social like transistors and sensors can now be printed with conductive
lives. Piezoelectric thick films prepared by aerosol deposition inks and thin layers of electroactive polymers, for which it has
technique are being used for several piezoelectric devices, suit- now become feasible to fabricate electronic devices on flexible
able for sensor and actuator applications.[23] National Insti- substrates like paper, fabric, or plastics.[26,27]
tute of Aerospace (NIA), USA demonstrated a hybrid PEH The market demand for piezoelectric polymers and polymer/
(“33”-longitudinal mode) of four times higher power output ceramic composites has been expanding through these years.
than a traditional “31” harvester constructed with innovative The number of scientific research articles in piezoelectric
structures.[20] In 2012, Stewart et al.[24] discovered that max- energy harvesting field has been increasing tremendously
imum power output can be harvested from a device by covering since the last decade considering their broad potentiality. The
the two-third length of the cantilever beam with active piezoelec- multidisciplinary approaches of PEH are making itself a chal-
tric materials. An exceptional soccer field has been constructed lenging area in several disciplines including electrical energy,
from piezoelectric elements in Rio de Janeiro, Brazil by a material science, applied physics, and mechanical engineering.
British energy company, PAVEGEN to harvest electrical energy The global energy harvesting device market by using polymers,
by utilizing the running and walking of people’s kinetic energy ceramics, and ceramic/polymer composites continues to grow
in the field. This harvested energy is being used to power six for piezoelectric actuators and motors owing of their diversified
LED lights at night so that it could light up the slum areas.[25] applications in IT sector, robotics, automotive, biomedical engi-
Korea Institute of Machinery and Materials (KIMM) developed neering, ecology, and energy engineering.[28]
the world’s first artificial basilar membrane by utilizing piezo-
electric energy harvesting technique. This device is capable of
enhancing the hearing function by replicating the cochlea in 4. Material Specialization for PEHs
human ears. A trapezoid shaped nano-piezoelectric material is
used in the cochlea, which distinct the frequency by the basilar Piezoelectric materials are classified into four major catego-
membrane and transforms this signal into an electric signal. ries such as ceramics, single crystals, polymers, and polymer
Produced electric signal helps in stimulating the auditory composites/nanocomposites. Common examples of each
nerves by allowing the user to hear sound through it.[25] category are represented in Figure 8. Since the selection of
Growing advancement in technological products leads to piezoelectric materials for a specified application is not only
larger investment in R&D sector which helps many companies/ limited to their piezoelectric properties but also depends upon
industries to survive in piezo-market while gaining popularity. the functionality of the application sector, one must consider
Arkema, a globalized manufacturer of chemical products, has the versatility of different class of materials from a wider
developed ultra-high value-added electroactive polymers such as perspective.[12]
PVDF and PVDF films which could be used as a future mate-
rial for a wide range of applications in aerospace, automotive,
robotics, and electronic sectors. As an important part of textiles, 4.1. Piezoelectric Single Crystals
these classes of polymers are also capable of making clothing
items smart and well-acceptable. These textiles containing These materials possess outstanding piezoelectric properties
numerous sensors with sensing properties are efficient enough and are mainly found in applications in various actuators and
to transmit the individual’s biomedical data. Piezotech, a part sensors.[29] The presence of regularly ordered positive and nega-
of Arkema group, provides a special range of electroactive inks tive ions throughout the single crystal structure leads to proper
prepared from piezo-polymers that fulfills the requirements of alignment of the dipoles which is primarily responsible for
Figure 8. Different classes of piezoelectric materials.
their piezoelectric behavior. The most commonly used piezo- In the case of polymer-ceramic composites, the matrix and
electric single crystals are: lithium niobate (LiNbO3), lead mag- reinforcement dispersion geometry also alter their piezoelectric
nesium niobate-lead titanate solid solution (PMN-PT), lead properties. Piezoelectric composites with 0–3 geometry (fillers
zinc niobate-lead titanate (PZN-PT), etc.[12,29] These materials in the form of particles in polymer matrix) shows poor piezo-
found applications in different electromechanical sectors such electric properties, while composites with 1–3 (fillers in the
as hydrophones, sonar transducers, accelerometer, actuators, form of fiber) or 2-2 (fillers in the form of laminates) geom-
and medical ultrasonic devices due to their higher piezoelectric etry exhibits superior piezoelectric properties, when the longi-
coefficients (d33 = 2200pC N−1, k33 = 93%).[30] tudinal direction of the fillers remains parallel to the direction
of poling.[32]
4.2. Piezoelectric Ceramics

5. Piezoelectric Polymers: A Productive Alternative
Piezo-ceramics are polycrystalline materials of perovskite
to Piezo-Ceramics
crystal structure composed of numerous single crystal “grains”
possessing identical chemical composition. However, the orien- Piezoelectricity and ferroelectricity were first discovered by
tation in the single grain is different from one another, there Kaway in PVDF in the year 1969. Researchers have been
exists slight different space between the ions. These materials working on the development of an alternative material for
are characterized by superior piezoelectric properties and lead- existing ceramic system, and piezo-polymers have emerged as
zirconate-titanate (PZT) is considered as the important piezo- the potential candidates. Table 2 presents most of the important
ceramic which is widely used for energy harvesting and storage distinguishable parameters between piezo-ceramics and piezo-
applications. Other examples of ceramics include barium polymers. Though piezoelectric polymers show a lower strain
titanate (BaTiO3), potassium niobate (KNbO3).[12] coefficient (d33) in comparison to ceramics, the low permittivity
value leads to higher voltage coefficients (g33) value which sig-
nifies them as excellent sensor materials. Furthermore, other
4.3. Piezoelectric Polymers properties such as design flexibility, light weight, low density,
low cost, low refractive index make them crucial for different
This class of material belong to carbon-based materials with long energy harvesting applications.[31] These polymers are usually
polymer chains and specified by their excellent flexibility than a semi-crystalline material with crystalline regions embedded
single crystals and ceramics.[12] They have the capability to with- inside an amorphous matrix. They typically possess non-
stand much higher strain due to their inherent flexibility, making polarizable phases after cooling from melt during the fabrica-
them more suitable for applications demanding a large amount tion process. To become piezoelectric, stretching or drawing
of bending or twisting. Polyvinylidene fluoride (PVDF), polyvi- these polymers uniaxially or biaxially is required to covert non-
nylidene fluoride-trifluoro ethylene (PVDF-TrFE), cellulose and polar phases into polar ones or induce polarity through solu-
their derivatives, polyamides (PA), polylactic acids (PLA), etc. are tion casting and align the dipoles through electrode or corona
some well-known piezoelectric polymers among which PVDF poling treatment.[33]
has been studied extensively. This material is found suitable for Other polymers such as nylons, polyimide (PI), PLA, poly-
a variety of energy-related applications such as ultrasonic trans- amides, cellulose and their derivatives, PU, polyurea also show
ducers, audio transducers, medical transducers, display devices, piezoelectric behavior to some extent. Table 3 represents some
vibrometers, shock sensors, pressure sensors.[9,31] of the most important piezoelectric parameters of different pie-
zoelectric polymers.
4.4. Piezoelectric Polymer Composites and Table 2. Comparative view of piezo-ceramics versus piezo-polymers.
Nanocomposites
Properties/parameters Piezo-ceramics (PZT) Piezo-polymers (PVDF)
To modulate and enhance the properties of
Piezoelectricity High Low
different piezoelectric materials, relevant
composites/nanocomposites have been devel- Acoustic impedance (10 6 kg
m−2 s−1)a) High (30)[34] Low (2.7)[34]
oped.[31] PZT particle reinforced polymer Density (103 kg m−3) 7.5 [34]
1.78[34]
composites have been studied effectively by Relative permittivity (ε/ε0) 1200[34] 12[34]
combining the superior piezoelectric prop- Piezo-strain constant (10−12 C N−1) d31 = 110,[34] d33 = 225–590[35] d31 = 23,[34] d33 = −33[34]
erties of PZT ceramics with the mechanical
Piezo-stress constant (10−3 V m N−1)a) g31 = 10,[34] g33 = 26[36] g31 = 216,[34] g33 = −330[34]
flexibility of polymers. The composites have
been found to exhibit several improved prop- Electromechanical coupling factor k31 = 30[34] k31 = 12[34]
erties as compared to only ceramics and (% at 1 KHz)
polymer-based materials.[12] Also, other fillers Dielectric constant 1180[37] 10–15[37]
of different classes (ceramics, metal-based, Mechanical flexibilitya) Poor Outstanding
hybrid material, bio-materials, etc.) in macro, Curie temperature (°C) 386[37] 80[37]
micro, and nano sizes are being investigated
for improved performance and tailor ability. a)Exceptional properties of PVDF for energy harvesting application vis-à-vis PZT ceramics.
Table 3. Piezoelectric properties of different piezoelectric materials.
Polymers Structure Piezoelectric coefficients dij [pC N−1] Piezoelectric Relative Electrome-
voltage coefficient permittivity chanical coupling
×10−3 [Vm N−1] coefficient
d33 d31 d14 g33 εr k33 k31
PVDF −24 to −34[38] 8–22[39] — —330[34] 6–12[40] 0.20[41] 0.12[9]
PVDF-TrFE −25 to 40[42,43] 12[33] to 25[42] — 380[44] 18[45] 0.29[41] 0.16[46]
PVDF-HFP −24[47] 30[48] — — 11[49] 0.36[49] 0.187[50]
PLA — 1.58[51] 9.82[52] — 3–4[53] — —
Polyamide 11 4[54] 14[55] — — 5[54] — 0.049[9]

