micromachines

Review
Flexible Electronics: Advancements and Applications of Flexible
Piezoelectric Composites in Modern Sensing Technologies
Jinying Zhang 1,2, *,† , Jiacheng Wang 1,† , Chao Zhong 3 , Yexiaotong Zhang 1 , Yajuan Qiu 3 and Lei Qin 3, *

1 Beijing Key Laboratory for Precision Optoelectronic Measurement Instrument and Technology, School of
Optics and Photonics, Beijing Institute of Technology, Beijing 100081, China; 3120225346@bit.edu.cn (J.W.);
3120220661@bit.edu.cn (Y.Z.)
2 Yangtze Delta Region Academy of Beijing Institute of Technology, Jiaxing 314001, China
3 Beijing Key Laboratory for Sensors, Beijing Information Science & Technology University, Beijing 100101,
China; 20192289@bistu.edu.cn (C.Z.); q18804096327@163.com (Y.Q.)
* Correspondence: jyzhang@bit.edu.cn (J.Z.); qinlei@bistu.edu.cn (L.Q.); Tel.: +86-182-1002-3679 (J.Z.);
+86-134-6666-1000 (L.Q.)
† These authors contributed equally to this work.

Abstract: The piezoelectric effect refers to a physical phenomenon where piezoelectric materials
generate an electric field when subjected to mechanical stress or undergo mechanical deformation
when subjected to an external electric field. This principle underlies the operation of piezoelectric
sensors. Piezoelectric sensors have garnered significant attention due to their excellent self-powering
capability, rapid response speed, and high sensitivity. With the rapid development of sensor tech-
niques achieving high precision, increased mechanical flexibility, and miniaturization, a range of
flexible electronic products have emerged. As the core constituents of piezoelectric sensors, flexible
piezoelectric composite materials are commonly used due to their unique advantages, including high
conformability, sensitivity, and compatibility. They have found applications in diverse domains such
as underwater detection, electronic skin sensing, wearable sensors, targeted therapy, and ultrasound
diagnostics for deep tissue. The advent of flexible piezoelectric composite materials has revolution-
ized the design concepts and application scenarios of traditional piezoelectric materials, playing a
crucial role in the development of next-generation flexible electronic products. This paper reviews
Citation: Zhang, J.; Wang, J.; Zhong,
the research progress on flexible piezoelectric composite materials, covering their types and typical
C.; Zhang, Y.; Qiu, Y.; Qin, L. Flexible
fabrication techniques, as well as their applications across various fields. Finally, a summary and
Electronics: Advancements and
outlook on the existing issues and future development of these composite materials are provided.
Applications of Flexible Piezoelectric
Composites in Modern Sensing
Technologies. Micromachines 2024, 15,
Keywords: sensors; flexible electronics; piezoelectric composite material; precision machining
982. https://doi.org/10.3390/
mi15080982

Academic Editor: Wei Gao

1. Introduction
Received: 16 June 2024 Sensors are core components of modern instrumentation that play a crucial role in de-
Revised: 14 July 2024 tecting and transmitting signals, enabling the accurate acquisition of external information.
Accepted: 18 July 2024 With the continuous advancement and innovation of instrumentation systems, there is an
Published: 30 July 2024 increasing demand for the development of novel sensors [1–3]. Nowadays, the main types
of sensors are piezoelectric, piezoresistive, capacitive, and inductive sensors. Depending on
the requirements of different fields, they are utilized in various testing instruments and de-
vices. The different types of sensors, their main application areas, and their advantages and
Copyright: © 2024 by the authors.
disadvantages are shown in Table 1. Among various types of sensors, piezoelectric sensors,
Licensee MDPI, Basel, Switzerland.
This article is an open access article
made from piezoelectric materials, are widely used in multiple technical fields, such as
distributed under the terms and
weapon guidance, industrial inspection, marine exploration, and medical diagnosis [4–10],
conditions of the Creative Commons
due to their advantages of high sensitivity, strong temperature stability, and fast response
Attribution (CC BY) license (https:// speed [4]. A piezoelectric sensor operates on the principle of the piezoelectric effect. When
creativecommons.org/licenses/by/ a piezoelectric material is subjected to mechanical stress, it generates electric charges on its
4.0/).

Micromachines 2024, 15, 982. https://doi.org/10.3390/mi15080982 https://www.mdpi.com/journal/micromachines

Micromachines 2024, 15, 982 2 of 49

surface (positive piezoelectric effect). Conversely, when an electric field is applied to the sur-
face of the piezoelectric material, it generates mechanical deformation (inverse piezoelectric
effect). Depending on whether the direct or inverse piezoelectric effect is utilized, piezoelec-
tric materials can be designed as either passive or active sensors. The schematic diagram of
the principle of the piezoelectric effect is shown in Figure 1. Besides, piezoelectric sensors
also exhibit excellent electrical response characteristics. Because piezoelectric materials can
sense varying degrees of stress and strain, researchers can evaluate mechanical information
through changes in the amplitude or phase of the output voltage or current. This is an
important reason why these sensors have been actively used in various research fields
and have developed rapidly in recent years. Figure 2 displays the response curves of two
types of piezoelectric sensors to mechanical changes: (a) the relationship between various
degrees of finger bending and the output voltage of the sensor [11], and (b) the relationship
between the output current of sensors with different MoS2 doping contents under stress
conditions [12]. When an external force is applied, the electrical response output by the
piezoelectric sensor is quite significant. Traditional piezoelectric materials are primarily
classified into three types [13,14]: piezoelectric single crystals, piezoelectric polymers, and
piezoelectric ceramics. However, over time, the limitations of piezoelectric materials have
become increasingly apparent. Piezoelectric single crystals, such as natural quartz, Rochelle
salt, and lithium niobate, were crucial in the early development of piezoelectric sensors.
However, they are characterized by high brittleness and difficult processing, making it
challenging to meet the requirements for low-cost production. Piezoelectric polymers, such
as PVDF and PVC, possess high flexibility and strong compatibility. Although they meet
the adaptability and biocompatibility of sensors, they suffer from undesired piezoelectricity.
Piezoelectric ceramics, such as lead zirconate titanate (PZT), lead titanate (PTO), and barium
titanate (BTO) exhibit high electromechanical conversion efficiency and good temperature
stability. However, they also face significant brittleness issues, making them unsuitable
for high adaptability and low acoustic impedance environments. Therefore, to address
the inherent drawbacks of traditional piezoelectric materials, researchers have developed
piezoelectric composite materials, broadening their application spectrum [13,15–17].

Table 1. Types, applications, and characteristics of common sensors.

Types of Sensors Main Applications Advantages Disadvantages

strong self-powering, capability,
weapon guidance,
rapid response speed, limited frequency response,
industrial inspection,
piezoelectric [13,14,16] flexible structure, weak direct current response,
ocean exploration,
excellent transmitting/receiving high cost
medical diagnosis
performance
weak temperature stability,
easy integration,
pressure sensing, complex fabrication process,
piezoresistive [18] simple structure,
motion monitoring susceptible to external
low power consumption
interference
liquid level measurement high precision, weak anti-interference capability,
Magnetostrictive
acoustic measurement, large measuring range, short product lifespan,
[19,20]
structural monitoring fast response speed complex signal processing
pressure sensing, high resolution, complex power supply system,
Capacitive [20] industrial inspection, fast response speed, high maintenance requirements,
motion monitoring great dynamic response high cost
displacement measurement, high sensitivity, weak anti-interference capability,
Inductive [20,21] humidity measurement, strong durability, high-temperature error,
non-destructive testing great dynamic response large volume
Micromachines2024,
Micromachines 2024,15,
15,982
x FOR PEER REVIEW 33 of
of 49
50

Figure1.1. Schematic
Figure Schematic diagram
diagram ofofthe
theprinciples
principlesofofthe
thepiezoelectric
piezoelectriceffect.
effect.(i)
(i)Inverse
InversePiezoelectric
Piezoelectric
Effect. (ii) Positive Piezoelectric Effect.
Effect. (ii) Positive Piezoelectric Effect.

Figure2.2.(a)
Figure (a)Output
Outputvoltage
voltageresponse
responseof
ofthe
thepiezoelectric
piezoelectricsensor
sensorunder
underdifferent
differentdegrees
degreesof
offinger
finger
bending
bending[11].
[11].(b)
(b)The
Thecurrent response
current curve
response of the
curve of piezoelectric nanogenerator
the piezoelectric under under
nanogenerator different MoS2
different
MoS2 doping
doping contents contents
[12]. [12].

Piezoelectric
Piezoelectric composite
composite materials,
materials, formed
formed byby blending
blending piezoelectric
piezoelectric materials
materials and
and
polymers
polymers in specific proportions, originated in the late 1970s. They can be categorizedinto
in specific proportions, originated in the late 1970s. They can be categorized into
ten
teninterconnected
interconnected structures
structures based
based on
on spatial
spatial arrangement,
arrangement, as as depicted
depicted inin Figure
Figure 33 [22].
[22].
The advantages of polymer materials, including low acoustic impedance, low
The advantages of polymer materials, including low acoustic impedance, low density, and density, and
high
highflexibility,
flexibility,can
cansignificantly
significantlyimprove
improvethetheshortcomings
shortcomings ofof
traditional piezoelectric
traditional piezoelectricmate-
ma-
rials, endowing piezoelectric composite materials with numerous novel attributes
terials, endowing piezoelectric composite materials with numerous novel attributes dis- distinct
from
tinct those of traditional
from those materials
of traditional [14,23–25].
materials EarlyEarly
[14,23–25]. studies on piezoelectric
studies composite
on piezoelectric compo-
materials primarily focused on the PZT-epoxy type, which has been extensively
site materials primarily focused on the PZT-epoxy type, which has been extensively utilized
uti-
in various domains, including underwater acoustics [26–34], medical diagnosis [35–40],
lized in various domains, including underwater acoustics [26–34], medical diagnosis [35–
and health monitoring [41–44]. This type of composite material is characterized by high
40], and health monitoring [41–44]. This type of composite material is characterized by
hardness and strong electromechanical and piezoelectric properties, making it a crucial
high hardness and strong electromechanical and piezoelectric properties, making it a cru-
sensitive material for developing acoustic transducers [45,46]. MSI, a company in the
cial sensitive material for developing acoustic transducers [45,46]. MSI, a company in the
United States, reported a curved transducer array based on the PZT-epoxy type, fabricated
United States, reported a curved transducer array based on the PZT-epoxy type, fabri-
using thermoforming [28]. The transducer array, composed of eight structurally similar
cated using thermoforming [28]. The transducer array, composed of eight structurally
composite material elements, can meet the requirements of wide-beam transmission (>60◦ )
similar composite material elements, can meet the requirements of wide-beam transmis-
and high-sensitivity reception (~178 dB) for underwater detection. Badcock et al. [47] em-
sion (>60°) and high-sensitivity reception (~178 dB) for underwater detection. Badcock et
bedded PZT powder into an epoxy resin matrix to produce a 0-3 type composite material.
al. [47] embedded PZT powder into an epoxy resin matrix to produce a 0-3 type composite
Upon testing, this composite material not only effectively absorbed Lamb waves but also
material. Upon testing, this composite material not only effectively absorbed Lamb waves
generated a sensitivity response twice as high as PVDF. Zhang et al. [40] proposed a lateral
but also generated a sensitivity response twice as high as PVDF. Zhang et al. [40] proposed
Micromachines 2024, 15, x FOR PEER REVIEW 4 of 50
Micromachines 2024, 15, 982 4 of 49

a lateral mode 2-2 type piezoelectric composite material composed of PZT-5H and rigid
moderesin.
epoxy 2-2 type piezoelectric
The material composite
achieves material
an effective fluidcomposed of PZT-5H
static pressure and(drigid
coefficient h) of epoxy
6000
resin.making
pC/N, The material achieves
it suitable an effectiveunderwater
for developing fluid static pressure
transducerscoefficient
capable(dofh )withstanding
of 6000 pC/N,
making
high it suitable
hydrostatic for developing
pressure. Fleury et underwater transducers
al. [38] utilized capable
a lay-up and of withstanding
casting method to fabri- high
hydrostatic pressure. Fleury et al. [38] utilized a lay-up and casting method
cate 1-3 type piezoelectric composite materials, extending their application to high-power to fabricate 1-3
type piezoelectric composite materials, extending their application to
diagnosis and therapy. With a high electromechanical coupling coefficient (around 0.6) high-power diagnosis
andlower
and therapy. Withimpedance,
acoustic a high electromechanical
the transducercoupling coefficient
can generate (around
ultrasound power0.6) and
up tolower
30
acoustic impedance, 2
Watts/cm², maintainingthe transducer
long-term can generate
stability ultrasound
at mechanical power up
efficiencies of to 30 Watts/cm
around 50% to ,
maintaining
60%. long-term
This technology has stability
significant at mechanical
application valueefficiencies of around
for real-time 50% to 60%.
ultrasound monitor-This
technology has significant application value for real-time ultrasound monitoring.
ing. Furthermore, researchers have reported various modifications to the structure of PZT- Further-
more, researchers
epoxy-base compositehave reported
materials variousresulting
[48–53], modifications to the
in notable structure of PZT-epoxy-base
enhancements in energy con-
composite materials [48–53], resulting in notable enhancements
version efficiency, temperature stability, and mechanical properties. in energy conversion
The PZT-epoxy effi-
type
ciency, temperature stability, and mechanical properties. The PZT-epoxy
piezoelectric composite material, with its excellent performance, has enabled break- type piezoelectric
composite material, with its excellent performance, has enabled breakthroughs in acoustic
throughs in acoustic transducer performance in terms of high electroacoustic response,
transducer performance in terms of high electroacoustic response, mechanical stability,
mechanical stability, and high-power output. However, despite these many advantages,
and high-power output. However, despite these many advantages, the high hardness
the high hardness of piezoelectric ceramics and the high rigidness of epoxy resin polymers
of piezoelectric ceramics and the high rigidness of epoxy resin polymers often confine
often confine the design of PZT-epoxy type composite materials to rigid, non-bendable
the design of PZT-epoxy type composite materials to rigid, non-bendable forms, making
forms, making it difficult to exhibit flexible characteristics. This severely limits the appli-
it difficult to exhibit flexible characteristics. This severely limits the application of these
cation of these materials in the field of flexible sensors.
materials in the field of flexible sensors.

Figure 3. Diagram of ten connected structures of piezoelectric composite materials [22].

Figure 3. Diagram of ten connected structures of piezoelectric composite materials [22].
In recent years, a series of flexible devices have emerged to meet the demands for high
In recent
precision, years, a series
mechanical of flexible
flexibility, devices have emerged
and miniaturization in sensingto meet the This
[54–60]. demands
trendforhas
high precision, mechanical flexibility, and miniaturization in sensing [54–60].
steered the development of piezoelectric composite materials towards enhanced adaptabil- This trend
hasity,steered the reliability,
sensitivity, development and of piezoelectric
performance composite materials
compatibility, moving away towards
fromenhanced
traditional
adaptability, sensitivity, reliability, and performance compatibility,
PZT-epoxy-type structural designs. Huang et al. [61] proposed a porous PVDF moving away from
polymer
traditional
with highPZT-epoxy-type
piezoelectricity.structural designs.
This material Huang et al.
is composed of [61] proposed
traditional a porous PVDF
polyvinylidene flu-
polymer with high piezoelectricity. This material is composed of traditional
oride and barium titanate, compressed and molded to demonstrate high flexibility and polyvinyli-
dene fluoride
excellent and bariumproperties.
piezoelectric titanate, compressed
Experimental andfindings
molded to demonstrate
indicate that thehigh flexibil-
material can
ityincrease
and excellent piezoelectric properties. Experimental findings indicate that
d33 (piezoelectric strain coefficient) to 51.20 pC/N and achieve a high sensitivity the material
canof increase d33 (piezoelectric
132.87 mV/kPa, offering astrain
novelcoefficient)
pathway for to 51.20 pC/N and
developing achieve a flexible
self-powered high sensitiv-
sensors.
ity of 132.87
Jiang mV/kPa,
et al. [62] offering
reported a novel
a flexible pathwaymaterial
composite for developing self-powered
synthesized from PZTflexible sen-
and silicone
sors. Jiang
resin, withetYoung’s
al. [62] reported
modulus aofflexible composite
34.2 MPa, material
exhibiting synthesized
greater flexibility from PZT and
than traditional
silicone
PVDF. resin,
Uponwith Young’s
testing, modulus ofmaterial
this composite 34.2 MPa, exhibiting
showed greater
a yield failureflexibility
strain ofthan
7.2%tradi-
and a
tional
fatiguePVDF. Upon
failure testing,
strain thisµε,
of 9200 composite material
demonstrating showed apotential
significant yield failure strain ofdamage
for impact 7.2%
and a fatigue failure
monitoring strain of
applications. 9200etμε,
Chen al.demonstrating
[63] prepared asignificant potential (CNT)/polyvinyl
carbon nanotubes for impact dam-
alcohol (PVA)/zinc oxide (ZnO) composite material. Under pulse loading, this compos-
Micromachines 2024, 15, 982 5 of 49

ite material displayed piezoelectric sensitivity, linear stability, and response accuracy of
4.87 mV/lbf, 3.42%, and 1.496 ms, respectively, demonstrating rapid response and high-
precision sensing features. The development of flexible sensors has been driven by advances
in flexible piezoelectric composite materials, rapidly expanding into various fields such
as underwater detection, wearable sensors, flexible electronic skins, targeted therapy, and
ultrasound diagnostics for deep tissue. Therefore, the research and development of flexible
piezoelectric composite materials is of paramount importance. This paper reviews the
research progress of flexible piezoelectric composite materials, enumerates their types and
common fabrication methods, outlines their applications in various domains, and finally,
discusses future development directions.

2. Types of Flexible Piezoelectric Composite Materials

Flexible piezoelectric composite materials are a type of composite that balances me-
chanical stretchability and piezoelectricity, serving as the core component of flexible sensors.
Based on their connectivity structure, flexible piezoelectric composite materials are pri-
marily categorized into 0-3 and 1-3 types. In recent years, flexible sensors have gained
increasing attention in the medical field. This is mainly due to the advantages of flexible
piezoelectric composite materials, such as high biocompatibility, high flexibility, and high
sensitivity. However, since these sensors often need to be implanted in human tissue or
attached to human skin, it is also important to develop flexible piezoelectric composite
biomaterials that are biodegradable and non-toxic.

2.1. 0-3 Type

0-3 types of flexible piezoelectric composite materials [15,64] are two-phase materi-
als that are composed of zero-dimensional piezoelectric particles and three-dimensional
flexible polymers, typically in the form of thin films. These composite materials integrate
the piezoelectricity of these particles with the flexibility of polymers, making them highly
popular in current research on flexible sensing. Regarding material composition, the two
constituent phases serve distinct roles: piezoelectric particles are usually made from highly
piezoelectric powders to ensure strong force-electric response characteristics while the
polymer matrix needs to be highly flexible and stretchable to provide the material with
a high strain capacity. 0-3 type flexible piezoelectric composite materials are favored for
their high sensitivity, good flexibility, and strong compatibility, holding significant practical
value in developing the next generation of flexible electronic devices [65,66]. This paper cate-
gorizes 0-3 type flexible piezoelectric composite materials into PVDF series matrix type and
non-PVDF series matrix type based on whether the polymer matrix possesses piezoelectricity.

2.1.1. PVDF Series Matrix Type

Polyvinylidene fluoride (PVDF) is a common polar crystalline piezoelectric poly-
mer. It has become an important material for developing flexible sensors due to its
high flexibility and compatibility [67–69]. However, the piezoelectricity of PVDF is rel-
atively weak. Researchers typically enhance its piezoelectric properties by doping the
PVDF matrix with highly piezoelectric particles, creating PVDF-based 0-3 piezoelectric
composite materials. This method addresses the low piezoelectricity of pure PVDF
and is the mainstream modification approach, which has been extensively reported in
the field of flexible piezoelectric composites. Additionally, PVDF derivatives such as
polyvinylidene fluoride-trifluoroethylene (P(VDF-TrFE)) and polyvinylidene fluoride-
chlorotrifluoroethylene (P(VDF-CTFE)) are similarly modified.
Ail et al. [70] electrospun ZnO@ZnS nanoparticles with PVDF slurry to create a PVDF-
based nanocomposite material, combining flexibility and high piezoelectricity. The in-
corporation of ZnO@ZnS nanoparticles facilitated the transformation to the electroactive
β-phase in PVDF, greatly improving the piezoelectric properties of the composite material.
Experimental results showed that the conversion sensitivity of conventional PVDF devices
is around 0.091 V/N·mm3 , whereas this composite material device achieves a conversion
Micromachines 2024, 15, x FOR PEER REVIEW 6 of 50

incorporation
incorporation of of ZnO@ZnS
ZnO@ZnS nanoparticles
nanoparticles facilitated
facilitated the the transformation
transformation to to the
the electroactive
electroactive
Micromachines 2024, 15, 982 β-phase
β-phase in PVDF, greatly improving the piezoelectric properties of the composite mate-
in PVDF, greatly improving the piezoelectric properties of the composite mate-
6 of 49
rial.
rial. Experimental
Experimental results results showed
showed that that thethe conversion
conversion sensitivity
sensitivity of of conventional
conventional PVDF PVDF
devices
devices is is around
around 0.091 0.091 V/N·mm
V/N·mm3,, whereas
3
whereas this this composite
composite material material device
device achieves
achieves aa con- con-
version
version sensitivity
sensitivity of
of 0.153
0.153 V/N·mm
3
V/N·mm
3, an increase of nearly 70%. This demonstrates that
3, an increase of nearly 70%. This demonstrates that
sensitivity of 0.153 V/N·mm , an increase of nearly 70%. This demonstrates that the en-
the
the enhancement
enhancement
hancement in PVDF’s in
in PVDF’s
PVDF’s piezoelectric
piezoelectric
piezoelectric properties properties
properties
is closely is
is closely
relatedrelated
closely related to
to the
the optimization
to the optimization optimization
of the
of the
device’s device’s
of the device’s sensing
sensingsensing characteristics.
characteristics.
characteristics. Talab et Talab
Talab et al.
et al.
al. [71] [71] reported
[71] reported
reported a BTO/P(VDF-TrFE)
a BTO/P(VDF-TrFE)
a BTO/P(VDF-TrFE) composite com-
com-
posite
material. material.
posite material.
Due to DueDue to the incorporation
to the incorporation
the incorporation of BTOof of BTO ceramic
BTO ceramic
ceramic powder, powder,
powder, this composite
this composite
this composite material material
material
simul-
simultaneously
simultaneously
taneously enhances enhances
enhances
mechanical mechanical
propertiesproperties
mechanical properties and
and piezoelectricity.
and piezoelectricity. Experiments Experiments
piezoelectricity. Experiments
showed that
showed
showed
this that
that this
composite this composite
composite
material has material
material
a g33 value has aa gg33 value (piezoelectric
has(piezoelectric
33 value (piezoelectric
voltage constant)voltage
voltageofconstant)
205 mV·of
constant) of
m/N205
205
mV·m/N
mV·m/N
and and
a polarization a polarization
and a polarization
value of 6.18 value
value
µC/cmof 6.182 μC/cm
of 6.18, representing
2, representing increases of approximately
μC/cm , representing
2 increases increases of approximately
of approximately 30% and
30%
30% and
46%, and 46%,
46%, respectively,
respectively, comparedcompared
respectively, to
to pure
to pure P(VDF-TrFE),
compared pure P(VDF-TrFE),
demonstrating
P(VDF-TrFE), demonstrating
significantly
demonstrating significantly
enhanced
significantly
enhanced
inverse
enhanced inverse
inverse piezoelectricity.
piezoelectricity. Furthermore,
piezoelectricity. Furthermore,
researchers
Furthermore, researchers
explored the
researchers explored
sensing
explored the
the sensing
sensing proper-
properties of this
proper-
ties of
composite this composite
ties of this material.
compositeFigure material.
material. Figure
4 shows
Figure 4 shows
the4 voltage
shows the the voltage
response response
voltagecurvesresponse curves
curves of
of BTO/P(VDF-TrFE)of BTO/P(VDF-
BTO/P(VDF- and
TrFE)
TrFE) andand P(VDF-TrFE)
P(VDF-TrFE) materials in
P(VDF-TrFE) materials in
the g31 mode.
materials in the
the ggAs31 mode. As
the finger
31 mode. As the
the finger
varies
finger varies
under
varieslow,under
under low,
low, moder-
moderate, and
moder-
ate,
ate, and
high high
bending
and high bending
bending conditions,
conditions, the output
conditions, the output
thevoltage
output of voltage of
of the
the BTO/P(VDF-TrFE)
the BTO/P(VDF-TrFE)
voltage BTO/P(VDF-TrFE) sensor issensoralmost
sensor is
is
almost
twice twice
that of that
the of the
P(VDF-TrFE) P(VDF-TrFE)
sensor. sensor.
Meanwhile, Meanwhile,
the
almost twice that of the P(VDF-TrFE) sensor. Meanwhile, the output power is 4.6 times output the output
power is 4.6power
times is 4.6
that times
of the
that
that of
of the
P(VDF-TrFE)the P(VDF-TrFE)
sensor, fullysensor,
P(VDF-TrFE) fully
fully demonstrating
demonstrating
sensor, the application
demonstrating the
the application
value of this
application value of
of this
flexible
value flexible
composite
this flexible
composite
material
composite material
in material in sensing,
sensing, actuation,
in sensing,and actuation,
energyand
actuation, and energy
harvesting harvesting
devices. Xiong
energy harvesting devices. Xiong
et al.Xiong
devices. et
et al.
[72] combinedal. [72]
[72]
combined
BTO BTO
BTO nanoparticles
nanoparticles
combined with P(VDF-CTFE)
nanoparticles with
with P(VDF-CTFE)
to create ato
P(VDF-CTFE) create
create aa BTO/P(VDF-CTFE)
BTO/P(VDF-CTFE)
to BTO/P(VDF-CTFE) composite composite
material
composite
material
with highwith
material energy
with high
high energy
storage storage
storage characteristics,
energycharacteristics, as shownas
characteristics, inshown
as Figure in
shown 5. Figure
in 5.
5. The
The composite
Figure The composite
material
composite
material
employs employs a layered design, with the top and bottom
material employs a layered design, with the top and bottom layers of P(VDF-CTFE) effec-
a layered design, with the top and bottom layers of layers of
P(VDF-CTFE) P(VDF-CTFE)
polymer poly-
poly-
mer
mer effectively enhancing the composite’s breakdown field strength and dielectric con-
tively effectively
enhancing enhancing
the the
composite’s composite’s
breakdown breakdown
field strengthfield strength
and and
dielectric dielectric
constant. The
con-
stant.
middle The
layer middle
consists layer
of consists of
dopamine-modified dopamine-modified
and
stant. The middle layer consists of dopamine-modified and BTO-doped BTO/P(VDF- BTO-doped and BTO-doped
BTO/P(VDF-CTFE) BTO/P(VDF- film,
improving
CTFE)
CTFE) film,film,charge-discharge
improving efficiency and polarization
improving charge-discharge
charge-discharge efficiency
efficiency and strength.
and Experiments
polarization
polarization have Experi-
strength.
strength. shown
Experi-
that
ments
mentsthis layered
have
have shown
shown BTO/P(VDF-CTFE)
that
that this
this layered composite material composite
layered BTO/P(VDF-CTFE)
BTO/P(VDF-CTFE) has a dielectric
composite materialconstant
material has aaof
has 10.44, a
dielectric
dielectric
maximum
constant ofbreakdown
10.44, a field
maximum strength
breakdown of 362.25fieldkV/mm,
strength
constant of 10.44, a maximum breakdown field strength of 362.25 kV/mm, and a charge- andof a charge-discharge
362.25 kV/mm, and efficiency
a charge-
of 86.63% under
discharge
discharge efficiencyan electric
efficiency of
of 86.63%fieldunder
86.63% strength
under anof
an 500 kV/cm,
electric
electric field indicating
field strength
strength ofexcellent
of 500
500 kV/cm,
kV/cm, dielectric
indicating
indicatingand
energy
excellent storage properties.
dielectric and energy storage
excellent dielectric and energy storage properties. properties.