(at 100–200 °C)
Celluloses 5.7 ± 1.2[56] 1.88–30.6[57] −35 to — — — —

(for CNF) (at 0 °C, 45 °C, 60[58,59]
90 °C)
Polyurethane — 27.2[60] — — 4.8[60] to — —

6.8[61]
Polyurea 19 at 60 °C[62] 21 10[46] — — — — 0.08[46]

at 180 °C[62]
(Continued )
Table 3. Continued.
Polymers Structure Piezoelectric coefficients dij [pC N−1] Piezoelectric Relative Electrome-
voltage coefficient permittivity chanical coupling
×10−3 [Vm N−1] coefficient
d33 d31 d14 g33 εr k33 k31
Polyimide 2.5–16.5[8] - — — 3.34[63] — —
PAN — 2[9] — — — —
PVDF, polyvinylidene fluoride; PVDF-TrFE, polyvinylidene fluoride-trifluoro ethylene; PVDF-HFP, polyvinylidene fluoride-hexafluoro propylene; PLA, polylactic acid; PAN,
polyacrylonitrile; CNF, cellulose nanofibrills; d31 and K31, transverse mode; d33 and K33, longitudinal mode; d14, shear mode piezoelectric coefficients.
5.1. Polyvinylidene Fluoride and Copolymers to render the material piezoelectric. Also, PVDF and its copoly
mers can be dissolved in liquid solvents so that they can be
Considering the ease of processability, availability, and piezo- extruded or molded into desired shapes or directly coated onto
electric coefficients, PVDF has emerged as the competitive a substrate, adding more flexibility in transducer design.[9,33]
alternate for existing ceramic systems. Other representatives
of PVDF family with desired properties are poly(vinylidene
fluoride-trifluoroethylene) ([PVDF-TrFE]), poly(vinylidene flu- 5.1.1. Approaches to Enhance Piezoelectricity of Polymers
oride-tetrafluoroethylene) ([PVDF-TeFE]), and poly(vinylidene
cyanide-vinyl acetate) ([PVDCN-VAC]) and poly(vinylidene flu- Since β-phase is the prominent phase directly related to the pie-
oride-hexafluoropropylene) ([PVDF-HFP]).[12] zoelectric behavior of PVDF-based systems, most of the litera-
Polyvinylidene fluoride (PVDF) with the chemical formula ture discovered that β-phase content of PVDF can be promoted
(CH2–CF2)n was the first polymer to demonstrate relatively by the inclusion of certain fillers; in particular clays, or carbon
strong piezoelectricity. This polymer contains about 50% nanotubes, graphene, metal oxides, etc. or by blending with other
lamellar crystals that are tens of nanometers thick and up to polymers, like PVDF-TrFE, polymethyl methacrylate (PMMA), or
100 nano-meters long embedded in an amorphous matrix. Five ionic liquids. Also, stretching (uniaxial or biaxial) of the sample
different crystalline phases such as α, ß, γ, δ, and ε exist for in particular directions allows the chains to rearrange in a more
PVDF among which α, β, and γ phases are investigated the elongated conformation, thus increasing the β-phase fraction.[31]
most and commonly used polymorphs of PVDF (Figure 9). The The different type of fillers, which possesses a significant role in
α-phase has semi-helical TGTG′ (trans-gauche–trans-gauche) improving the piezo-responsiveness of polymers, is classified into
conformation and is of non-polar nature due to the anti-parallel several categories such as ceramic fillers, carbon-based fillers,
packing of dipoles inside the unit cell, resulting in no electroac- hybrid fillers, and bio-based fillers depending upon their origin.
tive properties. In case of β (all Trans TTT chain conformations) Ceramic fillers: Ceramic fillers are considered as non-metallic
and γ (T3GT3G′ conformations) phases, all dipoles of indi- solid materials consisting of an inorganic compound of a metal,
vidual molecules are arranged parallel to each other producing non-metal, or metalloid atoms. Piezo-ceramic filled polymer
a non-zero dipole moment and induce polarity. As electroactive composites have been the subject of immense interest in the
properties of a material depend on its polar structure, β phase last few decades owing to the synergism this blending is pro-
PVDF shows highest electroactive (piezo, pyro, and ferroelec- posed to display. There exist some well known piezo-ceramic
tric) properties due to their highest dipole moment (8 × 10−30 C fillers which shows excellent piezoelectric and dielectric proper-
m) as compared to other crystalline phases.[33,64] PVDF and its ties; but few of their inherent properties, such as brittleness,
copolymers such as (PVDF-TrFE), (PVDF-TeFE), and (PVDCN- non-ductility, and poor shapeability limit their applications to
VAC) are the most common piezoelectric polymers used in be used in a multi-phase system. Some well-known ceramic
energy harvesting applications. Among them, (PVDF-TrFE) and fillers including lead-zirconate-titanate (PZT), barium titanate
(PVDF-TeFE) can directly form a polar phase through copolym- (BaTiO3), sodium potassium niobate (KNN), bismuth sodium
erization without the need of stretching or drawing, because the titanate (BNT) have drawn major attention in the field of energy
extra fluorine atoms introduced into the polymer chain by TrFE harvesting and storage technology owing to their highest piezo-
and TeFE result in steric hindrance which prevents the forma- electric coefficients. Hence, the main objective of this section is
tion of the non-polar α phase. However, poling is a prerequisite to understand how the incorporation of different piezo-ceramic
Figure 9. Structural configuration of three major phases of PVDF.
fillers affects the piezoelectric as well as the dielectric behavior matrix. Here, dopamine was used to form a bridge between
of PVDF-based composites. PVDF and BaTiO3. The –OH and –NH2 groups present in
In 2009, Greeshma et al.[65] studied the role of lead zirconate dopamine reacted with BaTiO3 to form cladded BaTiO3 (CBT)
titanate (PZT) particles in the phase formation of PVDF and nanoparticles. Cross-linking reaction between individual dopa-
evaluated their electrical and structural properties by preparing mine molecules present in CBT forms polydopamine struc-
PZT-PVDF composites (50 vol%) with 0–3 connectivity. PZT ture to which fluorine atoms of PVDF molecule gets attached
particle sizes varying from micron to nano (40 nm to 106 mm) by strong adhesive force as shown in Figure 10. As a result,
were used and ß-phase of the composite was found to follow polymer chains get aligned in such a manner to induce all trans
a decreased order with a decrease in PZT particle size. The ß-phase pattern, thus improving the dielectric properties of the
highest value of the fraction of ß-phase content, F (β) = 57% nanocomposite. They demonstrated an increase in breakdown
was obtained for a particle of size 106 µm. The highest value of strength and energy storage density with a gradual increase in
d33 (14 pC N−1) and remnant polarization (0.094 µC cm−2) was the loading of BaTiO3 nanoparticles. At 1 vol% BaTiO3 loading,
obtained for the composites with PZT particle size (106 µm) maximum breakdown strength of ≈340 MV m−1 and energy
and both the properties were found to decrease with PZT par- density of ≈6.37 J cm−3 were obtained, indicating increased sta-
ticle size. The energy loss of the ferroelectric composite was bility of PVDF/BaTiO3 nanocomposite system.
found to decrease from 1757 to 473 µJ cm−2 with a decrease in In 2013, Chuan et al.[68] studied the effect of calcination of
PZT particle size. PZT powders on the dielectric properties of PZT/PVDF-TrFE
In 2012, Kakimoto et al.[66] fabricated a fibrous BaTiO3- composites films. They reported that high calcination temper-
reinforced PVDF composite (30/70 vol%) sheet, which ature created strong polar groups on the surfaces of ceramic
produced the highest energy output of 0.63 J m−3 per unit cycle powders and improved the surface properties of ceramic par-
at a frequency of 100 Hz, for the sheet with BaTiO3 orientation ticles, which accelerates the compatibility between PVDF-TrFE
ratio of 83%, which is 26% higher than pure PVDF sheet. and PZT particles and forms excellent bonding. An increment
In 2013, Yafang et al.[67] investigated the effect of the uniform in 20% higher pyroelectric coefficient, p′ (96 µCm−2 K−1) was
distribution of low BaTiO3 nanoparticle content in the PVDF observed for the composite films containing PZT powders
composite films at lower frequencies. The dielectric constant

followed an increasing trend (reached around 14 at 1 kHz for
the 10.94 vol% PVDF-TrFE/PZT with MWCNT film) with an
increase in PZT volume fraction.
In 2017, Li et al.[71] reported a novel method to modify the
electrical properties of BaTiO3/PVDF composites by the incor-
poration of calcined BaTiO3 ceramic powders. The outcome
showed that an appropriate calcination temperature resulted in
the improved electrical behavior of the composite. Calcination
of BaTiO3 powders at 950 °C assisted in improving the dielectric
constant and piezoelectric strain constant (d33) up to maximum
values of 166.38 and 25 pC N−1, respectively. The decrease in
dielectric loss (tanδ) in the low-frequency test section (less than
104 Hz) and an increase in tanδ in the high-frequency test sec-
Figure 10. Schematic representation of the interface modification reac-
tion (more than 104 Hz), was also reported, majorly attributed
tion between PVDF BaTiO3 nanoparticles. Reproduced with permis-
sion.[67] Copyright 2015, The Royal Society of Chemistry. to the existence of interfacial polarization effect.
Recently in 2018, a flexible piezoelectric-polymer nanocom-
posite film comprising gallium ferrite nanoparticles (GFO)
calcined at 700 °C. This improvement of pyroelectric properties and PVDF was developed for mechanical energy harvesting
resulted from the enhanced coupling interactions between the by Mishra et al.[72] The authors reported an output voltage of
polymers and calcined ceramics. ≈3.5 V and current of 4 nA, during mechanical pressing and
In 2015, Tiwari et al.[69] prepared a piezoelectric composite releasing conditions, respectively, in 30 wt% GFO-PVDF com-
film of PZT and PVDF of 0–3 connectivity with different posite film.
volume fractions (0%, 10%, 20%, and 30%) of PZT ceramics Carbon-based fillers: Carbon-based fillers have attracted
by solution casting technique. They found that an increase in major interest as reinforcing fillers for polymer nanocompos-
PZT content within PVDF matrix (15 wt% solutions) not only ites owing to their inherent multifunctional characteristics,
increases the dielectric constant of the composite but also including high stiffness, low density, electrical and thermal
helps in enhancing the ß-phase up to 75% by suppressing α conductivity.[73] A wide research on carbon-based materials
and γ phases of the polymer as shown in Figure 11a,b. The used for the improvement of piezoelectric as well as dielectric
dielectric permittivity was gradually increased from 60 to 72 characteristics of PVDF reveals that carbon nanotube (CNT),
while the piezoelectric coefficient (d33) of the neat PVDF film graphene oxide (GO), reduced graphene oxide (rGO) are the
increased from −32 pC N−1 to 84 pC N−1, with an increase in most popular and promising materials for this motive.
the volume content of PZT from 0% to 30%. The authors nar- In 2008, Kim et al.[74] revealed that the inclusion of CNT
rated this improvement in dielectric permittivity occurs due to permits the dielectric properties of the PVDF material to be
the growing contribution of PZT particles as well as the pres- regulated such that even lower poling voltages can induce a
ence of increased ß-phase content, which resulted in the overall permanent piezoelectric effect in the composite. The role of
improved dielectric and piezoelectric behavior of the system. surface functionalized MWCNTs on the formation of ß-phase
In 2015, multi-walled carbon nanotube (MWCNT) was PVDF was reported by Kai et al.[75] The mechanism for possible
doped with PVDF-TrFE/PZT nanocomposites films by Batra interaction between MWCNT and PVDF is schematically rep-
et al.[70] to study the changes in their dielectric behavior and resented in Figure 12. The strong electronegativity of fluorine
concluded with an increase in the dielectric constant of the atom in –CF2 dipole reacted with the π-electron rich surface of
Figure 11. a) Variation in the F (β)% of PVDF with an increase in volume% of PZT particles. b) Variation in the dielectric permittivity with temperature
for different volume fractions of PZT particles in the PZTx/PVDF (1-x) composite. Reproduced with permission.[69] Copyright 2015, Elsevier.
Figure 12. Scheme showing role of MWCNTs on the formation of ß-phase in PVDF: a) chemical interaction between functionalized MWCNTs and
PVDF chains; b) the adsorbed PVDF chains on the surface of MWCNTs influenced by the dispersion of MWCNTs. Reproduced with permission.[75]
Copyright 2014, Elsevier.
MWCNT thus forming PVDF chains with all trans-trans zigzag electric field-induced strain up to Smax/Emax (ratio of maximum
conformation. strain to electric field) = 16.66 pm V−1 for 0.3 wt% GO loading
In 2012, Achaby et al.[76] studied the piezoelectric ß-phase and increase in dielectric constant from 16 to 69 at 1 kHz.
formation in graphene oxide nano-sheets (GOn)-PVDF nano- In 2014, Huang et al.[81] prepared a PVDF/graphene (PVDF/
composite films. They succeeded in preparing a purely piezoe- GO and PVDF/rGO) ferroelectric composite film by in situ
lectric ß-polymorph at only 0.1 wt% GOn content. The mechan- reduction with hydrobromic acids in a two-step process and
ical strength of the reported film was found to be increasing reported the formation of nearly all ß-phase PVDF film with
with Young’s modulus up to 192% and tensile strength up to 0.1 wt% rGO loading. In their study, the dielectric constant
92% with a minimal GOn loading of 2 wt%. In the same year, increased from 10 for the neat PVDF to 41 for PVDF-rGO
Alamusi et al.[77] evaluated the piezoelectric property of rGO– (0.1%) at 1 kHz. The piezoelectric constant and remnant polari-
PVDF nanocomposite film wherein the film was stretched at zation of the PVDF-rGO (0.1%) film also increased by 78.6%
a drawing rate of 10 mm min−1 up to 400–500% at 60 °C and and 69.3%, respectively, compared with those of the neat PVDF.
poled at 60 MV m−1 in a poling interval of 8 min for inducing In 2014, Wu et al.[82] made a composite film composed of
ß-phase. The experimental results showed that the rGO–PVDF PVDF-HFP and carbon black (CB) wherein the output voltage
nanocomposite film with 0.05 wt% rGO loading possesses the of the prepared film with 0.5 wt% CB content was found to be
highest output voltage (3.28 V) at a frequency of 30 Hz, which 204% of the pristine PVDF-HFP film. Its harvested electrical
is around 293% of that of the pure PVDF film. power density at 0.5 wt% CB content was increased to 464% for
In 2012, Batth et al.[78] investigated the electrical behavior AC test and 561% for DC test than that of pristine PVDF-HFP
of PVDF-HFP/SWNT composite and found an increase in (6.1 W m−3) film, respectively.
piezoelectric response of the composite film by a factor of 1.5–3 In 2015, Bhavanasi et al.[83] reported about poled PVDF-TrFE
for a loading of 0.02 wt% SWNT. This value decreased for higher and GO bi-layer films with enhanced piezoelectric energy har-
concentrations of SWNT. The authors explained this behavior as vesting capability. The authors explained the combined effect of
a function of solubility limit of SWNTs which disperses well up electrostatic forces, residual tensile stress, and the presence of
to 0.02 wt% and became clustered for higher loading values. space charge at the interface of the PVDF-TrFE and GO films,
In 2013, Ataur Rahman et al.[79] fabricated a PVDF/rGO nano- contributed toward the enhancement of voltage and power
composite energy harvesting device by in situ thermal reduction output. A voltage output of ≈4 V and power output of ≈4.41 µW
of PVDF/GO films, which was capable of scavenging a max- cm−2 was obtained for the bi-layer film which was about three
imum power of 36 nW against a load resistance of 704 kΩ at times that of the poled PVDF-TrFE film (Figure 13 a–d). Cycling
0.1 wt% of GO loading. M. A. Rahman and G. S. Chung[80] also stability of the prepared bi-layer device was also tested under a
prepared a PVDF/rGO film by the similar method possessing an compression pressure of 0.32 MPa at a frequency of 1 Hz, as
Figure 13. Scheme showing a) piezoelectric voltage output from the poled PVDF-TrFE film; b) electrostatic component (voltage output from the bi-layer
films, with non-poled PVDF-TrFE layer); c) voltage output from the bi-layer films device comprising both electrostatic and piezoelectric components.
d) Power output of the bi-layer and PVDF-TrFE films. e) Cycling stability of bi-layer films. Reproduced with permission.[83] Copyright 2016, American
Chemical Society.
shown in Figure 13e, indicating constant output voltage even an open circuit output voltage of 2.5 and 1.2 V, respectively. A
after 1000 repeating cycles. short-circuit rectified current of nearly 700 and 300 nA was also