Figure
Figure 4.
Figure 4. Voltage
Voltageresponse
Voltage responseof
response BTO/P(VDF-TrFE)
ofof and
BTO/P(VDF-TrFE)
BTO/P(VDF-TrFE) pure
andand P(VDF-TrFE)
purepure materials
P(VDF-TrFE)
P(VDF-TrFE) under
materials
materials gg31
under
under mode
g31
31 mode
[71].
mode
[71]. [71].

Figure 5. Layered structure of BTO/P(VDF-CTFE) composite material [72].

Besides enhancing piezoelectricity, some studies also aim to improve other physical
properties of PVDF to further enhance device functionality and sensing characteristics.
Micromachines 2024, 15, 982 7 of 49

Traditional PVDF exhibits poor melt processability and cannot withstand high voltage,
significantly limiting its application in devices. To address this issue, He et al. [73] proposed
a PVDF-PLLA-C1 nanocomposite material. By incorporating small amounts of crystalline
polymer (PLLA) and fluorescent material (Tb(TTA)3 (TPPO)2 ), they significantly promoted
the melting and crystallization behavior of the PVDF matrix. Experiments showed that
this composite material sensor could produce a sensitivity response four times higher than
that of traditional PVDF sensors, with an output voltage of up to 2.5V. Additionally, it can
absorb ultraviolet light and emit visible light, making it suitable for developing highly
responsive force-sensitive sensors and self-powered conformal devices.
In summary, PVDF series matrix-type composite materials generally optimize their
piezoelectric properties through doping, often using a 0-3 type composite structure (doped
phase-PVDF matrix phase). The greatest advantage of these composite materials is that
they retain the inherent high conformability and high compatibility of PVDF materials,
offering significant potential for developing high-strain, high-sensitivity sensors.

2.1.2. Non PVDF Series Matrix Type

Another type of 0-3 flexible piezoelectric composite material is composed of highly
piezoelectric particles and non-piezoelectric polymers. Since the polymer primarily pro-
vides mechanical stretchability and deformability, the piezoelectricity of this 0-3 type
composite material comes entirely from the doped piezoelectric particles. Compared to
the PVDF series matrix type, non-PVDF matrix type composite materials might exhibit a
lower piezoelectric coefficient. To balance the issue of piezoelectricity, researchers typically
select piezoelectric ceramic powders with high piezoelectric coefficients that are also easy
to manufacture as the piezoelectric phase material for the composites.
Jiang et al. [74] combined PZT powder with silicone resin to prepare a highly flexible
0-3 PZT/silicone resin composite material, as shown in Figure 6a. They conducted studies
on the effects of polarization conditions and PZT structural parameters on the piezoelectric
properties of the composite material. Experiments demonstrated that the piezoelectric
strength of the 0-3 PZT/silicone resin composite material is closely related to the polariza-
tion conditions. The optimal sensing sensitivity was achieved when the polarization time
was 25 min, the polarization field was 4 kV/mm, the polarization temperature was 100 ◦ C,
the PZT doping volume fraction was 50%, and the powder particle size was 170–212 µm.
Moreover, within the environmental temperature range of −55 to 75 ◦ C, the 0-3 type sensor
exhibited excellent flexibility and sensitivity in detecting guided wave signals. Bradley
et al. [75] mixed PZT powder with fluorinated suspensions and used screen printing, tem-
plate printing, and dip-coating techniques to produce a 0-3 PiezoPaint composite material
with a wideband acoustic response. Compared to 1-3 type and 2-2 type composite materi-
als, this 0-3 type material has a thinner thickness and smaller size (thickness 50 µm, area
1 mm2 ), making it easy to integrate into medical devices such as catheters and probes. The
team proposed a structure of an integrated photoacoustic probe comprising 0-3 PiezoPaint
composite material and a fiber Bragg grating (FBG). This probe features high frequency,
small size, and high flexibility, capable of achieving pulse-echo responses of up to 20 MHz
and radiofrequency responses at common MRI frequencies. JO et al. [76] developed a
PZT/PVB 0-3 type composite material using PZT powder and polyvinyl butyral (PVB). The
high thermoplasticity of the PVB material enables the 0-3 composite material to maintain ex-
cellent piezoelectric performance even at high temperatures. Additionally, they fabricated
this composite material into a force-sensitive sensor, as shown in Figure 6b. Experimental
results demonstrated that this sensor had sensitivities of 1.368 V/N and 0.815 V/N on
aluminum oxide and polyester substrates, respectively, with response times within 45 ms,
indicating high sensitivity and fast response characteristics.
The doping of a certain amount of piezoelectric ceramics significantly enhances the
activity of 0-3 composite materials, unleashing the powerful potential of these materials to
perceive weak signals. Recent research has uncovered the following features regarding the
application of 0-3 piezoelectric composite materials: firstly, these materials are typically
 The doping of a certain amount of piezoelectric ceramics significantly enhances the
activity of 0-3 composite materials, unleashing the powerful potential of these materials
Micromachines 2024, 15, 982 to perceive weak signals. Recent research has uncovered the following features regarding 8 of 49
the application of 0-3 piezoelectric composite materials: firstly, these materials are typi-
cally used in the form of small-sized films with a thickness of less than 1 mm, making
them in
used mostly
the formsuitable for developing
of small-sized filmshigh-frequency
with a thickness micro-sensing
of less than series
1 mm,ofmaking
piezoelectric
them
mostly suitable for developing high-frequency micro-sensing series of piezoelectrichigh
sensors; and, secondly, 0-3 piezoelectric composite materials generally exhibit me-
sensors;
chanical flexibility, with some also demonstrating excellent high-temperature
and, secondly, 0-3 piezoelectric composite materials generally exhibit high mechanical resistance.
Nevertheless,
flexibility, withasome
directalso
trade-off exists between
demonstrating thehigh-temperature
excellent piezoelectricity and flexibility
resistance. of these
Neverthe-
composite
less, a directmaterials.
trade-off With
existsan increase
between inpiezoelectricity
the the content of piezoelectric
and flexibilityceramics,
of thesethe piezoe-
composite
lectric coefficient
materials. With anof 0-3 composite
increase materials
in the content will increase
of piezoelectric significantly,
ceramics, while flexibility
the piezoelectric coeffi-
will decrease accordingly. To achieve the optimal balance between flexibility
cient of 0-3 composite materials will increase significantly, while flexibility will decrease and piezoe-
lectricity, it isToimperative
accordingly. achieve thetooptimal
avoid excessively high doping
balance between amounts
flexibility of piezoelectricitce-
and piezoelectricity, is
ramic powder,
imperative thusexcessively
to avoid ensuring that
highthe piezoelectric
doping amounts strain coefficient
of piezoelectric remains
ceramic withinthus
powder, the
application
ensuring thatrange of tens of pC/N.
the piezoelectric strainHence, the advancement
coefficient remains within of the
piezoelectric
applicationmaterials
range of with
tens
enhanced
of piezoelectric
pC/N. Hence, properties and
the advancement improved compatibility
of piezoelectric materials with can significantly
enhanced enhance
piezoelectric
the performance
properties and expand
and improved the application
compatibility can scope of 0-3 type
significantly piezoelectric
enhance composite and
the performance ma-
terials. the application scope of 0-3 type piezoelectric composite materials.
expand

Figure 6. (a) Sample of 0-3 PZT/Silicon

Figure 6. PZT/Siliconresin
resincomposite
compositematerial
material[74].
[74].(b)
(b)Force-sensitive
Force-sensitive sensor
sensor ofof
0-
0-3 PZT/PVB
3 PZT/PVB type
type [76].
[76].

2.2.
2.2. 1-3
1-3 Type
Type
Among
Amongthe thetenten
connectivity structures,
connectivity 1-3 piezoelectric
structures, composite composite
1-3 piezoelectric materials [4,13,77–79]
materials
are the most prevalent and extensively utilized type, celebrated for their distinctive thick-
[4,13,77–79] are the most prevalent and extensively utilized type, celebrated for their dis-
ness vibration mode, low acoustic impedance, and high piezoelectric coefficient. They are
tinctive thickness vibration mode, low acoustic impedance, and high piezoelectric coeffi-
widely employed in the realms of underwater acoustic detection and ultrasound imaging.
cient. They are widely employed in the realms of underwater acoustic detection and ul-
This involves embedding one-dimensional linear arrays of piezoelectric materials into a
trasound imaging. This involves embedding one-dimensional linear arrays of piezoelec-
three-dimensional polymer matrix composite. Conventionally, piezoelectric ceramics and
tric materials into a three-dimensional polymer matrix composite. Conventionally, piezo-
epoxy resins are utilized in composite fabrication, yielding predominantly planar structures
electric ceramics and epoxy resins are utilized in composite fabrication, yielding predom-
with limited flexibility. Recently, there has been a continuous rise in demand for curved
inantly planar structures with limited flexibility. Recently, there has been a continuous
sensors [80–83]. In response, researchers have proposed combining piezoelectric ceram-
rise in demand for curved sensors [80–83]. In response, researchers have proposed com-
ics with flexible polymers, resulting in the development of a series of highly adaptable
bining piezoelectric ceramics with flexible polymers, resulting in the development of a
1-3 flexible piezoelectric composite materials. Moreover, the electromechanical properties
series of highly adaptable 1-3 flexible piezoelectric composite materials. Moreover, the
of traditional 1-3 type composite materials have been enhanced due to the capability of
electromechanical
flexible polymers toproperties
promote the of thickness
traditionalvibration
1-3 typeofcomposite
piezoelectricmaterials have been en-
materials.
hancedKim et al. [84] fabricated a 1-3 flexible piezoelectric composite material vibration
due to the capability of flexible polymers to promote the thickness comprising of
piezoelectric
PZT-5H materials.
ceramics and polydimethylsiloxane (PDMS). This design combines the robust
Kim et al. [84] fabricated
piezoelectric properties of the aceramics
1-3 flexible piezoelectric
with composite flexibility
the high mechanical material comprising
of PDMS,
PZT-5H ceramics and polydimethylsiloxane (PDMS). This design
achieving a thickness electromechanical coupling coefficient (kt ) of the 1-3 combines thecomposite
robust pi-
ezoelectric properties of the ceramics with the high mechanical
material of up to 0.74, comparable to the length electromechanical coupling coefficient flexibility of PDMS,
achieving a thickness electromechanical coupling coefficient (k t) of the 1-3 composite ma-
(k33 ) of PZT-5H, along with an approximately 50% −6 dB bandwidth. Serving as the
terial of
active up toPDMS
phase, 0.74, comparable to the length
effectively mitigated theelectromechanical coupling in
planar coupling observed coefficient (k33)
epoxy resin
of PZT-5H, along with an approximately 50% −6 dB bandwidth. Serving
in traditional 1-3 composite materials, demonstrating robust flexibility in the thickness as the active
phase, PDMS
vibration of theeffectively
piezoelectricmitigated
ceramicstheandplanar coupling
minimizing the observed in epoxy
loss of vibration resinLikewise,
energy. in tradi-
tional 1-3 composite materials, demonstrating robust flexibility in the
Hou et al. [85] utilized PDMS to fabricate PZT-8/PDMS 1-3 flexible composite material, thickness vibration
of the piezoelectric
depicted in Figure 7ceramics andthe
illustrating minimizing the loss of structure
three-dimensional vibration of energy. Likewise, Hou
this composite. The
transducer made from this composite material exhibits robust mechanical flexibility and
exceptional acoustic performance in terms of frequency (~1.51 MHz) and electromechanical
coupling coefficient (kt ~ 0.74).
 et al. [85] utilized PDMS to fabricate PZT-8/PDMS 1-3 flexible composite material, de-
picted in Figure
et al. [85] 7 illustrating
utilized PDMS to the three-dimensional
fabricate PZT-8/PDMSstructure of this
1-3 flexible composite.
composite The trans-
material, de-
ducer
pictedmade from7 this
in Figure composite
illustrating the material exhibits robust
three-dimensional mechanical
structure flexibility and
of this composite. Theexcep-
trans-
tional
ducer acoustic
made from performance in terms
this composite of frequency
material exhibits (~1.51
robustMHz) and electromechanical
mechanical cou-
flexibility and excep-
Micromachines 2024, 15, 982 pling
tionalcoefficient (kt ~ 0.74). in terms of frequency (~1.51 MHz) and electromechanical9 cou-
acoustic performance of 49
pling coefficient (kt ~ 0.74).

Figure 7. Structure of 1-3 PZT-8/PDMS flexible composite material [85].

Figure 7.
Figure 7. Structure
Structure of
of 1-3
1-3 PZT-8/PDMS
PZT-8/PDMS flexible composite material [85].
In addition to their applications in medical ultrasound, 1-3 flexible piezoelectric com-
positeInmaterials
In addition to
addition play
totheira crucial
their role ininunderwater
applications
applications in medical
medical acoustics1-3
ultrasound,
ultrasound, engineering.
1-3 flexible
flexible Topiezoelectric
addresscom-
piezoelectric the
low
positemechanical
composite materials flexibility,
materials
playplay Hao
a crucial
a crucial et
role
role al.in
in [86,87] employed
underwater
underwater a combination
acoustics
acoustics engineering. To
engineering. of
To the dice-fill
address the
the
low mechanical
method and flexibility,
island bridge Hao et al.
electrode [86,87] employed
structure to a combination
fabricate a of the
PZT-5A/rubber
low mechanical flexibility, Hao et al. [86,87] employed a combination of the dice-fill dice-fill
1-3 method
flexible
and island
underwater
method bridge
and islandelectrode
transducer,
bridge structure
depicted
electrode tostructure
in Figurefabricate a PZT-5A/rubber
8. Unlike
to PDMSamaterial,
fabricate 1-3 flexible underwater
the silicone
PZT-5A/rubber rubber
1-3 flexible
transducer,
material
underwater candepicted
achieve in
transducer, Figure
a reliable 8.
depicted Unlike
connection
in Figure PDMS material,
of8.piezoelectric
Unlike PDMSthe siliconethrough
elements
material, rubber material
flexible
the silicone can
elec-
rubber
achieve
tric
material acan
reliable
bridges, connection
eliminating
achieve ofconnection
the need
a reliable piezoelectric
for complex elements
nano silverthrough
of piezoelectric wire flexible
electrode
elements through electric
preparationbridges,
flexible tech-
elec-
eliminating
niques.
tric bridges, the
Tested need for
results
eliminating complex
showed
the need nano
that the
for silver wire
PZT-5A/rubber
complex nano electrode preparation
1-3wire
silver flexible techniques.
composite
electrode material
preparation Tested
can
tech-
results
bend showed
with that
curvature the
radii PZT-5A/rubber
ranging from 1-3
100 mmflexible
to 200composite
mm, material
offering
niques. Tested results showed that the PZT-5A/rubber 1-3 flexible composite material can valuablecan bend
insightswith
for
curvature
developing radii ranging from
a new generation
bend with curvature 100
radii ranging mm to
of underwater 200
from 100 mm mm, offering
transducers
to 200 mm,valuable
with insights
enhanced
offering valuablefor developing
sensitivity
insightsandfor
aflexibility.
new generation
developing a newofgeneration
underwater oftransducers
underwaterwith enhancedwith
transducers sensitivity
enhanced andsensitivity
flexibility. and
flexibility.

Figure 8.
Figure 8. Flexible
Flexible underwater
underwater acoustic transducer
transducer with
with significant
significant deformability
deformability [86].
[86].
Figure 8. Flexible underwater acoustic transducer with significant deformability [86].
1-3
1-3 flexible
flexiblepiezoelectric
piezoelectriccomposite
compositematerials,
materials,characterized
characterized byby their unique
their unique advan-
ad-
tages
vantagesof high electromechanical
of high electromechanical
1-3 flexible properties, which
properties,
piezoelectric composite are known
which characterized
materials, for
are known for bytheir
their piezoelectricity
piezoelectricity
their unique ad-
and
and exceptional
of highflexibility,
exceptional
vantages flexibility, have
have paved
electromechanical paved the
the way for
for the
waywhich
properties, the advancement
advancement
are known for theirof
of next-generation
next-generation
piezoelectricity
flexible
flexible
and exceptionalcurved
and curved surfacesensing
surface
flexibility, sensing
have devices.
devices.
paved The
The
the way twotwo
for constituent
constituent
the phases
phases
advancement of 1-3 flexible
ofofnext-generation
1-3 flexible pi-
piezoelectric
ezoelectric composite
composite materials
materials serve
serve distinct
distinct roles:
roles: piezoelectric
piezoelectric ceramics
ceramics are
are
flexible and curved surface sensing devices. The two constituent phases of 1-3 flexible pi- commonly
commonly
employed
ezoelectricin
employed in the
thepiezoelectric
piezoelectric
composite phase,
materialsphase,offering
serve distincthigh
offering high piezoelectric
roles: piezoelectriccoefficients
piezoelectric ceramicsand
coefficients facilitating
and
are facilitat-
commonly
thickness
employed in the piezoelectric phase, offering high piezoelectric coefficients andpreferred
vibration modes, while materials such as PDMS and silicone rubber are facilitat-
in the polymer phase due to their high flexibility and robust decoupling ability, enabling
the composite material to achieve bending capabilities and enhance its electromechanical
conversion efficiency. According to this design approach, meticulous consideration of
the selection of the two constituent phases will be crucial for the development of high-
performance 1-3 flexible piezoelectric composite materials and their sensors.
Micromachines 2024, 15, 982 10 of 49

2.3. Special Structural Design

Besides typical structures like 0-3 and 1-3 types, certain flexible composite materials
prioritize characteristics such as piezoelectricity, electromechanical properties, stability, and
compressive strength. This makes the developed flexible piezoelectric composites more
suitable for specific applications, showing significant prospects for advancement. However,
due to increasingly diverse fillers, these composite materials may exhibit relatively complex
multiphase interconnected structures.
Improving the piezoelectric properties has always been an important topic for PVDF
series polymers. However, the enhancement of the piezoelectric performance of these
polymer materials is not limited to doping with high-piezoelectric powders. Particularly in
recent reports, the rational doping of certain two-dimensional conductive fillers has also
been proven to effectively enhance the piezoelectricity of PVDF series polymers. Wang
et al. [88] combined a two-dimensional conductive filler known as MXenes with P(VDF-
TrFE) polymer, creating an enhanced composite fiber sensor with high piezoelectricity.
Figure 9a shows the structure of this enhanced composite fiber and the sensor configuration.
They found that MXene not only has a large number of surface functional groups that can
interact with the dipoles of P(VDF-TrFE) molecular chains but also has high conductivity,
which can increase the polarization of PVDF-TrFE during electrospinning. Compared with
pure P(VDF-TrFE), the MXene-doped P(VDF-TrFE) sample exhibited higher output voltage
and current amplitude under the same pressure stimulus, resulting in better piezoelectric
response, as shown in Figure 9b. Similarly, Sharma et al. [89] also prepared this type of
MXenes and P(VDF-TrFE) polymer-enhanced composite fibers based on electrospinning
technology, as shown in Figure 10. The large surface area and strong adhesion of MXenes
ensure a more uniform internal structure of the piezoelectric polymer. Experimental results
showed that this doped enhanced composite film has an extremely low detection limit
of 1.5 Pa, a wide pressure range of up to 400 kPa, and excellent stability (achieving over
10,000 cycles under high pressure of ~167 kPa). It not only has good reliability but can
also be used to develop pressure sensors for detecting large deformations. In addition to
MXenes, related researchers have demonstrated that the use of graphene also significantly
enhances the output voltage and power of P(VDF-TrFE) [90]. Thus, it can be seen that
two-dimensional conductive fillers also have significant value in improving PVDF series
polymers. In addition to high conductivity, these two-dimensional conductive fillers
also possess notable high mechanical stability, dielectric properties, and electrochemical
characteristics, providing important insights for the development of high-performance
piezoelectric composite fibers.
To achieve a balance between compression resistance and flexibility, Qin [91] intro-
duced a large-scale 1-3 piezoelectric composite material array with a binary polymer
structure, illustrated in Figure 11a. This piezoelectric composite material array consists of
several identical structures of 1-3 PZT/epoxy units spliced together. The strong rigidity
of epoxy resin enhances the stability and compression resistance of each unit. Silicone
rubber material connects each 1-3 PZT/epoxy unit. With its high flexibility, silicone rubber
significantly suppresses the lateral coupling effect and adds flexibility to this composite
structure, thereby enhancing the piezoelectric coefficient and adaptability of the material.
To maintain both compression resistance and flexibility, Wang et al. [92] introduced a nested
piezoelectric composite material with semi-flexible characteristics, depicted in Figure 11b.
This composite material utilizes both rigid and flexible materials as filling polymers, provid-
ing the composite material with axial compression resistance and unidirectional bending
capability, making it suitable for developing horizontally wide-beam directional curved
transducers. The designs of the aforementioned flexible composite materials, while re-
taining the stability advantages of traditional 1-3 types, have significantly enhanced the
adaptability of the materials by introducing a third phase of silicone rubber to increase
material decoupling and shape adaptability.
Micromachines
Micromachines2024, 15, x FOR PEER REVIEW 11 of 50
2024,15,
Micromachines2024, 15,982
x FOR PEER REVIEW of4950
11 of

Figure9.9.(a)(a)
Figure Structure
Structure of of
thethe piezoelectric
piezoelectric composite
composite fiberfiber
andand sensor
sensor of XNenes/P(VDF-TrFE)
of XNenes/P(VDF-TrFE) de-
Figure 9. (a) Structure of the piezoelectric composite fiber and sensor of XNenes/P(VDF-TrFE) de-
developed
veloped by Wang
by Wang et al.
et al. (b)(b) Piezoelectric
Piezoelectric response
response test
test results
results ofofXNenes/P(VDF-TrFE)
XNenes/P(VDF-TrFE)compared
comparedtoto
veloped by Wang et al. (b) Piezoelectric response test results of XNenes/P(VDF-TrFE) compared to
pure
pureP(VDF-TrFE)
P(VDF-TrFE)[88]. [88].
pure P(VDF-TrFE) [88].

Figure 10. Enhanced composite film of XNenes/P(VDF-TrFE) developed by Sharma et al. [89].
Figure10.
Figure 10.Enhanced
Enhancedcomposite
compositefilm
filmofofXNenes/P(VDF-TrFE)
XNenes/P(VDF-TrFE)developed
developedby
bySharma
Sharmaetetal.
al.[89].
[89].

ToTo achieve adielectric

balance between compression resistance andetflexibility, Qin [91] intro-
Toaddress
achieve a balanceand mechanical
between mismatches,
compression Tang
resistance andal. [93] utilized
flexibility, Qina[91]
(P(VDF-
intro-
duced
TrFE-CFE)a large-scale
copolymer 1-3 piezoelectric
doped with composite
PZT, PDMS, material
and CNTs array
to with
develop aa binary
3-3-3 polymer
piezoelectric
duced a large-scale 1-3 piezoelectric composite material array with a binary polymer
structure,
composite illustrated
material.inin Figure 11a.
Initially, This piezoelectric composite material array consists of
structure, illustrated Figure PZT and
11a. This PDMS were
piezoelectric connected
composite in a 3-3
material configuration,
array consists of
several
forming identical
a stablestructures of 1-3 PZT/epoxy
interconnected PZT framework units within
splicedthetogether.
PDMSThe strong
matrix. rigidity of
Subsequently,
several identical structures of 1-3 PZT/epoxy units spliced together. The strong rigidity of
epoxy
this resin enhances PZT
interconnected the stability and compression resistance of (P(VDF-TrFE-CFE)
each unit. Silicone rubber
epoxy resin enhances theframework
stability andwas embedded
compression into the
resistance of each unit. Siliconedoped rubber
material
with connects
CNTs, each in
resulting 1-3a PZT/epoxy
3-3-3 unit. Here,
structure. With itsPZThigh flexibility,
acts as silicone rubber
the interconnected signif-
structure,
material connects each 1-3 PZT/epoxy unit. With its high flexibility, silicone rubber signif-
icantly suppresses
effectively the lateral
transmitting load coupling
paths effect
during the and adds flexibilitycoupling
electromechanical to this composite
process, struc-
whereas
icantly suppresses the lateral coupling effect and adds flexibility to this composite struc-
ture, thereby enhancing
(P(VDF-TrFE-CFE) serves theaspiezoelectric
transition coefficient and adaptability of the material. To
ture, thereby enhancing the apiezoelectric layer for adjusting
coefficient the electric
and adaptability field
of thedistribution
material. To
maintain
within both
the PZT compression
framework. resistance
12 and flexibility, Wang et al. piezoelectric
[92] introduced a nested
maintain both compressionFigure resistanceillustrates the exceptional
and flexibility, Wang et al. [92] introduced performance
a nested
piezoelectric
ofpiezoelectric compositematerial,
the 3-3-3 composite materialwith
withasemi-flexible
measured characteristics,
piezoelectric depicted
coefficient of in to
up Figure
250 11b.
pm/V,
composite material with semi-flexible characteristics, depicted in Figure 11b.
This
an composite material
electromechanical utilizes
coupling both rigid
coefficient of andanflexible
0.65, ultra-lowmaterials
acoustic as filling polymers,
impedance of 3MRyl,
This composite material utilizes both rigid and flexible materials as filling polymers,
providing the composite material with axial compression resistance and unidirectional
providing the composite material with axial compression resistance and unidirectional
 Micromachines 2024, 15, x FOR PEER REVIEW 12 of 50

Micromachines 2024, 15, 982 12 of 49

bending capability, making it suitable for developing horizontally wide-beam directional
curved transducers. The designs of the aforementioned flexible composite materials,
while
and retaining
high the stability
cyclic stability underadvantages of traditional
50% compression 1-3synergistic
strain. The types, have significantly
integration en-
of ultra-
hanced
high the adaptability
piezoelectric of the materials
performance by introducing
and superior flexibilityaholds
third promise
phase of for
silicone rubberthe
advancing to
increase material
emerging decoupling
applications andsmart
of flexible shapeelectronic
adaptability.
products.

Micromachines 2024, 15, x FOR PEER REVIEW 13 of 50

Figure 11.(a)
Figure11. (a)Large-scale
Large-scale1-3
1-3piezoelectric
piezoelectriccomposite
compositearray [91].
array [91].(b) Structure
(b) diagram
Structure of of
diagram semi-flexible
semi-flex-
ible nested
nested piezoelectric
piezoelectric composite
composite material
material [92]. [92].

To address dielectric and mechanical mismatches, Tang et al. [93] utilized a (P(VDF-
TrFE-CFE) copolymer doped with PZT, PDMS, and CNTs to develop a 3-3-3 piezoelectric
composite material. Initially, PZT and PDMS were connected in a 3-3 configuration, form-
ing a stable interconnected PZT framework within the PDMS matrix. Subsequently, this
interconnected PZT framework was embedded into the (P(VDF-TrFE-CFE) doped with
CNTs, resulting in a 3-3-3 structure. Here, PZT acts as the interconnected structure, effec-
tively transmitting load paths during the electromechanical coupling process, whereas
(P(VDF-TrFE-CFE) serves as a transition layer for adjusting the electric field distribution
within the PZT framework. Figure 12 illustrates the exceptional piezoelectric performance
of the 3-3-3 composite material, with a measured piezoelectric coefficient of up to 250
pm/V, an electromechanical coupling coefficient of 0.65, an ultra-low acoustic impedance
of 3MRyl, and high cyclic stability under 50% compression strain. The synergistic integra-
tion of ultra-high piezoelectric performance and superior flexibility holds promise for ad-
vancing the emerging applications of flexible smart electronic products.