Furthermore, in 2016, Nandi and coworkers[84] prepared a detected by the CNT/PVDF and Fe-RGO/PVDF-based piezo-
hierarchical nanostructured polymeric composite by incorpo- electric energy harvesting device.
rating polyaniline-grafted-graphene oxide (G-graft-PANI) on Metal-based fillers: Many researchers have reported that the
PVDF matrix which resulted in the transformation of non- piezoelectric activity of PVDF-based materials can increase sig-
polar α-phase of PVDF to 91% of polar β-phase for 5 wt% filler. nificantly when incorporated with metallic fillers. Metallic filler
The dielectric permittivity and dielectric loss were increased to particles such as zinc oxide (ZnO), titanium dioxide (TiO2),
264 and 1.125, respectively, at 102 Hz frequency and the DC ferrites, iron oxide (Fe3O4) could greatly enhance the piezo-
conductivity was increased by eight orders for the same filler response of polymers to a major extent.
loading. In 2012, Dodds et al.[86] explored the piezoelectric response
In 2017, Pusty et al.[85] carried out a comparative study on of PVDF-TrFE/ZnO nanoparticle-based thin films prepared by
the enhanced piezoelectric performance between CNT/PVDF spin coating. In their report, they explained about the enhanced
nanocomposite and iron-reduced graphene oxide (Fe-RGO)/ piezoelectricity of the as-prepared film while maintaining their
PVDF nanocomposite. Conductivity measurements reflected mechanical flexibility. The remnant polarisation was found to
that the addition of CNT and Fe-RGO in PVDF increases the increase from 5.8 to 15.2 mC m−2 under the applied electric
conductivity of the nanocomposite films. The CNT/PVDF and field of 60 MV m−1, while increasing concentration of ZnO
Fe-RGO/PVDF piezoelectric energy harvesting device produced from 0% to 20%.
In 2014, Wu and coworkers[87] investigated the mechanical In order to achieve superior properties through synergism,
and piezoelectric properties of PVDF/iron oxide (Fe3O4) com- hybrid fillers act as the potential pathway. This may also help
posites and revealed an increase in the piezoelectric response of in reducing the filler loading and therefore, the cost and pro-
PVDF/iron oxide composites about five times with an electrical cessing difficulties. In this section, the diversified effects of
field poling of 35 MV m−1. Mechanical behavior of as-prepared hybrid fillers on the piezoelectric and pyroelectric response of
2 wt% PVDF/iron oxide composites indicated a significant PVDF-based systems are reviewed and discussed.
improvement in the storage modulus and enhancement in the In 2014, Jaleh et al.[94] evaluated the dielectric properties of
thermal stability about 28 °C as compared to that of PVDF. rGO/ZnO doped PVDF nanocomposite films and reported a
Gan et al.,[88] in the same year, prepared a PVDF composite maximum ß-phase content of 83% for the nano-hybrid com-
by using TiO2 nanoparticles with different volume fractions posite film. Thermal properties of the film were also improved
(0–30 wt%) and reported an increase DC conductivity, leading by the addition of a hybrid filler system.
to an easier poling process requiring less electric field (from In the same year, Qiu and coworkers[95] prepared a nanocom-
260 to 120 MV m−1). posite by adding TiO2/MWCNTs nanoparticles in PVDF matrix
In 2016, Bhunia et al.[89] used freestanding flexible nano-ZnO for enhancing the dielectric and ferroelectric behavior. They
to prepare PVDF composite films by sol–gel technique. They coated MWCNTs with a uniform layer of TiO2 nanoparticles
observed a significant increase (ten times) in output voltage through the hydrothermal process to prepare TiO2@MWCNT
with the incorporation of nano-ZnO in the PVDF matrix for hybrid filler and developed PVDF/TiO2@MWCNT composite
poled samples. They also reported an open-circuit AC voltage films by simple solution casting method. As-prepared films
of 4 V for composite films with higher ZnO content and an showed enhanced dielectric constant, breakdown strength
increased piezoelectric charge constant (d33) and piezoelectric (≈210 V µm−1 at 0.3 wt% of TiO2@MWCNTs) and lower dielec-
voltage constant (g33). In the same year, Ling and coworkers[90] tric loss compared to the pristine MWCNT/PVDF composite
prepared aluminum (Al)-doped ZnO and PVDF composite and film. Yang et al.[96] (2015) also examined the piezoelectric prop-
compared their dielectric behavior with pure ZnO/PVDF com- erties of PVDF composites by incorporating aligned TiO2@
posite. They detected an increase in the dielectric constant of MWCNTs which was prepared by a two-step method involving
the composite while increasing the Al content. A composite solution casting followed by mechanical rolling. They revealed
carrying 10% ZnO with 7% Al exhibited a dielectric constant a maximum piezoelectric coefficient (d33) of ≈41 pC N−1 in com-
of 18.5 at 100 Hz, which was twice of the pure ZnO/PVDF posites at 0.3 wt% filler concentration, which was nearly double
composites. that of the pure PVDF.
Another investigation for improving the sensitivity of silver In 2015, Karan et al.[97] reported a superior piezoelectric
nano-filler incorporated PVDF-TrFE composite film was con- energy harvesting device prepared from Fe-doped rGO (Fe-
ducted by Chen et al.,[91] in 2016. Silver nano-fillers of different RGO)/ PVDF nanocomposite film. The reported film favors
morphologies (nanoparticle and nanowire) were used in this the formation of ≈99% polar γ-phase thus providing an open
study to upgrade the ß-phase crystallization as well as the pie- circuit output voltage of 5.1 V and short circuit current of
zoelectric response. The authors observed that the ß-phase of 0.254 µA, corresponding to repetitive human finger imparting.
PVDF-TrFE was influenced by the addition of silver nanowires This enhancement was attributed to the electrostatic interac-
(AgNWs), but not by the incorporation of spherically shaped tion between the dipoles of PVDF (CH2 and CF2), delocalized
silver nanoparticles. A higher output voltage of 48 mV was π-electrons and oxygen functionality of Fe-doped RGO through
obtained for PVDF-TrFE/AgNWs (35 nm in diameter) films as ion-dipole and/or hydrogen bonding interaction.
compared to other films (PVDF-TrFE, PVDF-TrFE/AgNPs, and In 2016, Abdelhamid et al.[98] prepared self-standing flex-
PVDF-TrFE/AgNWs-120 nm in diameter). Finally, they con- ible PVDF composite films containing hybrid fillers (com-
cluded that the piezoelectric property and polar ß-phase can prising rGO, ZnO, and Fe3O4 nanoparticles) and investigated
be further modified by reducing the diameter of AgNWs or their dielectric behavior with respect to the filler type. A higher
increasing the concentration of AgNWs. percentage of ß-phase content (80%) was reported for both
In 2017, K. Choi et al.[92] explored the enhanced piezoelec- pure PVDF and PVDF–rGO films whereas a reduction in the
tric behavior of PVDF/ZnO nanowires based nanocomposite. ß-phase amount (50%) was observed for PVDF–rGO–Fe3O4
In this study, AC dielectrophoresis technique was used for the and PVDF–rGO–Fe3O4–ZnO films. Both PVDF–rGO and
aligning of ZnO nanowires. The obtained results demonstrated PVDF–ZnO films showed an increased dielectric constant
an increase in dielectric constant of 400% with aligned ZnO (25–30 at 1 Hz), whereas PVDF–rGO–Fe3O4 and PVDF–RGO–
nanowires by increasing the poling effect compared to that Fe3O4–ZnO nanocomposite films displayed a reduced dielectric
of a randomly oriented nanowire composite without a poling constant (≈12). Fe3O4-loaded hybrid PVDF films exhibited a
process. multi-ferroic behavior with a magnetodielectric coupling con-
Further in 2017, Issa et al.[93] prepared PVDF electro-spun stant ≈0.04%. The results indicated that excess hybridization
mats containing silver nanoparticles (Ag-NPs) showed an would result in loss of properties.
increase in ß-phase content by about 8% for Ag-NPs content of Further, in 2017, Al-Saygh et al.[99] fabricated a PVDF-based
0.4–0.6%. Ag-NPs also contributed toward the enhancement of flexible pressure sensor containing rGO and TiO2 nanolayers
tensile strength and thermal stability of the mats. (TNL). Higher ß-phase content (75.68%) for the hybrid PVDF/
Hybrid fillers: Generally, hybrid fillers comprise two compo- rGO-TNL film was obtained as compared to PVDF (70.37%),
nents at the nanometre or molecular level among which, one PVDF/rGO (72.73%), and PVDF/TNL (73.5%) films. Mechan-
is inorganic compound and the other one is organic in nature. ical property studies of the films represented an increased
and property of each component.[102] Polymer blends are