Figure
Figure 12.
12. Performance
Performancetest test chart
chart of
of 3-3-3
3-3-3 piezoelectric
piezoelectric composite
composite material
material [93].
[93]. (a)
(a) The
The S-E
S-E loop
loop of
of
‘3-3’, ‘3-3-3’, and CNT@‘3-3-3’ composites with 14% PZT volume fraction, and
‘3-3’, ‘3-3-3’, and CNT@‘3-3-3’ composites with 14% PZT volume fraction, and the ‘0-3’ compositethe ‘0-3’ composite
with
with 20%
20% PZT
PZT volume
volume fraction.
fraction. (b)
(b)The
Therelationship
relationship between
betweenthe thepiezoelectric
piezoelectric charge
charge coefficient
coefficient and
and
PZT volume fraction for the ‘3-3’, ‘3-3-3’, and CNT@‘3-3-3’ composites. (c) Finite element simulation
PZT volume fraction for the ‘3-3’, ‘3-3-3’, and CNT@‘3-3-3’ composites. (c) Finite element simulation
results of maximum strain distribution under uniaxial tension (nominal strain = 5%) for ‘0-3’ and ‘3-
results of maximum strain distribution under uniaxial tension (nominal strain = 5%) for ‘0-3’ and ‘3-3’
3’ composites. (d) Comparison of d33 (solid symbols) and d33* (hollow symbols) at maximum elastic
composites.
strain between (d)CNT@‘3-3-3’ of d33 (solid
Comparisoncomposites symbols)
(red star) and d33 * representative
andother (hollow symbols) at maximum
piezoelectric elastic
materials.
strain between CNT@‘3-3-3’ composites (red star) and other representative piezoelectric
(e) The variation of d33 and d31 with PZT skeleton volume fraction in CNT@‘3-3-3’ composites. The materials.
(e) The variation
hydrostatic of d33 and
piezoelectric d31 withdPZT
coefficient skeleton
h follows the volume
equationfraction
dh = d33in+ CNT@‘3-3-3’
2d31, where the composites.
d31 values The
for
both PZT and
hydrostatic PZT-based coefficient
piezoelectric compositesdhare negative.
follows the equation dh = d33 + 2d31 , where the d31 values for
both PZT and PZT-based composites are negative.
2.4. Flexible Piezoelectric Composite Biomaterials
Compared to lead-containing piezoelectric ceramics, which are high in lead content
and prone to pollution, flexible piezoelectric composite biomaterials that balance piezoe-
lectricity and safety are highly favored by medical researchers. The development of these
composite materials holds profound significance for a range of biosensors suitable for bi-
Micromachines 2024, 15, 982 13 of 49

2.4. Flexible Piezoelectric Composite Biomaterials

Compared to lead-containing piezoelectric ceramics, which are high in lead content
and prone to pollution, flexible piezoelectric composite biomaterials that balance piezo-
electricity and safety are highly favored by medical researchers. The development of these
composite materials holds profound significance for a range of biosensors suitable for
biological detection or treatment. Firstly, these materials offer broad application potential in
the biomedical field, such as in implantable medical devices and biosensors. Their degrad-
ability and non-toxicity allow for safe degradation within the body, thereby reducing the
side effects of implants on the human body and lowering the risk of secondary surgeries.
Secondly, their inherent piezoelectric properties enable the conversion of mechanical energy
into electrical energy, making them suitable for self-powered devices and energy harvest-
ing systems, thus enhancing the intelligence and sustainability of medical equipment.
Furthermore, the development of these materials promotes green technology, reduces
environmental pollution, and aligns with the global trend of sustainable development.
Therefore, the research and development of flexible piezoelectric composite biomaterials
are not only poised to bring breakthroughs in both technological and medical fields but
also to foster positive advancements in environmental protection and health.
Yang et al. [94] proposed a flexible composite film based on γ-glycine crystals embed-
ded in a PVA-glycine-PVA structure, as shown in Figure 13a. In this film, strong hydrogen
bonds can form between the oxygen atoms in glycine and the hydroxyl groups on the
PVA chains, leading to the nucleation and growth of γ-glycine as well as the oriented
alignment of electric domains. This structure endows the film with excellent piezoelectric
properties and biocompatibility. Testing revealed that the g33 of the PVA-glycine-PVA
film reached 157.5 × 10− 3 Vm/N, demonstrating piezoelectric performance comparable
to that of commercial PVDF. This makes it suitable for developing transient implantable
electronic devices. Chorsi et al. [95] combined polycaprolactone (PCL) with glycine to
create a stable piezoelectric composite fiber material with an ultrasonic output reaching
up to 334 kPa, as illustrated in Figure 13b. Each fiber in this composite material consists of
uniformly dispersed glycine particles within a PCL matrix. The piezoelectric properties
of glycine, combined with the flexibility of the PCL matrix, give this composite excellent
electromechanical coupling and mechanical flexibility. Studies have shown that this com-
posite material’s ultrasonic transducers can be effectively used for glioblastoma (GBM)
mediated therapy. Among various control groups, the combined treatment mediated by
the glycine-PCL transducer exhibited the best anti-GBM activity, significantly extending
the survival time of mice (up to 72 days) and demonstrating its potential application in
medical auxiliary treatments. Wang et al. [96] fabricated a bio-composite film made of PVA
and glycine using electrospinning, as shown in Figure 13c. This film not only possesses
excellent piezoelectric properties but also has degradable and self-charging capabilities.
During breathing, the airflow deforms the composite material, generating charges through
the piezoelectric effect, which enhances the filter membrane’s ability to adsorb fine particles.
Experiments showed that masks made from the glycine-PVA composite film achieved a fil-
tration efficiency of 97.1% for 0.3 µm particles, providing significant respiratory protection.
Additionally, degradation experiments indicated that these masks could biodegrade in soil
within approximately six weeks, effectively preventing environmental pollution.
Therefore, glycine, as a crystal with unique properties, holds significant advantages
in the development of piezoelectric composite biomaterials. Due to the piezoelectricity,
non-toxicity, and biodegradability of glycine crystals, these bio-composite materials have
made many breakthroughs in the field of implantable medical devices. The appropriate
selection of piezoelectric phase materials is a necessary prerequisite for developing high-
performance, compatible piezoelectric composite biomaterials. According to the existing
literature, piezoelectric glycine is often used as the piezoelectric phase in piezoelectric
composite biomaterials. Glycine’s uniqueness lies in its polymorphic nature as an amino
acid crystal, primarily existing in α, β, and γ crystal structures [97]. Among these, the α
form is non-piezoelectric, while the β and γ forms are noted for their high shear piezoelec-
Micromachines 2024, 15, x FOR PEER REVIEW 14 of 50

Micromachines 2024, 15, 982 14 of 49

the PVA chains, leading to the nucleation and growth of γ-glycine as well as the oriented
alignment of electric domains. This structure endows the film with excellent piezoelectric
properties and biocompatibility. Testing revealed that the g33 of the PVA-glycine-PVA film
tricity and thickness piezoelectricity, respectively. However, inducing and preparing these
reached 157.5 × 10−3 Vm/N, demonstrating piezoelectric performance comparable to that
glycine crystal structures require stringent technical conditions, such as specific thermo-
of commercial PVDF. This makes it suitable for developing transient implantable elec-
dynamic and kinetic conditions. To address this challenge, Zhang et al. [98] proposed an
tronic devices. Chorsi et al. [95] combined polycaprolactone (PCL) with glycine to create
active self-assembly strategy to prepare β-glycine films using electrohydrodynamic spray
a stable piezoelectric composite fiber material with an ultrasonic output reaching up to
methods, as shown in Figure 14. The synergistic effects of nanoscale confinement and
334 kPa, as illustrated in Figure 13b. Each fiber in this composite material consists of uni-
in-situ polarization cause the crystal grains to align in the strongest polarization direction,
formly dispersed glycine particles within a PCL matrix. The piezoelectric properties of
resulting in films with excellent uniform piezoelectricity. Studies found that the d33 of the
glycine,
β-glycinecombined
film is 11.2with theand
pm/V, flexibility of×the
g33 is 252 10−PCL matrix,
3 Vm/N. give this composite
Additionally, the thermalexcellent
stability
electromechanical coupling and
of these films significantly mechanical
improved underflexibility. Studies
the nanoscale have showneffect,
confinement that this com-
reaching
posite material’s
◦ ultrasonic transducers can be effectively used for
up to 192 C. This approach addresses the long-standing challenge of synthesizing large-glioblastoma (GBM)
mediated therapy. Among
scale high-performance various control
piezoelectric groups, the
biomaterials. combined
Beyond treatment
glycine crystals,mediated by
researchers
the glycine-PCL transducer exhibited the best anti-GBM activity, significantly
have discovered high piezoelectricity in molecular crystals such as HOCH2 (CF2 )3 CH2 OH extending
the survival time of mice (up to 72 days)
[2,2,3,3,4,4-hexafluoropentane-1,5-diol and demonstrating
(HFPD)], with a d33 ofits potential application
approximately 138 pC/N in
medical auxiliary treatments.
− 3 Wang et al. [96] fabricated a bio-composite
and g33 up to 2450 × 10 Vm/N, also demonstrating good biocompatibility and safety film made of PVA
and glycine using
for biological cellselectrospinning,
[99]. Moreover, as shown
certain in Figuretissues
biological 13c. This
withfilm not only
special possesses
structures can
excellent piezoelectric properties but also has degradable and self-charging
be used to develop highly compatible piezoelectric biomaterials. The layered structure of capabilities.
During
the smallbreathing, the airflow(SIS)
intestinal submucosa deforms
has been the confirmed
compositetomaterial,
possess weakgenerating charges
piezoelectricity.
through
Zhang etthe al. piezoelectric
[100] used van effect,
der which
Waals enhances
exfoliationtheto filter membrane’s
prepare ability
an ultra-thin SIStofilm
adsorb
and
fine particles.
employed PFM Experiments
technologyshowed
to reveal that
themasks made from theinglycine-PVA
bio-piezoelectricity composite
SIS, with a shear film
piezoelec-
achieved a filtration
tric coefficient of 4.1efficiency of 97.1%
pm/V, showing for 0.3
great μm particles,
potential providing
in developing significant
biosensors, as respir-
shown
atory protection.
in Figure 15. TheseAdditionally,
piezoelectricdegradation
preparation experiments
methods indicated that these
are of profound masks could
significance for
biodegrade in soil within approximately six weeks, effectively preventing
the development of high-performance piezoelectric composite biomaterials, significantly environmental
pollution.
advancing the progress of bio-device development.

Figure 13. (a)

Figure 13. (a) Three-layer
Three-layersandwich-structured
sandwich-structuredPVA-glycine-PVA
PVA-glycine-PVA bio-composite
bio-composite film
film [94].
[94]. (b) (b) Gly-
Glycine-
cine-PCL fiber composite material [95]. (c) A glycine-PVA composite mask
PCL fiber composite material [95]. (c) A glycine-PVA composite mask [96]. [96].

Therefore, glycine, as a crystal with unique properties, holds significant advantages

in the development of piezoelectric composite biomaterials. Due to the piezoelectricity,
non-toxicity, and biodegradability of glycine crystals, these bio-composite materials have
 weak piezoelectricity. Zhang et al. [100] used van der Waals exfoliation to prepare an ul-
tra-thin SIS film and employed PFM technology to reveal the bio-piezoelectricity in SIS,
with a shear piezoelectric coefficient of 4.1 pm/V, showing great potential in developing
biosensors, as shown in Figure 15. These piezoelectric preparation methods are of pro-
Micromachines 2024, 15, 982 found significance for the development of high-performance piezoelectric composite 15bio-
of 49
materials, significantly advancing the progress of bio-device development.

Figure
Figure14.
14.Schematic
Schematicdiagram
diagramof ofthe
theprinciple
principleforforpreparing
preparingβ-glycine
β-glycinepiezoelectric
piezoelectricnanocrystal
nanocrystalfilms
films
using
using a coordinated approach of nanoscale confinement and in-situ polarization [98]. (a)(a)
a coordinated approach of nanoscale confinement and in-situ polarization [98]. Diagram
Diagram of
of the synthesis principle of a bio-organic thin film printer and β-glycine film. (b) Schematic diagram
the synthesis principle of a bio-organic thin film printer and β-glycine film. (b) Schematic diagram of
of the nano microdroplets of glycine solution and its crystallization process. (c) Free energy (ΔGcryst)
the nano microdroplets of glycine solution and its crystallization process. (c) Free energy (∆Gcryst)
Micromachines 2024, 15, x FOR PEERcurve
REVIEWof crystal nucleation as a function of crystal radius r. (d) Size-related free energy distribution 16 of 50
curve of crystal
diagrams nucleation
of the two as a function
competing of crystal radius
nuclei corresponding r. (d) Size-related
to α-glycine free energy
and β-glycine.(e) distribution
Schematic dia-
diagrams of the two competing nuclei corresponding to α-glycine and β-glycine. (e) Schematic
diagram of the orientation arrangement of glycine molecules during the homogeneous nucleation
gram of the
process. (g) orientation arrangement
Photos of the thin film onof a
glycine
4-inchmolecules
silicon waferduring theand
(left) homogeneous
the thin filmnucleation pro-
on a flexible
cess. (g) Photos of the thin film on a 4-inch silicon wafer (left) and the thin film on
gold-plated polyethylene terephthalate (PET) substrate (right). (f) Schematic of the film formationa flexible gold-
plated polyethylene
process showing the terephthalate (PET) substrate
compact nanograins (right).
with uniform and(f)consistent
Schematic polarization
of the film formation process
orientation (red
showing the compact nanograins with uniform and consistent polarization orientation (red spot and
spot and red arrow in nanograins). The top two images are the surface view of the films, and the
red arrow in nanograins). The top two images are the surface view of the films, and the bottom
bottom image is the cross-sectional view.
image is the cross-sectional view.

Figure 15. Process flow for preparing SIS thin films and PFM sample preparation [100].
Figure 15. Process flow for preparing SIS thin films and PFM sample preparation [100].

3. Fabrication Process of Flexible Piezoelectric Composite Materials

3.1. Fabrication Process
3.1.1. Molding by Hot Pressing
The fundamental concept of hot pressing molding [101,102] involves melting the pol-
ymer into a solution in a high-temperature environment, then blending it with piezoelec-
tric material powder, and subsequently mechanically shaping it. Finally, the formed ma-
terial needs to undergo polarization before it can be used. This processing method offers
the advantages of one-time molding, pore-free material, and suitability for industrial pro-
duction. Currently, it is widely employed in the preparation of 0-3 series flexible piezoe-
Micromachines 2024, 15, 982 16 of 49

3. Fabrication Process of Flexible Piezoelectric Composite Materials

3.1. Fabrication Process
3.1.1. Molding by Hot Pressing
The fundamental concept of hot pressing molding [101,102] involves melting the poly-
mer into a solution in a high-temperature environment, then blending it with piezoelectric
material powder, and subsequently mechanically shaping it. Finally, the formed material
needs to undergo polarization before it can be used. This processing method offers the
advantages of one-time molding, pore-free material, and suitability for industrial produc-
tion. Currently, it is widely employed in the preparation of 0-3 series flexible piezoelectric
composite materials, as illustrated in the preparation process depicted in Figure 16. Fur-
thermore, due to variations in melting points among different polymers, this process offers
a high degree of temperature selectivity. Wang et al. [103] fabricated 0-3 rubber-based
damping composite materials using hot pressing molding and assessed various properties,
including cross-sectional morphology and piezoelectric strain coefficient. Figure 17 shows
the micrographs of 0-3 rubber-based damping composite materials at different magnifi-
cations. The experiments demonstrated that the PZT piezoelectric ceramic powder was
well dispersed in the rubber matrix material, exhibiting good compatibility. Moreover, the
piezoelectric effect of PZT significantly contributed to enhancing the damping performance
of 0-3 composite materials. Utilizing this method to prepare flexible piezoelectric compos-
ite materials offers the advantages of simplicity and high yield. However, there may
Micromachines 2024, 15, x FOR PEER REVIEW
be
17 of 50
Micromachines 2024, 15, x FOR PEER REVIEW 17 of 50
instances of piezoelectric particle agglomeration, potentially impacting the piezoelectric
performance of the composite material.

16. Schematic diagram of preparing flexible piezoelectric composite material film by hot
Figure 16.
16.
Figure Schematic diagram of preparing flexible piezoelectric composite material film by hot
pressing method.
pressing method.
method.
pressing

Figure 17. Cont.

Micromachines 2024, 15, 982 17 of 49

Figure 17.
Figure Microscopicimages
17. Microscopic images
of of
0-30-3 rubber-based
rubber-based damping
damping materials
materials at different
at different magnifica-
magnifications
[103].
tions [103].

3.1.2. Electrospinning
3.1.2. Electrospinning
Electrospinning is
Electrospinning is aa process
process that
that employs
employs an
an electric
electric field
field to
to produce
produce nanofibers
nanofibers from
from
polymer solutions. This technique has matured with continuous improvements
polymer solutions. This technique has matured with continuous improvements and tech- and tech-
nological advancements [104–106]. Electrospinning is suitable for producing fiber-based
nological advancements [104–106]. Electrospinning is suitable for producing fiber-based
piezoelectric composite material films and is also crucial for developing highly flexible
piezoelectric composite material films and is also crucial for developing highly flexible
nanogenerators. Figure 18 illustrates the schematic diagram of an electrospinning appara-
nanogenerators. Figure 18 illustrates the schematic diagram of an electrospinning appa-
tus [107], consisting of three components: a high-voltage power supply module, a syringe
pump module, and a collector module. In the electrospinning process, the high-voltage
power supply is connected to both the syringe pump module and the collector module
to create an electric potential difference. When the spinning solution exits the needle, a
droplet forms at the tip, which deforms under the influence of electrostatic forces from the
electric field. As the electric field strength increases, the droplet gradually forms a Taylor
cone before being deposited onto the collector plate. During flight, the jet is also subjected
to the electric field force. Accelerating flight decreases the jet diameter, and the solvent
in the jet evaporates to form fibers during flight, which are ultimately collected by the
receiving system. It is worth noting that according to Su [107], electrospinning is influenced
by six factors: electric field strength, infusion rate, distance to the receiving end, roller
speed, polymer concentration, solution viscosity, and environmental factors. These factors
directly affect fiber structure size, product quality, and spinning efficiency. Chen et al. [108]
developed a PVDF/PDMS composite film using electrospinning technology, as shown
in Figure 19. This composite film can withstand various forms of deformation, such as
stretching and bending while maintaining high flexibility and exhibiting excellent elec-
tromechanical conversion efficiency. Experimental results revealed that this composite film
possesses an outstanding electrical response, with a maximum power density of up to
286 mW/m2 . Moreover, after 5000 test cycles, the composite film showed no significant
damage or interlayer separation, demonstrating its durability and stability. Luo et al. [109]
reported a sandwich-structured piezoelectric nanocomposite film with high voltage and
sensitivity. This film was fabricated by electrospinning a mixture of P(VDF-TrFE), tin
oxide (SnO2 ) nanoparticles, and graphene (GR). The rational doping of conductive fillers
facilitated the synthesis of the β phase in P(VDF-TrFE), endowing the composite film with
superior piezoelectric properties. Tests showed that the sensor made from this composite
film achieved a maximum instantaneous output power of 64.578 µW and an open-circuit
voltage peak of 22.43 V. Additionally, this sensor can charge a capacitor, enabling it to
power a commercial LCD thermometer or approximately 80 LED lights for about 1.6 s,
providing a potential solution for the development of self-powered devices.
 cilitated the synthesis of the β phase in P(VDF-TrFE), endowing the composite film with
superior piezoelectric properties. Tests showed that the sensor made from this composite
film achieved a maximum instantaneous output power of 64.578 μW and an open-circuit
voltage peak of 22.43 V. Additionally, this sensor can charge a capacitor, enabling it to
Micromachines 2024, 15, 982 power a commercial LCD thermometer or approximately 80 LED lights for about181.6 s,
of 49
providing a potential solution for the development of self-powered devices.

Micromachines 2024, 15, x FOR PEER REVIEW 19 of 50

Figure 18. Schematic
Figure18. Schematic diagram
diagram of
of electrospinning
electrospinningapparatus
apparatus[91].
[91].

(A) (B) (C)

Figure 19.
Figure 19. PVDF/PDMS
PVDF/PDMS composite
composite film
film prepared
prepared byby electrospinning
electrospinning [108]. ((A)
((A) Picture
Picture of
of
PVDF/PDMS composite film under tension. (B) Picture of PVDF/PDMS composite
PVDF/PDMS composite film under tension. (B) Picture of PVDF/PDMS composite film underfilm under fold-
ing. (C) Microscopic
folding. images
(C) Microscopic of PVDF/PDMS
images of PVDF/PDMS composite films.).
composite films.).

3.1.3.
3.1.3. Electrospray Deposition
Electrospray
Electrospray deposition
depositionisisaamaterial
materialpreparation
preparationtechnique
techniquethat thatuses
uses voltage
voltage to to
atom-
at-
ize a solution
omize or suspension
a solution or suspension intointo
fine fine
droplets, which
droplets, are then
which deposited
are then ontoonto
deposited a substrate.
a sub-
By controlling
strate. conditions
By controlling such as
conditions suchtheaselectric field field
the electric and flow rate, rate,
and flow this this
method
methodcan can
pre-
cisely form
precisely uniform
form uniformthinthin
films andand
films nanoparticles. It offers
nanoparticles. high
It offers flexibility,
high uniformity,
flexibility, uniformity, and
adaptability.
and adaptability.Similar to the
Similar to electrospinning
the electrospinning method
methodmentioned,
mentioned, both techniques
both techniques control
con-
the deposition behavior of liquids through an electric field. The electrospray
trol the deposition behavior of liquids through an electric field. The electrospray deposi- deposition
process is relatively
tion process simple
is relatively and consists
simple of several
and consists steps: steps:
of several First, dissolve the polymer
First, dissolve matrix
the polymer
material in a solvent
matrix material and addand
in a solvent piezoelectric particles,
add piezoelectric ensuringensuring
particles, they aretheyevenly
aredispersed
evenly dis- in
the mixture.
persed in theNext, loadNext,
mixture. the prepared
load the solution
preparedinto the syringe
solution of syringe
into the the electrospray apparatus,
of the electrospray
adjusting
apparatus,the instrument
adjusting parametersparameters
the instrument to meet thetorequirements for thin film
meet the requirements fordeposition.
thin film
Then, activate the electrospray device; under the influence of an external
deposition. Then, activate the electrospray device; under the influence of an external elec- electric field,
the liquid forms a Taylor cone and is ejected as fine droplets, allowing
tric field, the liquid forms a Taylor cone and is ejected as fine droplets, allowing the mate- the material to
be uniformly deposited in the designated area. A schematic diagram
rial to be uniformly deposited in the designated area. A schematic diagram of the elec- of the electrospray
deposition principle principle
trospray deposition is shown is inshown
Figurein 20Figure
[110]. 20 [110].
 persed in the mixture. Next, load the prepared solution into the syringe of the electrospray
apparatus, adjusting the instrument parameters to meet the requirements for thin film
deposition. Then, activate the electrospray device; under the influence of an external elec-
tric field, the liquid forms a Taylor cone and is ejected as fine droplets, allowing the mate-
Micromachines 2024, 15, 982
rial to be uniformly deposited in the designated area. A schematic diagram of the19elec- of 49
trospray deposition principle is shown in Figure 20 [110].

Figure 20. Schematic diagram of the principle of electrospray deposition method [110].

One major
One major advantage
advantage of of this
this technique
technique is is its
its ability
ability to
to achieve
achieve uniform
uniform and
and large-area
large-area
material preparation, making it highly promising for developing
material preparation, making it highly promising for developing composite material composite material films.
Li et al.
films. Li [110]
et al. utilized electrospray
[110] utilized deposition
electrospray to create
deposition a hierarchically
to create interconnected
a hierarchically intercon-
piezoelectric composite textile (HIPCT) composed of PZT ceramic
nected piezoelectric composite textile (HIPCT) composed of PZT ceramic and P(VDF- and P(VDF-TrFE), as
shown in Figure 21a. This HIPCT exhibits high flexibility and can bend
TrFE), as shown in Figure 21a. This HIPCT exhibits high flexibility and can bend around around a pen. The
Micromachines 2024, 15, x FOR PEER researchers
REVIEW tested the HIPCT’s superior voltage response characteristics, 20 of in
as illustrated 50
a pen. The researchers tested the HIPCT’s superior voltage response characteristics, as
Figure 21b.inUnder
illustrated Figurea21b.pressure
Underofa 2.2 MPa and
pressure of 2.2a MPa
frequency of 30 Hz, the
and a frequency HIPCT
of 30 achieved
Hz, the HIPCT
a power density of approximately 200 µW cm − 2 at around 1 MΩ. Furthermore, under
achieved a power density of approximately 200 μW cm−2 at around 1 MΩ. Furthermore,
aunder
compressive load excitation
a compressive of 1 MPa
load excitation of 1 and
MPa30 andHz,30the
Hz,HIPCT could
the HIPCT charge
could capacitors
charge capac-
of 4.7of
itors and
µF4.7 μF10andµF10toμF
1.4toV1.4
andV 0.7andV,0.7
respectively, within
V, respectively, 60 s, 60
within fully demonstrating
s, fully demonstrating the
practical value
the practical of HIPCT
value in developing
of HIPCT in developingenergy harvesting
energy sensors.
harvesting sensors.

Figure (a)Photographs
Figure 21. (a) PhotographsofofHIPCT
HIPCTsamples
samples prepared
prepared byby electro-spray
electro-spray deposition
deposition andand
theirtheir
mi-
microstructures.
crostructures. (b)(b) Voltage
Voltage response
response test
test curve
curve ofof HIPCT
HIPCT [110].
[110].

Additionally,
Additionally,electrospray
electrospraydeposition
depositioncancanbe
beused
usedtotoprepare
preparethermal
thermalinterface
interfacemateri-
mate-
als. Avcıo
rials. ğlu et et
Avcıoğlu al.al.
[111] employed
[111] employed thisthis
method to fabricate
method an aluminum
to fabricate an aluminum nitride (AlN)-PVA
nitride (AlN)-
composite
PVA compositeand tested its thermal
and tested properties.
its thermal Figure
properties. Figure2222
shows
showsthermal
thermalimages
imagesof ofthree
three
samples with different AlN-PVA spray durations on graphite foil after heating
samples with different AlN-PVA spray durations on graphite foil after heating for 70 for 70 s. Thes.
“Uncoated Substrate” represents an aluminum alloy substrate without
The “Uncoated Substrate” represents an aluminum alloy substrate without any coating,any coating, while
while “AlN-15” and “AlN-30” represent samples sprayed with AlN-PVA material for 15
and 30 min, respectively. The study found that aluminum alloy substrates coated with
AlN-PVA material exhibited higher temperatures, which would promote better heat pen-
etration and diffusion in the aluminum alloy substrate. The AlN-15 sample showed the
highest thermal diffusivity, reaching up to 38.767 mm2/s, which is nearly a 30% improve-
Micromachines 2024, 15, 982 20 of 49

“AlN-15” and “AlN-30” represent samples sprayed with AlN-PVA material for 15 and
30 min, respectively. The study found that aluminum alloy substrates coated with AlN-PVA
material exhibited higher temperatures, which would promote better heat penetration and
diffusion in the aluminum alloy substrate. The AlN-15 sample showed the highest thermal
diffusivity, reaching up to 38.767 mm2 /s, which is nearly a 30% improvement compared to
Micromachines 2024, 15, x FOR PEER REVIEW 21 of 50
the uncoated aluminum alloy substrate (26.638 mm2 /s), confirming the value of AlN-PVA
in thermal interface applications.

Figure22.
Figure 22. Thermal
Thermal images
images of
of three
three samples
samples with
with different
different AlN-PVA
AlN-PVA spraying
spraying durations
durations (uncoated,
(uncoated,
sprayed for 15 min, and sprayed for 30 min) heated on graphite foil for 70 s [111].
sprayed for 15 min, and sprayed for 30 min) heated on graphite foil for 70 s [111].

3.1.4.
3.1.4. Dice-Fill
Dice-Fill
The
Thedice-fill
dice-fillmethod
methodcan canbebeused
usedtotoprepare
prepare1-3 1-3types
typesofofflexible
flexiblepiezoelectric
piezoelectriccompos-
compo-
ite
sitematerials,
materials,which
whichnotnotonly
onlyhave
haveaasimple
simpleprocess
processand andshort
shortprocessing
processingcyclecycle but
but also
also
can
can achieve large-sized composite material samples. The basic steps of this process areare
achieve large-sized composite material samples. The basic steps of this process as
as follows:
follows: First,
First, thethe polarized
polarized piezoelectric
piezoelectric material
material is cut
is cut along
along parallel
parallel andand perpendic-
perpendicular
ular directions
directions to form
to form a cutting
a cutting framework.
framework. Second,
Second, the cutting
the cutting framework
framework is washed
is washed with
with chemical reagents such as ethanol and dried. After that, a certain
chemical reagents such as ethanol and dried. After that, a certain amount of flexible amount of flexible
poly-
polymer solution
mer solution is uniformly
is uniformly injected
injected intointo the cutting
the cutting framework,
framework, followed
followed by vacuum
by vacuum cur-
curing. Then, the cured preliminary product is cut into a base and
ing. Then, the cured preliminary product is cut into a base and polished. Finally, metal polished. Finally,
metal electrodes
electrodes are placed
are placed on the onupper
the upper and lower
and lower surfaces
surfaces of the ofsample
the sample to complete
to complete the
the fab-
fabrication of the composite material, as shown in the schematic diagram
rication of the composite material, as shown in the schematic diagram of the specific pro- of the specific
process in Figure
cess in Figure 23a.23a. Given
Given thatthat the cutting
the cutting gap gap is directly
is directly generated
generated by thebyblade,
the blade, the
the dice-
dice-fill
fill method has a high requirement for the accuracy of the blade. Figure 23b shows the
method has a high requirement for the accuracy of the blade. Figure 23b shows the
PZT-rubber 1-3 type piezoelectric composite material fabricated by the dice-fill method [87].
PZT-rubber 1-3 type piezoelectric composite material fabricated by the dice-fill method
Due to the integral segmentation and shaping of the entire piezoelectric ceramic, each
[87]. Due to the integral segmentation and shaping of the entire piezoelectric ceramic, each
piezoelectric unit has highly similar structural characteristics, thus ensuring a high level of
piezoelectric unit has highly similar structural characteristics, thus ensuring a high level
consistency. Additionally, flexible polymers such as rubber can meet the bending capability
of consistency. Additionally, flexible polymers such as rubber can meet the bending capa-
of the composite material, making it highly suitable for the development of flexible array
bility of the composite material, making it highly suitable for the development of flexible
transducers. Hao et al. [87] pointed out that the reliability of the electrodes is a key factor
array transducers. Hao et al. [87] pointed out that the reliability of the electrodes is a key
affecting the 1-3 flexible piezoelectric composite materials. For 1-3 flexible piezoelectric
factor affecting the 1-3 flexible piezoelectric composite materials. For 1-3 flexible piezoe-
composite materials, traditional rigid electrode layers are prone to breakage during bend-
lectric composite materials, traditional rigid electrode layers are prone to breakage during
ing, making it difficult to adapt to the material’s bending deformation. Therefore, the
bending, making it difficult to adapt to the material’s bending deformation. Therefore, the
development of adaptive flexible electrodes to meet the interconnection of piezoelectric
development of adaptive flexible electrodes to meet the interconnection of piezoelectric
units is also a key factor affecting the material’s performance.
units is also a key factor affecting the material’s performance.
Micromachines 2024, 15, x FOR PEER REVIEW 22 of 50
Micromachines 2024,
Micromachines 2024, 15,
15, 982
x FOR PEER REVIEW 22
21 of 50
of 49

Figure 23. (a) Schematic diagram of the dice-fill process; (b) Interconnected electrode structure of 1-
Figure
3Figure 23.piezoelectric
flexible
23. (a)
(a) Schematic diagram
diagramof
composite
Schematic ofthe
thedice-fill
materials [87].process;
dice-fill process;(b)
(b)Interconnected electrode
Interconnected structure
electrode of of
structure 1-
3 flexible piezoelectric composite materials [87].
1-3 flexible piezoelectric composite materials [87].
3.1.5. Injection-Molding
3.1.5. Injection-Molding
The injection-molding method involves the preparation of piezoelectric composite
injection-molding method involves the preparation of
The injection-molding of piezoelectric
piezoelectric composite
composite
materials through ceramic injection, which is suitable for processing fine piezoelectric ce-
materials through
through ceramic
ceramicinjection,
injection,which
whichisissuitable
suitable forfor
processing
processing finefine
piezoelectric
piezoelectric ce-
ramic fiber composites [13,15,112,113]. The basic idea is to inject a mixture of a slurry of
ramic fiber
ceramic fibercomposites
composites[13,15,112,113].
[13,15,112,113].The Thebasic
basicideaideaisistotoinject
injectaamixture
mixture of of a slurry of
piezoelectric ceramics and adhesive powder into the corresponding mold. After drying
piezoelectric
piezoelectric ceramics and adhesive adhesive powder into into thethe corresponding
corresponding mold. mold. After dryingdrying
and burning off the mold, inject a certain amount of polymer. Then, polish the finished
and burning off the mold, inject a certain amount
mold, inject a certain amount of polymer. of polymer. Then, polish the finished
finished
product, and plate electrodes on the upper and lower surfaces of the material, finally ob-
product,
product, and and plate
plate electrodes
electrodeson onthetheupper
upperand and lower
lower surfaces
surfaces of the
of the material,
material, finally
finally ob-
taining
obtaining
the material product. The yield of the material produced by this method is rela-
taining thethe material
material product.
product. TheTheyieldyield
of the of material
the material produced
produced by method
by this this method is
is rela-
tively high,
relatively andand
high, the shape andand
the shape structure of the
structure piezoelectric
of piezoelectric
the piezoelectric phase
phase can be becontrolled bybythe
tively high, and the shape and structure of the phase can can controlled
be controlled by the
mold.
the However,
mold. However, in recent years,
in recent the literature
years, on this process has mostly focused onon1-3
mold. However, in recent years, the the literature
literature on this
on this process
process has has mostly
mostly focused
focused on 1-3
PZT/epoxy
1-3 PZT/epoxy composite materials
composite [114–116],
materials [114–116],indicating
indicating potential for
potential the development
fordevelopment
the development of 1-
PZT/epoxy composite materials [114–116], indicating potential for the of 1-
3offlexible seriesseries
1-3 flexible piezoelectric composite
piezoelectric materials.
composite materials.The specific process
The specific of injection
process mold-
of injection
3 flexible series piezoelectric composite materials. The specific process of injection mold-
ing is
molding shownis in
shown Figure
in 24.
Figure Figure
24. 25
Figure shows
25 the
shows piezoelectric
the ceramic
piezoelectric
ing is shown in Figure 24. Figure 25 shows the piezoelectric ceramic micro-pillar struc- micro-pillar
ceramic struc-
micro-pillar
tures with
structures
tures with withhigh aspect
high high
aspect ratios
aspect prepared
ratiosratios by
prepared
prepared Park
by Park by et et
Parkal.
al. et[112] using
al. [112]
[112] usingusinginjection molding.
injection
injection molding. They
molding.
They
found
They that
foundfound the
that the injection
thatinjection speed
the injection was
speedspeed crucial for
was crucial
was crucial the
for the successful
forsuccessful
the successful formation
formation
formation of the
of the ceramic
of ceramic
the ceramic mi-
mi-
cro-pillars.
cro-pillars. Based
micro-pillars. Based
Based on
on rheological
on rheological
rheological analysis, the injection
analysis,
analysis, the injection
the injection molding
molding wascarried
molding
was carried
was outatatout
carried
out aaspeed
speed
at a
of 140
speed mm/s,
of 140 ensuring
mm/s, that
ensuring the microcavities
that the microcavitiesin theinmold
the were
mold completely
were
of 140 mm/s, ensuring that the microcavities in the mold were completely filled with the completely filled with
filled the
with
raw
the material.
raw material.
raw material.

Figure
Figure 24.
Figure 24. Schematic
24. Schematic diagram
Schematic of the
diagram of injection-moldingprocess
the injection-molding
injection-molding process[112].
process [112].
[112].
Micromachines 2024,15,
Micromachines 2024,
Micromachines 15,x982
xFOR
FORPEER
PEERREVIEW
REVIEW 23
49 of 50
2322ofof 50

Figure 25. Microscope image of the prepared piezoelectric ceramic micro-pillar structures [112].
Figure25.
Figure 25.Microscope
Microscope image
image of the
of the prepared
prepared piezoelectric
piezoelectric ceramic
ceramic micro-pillar
micro-pillar structures
structures [112]. [112].
3.1.6.
3.1.6. Freeze-Casting
3.1.6.Freeze-Casting
Freeze-Casting
The
The freeze-casting
freeze-casting method,
method, also also known
known as as freeze
freeze alignment
alignment technology,
technology, is is aa material
material
The
preparation freeze-casting method, also known as freeze alignment technology, in is aori-
material
preparation process
processthat thatuses
usesthe theanisotropic
anisotropic solidification
solidification behavior
behavior of solvents
of solvents anin an
preparation
ented temperatureprocessfield that
as auses
templatethe anisotropic
to control solidification
the shaping of behavior
piezoelectric of solvents
particles in
in an
a ori-
oriented temperature field as a template to control the shaping of piezoelectric particles
ented
slurry. temperature
This technique field as a
is commonly template to control
used touseddevelop the shaping
piezoelectric of piezoelectric
ceramicsceramics particles
with porous in a
in a slurry. This technique is commonly to develop piezoelectric with
slurry.structures,
structures,
porous This technique
offering is advantages
advantages
offering commonly used
such as controllable
such as to controllable
develop
porosity,piezoelectric
high flexibility,
porosity, highceramicsand with
cost-ef-
flexibility, andporous
structures,
fectiveness. offering
Figure 26 advantages
illustrates thesuch as
general controllable
process of porosity,
preparing
cost-effectiveness. Figure 26 illustrates the general process of preparing flexible porous high
flexible flexibility,
porous and
Barium cost-ef-
fectiveness.
Calcium
Barium CalciumFigure
Zirconate 26 illustrates
Titanate
Zirconate (BCZT)/PDMS
Titanate the general process
composites
(BCZT)/PDMS of preparing
using
composites theusing flexible
freeze-casting porous
method
the freeze-casting Barium
Calcium
[117].
method First, Zirconate
a mold
[117]. Titanate
First,designed
a mold designed(BCZT)/PDMS
for freeze-casting composites
is created is
for freeze-casting using
to shape
created the tofreeze-casting
the BCZT the
shape ceramics.
BCZT method
[117].a First,
Next,
ceramics. Next,a mold
suspension of designed
BCZT ceramics
a suspension for freeze-casting
of BCZT and waterand
ceramics iswater
is pouredcreatedinto
is toa shape
poured PDMS intothe
mold, BCZT
a PDMS which ceramics.
mold, is
then
which placed
Next, isatheninplaced
a liquid
suspension nitrogen
inof container
BCZT nitrogen
a liquid to be water
ceramicscontainer
and cooled
to be isand frozen.
poured
cooled and The
into asuspension
frozen. PDMS mold,freezes
The suspension which is
from
thenthe
freezes bottom
from
placed in up,
the and the
abottom
liquid up,solvent
and the
nitrogen solidifies
solventto
container into
beacooled
porous
solidifies intostructure
and a porous
frozen. due to its
structure
The anisotropic
due to its
suspension freezes
properties.
anisotropic Once
from the bottom the
up,solvent
properties. Once
and thesublimates,
the solvent
solvent the porousinto aBCZT
sublimates,
solidifies the ceramic
porous
porous BCZT
structurestructure
due toisits
ceramic formed.
structure
anisotropic
isproperties.
formed.
Finally, theFinally,
BCZT the
theBCZT
Onceceramics are
solvent ceramics
polarized, areand
sublimates, polarized,
the porous
the PDMS andpolymer
the
BCZT PDMS polymer
is filled
ceramic into is
the
structurefilled isinto
ceramic formed.
the ceramic
pores. pores.
Electrodes Electrodes
are prepared are
on prepared
the top on
and the
bottomtop and bottom
surfaces
Finally, the BCZT ceramics are polarized, and the PDMS polymer is filled into the ceramic of surfaces
the sample, of the sample,
completing
completing
the preparation
pores. the preparation
Electrodesof the
areflexible of BCZT/PDMS
prepared the onflexible
the topBCZT/PDMS
composite
and bottom composite
surfaces material.
material. of the sample, completing
the preparation of the flexible BCZT/PDMS composite material.

Figure
Figure 26.
26. Process
Process flowchart
flowchart for
for preparing
preparing flexible BCZT/PDMS
BCZT/PDMScomposites
compositesusing
usingthe
thefreeze-casting
freeze-casting
method [117].
method [117].
Figure 26. Process flowchart for preparing flexible BCZT/PDMS composites using the freeze-casting
Figure 27a shows a sample of the BCZT/PDMS composite material prepared using
method [117].
the freeze-casting method. Yan et al. [117] pointed out that the piezoelectric composite
Figure 27a shows a sample of the BCZT/PDMS composite material prepared using
the freeze-casting method. Yan et al. [117] pointed out that the piezoelectric composite
Micromachines 2024, 15, 982 23 of 49

Micromachines 2024, 15, x FOR PEER REVIEW 24 of 50

Figure 27a shows a sample of the BCZT/PDMS composite material prepared using the
freeze-casting method. Yan et al. [117] pointed out that the piezoelectric composite materials
prepared by this method exhibit a high piezoelectric coefficient due to the dense porous
materials prepared
structure by this method
in the composite, which exhibit a high piezoelectric
effectively coefficient
transfers applied stressduetotothe
the piezoelectric
dense
porous Tests
phase. structure
haveinshown
the composite,
that the which
BCZT/PDMS effectively transfers material
composite applied stress to the piezo-
can achieve a maximum
delectric
33 of phase.
434 pC/N.TestsAdditionally,
have shown that withtheaBCZT/PDMS
porosity of composite
60 vol%, material
the can achieve
piezoelectric a
composite
maximum d 33 of 434 pC/N. Additionally, with a porosity of 60 vol%, the
material demonstrates a maximum power density of 96.2 µW/cm , showcasing its excellent 2 piezoelectric com-
posite material demonstrates a maximum power density of 96.2 μW/cm2, showcasing its
piezoelectric response and potential for use as an energy harvesting device. Xie et al. [118]
excellent piezoelectric response and potential for use as an energy harvesting device. Xie
used the freeze-casting method to fabricate a layered PZT structure and combined it with a
et al. [118] used the freeze-casting method to fabricate a layered PZT structure and com-
PDMS matrix to create a flexible PZT/PDMS piezoelectric composite material, as shown in
bined it with a PDMS matrix to create a flexible PZT/PDMS piezoelectric composite ma-
Figure
terial, as27b.
shownThey in found that They
Figure 27b. whenfoundthe porosity
that when reached 50 vol%,
the porosity the d50
reached of thethe
33 vol%, PZT/PDMS
d33
composite
of the PZT/PDMS composite material was as high as 750 pC/N, nearly 110% of that ceramics.
material was as high as 750 pC/N, nearly 110% of that of dense of
Furthermore,
dense ceramics.the material maintained
Furthermore, the material a high d33 value
maintained even
a high d33when
value bent
even towhena radius of about
bent to
10 mm, indicating
a radius of about 10 mm, goodindicating
piezoelectricgood performance and mechanical
piezoelectric performance flexibility.flex-
and mechanical The mold
used
ibility.inThethe freeze-casting
mold method largely
used in the freeze-casting determines
method the structure
largely determines of the piezoelectric
the structure of the
ceramics.
piezoelectric Byceramics.
adjusting Bythe mold structure,
adjusting PZT canPZT
the mold structure, be made
can beinto made various shapes such
into various
as rectangular,
shapes circular, and
such as rectangular, square,
circular, andoffering
square, a selective
offering processprocess
a selective compared to thetodice-fill
compared
the dice-fillHowever,
method. method. However,
this is notthisthe
is not the only
only wayway to alter
to alter thetheceramic
ceramicstructure.
structure. Some-
Sometimes,
times, changing
changing the direction
the direction of solvent
of solvent solidification(cooling
solidification (cooling conditions)
conditions)can canalso pro-
also produce
duce different
different porous porous structures
structures in the
in the ceramics.
ceramics. Fukushimaetetal.al.[119]
Fukushima [119]used
usedthe the freeze-casting
freeze-
casting method
method to createto create
3-1 and3-13-2
andconnected
3-2 connected alkali
alkali niobate
niobate ceramics(NKN)/epoxy
ceramics (NKN) /epoxy com- composites,
posites, as shown in Figure 28. The researchers employed
as shown in Figure 28. The researchers employed different cooling schemes for different cooling schemes forthe two
the two structures: for the 3-1 structure, they contacted the bottom aluminum foil of the
structures: for the 3-1 structure, they contacted the bottom aluminum foil of the mold with a
mold with a cooling ethanol bath and insulated the sides with polyurethane to prevent
cooling ethanol bath and insulated the sides with polyurethane to prevent tert-butyl alcohol
tert-butyl alcohol (TBA) from solidifying from the sides. Conversely, for the 3-2 structure,
(TBA) from solidifying from the sides. Conversely, for the 3-2 structure, they insulated the
they insulated the top and bottom of a tubular aluminum mold with the same polyure-
top and bottom of a tubular aluminum mold with the same polyurethane and used cold
thane and used cold air in an incubator to cool the TBA from the sides. This resulted in
air in
differentan connectivity
incubator tostructures
cool the in TBA from ceramics
the NKN the sides.despite
This resulted in different
using a similar connectivity
mold. There-
structures in the NKN ceramics despite using a similar mold. Therefore,
fore, the freeze-casting method offers considerable flexibility in preparing porous ceram- the freeze-casting
method
ics. Whenoffers considerable
developing flexible flexibility
piezoelectric incomposites
preparing with porous ceramics.
porous When
structures, developing
altering
flexible
the cooling piezoelectric
conditions composites
to achieve the with
desiredporous structures,
porous ceramic altering
structurethe cooling
is also conditions
a viable ap- to
achieve
proach worththe desired porous ceramic structure is also a viable approach worth considering.
considering.

Figure 27. (a) Sample image of BCZT/PDMS composite material prepared using the freeze-casting
method [117]. (b) PZT/PDMS composite material samples with different ceramic structures and their
morphology characterization under a microscope [118].
Micromachines 2024, 15, x FOR PEER REVIEW 25 of 50

Figure 27. (a) Sample image of BCZT/PDMS composite material prepared using the freeze-casting
Micromachines 2024, 15, 982 method [117]. (b) PZT/PDMS composite material samples with different ceramic structures and
24 of 49
their morphology characterization under a microscope [118].

Figure 28.
Figure 28. Micrographs
Micrographsofof3-1
3-1type
type(A)
(A)and
and3-2
3-2type
type
(B)(B) NKN/epoxycomposites
NKN/epoxy composites were
were prepared
prepared us-
using
ing the freeze-casting method with different cooling approaches
the freeze-casting method with different cooling approaches [119]. [119].

3.1.7.
3.1.7. 3D
3D Printing
Printing
3D
3D printing,
printing, also
also known
known as as additive
additive manufacturing
manufacturing (AM), (AM), is an emerging
is an emerging technology
technology
that
that rapidly
rapidly fabricates
fabricates materials
materials byby stacking
stacking layers
layers of of material.
material. Compared
Compared to to traditional
traditional
manufacturing methods, 3D printing technology offers advantages
manufacturing methods, 3D printing technology offers advantages such as high precision,such as high precision,
high efficiency, and low cost. In recent years, it has become increasingly
high efficiency, and low cost. In recent years, it has become increasingly active in active in the
the re-
re-
search of various piezoelectric composite materials. Grinberg et al. [120]
search of various piezoelectric composite materials. Grinberg et al. [120] introduced a introduced a basic
procedure
basic procedurefor using
for 3D printing
using to create
3D printing to BTO/polyamide
create BTO/polyamide composites (BTO/polyamide
composites (BTO/poly-
type); this is shown in Figure 29. The procedure is performed
amide type); this is shown in Figure 29. The procedure is performed as follows:as follows: Firstly, aFirstly,
solutiona
casting
solutionmethod
casting is used to
method dissolve
is used thermoplastic
to dissolve polyamide
thermoplastic 11 (PA11)
polyamide in dimethylac-
11 (PA11) in dime-
etamide at high temperatures. Pre-measured BTO powder
thylacetamide at high temperatures. Pre-measured BTO powder is then added is then added and the mixture
and theis
ultrasonically treated to ensure uniform dispersion of the particles in the solution. Secondly,
mixture is ultrasonically treated to ensure uniform dispersion of the particles in the solu-
the solution is filtered and washed with deionized water, then placed in a high-temperature
tion. Secondly, the solution is filtered and washed with deionized water, then placed in a
environment to evaporate the solvent. Thirdly, the resulting thin film material is hot-pressed
high-temperature environment to evaporate the solvent. Thirdly, the resulting thin film
to gradually melt the composite material under high-temperature conditions. Fourthly,
material is hot-pressed to gradually melt the composite material under high-temperature
the molten polymer is extruded through a low-temperature mold and cut to the required
conditions. Fourthly, the molten polymer is extruded through a low-temperature mold
length before being fed into the 3D printer. Finally, the printing parameters are adjusted
and cut to the required length before being fed into the 3D printer. Finally, the printing
to ensure the composite material is evenly deposited, completing the 3D printing of the
parameters are adjusted to ensure the composite material is evenly deposited, completing
composite material. Figure 30a shows a photograph of the processed BTO/polyamide-type
the 3D printing of the composite material. Figure 30a shows a photograph of the processed
sample. The preparation of pre-assembled materials is quite rigorous before 3D printing,
BTO/polyamide-type sample. The preparation of pre-assembled materials is quite rigor-
as it affects the printing results and material properties of the composite. Grinberg et al.
ous before 3D printing, as it affects the printing results and material properties of the com-
emphasized that there is a trade-off between the mechanical flexibility and the electrome-
posite. Grinberg
chanical responseetofal.the
emphasized
compositethat there isAa lower
material. trade-off between
volume the mechanical
fraction flexi-
of piezoelectric
particles results in better flexibility of the composite, while a higher volume fractionfrac-
bility and the electromechanical response of the composite material. A lower volume can
tion of piezoelectric particles results in better flexibility of the composite,
improve its electromechanical response. Therefore, reasonably adjusting the proportion while a higher
volume
of fraction caninimprove
each component its electromechanical
the flexible piezoelectric composite response. Therefore,
material is keyreasonably
to influencingad-
justing the
its performance.proportion of each component in the flexible piezoelectric composite material
is key to influencing
Additionally, oneits
ofperformance.
the major highlights of 3D printing technology is its ability to man-
ufacture extremely complex structures without the need for molds, breaking the limitations
of traditional piezoelectric composite material processing. This capability is particularly
beneficial for the future production of complex-structured flexible devices. Zeng et al. [121]
used 3D printing technology to create a honeycomb-like BTO/epoxy composite material,
as shown in Figure 30b. This material is classified as a 3-1 type piezoelectric compos-
Micromachines 2024, 15, 982 25 of 49

ite based on its connectivity. The BTO ceramic forms a uniformly arranged honeycomb
framework with three-dimensional connectivity, while the epoxy resin uniformly fills the
BTO ceramic pores in a one-dimensional arrangement, enhancing the material’s stability.
Sebastian et al. [122] employed 3D printing technology to fabricate an interconnecting PZT
scaffold, which was then combined with epoxy resin to produce a 3-3 type piezoelectric
composite material. The Scanning Electron Microscopy (SEM) image of the PZT scaffold is
shown in Figure 30c. Experiments revealed that by simply changing the infill parameters
during printing, the scaffold structure could be customized to have a wide range of PZT
volume fractions. Additionally, the relative dielectric constant, polarization, and piezo-
electric charge coefficient of the composite material could be tailored over a broad range.
Li et al. [123] developed a layered ferroelectric metamaterial using low-pressure-assisted
3D printing technology. The ferroelectric layer was composed of high Curie temperature
Li-KNN (lead-free potassium sodium niobate ceramics) material combined with highly
flexible polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) material. The electrode
layer was made from high-conductivity carbon black (CB) filler and highly biocompatible
polylactic acid (PLA). The ferroelectric and electrode layers were alternately arranged in
the thickness direction, forming the staggered periodic structure shown in Figure 30d. Ex-
perimental data indicated that this metamaterial exhibits a high longitudinal piezoelectric
strain coefficient (d33 > 150 pC/N) and superior fracture toughness (~5.5 MPa·m1/2 ), more
than three times higher than traditional PZT and BTO ceramics. This makes it valuable for
developing energy harvesters, self-powered sensors, and therapeutic electrical stimulators.
The current literature suggests that most 3D printing technologies are predominantly used
for processing small-sized, highly stable, and rigid piezoelectric composite materials. How-
Micromachines 2024, 15, x FOR PEER REVIEW 26 of 50
ever, this approach is highly valuable for developing new-generation flexible piezoelectric
composites (especially 0-3 type) and their sensors.

29. Schematic
Figure29.
Figure Schematic of
of BTO/Polyamide
BTO/Polyamide Composite Fabrication Using
Using 3D Printing
Printing Technology
Technology [120].
[120].

In addition to the
Additionally, oneabove
of theseven
majormainstream preparation
highlights of 3D printingmethods, thereisare
technology itsalso meth-
ability to
ods such as the alignment-casting method and dielectric method [15], which
manufacture extremely complex structures without the need for molds, breaking the lim- were important
schemes
itations ofused in the early
traditional development
piezoelectric of piezoelectric
composite compositeThis
material processing. materials. However,
capability is par-
due to issues such as high process costs, low consistency of ceramic
ticularly beneficial for the future production of complex-structured flexible devices.output, and Zeng
long
processing time, they are rarely used nowadays. The performance and application
et al. [121] used 3D printing technology to create a honeycomb-like BTO/epoxy composite value
of the developed
material, as shownpiezoelectric
in Figure 30b. composites vary
This material is depending
classified ason thetype
a 3-1 preparation methods
piezoelectric com-
used. Table 2 provides a summary of piezoelectric composites developed
posite based on its connectivity. The BTO ceramic forms a uniformly arranged honeycomb under different
preparation
framework with conditions, facilitating reader
three-dimensional analysis.
connectivity, This
while summary
the epoxy resinincludes information
uniformly fills the
BTO ceramic pores in a one-dimensional arrangement, enhancing the material’s stability.
Sebastian et al. [122] employed 3D printing technology to fabricate an interconnecting PZT
scaffold, which was then combined with epoxy resin to produce a 3-3 type piezoelectric
composite material. The Scanning Electron Microscopy (SEM) image of the PZT scaffold
is shown in Figure 30c. Experiments revealed that by simply changing the infill parame-
ters during printing, the scaffold structure could be customized to have a wide range of
Micromachines 2024, 15, 982 26 of 49

Micromachines
on2024, 15, x FOR PEERproperties,
piezoelectric REVIEW mechanical properties, advantages and disadvantages of the 27 of 50

preparation processes, and the potential value of the developed composites.