now receiving substantial attention in the research field for
their wide applications in energy harvesting and storage sec-
tors, because of their light weight, flexibility, and volume
efficient electrical elements, needed for implanted passive
technologies and others. The compatibility of PVDF with var-
ious polar polymers like poly(vinyl methyl ketone) (PVMK),
poly(tetramethylene adipate) (PTMA), poly(N-methylethyl-
enimine) (PME), poly(N,N,-dimethylacrylamide) (PDMA),
poly(N-vinyl-2-pyrrolidone) (PVP), poly(methyl methacrylate)
(PMMA), poly(vinyl acetate) (PVAc), poly(ethyl methacrylate)
(PEMA), poly(1,4-butylene succinate) (PBS), Polyamide (PA11
and PA6) helps in facilitating the formation of polar β- and
γ-phase in PVDF by forming intermolecular interactions.[35]
Figure 14. Scheme showing denaturation of DNA in DMF and formation In 2008, Abbas et al.[103] reported that blends of PVDF
of ß-enriched DNA-PVDF film. Reproduced with permission.[100] Copy- with PMMA and PVAc influences the polar phase content
right 2015, American Chemical Society. as well as piezoelectric constant (d33) value of PVDF. It was
noted that both the blends resulted in decreased crystallinity
tensile strength (≈47 MPa) and Young’s modulus (≈5010 MPa) with an increase in blend polymer concentration. For PVDF/
while the elongation at break (about 4%) decreased with the PMMA blends, when PMMA loading exceeds 10 wt%, γ to α
incorporation of nano-additives. Dielectric permittivity storage ratio decreased slightly wherein for PVDF-PVAc blends γ to α
was also increased for the hybrid PVDF/rGO-TNL composite ratio shows larger values due to better miscibility of both the
and the pressure sensitivity of hybrid composite was increased polymers. Here, d33 value followed a decreasing order from
by 333.46% at 5 kPa, 200.7% at 10.7 kPa, and 246.7% at 4 pC N−1 to ≈2 pC N−1 for PVDF-PVAc (80–20%) and 4 pC
17.6 kPa as compared to the PVDF/TNL composite. N−1 to ≈0.5 pC N−1 for PVDF/PMMA (80–20%) blend with an
Bio-based materials: Bio-based materials or biopolymers have increase in blend weight percentages.
always been the center of attraction for research and develop- Xiong et al.[102] (2008), prepared a polyamide 11/PVDF
ment, because of their easy availability, bio-compatibility, and blend to be used as a novel flexible material with high dielec-
multifunctional behavior. In a similar manner, low power tric constant suited for the flexible electronic application. The
energy harvesting devices have always been focused as a more blends showed high dielectric constant, ε = 20–40, with better
convenient technology, which would be reliable and durable frequency stability and superior mechanical properties while
for future use. Many research groups have developed several exhibited a moderately high dielectric loss (tanδ ≈ 0.17). A com-
PVDF-based biopolymer composites for enhancing the device patibilizer named as SMA (copolymer of styrene and maleic
performance as well as their reliability toward the next genera- anhydride) was also incorporated into the blend for reducing
tion. However, many kinds of literature are not available in this the dielectric loss value to 0.057, thus making it a potential
direction, a few available literatures are discussed below. material for dielectric applications. Piezoelectric properties of
In 2015, Tamang et al.[100] utilized deoxyribonucleic acid such prepared blends were also studied by the research group
(DNA) as a nucleating agent for the nucleation of electroac- and they reported a higher d33 value (9 pC N−1) for PA11/PVDF
tive β-phase and alignment of molecular dipoles in PVDF blend containing SMA with 50% loading of PA11.
which resulted in a self-poled PVDF film with increased piezo- The effect of reactive comb (RC) polymers on poly-l-lactic
electricity. They reported a ß-phase of ≈80% in the DNA-PVDF acid (PLLA)/PVDF blend was studied by Li and coworkers[104]
composite film. The interaction between phosphate ion and in 2016. This experiment resulted in improved compatibility of
hydrogen bonding present along the ssDNA (single-strand both the polymers while possessing excellent toughness. Upon
DNA) backbone interacts with –CH2 and –CF2 dipoles of uniaxial stretching to a maximum stretch ratio of 5 at room
PVDF molecular chain thus forming stabilized polar β-phase temperature, a transformation of non-polar α-phase into polar
(Figure 14). ß-phase (>95%) was observed for the prepared blend films.
A nanogenerator was also fabricated from the prepared film PVDF can also be blended with PVDF copolymers which
which showed an open circuit voltage of 6 V and short circuit can improve the properties without affecting the compat-
current of 0.088 µA in response to human finger touch when ibility of the system. Since PVDF-TrFE directly crystallizes
the applied stress was 13 kPa. In 2017, Roy et al.[101] studied into the polar ß-phase under the same conditions and shows
the effect of folic acid on PVDF composite film and reported higher piezoelectricity as compared to PVDF, polymeric blends
a modified film with high dielectric and electroactive β-phase of PVDF and PVDF-TrFE were prepared by Song and cow-
supplemented PVDF composite thin film. They disclosed orkers[105] to analyze the effect of blending on the crystalliza-
a remarkable improvement in both β-phase crystallization tion behavior and electroactive properties of PVDF. This study
(≈71.4%) and dielectric constant (218 at 20 Hz for 7.5 mass% of unveiled an increase in crystallization energy of PVDF film
folic acid) throughout the experiment. with an increase in PVDF-TrFE content for which PVDF-TrFE
Polymer blends: Blending of two or more polymers is an films had the lowest degrees of crystallinity (24.1%) and crystal-
important technique to achieve the required properties of line lamella thickness. Piezoelectricity measurements revealed
polymeric systems, which is associated with the structure that blends prepared in the ratio of 50:50 showed highest d33
values (51.2 pm V−1), as compared to other blends. Bilotti and films, while, in 2013, Varga et al.,[110] investigated the piezoelec-
coworkers[106] reported about the dielectric and ferroelectric tric responses of PLA/BaTiO3 composite fiber mats prepared by
properties of PVDF/PVDF-TrFE blended films prepared by melt electro-spinning and reported a d33 value of ≈0.5 nC N−1 and
extrusion. The blended film exhibited higher dielectric constant compression modulus Y ≈ 104–105 Pa which widened its appli-
as compared to pure polymers (PVDF and PVDF-TrFE). The cations from active implants to smart textiles. Additionally, the
ferroelectric test suggested an increase in remnant polarization authors reported that finger tapping of a (2 × 2) cm2 area fiber
0.040–0.077 C m−2 with increasing PVDF-TrFE content from 0 mat of 0.15 mm thickness was capable of powering a small
to 40 wt%. LCD. This has led to further improvement of PLA based piezo
systems by preparing a thermally stable cantilever device, uti-
lizing the piezoelectricity for vibration-based energy harvesting
5.2. Polylactic Acid applications by Zhao et al.[108] in 2017. They used two layers
of poly-l-lactic acid (PLLA) films which were attached together
Polylactic acid is considered as a promising substitute to and glued to a thick polyethylene terephthalate (PET) film as a
petroleum-based materials because of its biodegradability, passive layer thereby forming a PLLA/PET uniform multilayer
renewability, ease of fabrication, biocompatibility, and better structure (Figure 15a,b). Figure 15c demonstrates the shear
mechanical stability.[107] PLA-based polymers are becoming a mode piezoelectric coefficient, that is, d14 value of PLLA film
popular candidate for energy harvesting applications owing to which are thermally treated at 140 °C for several hours and a
their higher piezoelectric properties. The carbonyl groups pre- maximum d14 value of 9.57 pC N−1 value was observed when
sent in PLA structure induces polarity and it shows a d14 value the film was thermally treated for more than 24 h. The voltage
of 10 pC N−1 without additional poling step in its crystalline and power output of the fabricated device as a function of
structure.[108,109] annealing time were also explored and obtained plots are rep-
In 2012, Morvan et al.[109] developed a biocompatible fiber resented in Figure 15d,e. The fabricated device showed power
composite by dispersing BaTiO3 ceramic particles in PLA. output of 14.17 µW, and an open circuit voltage of 9.05 V under
The prepared fiber mats showed piezoelectric constant/weight load resistance of 0.9 MΩ, when the PLLA films were annealed
nearly two orders of magnitude than single crystal BaTiO3 at 140 °C for 4 h. (Figure 15d). Annealing of the film at 140 °C
Figure 15. a) Cross section view of PLLA/PET cantilever beam. b) Experimental setup for testing performance of PLLA/PET cantilever device. c) d14
value of the PLLA film after several hours of thermal treatment. d,e) Corresponding voltage and power output of the PLLA cantilever device comprising
PLLA films annealed at 140 °C for 4 h and at 140 °C for 24 h, respectively, under various resistance loads. Reproduced with permission.[108] Copyright
2017, Wiley-VCH.
for 24 h resulted in increased power (≈14.45 µW) and voltage