Figure 30. (a) BTO/Polyamide

Figure 30. (a) BTO/Polyamide composite.
composite [120]. [120]. (b) Honeycomb-structured
(b) Honeycomb-structured BTO/Epoxy BTO/Epoxy
compos-composite
[121]. (c) SEM image of PZT scaffold fabricated using 3D printing [122]. (d) Layered
ite [121]. (c) SEM image of PZT scaffold fabricated using 3D printing [122]. (d) Layered ferroelectric ferroelectric
metamaterial [123].
metamaterial [123].
In addition
3.2. Discussion on Factors Affectingtothe
thePiezoelectric
above sevenPerformance
mainstream preparation methods, Materials
of Flexible Composite there are also meth-
ods such as the alignment-casting method and dielectric method [15], which were im-
During the preparation process,
portant schemes used certain factors
in the early can lead to
development of unexpected
piezoelectric changes
compositeinmaterials.
the final performance of flexible
However, due topiezoelectric
issues such as composite
high processmaterials,
costs, low such as dielectric
consistency relax-
of ceramic output, and
ation and polarization intensity. time,
long processing These influencing
they are rarely factors are oftenThe
used nowadays. closely related and
performance to the
application
piezoelectricity, uniformity,
value of theand permeability
developed of the
piezoelectric materials,vary
composites anddepending
thus cannot be preparation
on the ignored meth-
during the preparation process,
ods used. Table 2especially
provides awhen developing
summary small-sized
of piezoelectric composite
composites films,
developed under dif-
ferent etc.
nano-composite fibers, preparation conditions, facilitating reader analysis. This summary includes infor-
mation on piezoelectric properties, mechanical properties, advantages and disadvantages
(1) Dielectric Relaxation Behavior
of the preparation processes, and the potential value of the developed composites.
The dielectric relaxation behavior in flexible piezoelectric composite materials refers
specifically to theTable 2. Summary of properties, characteristics, and applications of piezoelectric composites pre-
phenomenon where the polarization response of the material changes
pared by different preparation processes.
over time under the influence of an electric field. This property is inherent to dielectric
Electro-
Preparation materials. Since the performance
Piezoelectric of flexible composites
Maximum Maximum is highly dependent on their
Literature Bending Mechanical Fracture Fracture Potential
Process polarization characteristics,
Strain dielectric relaxation can lead
Output to delayed
Output polarization
Advantages responses,
Disadvantages
Source Radius Coupling Stress Strain Applications
Type Coefficient Voltage Current
thereby affecting their piezoelectric
Coefficient response speed and efficiency. However, this dielectric
relaxation behavior can be optimized under appropriate conditions. Simple pro- Wang et al. sta-
High thermal [124]
Molding by bility require- Actuators, en-
investigated the effects of fillers (barium titanate, silicon carbide, and graphite)
cess, suitable on the
Hot Press- He [101] ~45pC/N / ~0.12 / / / / ments, weak pie- ergy harvest-
dielectric relaxation behavior of PVDF. The study found that compared for mass pro- to barium titanate ers.
ing zoelectric perfor-
duction
ceramics, the conductive properties of silicon carbide and graphite significantly mance. suppressed
the dielectric/ relaxation of PVDF, 30~40
especially High preci- 60 wt%. This is
Ali [70] / / ~5.0%when 4.42the
V content/ exceeded
MPa sion, can pro-
because the addition of conductive materials not only promotesduce
2.25~4.3
theflexible
orientation
Low yield,of high
PVDF Wearable de-
Electro- dipoles
Su [107] but /also increases / / 35 MPa
the dielectric loss 200 V 0.5 μA
of the material. materials
Moreover, equipment opera-
% with the dielectric vices, implant-
spinning tion require-
relaxation
Chen
behavior of composites is temperature-dependent. As the high temperature
piezoe- increases,
ments.
able devices.
/ / / / 5.85 μA lectric proper-
the relaxation
[108] peak of barium titanate shifts/ to a higher
88 V
frequency region, and the higher
ties
the ceramic doping content, the more significant the suppression of the relaxation peak.
Ultra-fast
For semiconductive silicon carbide, the higher the temperature, the more pronounced
preparation Not suitable forthe
relaxation peak; for conductors, although the relaxation peak ofefficiency
PVDF and
is developing
also large- Wearable de-
suppressed,
Electrospray
Li [110] 560 pm/V / / / / 30 V / precision; ex- sized materials, vices, energy
Deposition new relaxation peaks appear, becoming more evident at higher temperatures, as shown in
cellent piezoe- relatively com- harvesters.
Figure 31. Therefore, the selection of fillers and temperature control can
lectric filmbothplexoptimize
process. the
dielectric relaxation behavior of flexible piezoelectric composite performance materials.
Dice-Fill Hou [85] / 30 mm 0.74 / / / /
Micromachines 2024, 15, 982 27 of 49

Table 2. Summary of properties, characteristics, and applications of piezoelectric composites prepared by different preparation processes.

Electro-
Piezoelectric Maximum Maximum
Preparation Literature Bending Mechanical Fracture Fracture Potential
Strain Output Output Advantages Disadvantages
Process Type Source Radius Coupling Stress Strain Applications
Coefficient Voltage Current
Coefficient
High thermal stability
Molding by Simple process, suitable for Actuators, energy
He [101] ~45pC/N / ~0.12 / / / / requirements, weak
Hot Pressing mass production harvesters.
piezoelectric performance.
30~40
Ali [70] / / / ~5.0% 4.42 V /
MPa High precision, can produce
Electro- Low yield, high equipment Wearable devices,
Su [107] / / / 35 MPa 2.25~4.3% 200 V 0.5 µA flexible materials with high
spinning operation requirements. implantable devices.
piezoelectric properties
Chen [108] / / / / / 88 V 5.85 µA
Ultra-fast preparation
Not suitable for developing
Electrospray efficiency and precision; Wearable devices, energy
Li [110] 560 pm/V / / / / 30 V / large-sized materials,
Deposition excellent piezoelectric film harvesters.
relatively complex process.
performance
Hou [85] / 30 mm 0.74 / / / / Simple process, suitable for Low processing precision, Underwater acoustic
Dice-Fill developing large-sized not suitable for developing transducers, and
Hao [86] 464.3 pC/N 150 mm 0.70 / / / / composite materials small-sized materials. ultrasonic transducers.
Simple process, developing Ultrasonic transducers,
Injection- High cost and high mold
Zhang [114] 530 pC/N / 0.65 / / / / composites with high aspect medical
Molding design requirements.
ratios or complex structures. diagnostic devices.

Freeze- Yan [117] 354~434 pC/N / / / / 30.2 V 13.8 µA Suitable for developing porous Long process cycle, high Energy harvesters, tactile
Casting Xie [118] 750 pC/N 8 mm / / / 1.2 V / ceramic-based composites. mold requirements. sensors.

Zeng [121] 60 pC/N / ~0.31 / / 0.18 V / Developing composites with Micro ultrasonic
3D High requirements for
complex structures, highly transducers, bionic
Printing Li [123] 153 pC/N / / 5.5 MPa / 6V 30.18 µA materials and equipment.
adaptable. sensors.
 Micromachines2024,
Micromachines 2024,15,
15,982
x FOR PEER REVIEW 29 of49
28 of 50

Figure31.
Figure 31.Study
Studyon
onthe
theDielectric
DielectricRelaxation
Relaxationof
ofPVDF
PVDFComposites
Compositeswith
withBarium
BariumTitanate,
Titanate,Silicon
Silicon
Carbide,and
Carbide, andGraphite
GraphiteFillers
Fillers[124].
[124].

(2)
(2) Polarization
Polarization
Polarization plays
Polarization plays aa crucial
crucialrole
roleininthe
theperformance
performance of piezoelectric
of piezoelectricmaterials. It refers
materials. It
to theto
refers process in which
the process the electric
in which dipoles dipoles
the electric within awithin
piezoelectric material material
a piezoelectric align along the
align
direction
along the of an external
direction of an electric field,
external whichfield,
electric is essential
which for the material
is essential for to
theachieve
material stable
to
piezoelectric
achieve stableproperties.
piezoelectric During the preparation
properties. During the of flexible
preparationpiezoelectric composite
of flexible mate-
piezoelectric
rials, the polarization
composite materials, the process is influenced
polarization processby is many factors,
influenced such as
by many electricsuch
factors, fieldasstrength,
electric
temperature,
field strength, polarization
temperature,time, and the choice
polarization time, of andconstituent
the choicephases. In recentphases.
of constituent years, var-
In
recent years, various
ious polarization polarization
methods aimed atmethods
enhancing aimed at enhancing of
the piezoelectricity thecomposites
piezoelectricity
have gar-of
composites have garnered
nered significant attention.significant
Hong attention.
et al. [125] Hong usedet al. [125] used
corona corona polarization
polarization to polarize
to polarize composite
BTO/PLA BTO/PLA fibers, composite fibers, an
an effective effectivefor
approach approach
increasingfor increasing
the output the output
voltage re-
voltage
sponse.response. The schematic
The schematic of the coronaof the corona polarization
polarization setup is shownsetupin is Figure
shown32a. in Figure 32a.
Tests indi-
Tests
catedindicated
that BTO/PLAthat BTO/PLA
fiber sensorsfiber sensors to
subjected subjected to corona polarization
corona polarization exhibited higherexhibitedV p-p
higher
valuesVunder
p-p values undernormal
different different normal
forces, forces, as
as shown in shown
Figure in Figure
32b. Yang32b. Yang
et al. [126] et reported
al. [126]
reported that the stepwise
that the stepwise pulse polarization
pulse polarization (PP) method(PP) method could increase
could increase the dof
the d33 value value
33 a of a
modified
modified PZT piezoelectric ceramic to 196 pC/N, which is a
PZT piezoelectric ceramic to 196 pC/N, which is a 54% improvement compared to the 54% improvement compared
to the direct
direct current
current polarization
polarization method,method, significantly
significantly enhancing
enhancing the piezoelectricity
the piezoelectricity of
of the ce-
the ceramic material. In summary, these methods are valuable references
ramic material. In summary, these methods are valuable references for developing highly for developing
highly piezoelectric
piezoelectric flexibleflexible composite
composite materials.
materials. Effective
Effective polarization
polarization can orderly
can orderly arrange
arrange elec-
electric dipoles,
tric dipoles, thereby
thereby improvingthe
improving thepiezoelectric
piezoelectricperformance
performance of of the
the materials,
materials, resulting
resulting
in
ingreater
greaterelectrical
electricaloutput
outputunderundermechanical
mechanicalstress stressor orgreater
greatermechanical
mechanicaldeformation
deformation
under an electric field.
under an electric field.
Micromachines 2024,
Micromachines 2024, 15,
15, 982
xx FOR
FOR PEER
PEER REVIEW
REVIEW 30
30 of
29of 50
of 50
49

Figure 32.
Figure
Figure 32. (a)
32. (a) Schematic
(a) Schematic of
Schematic of the
of the corona
the corona polarization
corona polarization setup
polarization setup for
setup for BTO/PLA
for BTO/PLA composite
BTO/PLA composite fibers.
composite fibers. (b)
fibers. (b) Voltage
(b) Voltage
Voltage
response
response of BTO/PLA fiber sensors with and without corona polarization under different
response of BTO/PLA fiber sensors with and without corona polarization under different normal
of BTO/PLA fiber sensors with and without corona polarization under different normal
normal
forces [125].
forces [125].
forces [125].

On the
On
On the other
theother hand,
otherhand, the
hand,the percolation
thepercolation
percolation ofof
of nanoparticle
nanoparticle
nanoparticle doping
doping
doping is also
is also necessary
necessary
is also necessary to discuss,
to discuss,
to dis-
as itit affects
as
cuss, affects the polarization
the
as it affects polarization behavior
behavior
the polarization of composite
of composite
behavior materials.
materials.
of composite Here, the
Here,
materials. the percolation
percolation
Here, thresh-
thresh-
the percolation
old can
old can be
threshold becanused
used to
beto characterize
characterize
used the material’s
the
to characterize material’s percolation.
percolation.
the material’s Tian et
Tian
percolation. et al.
Tianal.et
[127]
[127] suggested
suggested
al. [127] that
that
suggested
the
the doping
doping of
of conductive
conductive fillers
fillers significantly
significantly impacts
impacts the
the induced
induced
that the doping of conductive fillers significantly impacts the induced polarization behav- polarization
polarization behavior.
behavior.
Figure
Figure
ior. 33 shows
33
Figure shows
33 shows thethe
the curves
curves
curves of of
of induced
induced polarization
inducedpolarization
polarizationandand remanent
andremanent polarization
remanent polarization
polarization for for
MXene/PVDF
MXene/PVDF composites
composites at
at different
different MXene
MXene
MXene/PVDF composites at different MXene doping levels. It is doping
doping levels.
levels. It
It is
is evident
evident from
from Figure
Figure 33
33
that the
that the induced
induced polarization
polarization exhibits
exhibits nonlinear changes under
nonlinear changes under varying
varying doping
varying doping levels.
doping levels.
levels.
Particularly, when
Particularly, when the the MXene
MXene content
content approaches
approaches the the critical
critical percolation
percolation threshold
threshold of of the
the
composite
composite materialmaterial
materialat at 15%,
at15%, electrons
15%,electrons within
electronswithin
within the
the composite
composite
the composite material
material
material areare
are more
more likely
likely
more to mi-
to
likely mi-
to
grate and
grate
migrate andand form
formforminterfacial
interfacial
interfacialpolarization
polarization
polarization under
under thethe
the
under polarization
polarization
polarization field,
field, leading
leading
field, leadingto aato
to sharp
sharp in-
in-
a sharp
crease in
crease
increase inin induced
induced
induced polarization.
polarization.
polarization.

Figure 33.
Figure 33. Curves
Curves of
of induced polarization and
induced polarization and remanent
remanentpolarization
polarizationfor
polarization forMXene/PVDF
for MXene/PVDF composites
MXene/PVDF composites
at different
at different MXene
MXene doping
doping levels
levels [127].
[127].

(3)
(3) Determination
(3) Determination of
of Filler
Filler Content
Content
Doping piezoelectric
Doping piezoelectric oror conductive
conductive materials
materials can significantly enhance
can significantly
significantly enhance the
enhance the perfor-
the perfor-
perfor-
mance of
mance flexiblepiezoelectric
of flexible
flexible piezoelectriccomposites,
piezoelectric composites,not
composites, notonly
not onlyin
only inin terms
terms
terms ofof
of piezoelectricity
piezoelectricity
piezoelectricity but
but but also
also
also in
in
in mechanical
mechanical stability
stability and and temperature
temperature adaptability.
adaptability. However,
However, the the doping
doping
mechanical stability and temperature adaptability. However, the doping content of these content
content of of
these
these
fillersfillers
fillers should
should should
not benot
not be be excessively
excessively
excessively high. high.
high. Tian
Tian etTian
et et al.verified
al. [127]
al. [127] [127] verified
verified the of
the impact
the impact impact
of MXene
MXene of doping
MXene
doping
doping
levels onlevels
levels on the on the piezoelectric
the piezoelectric
piezoelectric properties
properties
properties of MXene/PVDF
of MXene/PVDF
of MXene/PVDF composites,
composites, composites,
as shown
as shown inas Figure
in shown34.
Figure in
34.
Figure 34. Figure 34a illustrates the relationship between different MXene content and
Micromachines 2024, 15, x FOR PEER REVIEW 31 of 50

Micromachines 2024, 15, 982 30 of 49

Figure 34a illustrates the relationship between different MXene content and the compo-
site’s d33 values (red
the composite’s represents
d33 values (red the composite
represents thedcomposite
33, blue represents
d33 , bluethe d33 in thethe
represents polymer
d33 in
matrix,
the polymer matrix, and green represents the interfacial polarization-coupled d33 ). Ascon-
and green represents the interfacial polarization-coupled d 33 ). As the MXene the
tent
MXeneincreases,
contentthe composite’s
increases, d33 initially rises
the composite’s d33 to 60 pC/N
initially and
rises tothen dropsand
60 pC/N backthen
to near its
drops
initial
back tovalue,
near with the highest
its initial d33 value
value, with achieved
the highest atvalue
d33 a 15%achieved
doping level. A moderate
at a 15% doping amount
level. A
of conductive
moderate amountmaterial facilitatesmaterial
of conductive electronfacilitates
migrationelectron
in the polarization
migration infield, enhancing
the polarization
piezoelectricity.
field, enhancing However, whenHowever,
piezoelectricity. the doping content
when exceedscontent
the doping the threshold,
exceedsthe thecomposite
threshold,
forms a continuous conductive network, providing a percolation
the composite forms a continuous conductive network, providing a percolation path for the path for the relaxation
of the polarized
relaxation of thecharges,
polarized thus suppressing
charges, the piezoelectricity
thus suppressing of the composite.
the piezoelectricity This prin-
of the composite.
ciple is also explained
This principle in Figure
is also explained 34b. Figure
in Figure 34b shows
34b. Figure the output
34b shows the outputvoltage response
voltage responseof
MXene/PVDF
of MXene/PVDF composites
composites under 25 N
under 25force
N forceat different
at differentMXene
MXene dopingdoping levels. It can
levels. be
It can
be seen
seen thatthat
the the MXene/PVDF
MXene/PVDF composite
composite achieves
achieves the highest
the highest output output
at a 15% at adoping
15% doping
level,
level,the
and and the voltage
peak peak voltage
responseresponse significantly
significantly decreases
decreases whenwhen the MXene
the MXene doping doping
level level
con-
continues to increase. Therefore, the doping of conductive materials
tinues to increase. Therefore, the doping of conductive materials is closely related to the is closely related to
the critical
critical percolation
percolation threshold.
threshold.

Figure 34.
Figure (a)Relationship
34. (a) Relationshipbetween
betweendifferent
differentMXene
MXenecontent andd33d33
contentand of of MXene/PVDF
MXene/PVDF compos-
composites
ites [127].
[127]. (b) The
(b) The output
output voltage
voltage response
response of of MXene/PVDF
MXene/PVDF composites
composites under2525NNforce
under forceat
at different
different
MXene doping levels.

Compared to
Compared toconductive
conductivefillers,
fillers,determining
determining thethe content
content of piezoelectric
of piezoelectric fillers
fillers is
is rel-
relatively complex. Based on whether the polymer material itself exhibits
atively complex. Based on whether the polymer material itself exhibits piezoelectricity, piezoelectricity,
the determination
the determination of of fillers
fillers can
can be
be divided
divided into
into two
two categories.
categories. The
The first
first category
category isisPVDF-
PVDF-
based composites. For these composites, doping with high piezoelectric
based composites. For these composites, doping with high piezoelectric particles should particles should
consider the
consider the content
content ofof the
the polar
polar electroactive
electroactive β-phase. Thirumalasetty et
β-phase. Thirumalasetty et al.
al. [128]
[128] tested
tested
the output voltage of lead-free barium zirconate titanate (BZT)/PVDF-HFP
the output voltage of lead-free barium zirconate titanate (BZT)/PVDF-HFP composites composites
with four
with four different
different doping
doping levels (0, 88 wt%,
levels (0, wt%, 16
16 wt%,
wt%, 24 24 wt%),
wt%), as
as shown
shown in in Figure
Figure 35a. The
35a. The
composite achieved a higher output voltage peak at a 16 wt% BZT ceramic doping level,
composite achieved a higher output voltage peak at a 16 wt% BZT ceramic doping level,
resulting in higher output power. When the doping level increased to 24 wt%, the output
resulting in higher output power. When the doping level increased to 24 wt%, the output
voltage of the BZT/PVDF-HFP composite significantly decreased. They analyzed that a
voltage of the BZT/PVDF-HFP composite significantly decreased. They analyzed that a
certain amount of ceramic doping facilitates the interaction between the negative charges
certain amount of ceramic doping facilitates the interaction between the negative charges
carried by the ceramics and the -CH groups in PVDF, enhancing the β-phase content
carried by the ceramics and the -CH22 groups in PVDF, enhancing the β-phase content
within the composite. However, excessive ceramic doping inhibits β-phase formation,
within the composite. However, excessive ceramic doping inhibits β-phase formation, re-
resulting in a loss of piezoelectricity. Verma et al. [129] doped PVDF polymers with KNN
sulting in a loss of piezoelectricity. Verma et al. [129] doped PVDF polymers with KNN
ceramics to create KNN/PVDF piezoelectric composites. Similar patterns were observed in
ceramics to create KNN/PVDF piezoelectric composites. Similar patterns were observed
their research. Figure 35b illustrates the relationship between different KNN doping levels
in their research. Figure 35b illustrates the relationship between different KNN doping
and the open-circuit voltage of the composites. It is evident that when the doping level
levels and the open-circuit voltage of the composites. It is evident that when the doping
exceeds 15 wt%, the piezoelectricity of the composite is significantly weakened. Therefore,
level exceedswith
for polymers 15 wt%,
inherentthepiezoelectricity,
piezoelectricityhigher
of thepiezoelectricity
composite is is significantly
not achievedweakened.
by simply
Therefore,
increasing the number of piezoelectric particles but by focusing on the synthesis is
for polymers with inherent piezoelectricity, higher piezoelectricity of not
the
achieved by simply increasing the number of piezoelectric particles but
β-phase after doping. The second category is non-PVDF-based composites. Since these by focusing on the
synthesis
polymersof dothe β-phase
not possessafter doping. The second
piezoelectricity, category is non-PVDF-based
the piezoelectricity of the composites composites.
depends
Since these polymers do not possess piezoelectricity, the piezoelectricity of the
on the piezoelectricity of the fillers. Thus, the larger the piezoelectric particle size and the composites
higher the doping level, the stronger the piezoelectricity of the composite; this corresponds
Micromachines 2024, 15, x FOR PEER REVIEW 32 of 50
Micromachines 2024, 15, x FOR PEER REVIEW 32 of 50

depends on the piezoelectricity of the fillers. Thus, the larger the piezoelectric particle size
Micromachines 2024, 15, 982 depends
and the on the piezoelectricity
higher the doping level,of the
thefillers.
strongerThus,
thethe larger the piezoelectric
piezoelectricity particle
of the composite; 31 size
ofthis
49
and the higher the doping level, the stronger the piezoelectricity of the composite;
corresponds to higher output voltage and power values, as shown in Figure 36 [74]. How- this
corresponds to higher
ever, increased output voltage
piezoelectric ceramicand power
content values,
also leadsastoshown in hardness
greater Figure 36 and
[74]. higher
How-
ever,
to increased piezoelectric
higher impedance
acoustic output voltage ceramic
andcomposites,
of the content
power values, also
as shown
requiring leads to greater
in Figurebased
a trade-off hardness
36 [74].onHowever,and higher
increased
the application re-
acoustic impedance
piezoelectric
quirements. ceramicof the composites,
content also leads torequiring a trade-off
greater hardness andbased onacoustic
higher the application
impedance re-
quirements.
of the composites, requiring a trade-off based on the application requirements.

Figure 35. (a) Output voltage values of BZT/PVDF-HFP composites with different doping levels
Figure 35. (a)
[128]. 35.
Figure (b) (a)Output
Outputvoltage
Open-circuitvoltagevalues
voltage of BZT/PVDF-HFP
values
values KNN/PVDF composites
ofofBZT/PVDF-HFP with
composites
composites different
with doping
different
at different KNN levelslevels
doping
doping [128].
levels
(b) Open-circuit
[128].
[129]. voltagevoltage
(b) Open-circuit values of KNN/PVDF
values composites
of KNN/PVDF at different
composites KNN doping
at different KNNlevels [129].
doping levels
[129].

Figure36.
Figure 36. Effect
Effect of
of PZT particle size and volume
volume fraction
fractionon
ondd3333ofof0-3
0-3PZT/silicone
PZT/siliconeresin composites
resin compos-
Figure
[74]. 36.
ites [74]. Effect of PZT particle size and volume fraction on d33 of 0-3 PZT/silicone resin composites

[74].
(4)
(4) Agglomeration
Agglomeration
(4) Agglomeration
Inpiezoelectric
In piezoelectric materials,
materials, thethephenomenon
phenomenon of of agglomeration
agglomeration refers refers to to the
thetendency
tendency
of In piezoelectric
ofpiezoelectric materials,
piezoelectric particles
particles to the
to cluster phenomenon
cluster together
together rather of agglomeration
rather than
thanbeing
beingevenly refers to
evenlydistributed the tendency
distributed within
within
of
thepiezoelectric
the material.
material. This particles
This leadsto
leads toan
to cluster
an uneven
uneven together ratherof
distribution
distribution than
ofthe being
the evenly
electric
electric field
field distributed
within
within thethe within
mate-
material,
the
rial,material.
causing
causing someThis
some leads to anparticles
piezoelectric
piezoelectric uneven distribution
particles of the
to inadequately
to inadequately electric field
contribute
contribute within
to
to the the thecharge
overall
overall material,
chargere-
causing
response some piezoelectric
[130].Consequently,
sponse [130]. Consequently, particles to inadequately
thisadversely
this adversely affectsthe
affects contribute
thepiezoelectric
piezoelectrictoperformance
the overall charge re-
of the ma-
sponse
terial. [130]. Consequently,
terial.Moreover,
Moreover, during
duringthe this adversely
polarization
the polarization affects
process,
process, theagglomeration
piezoelectric
agglomeration may performance
result
may ofnon-uni-
the ma-
in non-uniform
result in
terial. Moreover,
polarization, during
further the
degrading polarization
the process,
material’s agglomeration
performance and
form polarization, further degrading the material’s performance and efficiency. In sum- may result
efficiency. Inin non-uni-
summary,
form
mary,polarization,
agglomeration
agglomeration further
negatively degrading
impactsimpacts
negatively thethe
both material’s
both performance
piezoelectric properties
the piezoelectric andandefficiency.
properties In sum-
polarization
and polariza- of
mary, agglomeration
piezoelectric
tion of piezoelectric negatively
materialsmaterials
and should impacts
andbeshould both
minimized the piezoelectric
to ensure the
be minimized properties
stability
to ensure theand and polariza-
optimization
stability of
and opti-
tion of piezoelectric
material
mization of materialmaterials
performance. Silakaew
performance.andet should
al. [131]be
Silakaew etminimized
have al.suggested
[131] haveto ensure
that thethe
suggested stability
agglomeration and effect
that the agglomer-opti-
mization
caused byofthe
ation effect material performance.
incorporation
caused by Silakaew
of ceramic
the incorporation ofetceramic
particles al. [131] ahave
intoparticles suggested
polymer intomatrix that
canthe
a polymer agglomer-
significantly
matrix can
ation
degrade effect
the caused
electricalby the
and incorporation
mechanical of ceramic
properties of theparticles
composite into a polymer
material,
significantly degrade the electrical and mechanical properties of the composite material, as matrix
illustrated can
in
significantly
Figure 37. degrade
This is the
attributed electrical
to the and mechanical
anomalous properties
low-frequency of the
dielectric
as illustrated in Figure 37. This is attributed to the anomalous low-frequency dielectric composite
constant material,
behavior
as illustrated
induced by theindipolar
Figurepolarization
37. This is attributed
and interfacialto the anomalous
polarization low-frequency
between BTO ceramics dielectric
and
PVDF. Therefore, during the preparation process, using appropriate solvents and ultrasonic
treatments to control the particle size and distribution of the ceramic particles can help
mitigate agglomeration.
 constant behavior induced by the dipolar polarization and interfacial polarization be-
tween BTO ceramics and PVDF. Therefore, during the preparation process, using appro-
Micromachines 2024, 15, 982 32 of
priate solvents and ultrasonic treatments to control the particle size and distribution of49
the ceramic particles can help mitigate agglomeration.

Figure 37.
Figure 37. Scanning
Scanning electron
electron microscope images of the fracture
fracture surfaces
surfaces of
of BTO/PVDF
BTO/PVDFcomposites
composites
preparedusing
prepared usingthe
the dissolution
dissolution method
method at
at different
different BTO
BTO volume
volume fractions
fractions [131].
[131].

4.
4. Application
Application of Flexible Piezoelectric
Piezoelectric Composite
CompositeMaterials
Materials
4.1. Underwater Detection
4.1. Underwater Detection
Hydrophones
Hydrophones are areimportant
importantdevicesdevices forfor
sensing
sensingunderwater
underwater sound information.
sound information.With
the gradual deployment of UUVs and micro-robots underwater,
With the gradual deployment of UUVs and micro-robots underwater, hydrophone devel- hydrophone development
isopment
also gradually transitioning
is also gradually towardstowards
transitioning miniaturization, lightweight,
miniaturization, high precision,
lightweight, high preci-and
other directions [132–134]. In response to these underwater detection
sion, and other directions [132–134]. In response to these underwater detection needs, the needs, the utiliza-
tion of flexible
utilization piezoelectric
of flexible composite
piezoelectric materials
composite will will
materials provide valuable
provide valuabledesign
design ideas
ideasfor
developing
for developing hydrophones with high electromechanical properties and conformability.In
hydrophones with high electromechanical properties and conformability.
recent years,
In recent there
years, therehave
havebeenbeenrelatively
relatively fewfewreports
reportsononthetheunderwater
underwaterdetection
detectionapplica-
appli-
tions
cations of flexible piezoelectric composite materials in the literature, suggesting that thereis
of flexible piezoelectric composite materials in the literature, suggesting that there
considerable
is considerable research
research potential
potential in in
this field.
this field.
Wang
Wang et al. [135] achieved integratedmolding
et al. [135] achieved integrated moldingof oftransducer
transducerarrays
arraysusing
usingsemi-flexible
semi-flexi-
piezoelectric composite materials, as shown in Figure 38a.
ble piezoelectric composite materials, as shown in Figure 38a. Each transducer elementEach transducer elementisis
composed
composed alternately of piezoelectric ceramics and epoxy resin, giving the elements a co- a
alternately of piezoelectric ceramics and epoxy resin, giving the elements
columnar compressive
lumnar compressive resistance.
resistance. Flexible
Flexible rubber
rubber is infused
is infused between
between eacheach array
array element
element to
to facilitate
facilitate thethe vibration
vibration of elements
of elements and and attenuate
attenuate lateral
lateral coupling
coupling between between elements.
elements. Ad-
Additionally, influenced
ditionally, influenced byby improvements
improvements ininflexible
flexiblepolymers,
polymers,the theflexible
flexiblepiezoelectric
piezoelectric
composite material has the ability for unidirectional bending, which
composite material has the ability for unidirectional bending, which also has practical also has practical value
in developing curved transducers. Inspired by electronic sensing
value in developing curved transducers. Inspired by electronic sensing skin, Hao et al. skin, Hao et al. [86] de-
signed
[86] designed a patch-type flexible transducer, as shown in Figure 38b. This transducer isof
a patch-type flexible transducer, as shown in Figure 38b. This transducer is made
1-3
madetype
ofpiezoelectric composite
1-3 type piezoelectric material material
composite that can undergo three-dimensional
that can undergo deformation,
three-dimensional de-
hence possessing a certain level of conformability, making it suitable for meeting the surface
shell devices in the UUV series. In terms of performance, this transducer meets surface de-
formations ranging from 100 mm to 200 mm, with a reception response reaching −186.1dB,
thereby possessing application advantages of a broad detection range and strong sensing
capability. However, due to the adoption of an all-flexible design in composite materials,
the flexible composite material may undergo mechanical deformation [13], potentially
making this flexible transducer suitable for underwater application scenarios with low
 ing the surface shell devices in the UUV series. In terms of performance, this transducer
meets surface deformations ranging from 100 mm to 200 mm, with a reception response
reaching −186.1dB, thereby possessing application advantages of a broad detection range
and strong sensing capability. However, due to the adoption of an all-flexible design in
Micromachines 2024, 15, 982 composite materials, the flexible composite material may undergo mechanical defor- 33 of 49
mation [13], potentially making this flexible transducer suitable for underwater applica-
tion scenarios with low hydrostatic pressure or weak mechanical strength. Nevertheless,
this issue of mechanical
hydrostatic pressure ordeformation
weak mechanical can sometimes
strength. be addressed by
Nevertheless, thisenhancing the com-
issue of mechanical
pressive resistance of the piezoelectric units. As early as 2010,
deformation can sometimes be addressed by enhancing the compressive resistance of the Wang et al. [136] proposed
a piezoelectric
multi-element composite
units. As early array composed
as 2010, Wang et ofal.
piezoelectric
[136] proposed ceramics, epoxy resin,
a multi-element and
compos-
cork rubber,
ite array as shown
composed in Figure 38c.
of piezoelectric The elements
ceramics, epoxy resin, are integrally formedasby
and cork rubber, a 1-3in
shown
PZT/epoxy
Figure 38c.structure,
The elementsand theare ceramic base formed
integrally is retained by in the PZT/epoxy
a 1-3 composite material
structure, structure,
and the
ensuring
ceramic good base isstability
retainedand impact
in the resistance
composite for structure,
material each element. Here,good
ensuring corkstability
rubber and is
mainly used to strengthen the mechanical vibration of the
impact resistance for each element. Here, cork rubber is mainly used to strengthen thepiezoelectric columns and to
alleviate
mechanical the vibration
lateral effects
of the between the columns
piezoelectric elements,and facilitating
to alleviate a the
better concentration
lateral effects between of
thickness
the elements,vibration energy.
facilitating Although
a better this composite
concentration structure
of thickness resolves
vibration the issue
energy. Althoughof me- this
composite
chanical structure resolves
deformation, the ceramicthe issue of mechanical
base restricts deformation,
the bending the ceramic
capability base restricts
of this piezoelectric
the bending
composite capability
material and of this piezoelectric
introduces composite
higher lateral material
coupling and introduces
effects. In this design, higher
thelateral
bal-
coupling
anced use ofeffects. In this
rigid and design,
flexible the balanced
polymers provides useaofbalance
rigid and flexible
between thepolymers
compressive provides
re-
a balance between the compressive resistance of the piezoelectric
sistance of the piezoelectric units and the overall flexibility of the composite material. Sim- units and the overall
flexibility
ilarly, in theof1-3theimproved
compositepiezoelectric
material. Similarly,
compositein the 1-3 improved
array proposed piezoelectric
by Qin et al. composite
[91], the
array proposed
original ceramic base by Qin wasetremoved
al. [91], the original
(Figure ceramic
11a), base was
and silicone removed
rubber was used (Figure 11a),
as the con-and
siliconematerial
necting rubber was for used as the connecting
the elements, material
which greatly for the elements,
reduced which greatly
lateral coupling, leading reduced
to a
lateral
basic coupling,
increase leading
in the to a basic increase
electromechanical coupling in the electromechanical
coefficient of the elements coupling coefficient
to around 0.6.
of the elements to around 0.6. Due to the enhancement of
Due to the enhancement of the thickness mode, the overall bandwidth of the composite the thickness mode, the overall
bandwidth
array of the composite array
is also correspondingly is alsoIncreasing
extended. correspondingly extended.
the content Increasing
of silicone rubber thewill
content
re-
of silicone rubber will result in enhanced conformability
sult in enhanced conformability of this composite array. Thus, the balanced utilization of this composite array. Thus,
of
the balanced
rigid and flexible utilization
polymers of rigid and effectively
not only flexible polymers
improves nottheonlymechanical
effectivelydeformation
improves the
mechanical
problem deformation
of flexible problem
piezoelectric of flexible
composite piezoelectric
materials compositetheir
but also enhances materials but also
performance,
providing a new approach for the development of flexible transducers capable of flexible
enhances their performance, providing a new approach for the development of with-
transducers
standing highcapable of withstanding
hydrostatic pressure and high hydrostatic
exhibiting pressure
strong impact and exhibiting
resistance instrong impact
the future.
resistance in the future.

b c

Figure 38. (a) Structure of a piezoelectric composite array transducer with semi-flexible characteris-
tics [135]. (b) Adhesive-type flexible transducer [86]. (c) Multi-element piezoelectric composite array
formed by integral molding [136].

4.2. Wearable Sensor

The combination of flexible piezoelectric composite materials with the functions of
medical devices enables the development of wearable sensors adapted to human detection
needs [137–139]. Compared to traditional large-scale medical devices, wearable sensors
offer not only convenience in carrying but also greater flexibility and adaptability. Through
 4.2. Wearable Sensor
The combination of flexible piezoelectric composite materials with the functions of
Micromachines 2024, 15, 982
medical devices enables the development of wearable sensors adapted to human detection
34 of 49
needs [137–139]. Compared to traditional large-scale medical devices, wearable sensors
offer not only convenience in carrying but also greater flexibility and adaptability.
Through the signals of wearable sensors, people can also gain real-time control over phys-
the signals of wearable sensors, people can also gain real-time control over physiological
iological information, which has been the main reason for the rapid rise and development
information, which has been the main reason for the rapid rise and development of this
of this technology in recent years.
technology in recent years.
Tian et al. [140] proposed a wearable sensor for continuous monitoring of blood pres-
Tian et al. [140] proposed a wearable sensor for continuous monitoring of blood
sure and cardiac function, as depicted in Figure 39. The sensor is composed of a non-uni-
pressure and cardiac function, as depicted in Figure 39. The sensor is composed of a non-
form layered structure of MXene/boron nitride (BN)/P(VDF-TrFE) and was constructed
uniform layered structure of MXene/boron nitride (BN)/P(VDF-TrFE) and was constructed
usingcontrolled
using controlledelectrospinning
electrospinningcombined
combined withwith
hothot pressing
pressing technology,
technology, thereby
thereby over-
overcom-
coming
ing the intrinsic
the intrinsic limitations
limitations of traditional
of traditional piezoelectric
piezoelectric ceramic materials
ceramic materials which arewhich
hard and are
hard and brittle, while simultaneously balancing high piezoelectricity
brittle, while simultaneously balancing high piezoelectricity and flexibility. Leveraging the and flexibility. Lev-
eraging the
interfacial interfacial between
polarization polarization
MXene between
and the MXene
polymerandmatrix
the polymer
and the matrix and the
suppression sup-
of bulk
leakage current by BN, the piezoelectric composite material exhibits a piezoelectric chargea
pression of bulk leakage current by BN, the piezoelectric composite material exhibits
piezoelectric
coefficient of upcharge coefficient
to 41.67 pC/N and of up a to 41.67 pC/Nvoltage
piezoelectric and a piezoelectric
constant of 342.9 voltage constant
mV/mN. Theof
342.9 mV/mN.
sensor The sensor exhibits
exhibits high-pressure response high-pressure response sensitivity,
sensitivity, endowing the device with endowing the de-
the potential
vice with the potential for use in wearable cardiovascular monitoring
for use in wearable cardiovascular monitoring applications. Huang et al. [141] proposed applications. Huang a
et al. [141] proposed a modified sensor made of Polyacrylonitrile
modified sensor made of Polyacrylonitrile (PAN)/MXene/polydopamine-modified zinc (PAN)/MXene/polydo-
pamine-modified
oxide (PDA@ZnO-5) zincpiezoelectric
oxide (PDA@ZnO-5)composite piezoelectric composite
material (PMPO), material
capable (PMPO), ca-
of achieving a
pable of achieving a sensitivity response of 28.56 V/N within
sensitivity response of 28.56 V/N within a wide linear range. This sensor exhibited a wide linear range.excel-
This
sensor
lent exhibitedstability
mechanical excellentand mechanical
durabilitystability
duringand 3000durability during 3000 cycles ofwhich
cycles of loading-unloading, load-
ing-unloading,
offers which offers
multiple benefits multiple
such as sensingbenefits such as sensing
subtle pressure changessubtle pressure changes
and monitoring and
significant
monitoring
body movements.significant body movements.
As depicted in FigureAs 40,depicted in Figure
the sensor 40, thedifferent
can exhibit sensor can exhibit
electrical
different
signals in electrical
response to signals
subtleinpressure
response to subtlecaused
variations pressure variations
by changes in caused by changes
the volunteer’s in
facial
the volunteer’s facial expressions. Consequently, the integration of
expressions. Consequently, the integration of flexibility and piezoelectricity in flexible flexibility and piezoe-
lectricity in composite
piezoelectric flexible piezoelectric
materials has composite
ignited thematerials has ignited
market value the market
of wearable sensors. value
These of
wearable
sensors cansensors.
diagnose These
humansensors can diagnose
physiological human physiological
information through electrical information
signals, through
making
electrical
them signals, making
technological productsthem fortechnological productsoffor
the next generation the nextdiagnostics.
medical generation of medical
However,
since some ofHowever,
diagnostics. these devices
since require
some of long-term
these deviceswearing bylong-term
require patients to achievebydynamic
wearing patients
monitoring effects, the
to achieve dynamic continuous
monitoring and effective
effects, supply and
the continuous of energy
effectiveto the devices
supply is also to
of energy a
concern for researchers.
the devices is also a concern for researchers.

Figure39.
Figure 39.Wearable
Wearablecontinuous
continuousblood
bloodpressure
pressureand
andcardiac
cardiacfunction
functionmonitoring
monitoringsensor
sensor[140].
[140].

For the energy supply issue, most researchers have proposed nanogenerators as a solu-
tion, with many of these power supply devices also utilizing flexible piezoelectric composite
materials. Wang et al. [142] utilized electrospinning techniques to fabricate a composite
nanofiber comprising a blend of a piezoelectric functional layer and a frictional-electric
friction layer, as depicted in Figure 41a. In this design, multi-walled carbon nanotubes
are doped into another flexible friction layer patterned with PDMS to expand the initial
capacitance; the piezoelectric layer is fabricated using the P(VDF-TrFE) polymer, known
for its excellent shaping capability. This device can achieve energy output through dif-
ferent mechanisms, with the peak output voltage, power, and power density under the
frictional electric mechanism reaching 25 V, 98.56 µW, and 1.98 mW/cm3 , respectively.
Under the piezoelectric working principle, the peak output voltage, power, and power
density are 2.5 V, 9.74 µW, and 0.689 mW/cm3 , respectively, providing continuous effective
electrical energy for wearable sensors. Thirumalasetty et al. [128] reported on a flexible
 Micromachines 2024, 15, 982 35 of 49

nanogenerator based on BZT ceramic fibers, which not only serves as a power supply de-
vice for small wearable devices but also provides a development path for environmentally
friendly sensing technologies. Figure 41b illustrates the three-dimensional structure of
the nanogenerator after exploding. The sensitive core of this device consists of a mixture
of PVDF and BZT phases, exhibiting high energy storage efficiency and piezoelectricity.
Research indicates that the 16 wt% BZT composite ink exhibits higher electrical activity in
the β-phase. Furthermore, under an external force of 3 N, the device achieved an optimized
open-circuit voltage and short-circuit current of 7 Vpp and 750 nA, respectively, demon-
strating the significant value of environmentally friendly BZT-based materials in flexible
electronics. Additionally, some researchers employ PVDF-based composite materials to
address the energy supply issue. Huang et al. [61] modified PVDF polymer with BTO
material to produce PVDF/BTO composite material, achieving an output voltage of up to
~20.0 V and a sensitivity of ~132.87 mV/kPa. This significant piezoelectricity and sensitivity
enable it to adapt to various human wearable positions, as shown in Figure 41c. Energy
harvesting experiments have shown that under a pressure of 10 N, the power density can
Micromachines 2024, 15, x FOR PEER REVIEW 36 of 50
reach ~58.7 mW/m2 , indicating long-term durability. This finding provides an important
development direction for sustainable self-powered sensors and energy harvesting sensors.

Figure
Figure40.
40.The
ThePMPO
PMPOsensor
sensor isis used to
to monitor
monitorsubtle
subtlebody
bodysignals:
signals:(a)(a) breathing,
breathing, (b)(b) abdominal
abdominal
breathing,
breathing,(c)
(c)speaking,
speaking,(d)
(d) frowning, (e) smiling,
frowning, (e) smiling,(f)
(f)cheek
cheekpuffing.
puffing.(g)
(g)blowing
blowingairair
at at a distance
a distance of of
2 cm
2 cmfrom
fromthe
thePMPO
PMPOpiezoelectric sensor [141].
piezoelectric sensor [141].

For the energy supply issue, most researchers have proposed nanogenerators as a
solution, with many of these power supply devices also utilizing flexible piezoelectric
composite materials. Wang et al. [142] utilized electrospinning techniques to fabricate a
composite nanofiber comprising a blend of a piezoelectric functional layer and a frictional-
electric friction layer, as depicted in Figure 41a. In this design, multi-walled carbon nano-
tubes are doped into another flexible friction layer patterned with PDMS to expand the
initial capacitance; the piezoelectric layer is fabricated using the P(VDF-TrFE) polymer,
known for its excellent shaping capability. This device can achieve energy output through
different mechanisms, with the peak output voltage, power, and power density under the
 up to ~20.0 V and a sensitivity of ~132.87 mV/kPa. This significant piezoelectricity and
sensitivity enable it to adapt to various human wearable positions, as shown in Figure 41c.
Energy harvesting experiments have shown that under a pressure of 10 N, the power den-
sity can reach ~58.7 mW/m², indicating long-term durability. This finding provides an im-
Micromachines 2024, 15, 982 36 of 49
portant development direction for sustainable self-powered sensors and energy harvest-
ing sensors.

Figure 41.
Figure 41.(a)
(a)Flexible
Flexiblenanogenerator
nanogenerator with
with piezoelectric
piezoelectric layer/friction
layer/friction layer
layer [142];
[142]; (b) (b) Environmen-
Environmentally
friendly nanogenerator with PVDF/BZT composite material [128]; (c) Voltage signal testtest
tally friendly nanogenerator with PVDF/BZT composite material [128]; (c) Voltage signal results
results of
of PVDF/BTO at different wearing positions [61].
PVDF/BTO at different wearing positions [61].

Flexible piezoelectric
Flexible piezoelectric composite
composite materials
materials play
play various
various roles
roles inin the
the field
field of
of wearable
wearable
sensors. Simultaneously, the development of flexible piezoelectric composite
sensors. Simultaneously, the development of flexible piezoelectric composite materials has materials
has greatly
greatly inspired
inspired research
research on various
on various functionalities
functionalities of wearable
of wearable sensorssensors
and hasand has
demon-
demonstrated enormous potential in the field of medical detection. As
strated enormous potential in the field of medical detection. As research goes deeper, research goes
deeper, wearable
wearable sensors sensors will evolve
will evolve towardstowards high mechanical
high mechanical flexibility,
flexibility, high sensitivity,
high sensitivity, high
high energy
energy supply,
supply, high high integration,
integration, and comfort.
and comfort. Compared
Compared to bulky
to bulky andand single-func-
single-function
tion detection
detection methods,
methods, this technology
this technology undoubtedly
undoubtedly represents
represents a significant
a significant advanceadvance in
in medi-
medical
cal detection.
detection.

4.3.
4.3. Flexible
Flexible Electronic
Electronic Skin
Skin
Flexible electronicskin
Flexible electronic skinhas
hasemerged
emerged as as a hot
a hot research
research topictopic in recent
in recent years,years, pro-
providing
viding significant value in the development of alternative prosthetic sensing,
significant value in the development of alternative prosthetic sensing, automatic control, automatic
control, and human-machine
and human-machine interfaceinterface [143].
[143]. The Thematerials
sensing sensing materials of electronic
of electronic skin are
skin are typically
typically made of thin, soft, shape-adaptable, and high-sensitivity responsive
made of thin, soft, shape-adaptable, and high-sensitivity responsive thin film materials thin film
materials [144], which endow robot systems with strong sensing capabilities.
[144], which endow robot systems with strong sensing capabilities. Given these character- Given these
characteristics, flexible piezoelectric
istics, flexible piezoelectric composite
composite materials
materials also possess
also possess significant
significant application
application value
value in this
in this field. field.
Khanbareh et al. [145] reported on a flexible composite material electronic skin com-
posed of porous polyurethane (PU) and PZT composite, which can be used for information
interaction of soft robots, as shown in Figure 42. The uniform spherical micro-pores of
polyurethane polymer aim to enhance the piezoelectric voltage constant by reducing the
dielectric constant, thereby significantly improving the weak signal perception ability
of the electronic skin; while the PZT particles distributed in the polymer matrix endow
the material with strong piezoelectricity. Experimental results show that the g33 of this
electronic skin reaches up to 165 mV m/N, about 5 times higher than that achieved by
PZT bulk materials, which is beneficial for the development of highly sensitive tactile
 posed of porous polyurethane (PU) and PZT composite, which can be used for infor-
mation interaction of soft robots, as shown in Figure 42. The uniform spherical micro-
mation interaction of soft robots, as shown in Figure 42. The uniform spherical micro-
pores of polyurethane polymer aim to enhance the piezoelectric voltage constant by re-
pores of polyurethane polymer aim to enhance the piezoelectric voltage constant by re-
ducing the dielectric constant, thereby significantly improving the weak signal perception
ducing the dielectric constant, thereby significantly improving the weak signal perception
ability of the electronic skin; while the PZT particles distributed in the polymer matrix
Micromachines 2024, 15, 982 ability of the electronic skin; while the PZT particles distributed in the polymer matrix
endow the material with strong piezoelectricity. Experimental results show that the 37gof3349
of
endow the material with strong piezoelectricity. Experimental results show that the g33 of
this electronic skin reaches up to 165 mV m/N, about 5 times higher than that achieved by
this electronic skin reaches up to 165 mV m/N, about 5 times higher than that achieved by
PZT bulk materials, which is beneficial for the development of highly sensitive tactile sen-
PZT bulkLiu
sensors. materials,
et al. which
[146] is beneficial
designed for the development
a large-scale tactile array of highly sensitive tactile sen-
sors. Liu et al. [146] designed a large-scale tactile array of of electronic
electronic skin,
skin, asas shown
shown in
sors.
in Liu et
Figure43. al. [146]
43.Compared designed
Comparedtototraditionala large-scale tactile
traditional sandwich-structured array of electronic
sandwich-structured large sensors, this skin, as shown in
Figure this array-type
array-type
Figure 43.skin
electronic Compared to traditional sandwich-structured large sensors, thisprocess,
array-type
electronic skinisisexpected
expectedto to
have
havea thinner thickness,
a thinner simpler
thickness, manufacturing
simpler manufacturing process, and
electronic
greater skin is expected
stretchability. In thisto have
design, a thinner
the thickness,
flexible compositesimpler manufacturing
material unit is process,
composed of
and greater stretchability. In this design, the flexible composite material unit is composed
and greater
PZT stretchability.
particles embedded inIna this
PDMSdesign,
matrixthecomposite,
flexible composite
with goodmaterial unit isand
uniformity composed
passive
of PZT particles embedded in a PDMS matrix composite, with good uniformity and pas-
of PZT particles
driving mode, embedded
enabling in a PDMS matrix
high-resolution tactilecomposite,
sensing, with good uniformity
simplifying the and pas-
sive driving mode, enabling high-resolution tactile sensing, simplifying thedata
datacollection
collection
sive driving
process, mode, enabling high-resolution tactile sensing, simplifying the data collection
process,and
andreducing
reducingmanufacturing
manufacturingcosts. costs.
process, and reducing manufacturing costs.

Figure42.
Figure 42.Electronic
Electronicskin skin
is is composed
composed of PZT-PU
of PZT-PU composite
composite withwith microporous
microporous polyurethane
polyurethane and
and PZT
Figure
PZT 42. Electronic
phase [145]. (a) skin is3D-printed
Fully composedsoftof PZT-PU
robotic composite
hand.(b) witharea
Large microporous
flexible polyurethanepiezo-
micro-porous and
phase [145]. (a) Fully 3D-printed soft robotic hand. (b) Large area flexible micro-porous piezoelectric
PZT phase
electric [145].(c)(a)Sensor
sensor. Fully unit
3D-printed
lay-up. soft robotic hand.(b)
(d) Recorded signal Largerepeatedly
upon area flexible micro-porous
touching piezo-
the sensor.
sensor.
electric (c) Sensor
sensor. (c)unit lay-up.
Sensor unit (d) Recorded
lay-up. signal upon
(d) Recorded repeatedly
signal touchingtouching
upon repeatedly the sensor.
the sensor.

Figure 43. PZT/PDMS electronic skin for gesture recognition [146].

Figure 43.
Figure 43. PZT/PDMS
PZT/PDMS electronic
electronic skin
skin for
for gesture
gesture recognition
recognition [146].
[146].
As a source of information perception, electronic skin plays a crucial role in robotic
As a source information perception, electronic skin plays a crucial role in robotic
of information
systems. The development of electronic skin with better flexibility, stronger perception
systems. The
The development
development of of electronic
electronic skin with better flexibility, stronger perception
capability, and greater adaptability undoubtedly contributes significantly to the update and
iteration of robotic systems. Nowadays, the advancement of next-generation intelligent
sensing robots has begun, and this technology is rapidly advancing into fields such as
healthcare, industry, and energy [147–150]. With the organic integration of various elec-
tronic skins and complex algorithms, future intelligent sensing robots will be endowed
with greater vitality and capability.
 capability, and greater adaptability undoubtedly contributes significantly to the update
and iteration of robotic systems. Nowadays, the advancement of next-generation intelli-
gent sensing robots has begun, and this technology is rapidly advancing into fields such
as healthcare, industry, and energy [147–150]. With the organic integration of various elec-
Micromachines 2024, 15, 982 tronic skins and complex algorithms, future intelligent sensing robots will be endowed
38 of 49
with greater vitality and capability.

4.4.Targeted
4.4. TargetedTherapy
Therapy
Targetedtherapy
Targeted therapyisisan animportant
importantapplication
applicationof offlexible
flexiblepiezoelectric
piezoelectriccomposite
compositema- ma-
terials within the medical field. This technique is commonly
terials within the medical field. This technique is commonly combined with ultrasonics, combined with ultrasonics,
whichachieves
which achievesprecise
preciseandandnon-invasive
non-invasivetreatmenttreatmentofoftargeted
targetedtissues
tissuesby bycontrolling
controllingthethe
acousticfield
acoustic fieldofofthe
theultrasound
ultrasoundtransducer.
transducer.Targeted
Targetedtherapytherapyisismainly
mainlydivided
dividedinto
intotwo
two
categories:the
categories: thefirst
firstcategory
categoryinvolves
involvesmaking
makingflexible
flexiblepatches
patches(similar
(similarto towearable
wearablesensors)
sensors)
andimplanting
and implantingthem themintointothe
thebody,
body,achieving
achievingprecise
precisetreatment
treatmentofoflocal
localareas
areaswithin
withinthethe
bodythrough
body throughthe theapplication
applicationofofexternal
externalultrasound
ultrasoundstimulation.
stimulation.LiLietetal. al.[151]
[151]fabricated
fabricated
aawireless,
wireless,lead-free,
lead-free,battery-free
battery-freeferromagnetic
ferromagneticimplant implantusing usinga aPVDF/ZnO
PVDF/ZnOcomposite
composite
material,as
material, asshown
shown in in Figure 44. During
Duringuse, use,this
thisimplant
implantneedsneeds totobebe
wrapped
wrapped around
aroundthe
nerves
the nerves in in
thethe
targeted
targetedarea.
area.When
Whenthe theexternal
external transducer
transducer emits sound waves waves into
intothe
the
body,
body,the theimplant
implantcan canconvert
convertvibrations
vibrationsinto intoelectric
electricpulses,
pulses,thereby
therebyachieving
achievingelectrical
electrical
stimulation
stimulationininthe thenerves.
nerves.Wang
Wangetetal. al.[152]
[152]utilized
utilizedelectrospinning
electrospinningtechnology
technologytotoprepare
prepare
aananofiber
nanofiber composite material composed
composite material composedofofZnO@PCL ZnO@PCL(poly (poly (ε-caprolactone))/PVDF,
(ε-caprolactone))/PVDF, ex-
exhibiting various antibacterial, immune-modulating, and osteogenic
hibiting various antibacterial, immune-modulating, and osteogenic effects. After implan- effects. After im-
plantation
tation of this of this composite
composite material,
material, significant
significant morphological
morphological changes
changes were
were observedin
observed
inbone
bonetissue
tissuefrom
fromthe thesixth
sixth week
week to to the twelfth week.week. Experimental
Experimental results
resultsshowed
showedthat that
under
underultrasound
ultrasound regulation,
regulation, this composite material material significantly
significantlyenhanced
enhancedthe theprolifer-
prolif-
eration, migration,and
ation, migration, and osteogenic
osteogenic differentiation
differentiation of mouse mouse embryo
embryoosteoblast
osteoblastprecursor
precursor
cells,
cells, thereby expanding the application of flexible piezoelectric composite materialstoto
thereby expanding the application of flexible piezoelectric composite materials
bone
bonetissue
tissuerecovery.
recovery.Chen Chenetetal.al.[153]
[153]introduced
introducedaapomegranate-like
pomegranate-likestructured
structuredPEP@BT
PEP@BT
(piezoelectric
(piezoelectric polymer@BTO) flexible nanocomposite material, whichserves
polymer@BTO) flexible nanocomposite material, which servesas asaapotent
potent
wireless
wirelessneural
neuralmodulation
modulation tool
toolforfor
thetheeffective treatment
effective treatment of Parkinson’s
of Parkinson’s disease. Figure
disease. 45
Figure
depicts
45 depictsthe principle
the principleof the
of improvement
the improvement of Parkinson’s
of Parkinson’s disease by these
disease nanocomposite
by these nanocompo-
particles underunder
site particles ultrasound stimulation.
ultrasound Research
stimulation. indicatesindicates
Research that under ultrasound
that stimula-
under ultrasound
tion, this PEP@BT nanocomposite material effectively converts
stimulation, this PEP@BT nanocomposite material effectively converts ultrasound into ultrasound into electrical
energy,
electricalthereby
energy, regulating
thereby intracellular calcium signals
regulating intracellular and signals
calcium tyrosineand hydroxylase levels,
tyrosine hydrox-
activating neural activity and processes in deep brain tissue,
ylase levels, activating neural activity and processes in deep brain tissue, and thus and thus contributing to con-
the
regulation of Parkinson’s disease.
tributing to the regulation of Parkinson’s disease.