output (9.4 V) (Figure 15e). The authors explained this behavior
due to the enhanced crystallinity of the PLLA film when kept
for longer annealing temperature.
Furthermore, in 2017, Ando et al.[111] attempted the prepara-
tion of piezoelectric PLLA fabric from poly(l-lactic acid) yarns.
The twist yarn was prepared from the left-handed helical fibers
(S-yarn) and the reverse twist yarn was prepared from right-
handed helical fibers (Z-yarn). A piezoelectric constant of d14 =
10 pC N−1 was observed for 1% applied shear displacement.
The authors explained that generation of the electric field due
to extension and contraction of the twisted yarns leads to the
strong antibacterial effect of the as-prepared fabric. Thus PLA
and PLLA based systems opened new avenues for piezoelectric
textiles.
Figure 16. Scheme showing the piezoelectric behavior of CNCs thin films
and highly aligned PFM image. Reproduced with permission.[58] Copy-
5.3. Cellulose and Its Derivatives right 2012, American Chemical Society.
Cellulose is the most typical biomaterial available in nature as attached cellulose fibers, due to the strong electrostatic force of
it is the major constituent of a plant’s cell wall.[112] The biodeg- attraction. This low-cost paper showed the highest d33 value of
radability, renewability, and biocompatibility of cellulose-based ≈4.8 pC N−1, at 48 wt% loading of BaTiO3.
materials along with its interesting structure and properties In 2016, Hanninen et al.[119] prepared a layer structured
contributes to its immense application toward in several major free-standing film of chitosan and cellulose and measured
sectors like energy harvesting devices, strain sensors, actua- their piezo sensitivity. The authors reported piezoelectric sen-
tors. The existence of dipolar alignment and confined charges sitivity values of 21.03, 11.23, 8.74, and 5.99 pC N−1 for pure
are majorly responsible for the piezoelectric and pyroelectric chitosan, chitosan/cellulose nanocrystals (CNC), chitosan/
behavior of these polymers. The shear piezoelectricity owed by neutralized cellulose nano-crystals, and chitosan/Cellulose
cellulose-based biopolymers such as wood, amylase, chitin, and nano-fibrils (CNF) films, respectively. They concluded with the
starch can be comparable to that of quartz crystal.[113] Currently, fact that piezoelectric values of pristine chitosan were close to
cellulose-based electroactive papers (CEAP) which is a metal that of PVDF and it is strongly related to the selected chitosan-
electrode coated thin cellulose film, are considered as an impor- nanocellulose composition. Rajala et al.[56] in the same year pre-
tant promising material for biomimetic actuators due to some pared self-standing films by using native cellulose nano-fibrils
interesting properties including low cost, lightweight, biodegra- (CNF) and investigated its piezoelectric response. They found
dability, larger output with lower power consumption, and low dielectric permittivity of 3.47 and 3.38 along with loss tangent
actuating voltage.[114,115] value (tanδ) of 0.011 and 0.071at 1 kHz and 9.97 GHz, respec-
In 2010, Zhao et al.[116] investigated the direct piezoelectric tively. The authors also used this film as a sensing layer in pie-
response of CEAP under ambient conditions and found a max- zoelectric devices and reported sensitivity values between 4.7
imum piezoelectric constant (d31) of 53.2 pC N−1 for the elastic and 6.4 pC N−1. Finally, the authors concluded by suggesting
portion and 504 pC N−1 for plastic portion. The performance of this film as a suitable material for energy harvesting device as
CEAP was further described by Kim et al.[117] and it is found to well as storage application. In 2017, J. H. Kim and H. U Ko.[120]
be sensitive to the preparation process and material orientation invented a ZnO-cellulose nanocomposite using cellulose and
of cellulose film. This team reported the highest piezoelectric ZnO nanoparticles. The prepared nanocomposite film was
constant of 7.3 pC N−1 for the CEAP sample when stretched at characterized with increased piezoelectricity and mechanical
2.0 drawing ratio and aligned at 45°. Csoka et al.[58] reported pie- property when compared with simple CEAP. The maximum
zoelectric characteristics in cellulose nanocrystals (CNCs) with piezoelectric constant and Young’s modulus reported for this
shear piezoelectric constant (d25) value of 2.1 Å V−1 for aligned film was 420 pC N−1 and 4.1 GPa, respectively and the film was
CNCs. The mechanism behind emerging piezoelectricity and capable of to be used for LED and photovoltaic devices.
piezoelectric force microscope (PFM) image of highly aligned
CNCs are shown in Figure 16.
In 2014, Mahadeva et al.[118] fabricated a piezoelectric paper 5.4. Polyamides
from nanostructured BaTiO3 functionalized wood cellulose
fibers. The functionalization and interaction mechanism is Polyamides or nylons are semi-crystalline polymers which
presented in Figure 17. In a typical process, cellulose fibers show a low level of piezoelectricity. Kawai first reported piezo-
immersed into poly(diallyl-dimethyl-ammonium chloride) electric constant d3l = 0.5 pC N−1 for the stretched poled film of
PDDA solution (+) followed by poly(sodium 4-styrenesulfonate) nylon-11.[121] Among the odd and even numbered polyamides,
PSS (−), and then again in PDDA (+), forming a positively the odd ones exhibit piezoelectric and pyroelectric behavior
charged exterior on the wood fibers. These functionalized fibers because of their polar structure. In case of odd polyamides
were then immersed in BaTiO3 suspension, developing BaTiO3 such as Nylon-5 or Nylon-11, a dipole moment of 3.7D exists
Figure 17. Schematic representation of the piezoelectric hybrid paper fabrication process. Reproduced with permission.[118] Copyright 2014, American
Chemical Society.
between the even-numbered methylene group and one amide 6.5 pC N−1 (at 0.3 vol% of NaNbO3). Incorporating 30 vol%
group resulting in aligned dipoles with a net dipole moment of nanowires also increased the dielectric permittivity of the
whereas in case of even-numbered polyamides the amide dipole composite about two times greater than PA 11 at 100 Hz. The
cancels each other.[9] Takase et al.[55] observed maximum values authors also compared piezoelectricity of the as-prepared film
of piezoelectric strain constant (d31 = 14 pC N−1 for Nylon-11 with PA 11/BaTiO3 composite and reported that the piezoelec-
and 17 pC N−1 for Nylon-7), stress constant (e31 = 21 mC m−2 tric activity of the PA 11/NaNbO3 NWs over PA 11/BaTiO3.
for Nylon-11 and 27 mC m−2 for Nylon-7), and electromechan- In 2014, Carponcin et al.[124] prepared a three-phase multi-
ical coupling coefficient (k31 = 0.054 for Nylon-11 and 0.049 for functional nanocomposite composed of polyamide 11 (PA 11),
Nylon-7) of Nylon-11 and Nylon-7 films at temperature ranges PZT, and CNT. The authors reported that addition of 0.2 vol%
from 100 to 200 °C. of CNTs resulted in improvement of dielectric permittivity of
Because of the less piezoelectric characteristics of poly PA 11/PZT composite. The incorporation of 30 vol% of PZT
amides, many researcher groups focused on the development of particles with PA 11 increases its permittivity from 3 to 6.6 at
piezo- as well as the dielectric response of polyamides by incor- 1 kHz where as upon introduction of 0.2 vol% of CNT into
poration of certain fillers or by blending with other polymers. the two-phase composite attains a dielectric permittivity value
In 2011, Babu et al.[122] synthesized a PZT/ Liquid crystal- of 32. The outcomes of piezoelectric property study revealed a
line thermosets (LCT)/PA composite by hot pressing technique 26% increase in the d33 value of the PA 11/PZT/CNT composite
and reported an increased d33 and g33 value of the composite. at 0.2 vol% of CNT. Finally, the authors suggested this three-
For 50 vol% PZT loading, d33 and g33 values of about 42 pC N−1 phase composite film as a proposed material for energy har-
and 65 mVm N−1, respectively, was obtained under a low poling vesting technology for upcoming decades.
voltage of 60 kV cm−1 and 30 min of poling time. The flexibility Further research on PA11 was carried out by Leveque
of the material was also improved with the addition of PA 11 et al.,[125] in 2016, for its vibrational energy harvesting perfor-
which led to a lower elastic modulus. mance with the addition of layered silicates. They observed
In 2012, David et al.[123] developed a PA 11/sodium niobate an improvement in the mechanical properties of the prepared
nanowire (NaNbO3 NW) composites film containing different nanocomposites with the addition of layered silicates. The
volume fractions of NaNbO3 NWs. They found that the poling authors also reported that incorporation of polar Cloisite Na+
temperature and poling time greatly affects the piezoelectric filler (only 5 wt%) induces more polarity to the composite film
coefficient of the composite film. A poling voltage of 10 kVmm−1 thus providing a better piezoelectric response of 2.2 which is
for 10 min was applied to achieve a maximum piezoelectricity nearly equivalent to that of neat PA 11 film but, inclusion of
other nano-clays such as Cloisite 20A and Cloisite 10A did not to ≤24 pC N−1 and a d31 value of 1.3pC N−1. Later in 2001, a
improve the piezoelectric properties of the PA 11 films. The small amount of fine-grained carbon (C) filler was added into
prepared composites (PA11/Cloisite Na+ also) showed a lower the above-prepared composite with PZT/C/PU compositional
energy harvesting performance as compared to PA 11 because ratio of 59/1/40 vol% proportion. Incorporating 1 vol% of
of the increased mechanical stiffness of the nanocomposite carbon filler resulted in 25% increase in d33 value compared
samples by the addition of nano-clays. to the composite prepared without C-filler. C-filler loading
While, in 2017, Hua et al.[126] found that PA11/BaTiO3 piezo- also made the poling process easier and shorter by enhancing
electric composites prepared by solid-state mechano-chemical their electrical conductivity.[134] Another composite film com-
method showed an increasing order of dielectric constant while prising PU and PZT particles partially loaded with polyaniline
increasing the BaTiO3 volume fraction and decreasing order was prepared by Sakamotoi et al.,[135] in 2013, and was studied
with an increase in frequency. The incorporation of nanoparti- for structural health monitoring application. Addition of poly-
cles also altered the crystallization behavior leading to improved aniline resulted in easier poling process with shorter poling