Figure44.
Figure 44.Implantation
ImplantationofofPVDF/ZnO
PVDF/ZnOflexible
flexiblecomposite
compositematerial
materialand
anditsits ultrasound
ultrasound control
control prin-
princi-
ciple [151].
ple [151].
Micromachines 2024,Micromachines
15, 982 2024, 15, x FOR PEER REVIEW 39 of 49 40

Figurediagram
Figure 45. Schematic 45. Schematic diagram
of PEP@BT of PEP@BTpromoting
nanoparticles nanoparticles promoting
recovery recovery of
of Parkinson’s Parkinson’s dis
disease
neurons in mice under ultrasound stimulation [153].
neurons in mice under ultrasound stimulation [153].

In addition,
In addition, another approachanother approach
is the development is the development of focusedtransducers.
of focused ultrasound ultrasound transduc
Historically, early research indicates that transducers for medical ultrasound are typically are typic
Historically, early research indicates that transducers for medical ultrasound
constructed fromconstructed from rigidcomposite
rigid piezoelectric piezoelectric composite
materials materials
[36–40]. [36–40]. These
These transducers cantransducers
be
be classified into two types based on their internal material
classified into two types based on their internal material structure: the first type utilizes structure: the first type util
planar rigid
planar rigid structures structures ofcomposite
of piezoelectric piezoelectric composite
materials. Due materials.
to the lackDue to the lack
of curvature in of curva
the compositein the composite
material, material,
an acoustic lensanis acoustic lens is often
often necessary necessary
during during
fabrication tofabrication
achieve to ach
the desired beamthe focusing.
desired beam The focusing.
other typeThe other type
employs employs composite
piezoelectric piezoelectric composite
materials withmaterials w
inherently curved structures, thereby eliminating the need for an acoustic lens during fabri- during
inherently curved structures, thereby eliminating the need for an acoustic lens
rication.
cation. Nevertheless, bothNevertheless, both typescomposite
types of piezoelectric of piezoelectric
materialscomposite materials
are non-flexible, are non-flex
which
which may require longer production cycles and lower
may require longer production cycles and lower yields. In contrast, flexible piezoelectric yields. In contrast, flexible pi
electric composite materials can be easily shaped into
composite materials can be easily shaped into curved structures, eliminating the need for curved structures, eliminating
an acoustic lensneed for an acoustic
in transducer lens inand
fabrication transducer
facilitatingfabrication and facilitating
further optimization further optimizatio
of transducer
dimensions. The transducer dimensions.
1-3 PZT/PDMS The 1-3
focusing PZT/PDMS
transducer focusing transducer
developed by Kim et developed
al. [84] notby Kim e
only simplifies[84]
thenot only simplifies
traditional structure theoftraditional
acoustic lenses structurebutof acoustic
also has a lenses but also has a g
good acoustic
acoustic focusing effect. When the hydrophone
focusing effect. When the hydrophone moves along the xoy plane to the point where moves along the xoy plane
the to the p
sound pressure amplitude is maximum, the actual measured focal length of the sound length of
where the sound pressure amplitude is maximum, the actual measured focal
field is 6.5 mm,sound
whichfield is 6.5 mm,with
is consistent which theisdesign
consistent
value with the design
(6mm), proving value
the (6mm),
value ofproving
this the v
of this transducer in focused medicine. For example,
transducer in focused medicine. For example, the PZT-8/PDMS 1-3 focusing transducer the PZT-8/PDMS 1-3 focusing tr
ducer developed by Hou et al. [85] can achieve focusing
developed by Hou et al. [85] can achieve focusing performance without the use of acoustic performance without the us
lenses, as shownacoustic lenses,
in Figure 46. as shown
Within theincurvature
Figure 46.radius
Withinrangethe curvature radius range
of 17.5 mm~27.5 mm, ofthe17.5 mm~
mm,change
lateral resolution the lateral
rangeresolution
of the focalchange range is
position of 0.79
the focal position
mm~1.21 mm,is 0.79
and mm~1.21
the axial mm, and
axialrange
resolution change resolution
is 4.45change
mm~14.01 range mm.is 4.45 mm~14.01 mm.
High-resolution High-resolution
dynamic imaging can dynamic
be imag
can be achieved in a large spatial range, verifying the ability
achieved in a large spatial range, verifying the ability of this focusing transducer to perform of this focusing transduce
performfocusing
non-contact dynamic non-contact dynamic
imaging on a focusing
large spatialimaging
range.on a large spatial range.
The development of flexible composite materials is of significant importance in ex-
panding medical treatment methods and improving transducer structures. In the field of
targeted therapy, flexible piezoelectric composite materials serve as adjunctive therapies,
representing a burgeoning modern medical approach in recent years, expediting the tran-
sition of traditional large medical equipment towards miniaturization, convenience, and
efficiency, with promising prospects in the future. In addition to the above four main appli-
cation directions, flexible piezoelectric composite materials can also be used in research
directions such as motion perception and rehabilitation training [154–159]. These designs
generally utilize the force-sensitive sensing characteristics of flexible piezoelectric com-
posite materials to evaluate physiological information such as posture and touch through
pressure signals, and these applications are generally similar to the principles of wearable
sensors and electronic skins introduced earlier.
Micromachines 2024, 15,
15, 982
x FOR PEER REVIEW 41
40of 50
of 49

Figure 46.
Figure 46. Dynamic
Dynamic acoustic
acoustic field
field modulation
modulation experiment
experiment of focused transducer
of focused transducer under
under different
different
curvatures [85]. (a) Schematic diagram of the experimental device includes the size of the digitaldigital
curvatures [85]. (a) Schematic diagram of the experimental device includes the size of the plate
plate (imaging object) and the principle of dynamic multifocal imaging with the transducer at dif-
(imaging object) and the principle of dynamic multifocal imaging with the transducer at different
ferent curvatures. (b) Photogram of the experimental setup. (c) Ultrasound imaging of digital plates
curvatures. (b) Photogram of the experimental setup. (c) Ultrasound imaging of digital plates
based on continuous dynamic adjustment method. (d) Signal extraction and analysis of ultrasound
based
imagingonresults.
continuous dynamic adjustment method. (d) Signal extraction and analysis of ultrasound
imaging results.
The development
4.5. Ultrasound of flexible
Diagnostics for Deepcomposite
Tissue materials is of significant importance in ex-
panding medical treatment methods and improving transducer structures. In the field of
The ultrasound diagnosis of deep tissues has become a popular research area in
targeted therapy, flexible piezoelectric composite materials serve as adjunctive therapies,
recent years, primarily leveraging the strong penetration capability of ultrasound tech-
representing a burgeoning modern medical approach in recent years, expediting the tran-
nology. This technique involves placing one or several ultrasonic transducers (arrays) on
sition of traditional large medical equipment towards miniaturization, convenience, and
the surface of the skin or within the internal tissues of a biological organism. By utiliz-
efficiency, with promising prospects in the future. In addition to the above four main ap-
ing ultrasound feedback or stimulation, this approach achieves real-time monitoring or
plication directions, flexible piezoelectric composite materials can also be used in research
therapeutic effects, thus categorizing it under wearable sensors. Typically, these ultrasonic
directions such as motion perception and rehabilitation training [154–159]. These designs
transducers employ a 1-3 type piezoelectric composite structure for their piezoelectric
generally utilize the force-sensitive sensing characteristics of flexible piezoelectric compo-
elements (1-3 elements). This configuration allows for high-purity thickness vibration
site materials
energy to evaluate physiological
of the transducing elements whileinformation such
maintaining as insertion
low posture and
loss.touch through
Additionally,
pressure signals, and these applications are generally similar to the principles of
these transducers are equipped with flexible printed circuit boards or flexible packagingwearable
sensors and
substrates forelectronic skins
positioning or introduced
embeddingearlier.
the 1-3 elements that generate ultrasound waves.
This facilitates flexible/stretchable functionality, providing numerous important insights
4.5.the
for Ultrasound
design of Diagnostics
ultrasonicfor Deep Tissue
medical products.
The ultrasound
Faced diagnosis issues
with the mismatch of deepcaused
tissuesby has
thebecome a popular
large size research
and rigidity area in re-
of traditional
cent years, primarily leveraging the strong penetration capability of ultrasound
ultrasound equipment, Wang et al. [160] reported a stretchable ultrasound patch composed technol-
ogy.
of 1-3This technique
elements. The involves placing
1-3 elements one or
are used toseveral
suppress ultrasonic transducers
shear modes (arrays)
and enhance theon the
longi-
surface of
tudinal the skin or capability
transmission within theofinternal
acoustictissues
waves. of aThe
biological organism.
electrodes on the topBy utilizing
and bottom ul-
trasound
of feedback
the elements or stimulation, in
are interconnected this approach achieves
a serpentine structurereal-time
to improve monitoring or thera-
the stability of the
peutic effects,
elements. Tests thus
have categorizing
demonstrateditthatunder
this wearable
ultrasoundsensors. Typically,
patch exhibits thesemechanical
excellent ultrasonic
compliance, with a tensile
transducers employ strainpiezoelectric
a 1-3 type of up to 60%,composite
while alsostructure
being ablefortotheir
generate ultrasound
piezoelectric el-
waves at a depth of 4 cm. Furthermore, this stretchable ultrasound patch
ements (1-3 elements). This configuration allows for high-purity thickness vibration en- can adapt to
various positions
ergy of the on theelements
transducing body andwhile
can dynamically
maintainingand lowaccurately monitor
insertion loss. deep biological
Additionally, these
tissues or organs
transducers through non-invasive
are equipped methods,
with flexible printed offering
circuit newor
boards insights
flexiblefor the diagnosis
packaging sub-
and prediction
strates of cardiovascular
for positioning or embeddingdiseases
the in1-3a wearable
elements form. Jiang et al.
that generate [161] developed
ultrasound waves.
a flexible
This ultrasonic
facilitates retinal stimulation
flexible/stretchable piezoelectric
functionality, array numerous
providing (F-URSP) for providing
important pros-
insights
thetic vision to people with acquired
for the design of ultrasonic medical products.blindness. This device integrates a two-dimensional
 mechanical compliance, with a tensile strain of up to 60%, while also being able to gener-
ate ultrasound waves at a depth of 4 cm. Furthermore, this stretchable ultrasound patch
can adapt to various positions on the body and can dynamically and accurately monitor
deep biological tissues or organs through non-invasive methods, offering new insights for
Micromachines 2024, 15, 982 the diagnosis and prediction of cardiovascular diseases in a wearable form. Jiang41etof al. 49
[161] developed a flexible ultrasonic retinal stimulation piezoelectric array (F-URSP) for
providing prosthetic vision to people with acquired blindness. This device integrates a
two-dimensional
piezoelectric array,piezoelectric
rectifiers, andarray, rectifiers,
a 32-pixel and a 32-pixel
stimulating electrodestimulating
array on aelectrode array
single flexible
on a single
printed flexible
circuit board,printed circuit
achieving board,
a high levelachieving a high as
of integration, level
shown of integration,
in Figure 47. as Similar
shown
in the
to Figure 47. Similar
previously to the previously
mentioned work, thementioned
F-URSP also work, the F-URSP
employs severalalso 1-3 employs
elementsseveral
as the
ultrasonic
1-3 elementsarray, eachultrasonic
as the composedarray,
of lead magnesium
each composed niobate-lead titanate (PMN-PT)
of lead magnesium niobate-leadsingle
ti-
crystal with strongsingle
tanate (PMN-PT) piezoelectric properties
crystal with strongand epoxy resinproperties
piezoelectric with goodand stability.
epoxyThisresinconfig-
with
uration not onlyThis
good stability. provides a high electromechanical
configuration not only provides coupling
a highcoefficient (kt ~ 0.84)coupling
electromechanical but also
ensures a high −
(g33 ~ 40.3 ×voltage 3 − 1
coefficient (kt ~piezoelectric
0.84) but also voltage
ensures coefficient
a high piezoelectric 10 V coefficient
m N ). Experimental
(g33 ~ 40.3 ×
results
10−3 V mshow
N−1).that when the stimulating
Experimental results show electrode
that whenarray
theofstimulating
the F-URSPelectrode
is matched with
array of the
isolated
F-URSP retinal tissuewith
is matched of mice and induced
the isolated retinal bytissue
ultrasound,
of miceitand
caninduced
cause a 5% change in the
by ultrasound, it
average
can causefluorescence
a 5% change intensity
in the on the retina,
average verifyingintensity
fluorescence the feasibility
on the of retina,
ultrasound-induced
verifying the
activation
feasibility of neural cell activity. activation of neural cell activity.
ultrasound-induced

Figure 47.
Figure 47. A
A flexible
flexible ultrasonic
ultrasonic retinal
retinal stimulation
stimulation piezoelectric
piezoelectric array
array (F-URSP)
(F-URSP) [161].
[161].

Developing flexible/stretchable ultrasonic transducers

flexible/stretchable ultrasonic transducers (arrays)
(arrays) provides
provides feasible
feasible so-
so-
lutions for medical dynamic
medical dynamic monitoring and induced therapy, significantly enhancing
therapy, significantly enhancing
convenience. Besides
Besides external
external treatments, these ultrasonic transducers (arrays) can also
serve as targeted
targetedstimulation
stimulationimplants,
implants,which
which enables
enables ultrasound-induced
ultrasound-induced deep
deep tissue
tissue re-
repair.
pair. InInthis
thiscontext,
context,the
theenvironmental
environmentalfriendliness
friendlinessor
or biocompatibility
biocompatibility ofof the functional
materials is an an important
important consideration.
consideration. Wang et al. [162] developed
developed a flexible
flexible biphasic
biphasic
ultrasound implant (f-BUI), as shown in Figure 48.
Figure 48. The f-BUI contains
f-BUI contains 1-3 elements
elements with
with
different resonant frequencies, rectifiers, and transistors, all integrated into a small flexible
printed circuit board measuring 13.6 mm × 7.3 mm, achieving a high level of integration.
This study has two notable highlights: firstly, KNN was used in developing the 1-3 ele-
ments, balancing enhanced biocompatibility with piezoelectric properties. Secondly, the
researchers reverse-connected two pairs of rectifiers and transistors with 1-3 elements of
different resonant frequencies (1 MHz and 3 MHz). By regulating the ultrasound frequency
and phase, they achieved bipolar electrical stimulation, reducing charge accumulation
and adverse electrochemical reactions on the electrode surface, thereby minimizing tissue
damage. Experimental results demonstrated that, when induced by ultrasound, the f-BUI
effectively suppressed the overall intensity of abnormal electrocorticography (ECoG) sig-
nals in epileptic mice, alleviating the severity of epilepsy and confirming the reliability of
the f-BUI implant in treating epilepsy.
 quency and phase, they achieved bipolar electrical stimulation, reducing charge accumu-
lation and adverse electrochemical reactions on the electrode surface, thereby minimizing
tissue damage. Experimental results demonstrated that, when induced by ultrasound, the
f-BUI effectively suppressed the overall intensity of abnormal electrocorticography
Micromachines 2024, 15, 982 (ECoG) signals in epileptic mice, alleviating the severity of epilepsy and confirming
42 ofthe
49
reliability of the f-BUI implant in treating epilepsy.

Figure 48.
Figure 48. A
A flexible
flexible biphasic ultrasound implant
biphasic ultrasound implant for
for epilepsy
epilepsy regulation
regulation (f-BUI)
(f-BUI) [162].
[162]. (a)
(a) Schematic
Schematic
diagram of the f-BUI implanted in a rat brain. (b) Image of the f-BUI sample before encapsulation.
diagram of the f-BUI implanted in a rat brain. (b) Image of the f-BUI sample before encapsulation.
(c) f-BUI sample in a bent state before encapsulation. (d) Optical image showing the f-BUI encapsu-
(c) f-BUI sample in a bent state before encapsulation. (d) Optical image showing the f-BUI encap-
lated in silicone. (e) Micro-CT 3D rendering image of a rat brain after implantation of f-BUI on day
sulated
30. in silicone. (e) Micro-CT 3D rendering image of a rat brain after implantation of f-BUI on
day 30.
5. Conclusions
5. Conclusions and and Outlook
Outlook
This paper
This paper reviews
reviewsthe theprogress
progressofofresearch
research onon flexible
flexible piezoelectric
piezoelectric composite
composite ma-
materi-
terials
als bothboth domestically
domestically and and internationally;
internationally; introduces
introduces the types
the types and preparation
and preparation meth-
methods of
ods of flexible
flexible piezoelectric
piezoelectric compositecomposite materials;
materials; and explores
and explores their applications
their applications in various
in various fields.
fields. Flexible
Flexible piezoelectric
piezoelectric compositecomposite
materials materials have demonstrated
have demonstrated their valuetheir value indue
in research re-
search
to due tosensitivity,
excellent excellent sensitivity,
mechanicalmechanical
flexibility, flexibility, and high adaptability
and high adaptability to sensingtosystems.
sensing
systems.
In contrastIn with
contrast with traditional
traditional piezoelectric
piezoelectric composite composite
materials, materials, the emergence
the emergence of
of flexible
flexible piezoelectric
piezoelectric composite composite
materialsmaterials
will enable willthe
enable
creationthe of
creation of an abundance
an abundance of structuralof
structural
designs designs
and and application
application scenarios,scenarios, thusassisting
thus greatly greatly assisting in the development
in the development of futureof
future intelligent
intelligent systems. systems. At present,
At present, flexible flexible piezoelectric
piezoelectric composite composite
materialsmaterials are un-
are undergoing
rapid development.
dergoing Although many
rapid development. outstanding
Although achievements
many outstanding have already
achievements beenalready
have made,
there are stillthere
been made, aspects
are that
still require
aspects further optimization:
that require further optimization:
1.
1. One critical
One critical aspect
aspectisisnon-toxicity
non-toxicityand
andenvironmental
environmental sustainability. TheThe
sustainability. enhancement
enhance-
of piezoelectric
ment properties
of piezoelectric in flexible
properties piezoelectric
in flexible composite
piezoelectric materials
composite often involves
materials often in-
doping doping
volves with high leadhigh
with content
leadPZT powder,
content PZTwhich is a ceramic
powder, material
which is known
a ceramic for its
material
high lead
known forcontent,
its high which poses potential
lead content, harm
which poses to human
potential health
harm and thehealth
to human environment
and the
with prolonged use. Besides PZT, improved ZnO materials are occasionally consid-
ered for flexible piezoelectric composite materials. However, due to their toxic and
polluting nature, these inherent drawbacks may limit the potential applications of
such materials. Therefore, advancements in non-toxic and environmentally friendly
piezoelectric materials have the potential to further expand the application scope of
flexible piezoelectric composite materials. Furthermore, some researchers have inte-
grated lead-free ceramics like BZT into applications involving piezoelectric composite
materials, suggesting that flexible piezoelectric composite materials developed using
such piezoelectric materials may hold significant economic advantages.
2. Functional integration of sensing structures. The inception of wearable sensors and
electronic skin has initiated a new epoch in advancing the design of flexible piezoelec-
tric composite materials towards miniaturization, convenience, and mass accessibility.
However, many of these sensors are designed with relatively single functions, mak-
Micromachines 2024, 15, 982 43 of 49

ing it difficult to address complex integrated problems. For this reason, flexible
piezoelectric composite materials may require smaller structural sizes to promote the
multi-functional integration of sensors.
3. Further optimization of performance trade-offs is essential. The development of
flexible piezoelectric composite materials with high-performance trade-offs is crucial
for resolving various trade-offs. For example, in 0-3 type piezoelectric composite
materials, it is crucial to consider the balance between material flexibility and piezo-
electricity. When the piezoelectric ceramic powder is excessively doped, the material’s
flexibility will significantly decrease, while when the doping amount is too small,
the material’s piezoelectricity will be greatly compromised. However, piezoelectric
composites developed through doping tend to exhibit lower piezoelectricity com-
pared to existing piezoelectric ceramics. Therefore, to meet performance requirements,
the development of flexible piezoelectric materials that can simultaneously balance
flexibility and high piezoelectricity will become extremely important. On the other
hand, multi-component flexible piezoelectric composites, comprising three or more
materials, demonstrate great development potential. Since achieving compression
resistance and flexibility simultaneously in the same material poses challenges, this
multi-component design approach provides support for balancing compression resis-
tance and flexibility. In complex underwater environments, this approach might be
the most optimal solution.

Author Contributions: Conceptualization, J.Z., J.W. and L.Q.; methodology, J.Z., J.W. and C.Z.;
validation, J.Z., J.W., C.Z. and L.Q.; investigation, J.Z., J.W., C.Z. and Y.Q.; resources, J.W., Y.Z. and
Y.Q.; data curation, C.Z., Y.Q. and Y.Z.; writing—original draft preparation, J.W., Y.Z. and Y.Q.;
writing—review and editing, J.Z., Y.Z. and L.Q.; supervision, J.Z. and L.Q.; project administration,
J.Z. and L.Q.; funding acquisition, J.Z. and L.Q. All authors have read and agreed to the published
version of the manuscript.
Funding: This work was partially supported by the National Key Research and Development
Program of China (2018AAA0100301) and the National Natural Science Foundation of China
(No.62174012, U2006218). This work was also supported by the Project of Construction and Support
for High-level Innovative Teams of Beijing Municipal Institutions (BPHR20220124) and the Science
and Technology Innovation Program of Beijing Institute of Technology (2023CX01007).
Conflicts of Interest: The authors declare no conflicts of interest.

References
1. Xie, F. Natural polymer starch-based materials for flexible electronic sensor development: A review of recent progress. Carbohydr.
Polym. 2024, 337, 122116. [CrossRef] [PubMed]
2. Liu, Y.; Yue, W.; Zhang, Z. Application of Sensor Technology in Manufacturing Automation. Mech. Eng. Autom. 2023, 4, 162–164.
3. Sawane, M.; Prasad, M. MEMS piezoelectric sensor for self-powered devices: A review. Mater. Sci. Semicond. Process. 2023, 158,
107324. [CrossRef]
4. Zhang, Y. Research on High Frequency Spherical Broadband Transducer. Ph.D. Thesis, Beijing University of Posts and Telecom-
munications, Beijing, China, May 2022.
5. Berto, L.; Ettmayer, J.; Stutzer, D.; Nietzsche, S.; Niederhauser, T.; Burger, J.; Sculean, A.; Eick, S.; Hofmann, M. In-vitro effects
of novel periodontal scalers with a planar ultrasonic piezoelectric transducer on periodontal biofilm removal, dentine surface
roughness, and periodontal ligament fibroblasts adhesion. Clin. Oral Investig. 2024, 28, 294. [CrossRef]
6. Zhong, C.; Xu, J.; Hao, S.; Zhang, Y.; Wang, L.; Qin, L. High-frequency wide beam underwater transducer based on 1–3
piezocomposite. Ferroelectr. Lett. Sect. 2021, 48, 93–103. [CrossRef]
7. Zhao, H.; Li, H.; Wang, Y.; Liu, Z.; Bian, J.; Chen, J. A thickness-mode high-frequency underwater acoustic transducer with a low
sidelobe level. Actuators 2021, 10, 226. [CrossRef]
8. Li, J.; Gao, Y.; Zhou, Z.; Ping, Q.; Qiu, L.; Lou, L. An AlScN Piezoelectric Micromechanical Ultrasonic Transducer-Based
Power-Harvesting Device for Wireless Power Transmission. Micromachines 2024, 15, 624. [CrossRef]
9. Singh, A.; Singh, M. Electrochemical and piezoelectric monitoring of taurine via electropolymerized molecularly imprinted films.
J. Mol. Recognit. 2017, 30, e2652. [CrossRef]
10. Yein, T.; Wang, Q.; Kim, S. Piezoelectric catalytic driven advanced oxidation process using two-dimensional metal dichalcogenides
for wastewater pollutants remediation. Chemosphere 2024, 353, 141524. [CrossRef]
Micromachines 2024, 15, 982 44 of 49