thermal stability. The piezoelectric coefficients of the prepared time and enhanced piezoelectricity. Moody et al.,[136] in 2016,
composite also followed a linear relationship with filler volume developed flexible piezoelectric PU foams with massive piezo-
fraction as increasing the BaTiO3 loading from 5–50% resulted electric d33 coefficients up to 244 ± 30 pC/N at poling field of
in increased d33 value from 1.1 to 6.6 pC N−1. 400 V mm−1. The authors incorporated polar dopant molecule
such as 2-chloro-4-nitroaniline (CNA) into the polymer matrix
to increase their piezo-responsiveness several times higher
5.5. Polyureas than conventional piezoelectric ceramics and polymers. The
prepared piezo-material also showed better output voltage and
Polyureas, thermoset polymers synthesized from di-isocyanates current response corresponding to the very low applied force
and diamines, have found their major application as insulating produced from human body movement. The d33 value of this
materials.[9,127] Poyurea films exhibit piezo and pyroelectric material is directly proportional to the dipole moment of the
behavior succeeding to poling treatment. Aromatic polyurea dopant molecule as well as their concentration.
which is the first piezoelectric polyurea showed a d31 value of
10 pC N−1 and were stable up to 200 °C. Odd-numbered ali-
phatic polyurea, such as polyurea-9 and polyurea-5 obtain a 5.7. Other Piezoelectric Polymers
residual polarization after poling. Piezoelectric values e3l =
3 mC m−2, d3l = 1.7 pC N−1 are reported for poled polyurea-9, There also exist several polymers other than piezo-ceramics and
and pyroelectric values e3l = 9 mC m−2, p3 = 15 pC m−2 are PVDF-based polymers, which exhibit piezoelectric and pyro-
reported for poled polyurea-5.[128] Highest piezoelectric con- electric characteristics alone or when combined with certain
stant e31 = 20 mC m−2 and pyroelectric constant p = 20 µC m−2 fillers. Polymeric materials such as polypropylene (PP),[137] poly
K was obtained for films prepared at a stoichiometric ratio of ethylene oxide (PEO),[138] vinylidene cyanide copolymers,[139]
two monomers.[129] Aliphatic polyureas show a ferroelectric polyacrylonitrile (PAN),[140] and polyimides (PI)[141] are listed in
hysteresis while being piezoelectric when carrying odd num- this category and could be promising materials for energy har-
bers of methyl groups. Their thermal behavior as well as piezo- vesting applications.
electric coefficients strongly depend on the poling temperature In 2015, Wu et al.[137] fabricated a cellular PP based flexible
(70–150 °C) but shows a lower value than aromatic polyureas.[9] generator with a maximum peak power density of ≈52.8 mW m−2
Hattori et al.,[130] in 1996, studied the piezoelectric and ferro- for health monitoring and energy harvesting applications. The
electric properties of polyurea-5 thin films and reported piezo- multilayered PP film showed a d33 value ≈19 pC N−1 whereas
electric stress constant (e31) value of 10 mC m−2, d31 = 4 pC N−1, the value reached at ≈205 pC N−1 for the expanded cellular PP
and pyroelectric constant value of 15 mC m−2 K−1 for these and this value remained stable for several weeks up and up to
films. Koyama et al.[131] in 2009 proposed an energy harvesting 60 °C. In the same year, Khanbareh et al.[138] incorporated lead-
system to generate electric power from polyurea piezoelectric titanate (PT) ceramic particles within PEO matrix to prepare a
thin film. They achieved a maximum conversion efficiency of sensitive and flexible nanocomposite. They found that both the
0.233% from a thin film with increased resonance frequency of piezoelectric and the pyroelectric properties of the PT-PEO com-
the device. posite improve with an increase in the concentration of PT. A
maximum d33 and g33 values of 7.5 pC N−1 and 44 mVm N−1
were reported for the composite film containing 30% volume
5.6. Polyurethanes fraction of PT when poled at 10 kV mm−1 for 15 min.
An alternative copolymer of vinylidene cyanide and vinyl ace-
An isotropic polyurethane film shows transverse piezoelectricity tate, which is an amorphous polymer, was found to show piezo-
corresponding to electrostriction and a bias DC field. Polyure- electric activity because of the polarity of C-CN groups present
thane (PU) films with bias DC field of 5 MV m−1 shows piezo- in the polymer structure. The piezoelectric strain constant d31
electric constant (d31) of 38 pC N−1, which is almost double to reported for rolled films was 5 pC N−1 at room temperature.[139]
that of poled PVDF film and electromechanical coupling factor Piezoelectricity in PI is well explained by Zoubeida et al.[141]
(K31) of 0.14 similar to that of PVDF.[132] Polyimides are the most favorable amorphous piezoelectric
In 1999, Sakamoto et al.[133] prepared a PU/PZT composite polymers due to their higher Tg value. Dielectric properties
with 30 vol% of PZT particles and reported a d33 value up analysis revealed that piezoelectric coefficients and remnant
polarization are strongly dependent on the number of nitrile with conventional piezo-ceramics. Design/fabrication of the
dipoles available along the polymer backbone along with the device, compatibility with advanced technology, long durability
imidization process as well as poling parameters.[142] Recently, by meeting performance requirement also needs to be con-
in 2018, Zhao et al.[143] developed a self-powered flexible sensor sidered as significant factors. Scientists anticipate that PEH
from PAN nano-fiber containing barium titanate nanoparticles. market is going to take a 28.8% share of the complete energy
This sensor is capable of detecting pressure and curvature sepa- harvesting market very soon because of the increasing number
rately and concurrently by uniting triboelectric, piezoresistive, of eco-friendly piezoelectric energy related projects.[25] This will
and piezoelectric effects. create a revolution in the productivity of energy harvesting by
assembling innovation with technologies to shape the future
energy. Marching toward progress with continuous transfor-
6. Applications of Piezoelectric Energy mation and advancement of low-power electronics has made
the PEHs an important subject of research. Till date, PEH har-
Harvesting Devices
vesters with superior configuration, deliver power up to several
Piezoelectric polymer composites have found immense applica- milliwatts. By 2023, the growth of the international market for
tions in different fields including actuation, wireless sensing, PEH is expected to reach over US$800 million by exhibiting a
and energy harvesting systems.[144] These applications have rev- very sharp trend.[157]
olutionized the market trend of PEH devices because of their
multi-functionality, better reliability, low costs, and higher accu-
racy.[2] One of the major application areas includes biomedical 8. Conclusions
sector where polymers are considered as potential material for
artificial muscle actuators, explored as intrusive medical robots Piezoelectric polymers and composites are functional materials
for diagnosis and microsurgery, and used as actuator implants that can be possibly utilized for different energy harvesting
for stimulating the growth of bones and tissues. The biocom- applications. This literature basically aimed at exploring the
patibility of polymeric materials along with better impedance basic theory behind the piezoelectric behavior of polymeric and
matching to human tissues and body fluids makes them ideal composite systems. The global and national scenario of dif-
for such applications.[145,146] However, a large number of energy ferent types of PEHs are discussed, primarily considering the
harvesting applications of piezoelectric polymeric composites market demand and market growth with application potential.
starting from portable biomedical devices (wearable or implant- Specified piezoelectric materials used for energy harvesting
able) to biomedicines,[147] wireless sensor network,[147] robotics, technologies are reported with a focus on polymer-based devices
optics, environmental monitoring,[37] ultrasonics and acoustic as a productive alternative to piezo-ceramics. A detailed review
devices,[148] underwater and electro-acoustic transducers,[149] of several types of piezoelectric polymers, piezoelectric com-
piezoelectric roads,[150] etc. have been also reported. posite/nanocomposite based PEHs, and their performances
Furthermore, in recent years, development of PEH devices are provided in this present study. Also, the technology can be
from human body movement has been focused. Based on this groundbreaking by completely replacing piezo-ceramics owing
technology, piezoelectric shoe,[151,152] electronic skin and health to their lightweight and handy properties. Polymeric systems,
monitoring patch,[137,153,154] e-textiles,[155] piezoelectric dancing as explained in the earlier section, are more versatile in terms
floor,[156] etc. are developed which utilises vibrations proof flexibility, tailorability, processing, and availability. Even
duced from human body activities such as: walking, running, though PEH cannot be a substitute of fossil fuels and renew-
breathing, and dancing to power-up small electronic devices. It able energy sources, but it can play an important role in low-
has become imperative to develop piezoelectric systems from power electronic devices which demands repeated replacement
lightweight polymeric systems and is gaining commercial of the battery, thus providing uninterrupted power supply.
interest.
Acknowledgements
7. Future Perspective of PEHs This research was funded by M/s Bharat Electronics Limited, Bengaluru.
In order to reduce the overconsumption of fossil fuels as well as
renewable energy sources, piezoelectric materials are expected
to emerge as the most important functional material for energy Conflict of Interest
harvesting sector, since the twenty-first century.[157] Besides
emission of zero carbon and hassle-free battery systems, cor- The authors declare no conflict of interest.
respondent materials were characterized with greater function-
ality to harvest energy from unwanted mechanical vibration
sources. These systems are capable of providing cleaner power, Keywords
appreciable convenience along with significant time-saving.
composites, energy, harvesting, piezoelectric, polymers
However, commercialization and market growth of polymer-
based PEHs are strongly dependent on two major factor such Received: August 1, 2018
as improvement in energy efficiency of corresponding devices Revised: October 10, 2018
to match with the requirement and cost reduction to compete Published online: November 27, 2018
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REVIEW

Advances in Piezoelectric Polymer Composites for Energy

is a simplified technology which converts

flexibility, faster processing, lower fabrication cost, and biocom-

Figure 2. Direct and converse piezoelectric effect.

such as cymbal and stack type configuration have been also

Figure 6. Different structural configurations of PEH.

Table 1. Major advantages and disadvantages of different structural configurations.[12,17]

Type of configuration Features/advantages Disadvantages

Figure 8. Different classes of piezoelectric materials.

4.2. Piezoelectric Ceramics

Table 3. Piezoelectric properties of different piezoelectric materials.

PVDF −24 to −34[38] 8–22[39] — —330[34] 6–12[40] 0.20[41] 0.12[9]

PVDF-TrFE −25 to 40[42,43] 12[33] to 25[42] — 380[44] 18[45] 0.29[41] 0.16[46]

PVDF-HFP −24[47] 30[48] — — 11[49] 0.36[49] 0.187[50]

PLA — 1.58[51] 9.82[52] — 3–4[53] — —

Polyamide 11 4[54] 14[55] — — 5[54] — 0.049[9]

Celluloses 5.7 ± 1.2[56] 1.88–30.6[57] −35 to — — — —

Polyurethane — 27.2[60] — — 4.8[60] to — —

Polyurea 19 at 60 °C[62] 21 10[46] — — — — 0.08[46]

Polyimide 2.5–16.5[8] - — — 3.34[63] — —

Figure 9. Structural configuration of three major phases of PVDF.

composite films at lower frequencies. The dielectric constant

and property of each component.[102] Polymer blends are

for 24 h resulted in increased power (≈14.45 µW) and voltage

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