11. Shi, X.; Sun, Y.; Tian, H.; Liu, H.; Li, D. 3D-printed wearable BaTiO3 /PDMS piezoelectric nanogenerator for self-powered body
movement sensing. Flex. Print. Electron. 2023, 8, 045005. [CrossRef]
12. Hasan, M.; Rahman, M.; Sadeque, M.; Ordu, M. Self-Poled Piezoelectric Nanocomposite Fiber Sensors for Wireless Monitoring of
Physiological Signals. ACS Appl. Mater. Interfaces 2024, 16, 34549–34560.
13. Zhong, C. Research on Three-Phase Piezocomposite and Curved Surface Transducer. Ph.D. Thesis, Beijing University of Posts
and Telecommunications, Beijing, China, April 2019.
14. Luan, G.; Zhang, J.; Wang, R. Piezoelectric Transducers and Arrays; Beijing University: Beijing, China, 2005; pp. 73–100.
15. Li, L. Research on 1–3 Series Piezoelectric Composite and Underwater Transducer. Ph.D. Thesis, Beijing University of Posts and
Telecommunications, Beijing, China, May 2008.
16. Newnham, R.; Bowen, L.; Klicker, K.; Cross, L. Composite piezoelectric transducers. Mater. Des. 1980, 2, 93–106. [CrossRef]
17. Moulin, E.; Assaad, J.; Delebarre, C.; Kaczmarek, H.; Balageas, D. Piezoelectric transducer embedded in a composite plate:
Application to Lamb wave generation. J. Appl. Phys. 1997, 82, 2049–2055. [CrossRef]
18. Shi, Y. Structural Design and Performance Analysis of a Flexible Piezoresistive Pressure Sensor. Master’s Thesis, Xi’an University
of Technology, Xi’an, China, June 2023.
19. Wen, D. The Preparation and Application of Magnetoelectrical Composite Materials. Ph.D. Thesis, University of Electronic
Science and Technology of China, Chengdu, China, June 2018.
20. Teng, D.; Yang, H.; Li, D. Fundamentals of Underwater Acoustic Transducers; Northwestern Polytechnical University: Xi’an, China,
2016; pp. 21–26.
21. Nurkowski, J.; Nowakowski, A. Inductive sensor for measuring linear displacement and velocity-Version with stationary
magnetic core. Measurement 2023, 222, 113675. [CrossRef]
22. Xiao, Z. Structure Design and Electrical Output Performance of Flexible Piezoelectric Composites. Master’s Thesis, Central South
University, Changsha, China, June 2023.
23. Xu, L. Study on Fabrication, Structure and Peoperties of PZT5/Epoxy Resin 1–3 Composite. Ph.D. Thesis, Wuhan University of
Technology, Wuhan, China, May 2006.
24. Wang, H. Analysis for the effective properties of piezocomposite. Master’s Thesis, Beijing University of Technology, Beijing,
China, May 2006.
25. Li, N. Study on Preparation and Physical Properties of 1–3 Piezoelectric Composites. Master’s Thesis, Shandong University, Jinan,
China, 29 May 2019.
26. Richard, C.; Eyraud, P.; Eyraud, L.; Audigier, D.; Richard, M. An optimization of 1.3.1 PZT-polymer composite for deep underwater
hydrophone application. In Proceedings of the Eighth IEEE International Symposium on Applications of Ferroelectrics, Greenville,
SC, USA, 30 August 1992; pp. 255–258.
27. Howarth, T.; Ting, R. Development of a broadband underwater sound projector, Oceans’ 97. In Proceedings of the MTS/IEEE
Conference Proceedings, Halifax, NS, Canada, 6–9 October 1997; pp. 1195–1201.
28. Benjamin, K. Recent advances in 1–3 piezoelectric polymer composite transducer technology for AUV/UUV acoustic imaging
applications. J. Electroceramics 2002, 8, 145–154. [CrossRef]
29. Bowen, L.; Gentilman, R.; Fiore, D.; Hong, P.; Serwatka, W.; Near, C.; Pazol, B. Design, fabrication, and properties of sonopanelTM
1–3 piezocomposite transducers. Ferroelectrics 1996, 187, 109–120. [CrossRef]
30. Howarth, T.; Ting, R. Electroacoustic evaluations of 1–3 piezocomposite SonoPanelTM materials. IEEE Trans. Ultrason. Ferroelectr.
Freq. Control 2000, 47, 886–894. [CrossRef] [PubMed]
31. Robertson, D.; Cochran, S. Experimental investigation of alternative pre-stress components for a 3–1 connectivity multilayer
piezoelectric-polymer composite ultrasonic transducer. Ultrasonics 2002, 40, 913–919. [CrossRef] [PubMed]
32. Pei, L.; Roh, Y. Design of an Underwater Tonpilz Transducer with 1–3 Piezocomposite Materials. Jpn. J. Appl. Phys. 2008, 47,
4003–4006. [CrossRef]
33. Li, L.; Wang, L.; Qin, L.; Wang, G. Modified 1–3 Ceramic/Epoxy Piezocompsite and Cylinder Array Transducer. Ferroelectrics
2010, 409, 145–151. [CrossRef]
34. Benjamin, K.; Petrie, S. A new Navy calibration standard transducer using 1–3 piezocomposite. In Proceedings of the OCEANS
2000 MTS/IEEE Conference and Exhibition, Providence, RI, USA, 11–14 September 2000; pp. 1299–1304.
35. Safari, A.; Danforth, S.; Panda, R.; Lous, G.; Cornejo, I.; Kholkine, A. Novel piezocomposites for ultrasonic transducer applications.
In Proceedings of the 1998 IEEE Ultrasonics Symposium, Sendai, Japan, 5–8 October 1998; Volume 1, pp. 615–618.
36. Cochran, A.; Reynolds, P.; Hayward, G. Progress in stacked piezocomposite ultrasonic transducers for low frequency applications.
Ultrasonics 1998, 36, 969–977. [CrossRef]
37. Ritter, T.; Shrout, T.; Tutwiler, R.; Shuang, K. A 30-MHz piezo-composite ultrasound array for medical imaging applications. IEEE
Trans. Ultrason. Ferroelectr. Freq. Control 2002, 49, 217–230. [CrossRef]
38. Fleury, G.; de Lima, D.; Hynynen, K.; Berriet, R.; Baron, O.; Huguenin, B. New piezocomposite transducers for therapeutic
ultrasound. In Proceedings of the Thermal Treatment of Tissue: Energy Delivery and Assessment II, San Jose, CA, USA, 10 June
2003; Volume 4954, pp. 227–236.
39. Or, S.; Chan, H.; Liu, P. Piezocomposite ultrasonic transducer for high-frequency wire-bonding of microelectronics devices. Sens.
Actuators A Phys. 2007, 133, 195–199. [CrossRef]
Micromachines 2024, 15, 982 45 of 49

40. Zhang, Q.; Chen, J.; Wang, H.; Zhao, J.; Cross, L.; Trottier, M. A new transverse piezoelectric mode 2–2 piezocomposite for
underwater transducer applications. IEEE Trans. Ultrason. Ferroelectr. Freq. Control 1995, 42, 774–781. [CrossRef]
41. Yoon, K.; Shin, S.; Park, H.; Goo, N. Design and manufacture of a lightweight piezo-composite curved actuator. Smart Mater.
Struct. 2002, 11, 163. [CrossRef]
42. Schoenecker, A.; Gebhardt, S.; Roedig, T.; Keitel, U.; Brueckner, B.; Schnetter, J.; Daue, T. Piezocomposite transducers for smart
structures applications. In Proceedings of the Smart Structures and Materials 2005: Smart Structures and Integrated Systems, San
Diego, CA, USA, 17 May 2005; Volume 5764, pp. 34–41.
43. Schultz, M.; Hyer, M.; Williams, R.; Wilkie, W.; Inman, D. Snap-through of unsymmetric laminates using piezocomposite actuators.
Compos. Sci. Technol. 2006, 66, 2442–2448. [CrossRef]
44. Salas, K.; Cesnik, C.; Raghavan, A. Modeling of wedge-shaped anisotropic piezocomposite transducer for guided wave-based
structural health monitoring. In Proceedings of the 48th AIAA/ASME/ASCE/AHS/ASC Structures, Structural Dynamics, and
Materials Conference, Honolulu, Hawaii, 23–26 April 2007; p. 1723.
45. Gentilman, R.; Bowen, L.; Fiore, D.; Pham, H.; Serwatka, W. Injection molded 1–3 piezocomposite velocity sensors. In Proceedings
of the AIP Conference Proceedings, Mystic, CT, USA, 12–13 September 1995; Volume 368, pp. 312–319.
46. Yuan, Y. Measuring frozen soils with composite piezoelectric transducers of 1–3 and 2–2 connectivity. J. Appl. Acoust. 2003,
22, 39–44.
47. Badcock, R.; Birt, E. The use of 0–3 piezocomposite embedded Lamb wave sensors for detection of damage in advanced fibre
composites. Smart Mater. Struct. 2000, 9, 291. [CrossRef]
48. Kim, C.; Rittenmyer, K.; Kahn, M. 1–1–3 Piezocomposite for hydrophone transducer. Ferroelectrics 1994, 156, 19–24. [CrossRef]
49. Wang, L.; Wan, Y.; Li, L.; Qin, L.; Lu, Y. Investigation on stability of PZT/epoxy piezocomposite with pressure and temperature.
Acta Mech. Solida Sin. 2009, 22, 226–231. [CrossRef]
50. Qin, L.; Li, L.; Wang, L.; Sun, B. Research on Hydrostatic Characteristics of 3–2 Piezoelectric Composite. J. Funct. Mater. 2007,
11, 1824–1830.
51. Li, L.; Wang, L.; Qin, L.; Lv, Y. The theoretical model of 1–3–2 piezocomposites. IEEE Trans. Ultrason. Ferroelectr. Freq. Control 2009,
56, 1476–1482. [CrossRef] [PubMed]
52. Cheng, X.; Xu, D.; Lu, L.; Huang, S.; Jiang, M. Performance investigation of 1–3 piezoelectric ceramic-cement composite. Mater.
Chem. Phys. 2010, 121, 63–69. [CrossRef]
53. Potong, R.; Rianyoi, R.; Jaitanong, N.; Yimnirun, R.; Chaipanich, A. Ferroelectric hysteresis behavior and dielectric properties of
1–3 lead zirconate titanate–cement composites. Ceram. Int. 2011, 38, S267–S270. [CrossRef]
54. Hu, R.; Li, J.; Wu, F.; Lu, Z.; Deng, C. A dual function flexible sensor for independent temperature and pressure sensing. Chem.
Eng. J. 2024, 491, 152135. [CrossRef]
55. Sun, Y.; Yang, Y.; Yao, D.; Gao, X.; Chen, J.; Wang, H.; You, T.; Dong, Y.; Lu, Y.; Lu, C.; et al. Biomimetic multilayer flexible sensors
for multifunctional underwater sensing. Chem. Eng. J. 2024, 492, 152273. [CrossRef]
56. Dong, Y.; Xu, C.; Chen, S.; Wang, Z. Flexible piezoelectric pressure sensor based on BaTiO3 –CNT/RTV composite film with filter
paper microstructures for monitoring hand motions. Meas. Sci. Technol. 2024, 35, 085111. [CrossRef]
57. Zhang, C.; Yuan, C.; Zhu, Q.; Sun, H. Large-scale fabrication and performance improvement of polyvinylidene fluoride
piezoelectric composite films. Ceram. Int. 2023, 49, 27255–27265. [CrossRef]
58. Wei, X.; Xu, K.; Wang, Y.; Zhang, Z.; Chen, Z. 3D Printing of Flexible BaTiO3 /Polydimethylsiloxane Piezocomposite with Aligned
Particles for Enhanced Energy Harvesting. ACS Appl. Mater. Interfaces 2024, 16, 11740–11748. [CrossRef]
59. Zhao, Z.; Yu, Y.; He, L.; Wang, Z.; Kurita, H.; Narita, F. Effect of carbon black addition on electromechanical performance of
flexible piezoelectric composite films. Compos. Part A 2024, 180, 108103. [CrossRef]
60. Verma, K.; Sharma, R. Development of KNNLTS-PVDF-based flexible piezoelectric generator for energy-harvesting application.
Bull. Mater. Sci. 2024, 47, 38. [CrossRef]
61. Huang, Z.; Li, L.; Huang, Y.; Rao, W.; Jiang, H.; Wang, J.; Zhang, H.; He, H.; Qu, J. Self-poled piezoelectric polymer composites via
melt-state energy implantation. Nat. Commun. 2024, 15, 819. [CrossRef] [PubMed]
62. Jiang, S.; Shen, Y.; Wang, S.; Jiang, W.; Liu, Y.; Wu, Q. Flexible piezoelectric composite sensor for impact monitoring of curved
structures. Sens. Actuators A Phys. 2023, 362, 114655. [CrossRef]
63. Chen, S.; Luo, J.; Wang, X.; Li, Q.; Zhou, L.; Liu, C.; Feng, C. Fabrication and piezoresistive/piezoelectric sensing characteristics of
carbon nanotube/PVA/nano-ZnO flexible composite. Sci. Rep. 2020, 10, 8895. [CrossRef] [PubMed]
64. Suyambazhahan, S.; Rao, C.; Girma, D. Characterization of 0–3 piezoelectric polymer composites using FEA for biomedical
transducers applications. Ferroelectrics 2024, 618, 718–731. [CrossRef]
65. Guler, Z.; Vazquez, I.; Jackson, N. Multi-functional 0–3 composite polyimide films for microsystem applications. Smart Mater.
Struct. 2023, 32, 075015. [CrossRef]
66. Wang, L.; Wang, K.; Shi, S.; Wang, N.; Zhang, L.; Lu, B. 3D printed 0–3 type piezoelectric composites with high voltage sensitivity-.
Ceram. Int. 2022, 48, 12559–12568. [CrossRef]
67. Weng, F. Design, Fabrication and Application of Flexible Pressure Sensor Based on PVDF Piezoelectric Film. Master’s Thesis,
Hangzhou Dianzi University, Hangzhou, China, May 2023.
68. He, S. Preparation and Performance Study of PVDF Blended Composite Film and Its Application in Sensor. Master’s Thesis,
Beijing Institute of Petrochemical Technology, Beijing, China, June 2023.
Micromachines 2024, 15, 982 46 of 49

69. Li, Y.; Xu, L.; Wang, L.; Zhang, B.; Wang, P. Performance optimization of piezoelectric PVDF film and its application. New Chem.
Mater. 2023, 51, 8–12.
70. Ali, N.; Kenawy, E.; Wadoud, A.; Elhadary, M. Wearable Electrospun Piezoelectric Mats Based on a PVDF Nanofiber–ZnO@ ZnS
Core–Shell Nanoparticles Composite for Power Generation. Nanomaterials 2023, 13, 2833. [CrossRef]
71. Taleb, S.; Badillo, M.; Flores-Ruiz, F.; Acuautla, M. From synthesis to application: High-quality flexible piezoelectric sensors
fabricated from tetragonal BaTiO3 /P(VDF-TrFE) composites. Sens. Actuators A Phys. 2023, 361, 114585. [CrossRef]
72. Xiong, P.; Wu, R.; Ma, C.; Xu, J.; Wang, Q. Study on dielectric and energy storage characteristics of P(VDF-CTFE/dopa@BTO
laminated composite film. Insul. Mater. 2024, 54, 28–35.
73. He, S.; Xue, R.; He, Y.; Huang, Y.; Wu, Y.; Shi, Q. Preparation and Properties of Tb3+ Doped PVDF/PLLA Electrospun Multifunc-
tional Piezoelectric Nano fibers. Mater. Rep. 2024, 38, 250–255.
74. Jiang, S.; Shen, Y.; Wang, S.; Zhi, Y.; Han, B. Properties of novel 0–3 PZT/silicone resin flexible piezoelectric composites for
ultrasonic guided wave sensor applications. Front. Mater. 2022, 9, 958775. [CrossRef]
75. Bradley, L.; Yaras, Y.; Karahasanoglu, B.; Atasoy, B.; Degertekin, F. Application of low-temperature processed 0–3 composite
piezoelectric thick films in flexible, nonplanar, high-frequency ultrasonic devices. IEEE Sens. J. 2023, 23, 6672–6679. [CrossRef]
76. Jo, E.; Lee, Y.; Cho, Y.; Gunther, P.; Gebhardt, S.; Neubert, H.; Kim, H. The 0–3 Lead Zirconate-Titanate (PZT)/Polyvinyl-Butyral
(PVB) Composite for Tactile Sensing. Sensors 2023, 23, 1649. [CrossRef]
77. Zhang, J.; Wang, J.; Zhong, C.; Qin, L. 1–3-Type piezoelectric composites with three-layer cascade structure. Compos. Struct. 2023,
322, 117406. [CrossRef]
78. Zhou, C.; Zhang, J.; Su, W.; Cao, Y. Large thickness-mode electromechanical coupling and good temperature stability of 1–3
PZT/epoxy composites. J. Mater. Sci. Mater. Electron. 2021, 32, 4705–4712. [CrossRef]
79. Wang, J.; Chen, M.; Zhao, X.; Wang, F.; Tang, Y.; Lin, D.; Luo, H. Fabrication and high acoustic performance of high frequency
needle ultrasound transducer with PMN-PT/Epoxy 1–3 piezoelectric composite prepared by dice and fill method. Sens. Actuators
A Phys. 2021, 318, 112528. [CrossRef]
80. Zhao, Y.; Wang, L.; Liao, Q. Temperature stability of hyperboloid piezoelectric composite. J. Beijing Inf. Sci. Technol. Univ. Sci.
Technol. Ed. 2021, 36, 53–58.
81. Huang, Q. Research on High Frequency and Broadband Directional Controllable Cylindrical Transducer. Master’s Thesis, Beijing
Information Science and Technology University, Beijing, China, June 2021.
82. Sim, M.; Jeong, W.; Hong, C. An equivalent circuit based electro-vibro-acoustic model of a cylindrical transducer array. J. Acoust.
Soc. Am. 2021, 149, 3228–3240. [CrossRef]
83. Herickhoff, C.; Telichko, A.; Dahl, J. Cylindrical transducer for intravascular ARFI imaging: Design and feasibility. IEEE Trans.
Ultrason. Ferroelectr. Freq. Control 2019, 67, 760–769. [CrossRef] [PubMed]
84. Kim, T.; Cui, Z.; Chang, W.; Kim, H.; Zhu, Y.; Jiang, X. Flexible 1–3 composite ultrasound transducers with silver-nanowire-based
stretchable electrodes. IEEE Trans. Ind. Electron. 2019, 67, 6955–6962. [CrossRef]
85. Hou, C.; Li, Z.; Fei, C.; Wang, Y.; Zhao, T.; Quan, Y.; Chen, D.; Li, X.; Bao, W.; Li, Y.; et al. Active acoustic field modulation of
ultrasonic transducers with flexible composites. Commun. Phys. 2023, 6, 252. [CrossRef]
86. Hao, S.; Zhong, C.; Wang, L.; Qin, L. A High-Performance Flexible Hydroacoustic Transducer Based on 1–3 PZT-5A/Silicone
Rubber Composite. Sensors 2024, 24, 2081. [CrossRef] [PubMed]
87. Hao, S.; Zhong, C.; Zhang, Y.; Chen, Y.; Wang, L.; Qin, L. Flexible 1–3 Piezoelectric Composites with Soft Embedded Conductive
Interconnects for Underwater Acoustic Transducers. ACS Appl. Electron. Mater. 2023, 5, 2686–2695. [CrossRef]
88. Wang, S.; Shao, H.; Liu, Y.; Tang, C.; Zhao, X.; Ke, K.; Bao, R.; Yang, M.; Yang, W. Boosting piezoelectric response of PVDF-TrFE
via MXene for self-powered linear pressure sensor. Compos. Sci. Technol. 2021, 202, 108600. [CrossRef]
89. Sharma, S.; Chhetry, A.; Sharifuzzaman, M.; Yoon, H.; Park, J. Wearable Capacitive Pressure Sensor Based on MXene Composite
Nanofibrous Scaffolds for Reliable Human Physiological Signal Acquisition. ACS Appl. Mater. Interfaces 2020, 12, 22212–22224.
[CrossRef] [PubMed]
90. Bhavanasi, V.; Kumar, V.; Parida, K.; Wang, J.; Lee, P. Enhanced Piezoelectric Energy Harvesting Performance of Flexible
PVDF-TrFE Bilayer Films with Graphene Oxide. ACS Appl. Mater. Interfaces 2016, 8, 521–529. [CrossRef]
91. Qin, L. Mechanical and electrical coupling characteristics of 1–3 piezoelectric composite. J. Beijing Inf. Sci. Technol. Univ. Sci.
Technol. Ed. 2018, 33, 1–6.
92. Wang, J.; Zhong, C.; Hao, S.; Wang, L. Design and properties analysis of novel modified 1–3 piezoelectric composite. Materials
2021, 14, 1749. [CrossRef]
93. Tang, T.; Shen, Z.; Wang, J.; Xu, S.; Jiang, J.; Chang, J.; Guo, M.; Fan, Y.; Xiao, Y.; Dong, Z.; et al. Stretchable polymer composites
with ultrahigh piezoelectric performance. Natl. Sci. Rev. 2023, 10, nwad177. [CrossRef] [PubMed]
94. Yang, F.; Li, J.; Long, Y.; Zhang, Z.; Wang, L.; Sui, J.; Dong, Y.; Wang, Y.; Taylor, R.; Ni, D.; et al. Wafer-scale heterostructured
piezoelectric bio-organic thin films. Science 2021, 373, 337–342. [CrossRef] [PubMed]
95. Chorsi, M.; Le, T.; Lin, F.; Vinikoor, T.; Das, R.; Stevens, J.; Mundrane, C.; Park, J.; Tran, K.; Liu, Y.; et al. Highly piezoelectric,
biodegradable, and flexible amino acid nanofibers for medical applications. Sci. Adv. 2023, 9, eadg6075. [CrossRef] [PubMed]
96. Wang, Z.; Zhang, Z.; Peng, Z.; Yang, X.; Li, X.; Shan, Y.; Liu, B.; Xu, X.; Gao, Y.; Yang, Z. Self-charging and long-term face masks
leveraging low-cost, biodegradable and sustainable piezoelectric nanofiber membrane. Nano Mater. Sci. 2024, in press. [CrossRef]
Micromachines 2024, 15, 982 47 of 49

97. Yu, Q.; Bai, Y.; Li, Z.; Jiang, F.; Luo, R.; Gai, Y.; Liu, Z.; Zhou, L.; Wang, Y.; Li, C.; et al. Interface-induced high piezoelectric
γ-glycine-based flexible biodegradable films. Nano Energy 2024, 121, 109196. [CrossRef]
98. Zhang, Z.; Li, X.; Peng, Z.; Yan, X.; Liu, S.; Hong, Y.; Shan, Y.; Xu, X.; Jin, L.; Liu, B.; et al. Active self-assembly of piezoelectric
biomolecular films via synergistic nanoconfinement and in-situ poling. Nat. Commun. 2023, 14, 4094. [CrossRef] [PubMed]
99. Zhang, H.; Tang, Y.; Gu, Z.; Wang, P.; Chen, X.; Lv, H.; Li, P.; Jiang, Q.; Gu, N.; Ren, S.; et al. Biodegradable ferroelectric molecular
crystal with large piezoelectric response. Science 2024, 383, 1492–1498. [CrossRef] [PubMed]
100. Zhang, Z.; Liu, S.; Pan, Q.; Hong, Y.; Shan, Y.; Peng, Z.; Xu, X.; Liu, B.; Chai, Y.; Yang, Z. Van der Waals Exfoliation Processed
Biopiezoelectric Submucosa Ultrathin Films. Adv. Mater. 2022, 34, 2200864. [CrossRef] [PubMed]
101. He, Z. Study on preparation, structure and property of 0–3 type PZT/PVDF piezoelectric composite. Master’s Thesis, Wuhan
University of Technology, Wuhan, China, May 2003.
102. Jiang, X. Study on preparation and properties of acrylonitrile butadiene rubber piezoelectric composite. Master’s Thesis, Beijing
University of Chemical Technology, Beijing, China, May 2008.
103. Wang, W.; Liang, L.; Lin, X. Preparation and Performance of 0–3 Type Piezoelectric Ceramic/Rubber Composite. Dev. Appl. Mater.
2014, 29, 67–71.
104. Sorayani Bafqi, M.; Bagherzadeh, R.; Latifi, M. Fabrication of composite PVDF-ZnO nanofiber mats by electrospinning for energy
scavenging application with enhanced efficiency. J. Polym. Res. 2015, 22, 130. [CrossRef]
105. Szewczyk, P.; Gradys, A.; Kim, S. Persano, L.; Marzec, M.; Kryshtal, A.; Busolo, T.; Toncelli, A.; Pisignano, D.; Bernasik, A.; et al.
Enhanced piezoelectricity of electrospun polyvinylidene fluoride fibers for energy harvesting. ACS Appl. Mater. Interfaces 2020,
12, 13575–13583. [CrossRef] [PubMed]
106. Kumar, M.; Kumari, P. P (VDF-TrFE)/ZnO nanocomposite synthesized by electrospinning: Effect of ZnO nanofiller on physical,
mechanical, thermal, rheological and piezoelectric properties. Polym. Bull. 2023, 80, 4859–4878. [CrossRef]
107. Su, K. Study on Preparation of High Dielectric Composite Materials by Electrospinning. Master’s Thesis, Beijing University of
Chemical Technology, Beijing, China, June 2023.
108. Chen, Q.; Cao, Y.; Lu, Y.; Akram, W.; Ren, S.; Niu, L.; Sun, Z.; Fang, J. Hybrid Piezoelectric/Triboelectric Wearable Nanogenerator
Based on Stretchable PVDF–PDMS Composite Films. ACS Appl. Mater. Interfaces 2024, 16, 6239–6249. [CrossRef]
109. Luo, Y.; Liu, J.; Xiao, Y.; Zhang, J.; Wu, Y.; Zhao, Z. Investigation of the piezoelectric performance of P (VDF-TrFE)/SnO2 NPs/GR
composite film fabricated via electrospinning. Polym.-Plast. Technol. Mater. 2024, 63, 203–219.
110. Li, X.; Zhang, Z.; Peng, Z.; Yan, X.; Hong, Y.; Liu, S.; Lin, W.; Shan, Y.; Wang, Y.; Yang, Z. Fast and versatile electrostatic disc
microprinting for piezoelectric elements. Nat. Commun. 2023, 14, 6488. [CrossRef]
111. Avcıoğlu, S.; Uyan, P.; Yontar, O.; Cevik, S. Electrospray deposition of AlN-PVA composite coating as thermal interface material.
Mater. Lett. 2022, 318, 132235. [CrossRef]
112. Park, J.; Han, J.; Gal, C.; Oh, J.; Kim, J.; Kate, K.; Atre, S.; Kim, Y.; Park, S. Fabrication of micro-sized piezoelectric structure using
powder injection molding with separated mold system. Ceram. Int. 2018, 44, 12709–12716. [CrossRef]
113. Hao, Y.; Hou, Y.; Xu, H.; Gao, X.; Zheng, M.; Zhu, M. Enhancing the energy harvesting performance of PDMS based piezocompos-
ites via a synergistic effect. J. Mater. Chem. C 2021, 9, 14303–14308. [CrossRef]
114. Zhang, J.; Wang, Q.; Liu, A.; Tao, W.; Wei, H.; Li, C. Preparation of 1–3 Piezoelectric Ceramic/Polymer Composite by Ceramic
Injection Molding and Their Performance Study. Dev. Appl. Mater. 2017, 32, 86–88.
115. Han, J.; Gal, C.; Park, J.; Kim, J.; Lee, S.; Yeo, B.; Lee, B.; Park, S.; Park, S. Powder injection molding process for fabrication of
piezoelectric 2D array ultrasound transducer. Smart Mater. Struct. 2018, 27, 075058. [CrossRef]
116. Park, J.; Han, J.; Oh, J.; Park, S.; Kim, Y.; Jang, J.; Lee, W.; Park, S. Design, fabrication of honeycomb-shaped 1–3 connectivity
piezoelectric micropillar arrays for 2D ultrasound transducer application. Ceram. Int. 2020, 46, 12023–12030. [CrossRef]
117. Yan, M.; Zhong, J.; Liu, S.; Xiao, Z.; Yuan, X.; Zhai, D.; Zhou, K.; Li, Z.; Zhang, D.; Bowen, C.; et al. Flexible pillar-base structured
piezocomposite with aligned porosity for piezoelectric energy harvesting. Nano Energy 2021, 88, 106278. [CrossRef]
118. Xie, M.; Zhang, Y.; Kraśny, M.; Bowen, C.; Khanbareh, H.; Gathercole, N. Flexible and active self-powered pressure, shear sensors
based on freeze casting ceramic-polymer composites. Energy Environ. Sci. 2018, 11, 2919–2927. [CrossRef] [PubMed]
119. Fukushima, M.; Fujiwara, T.; Fey, T.; Kakimoto, K. One-or two-dimensional channel structures and properties of piezoelectric
composites via freeze-casting. J. Am. Ceram. Soc. 2017, 100, 5400–5408. [CrossRef]
120. Grinberg, D.; Siddique, S.; Le, M.; Liang, R.; Capsal, J.; Cottinet, P. 4D Printing based piezoelectric composite for medical
applications. J. Polym. Sci. Part B Polym. Phys. 2019, 57, 109–115. [CrossRef]
121. Zeng, Y.; Jiang, L.; Sun, Y.; Yang, Y.; Quan, Y.; Wei, S.; Lu, G.; Li, R.; Rong, J.; Chen, Y.; et al. 3D-printing piezoelectric composite
with honeycomb structure for ultrasonic devices. Micromachines 2020, 11, 713. [CrossRef] [PubMed]
122. Sebastian, T.; Bach, M.; Geiger, A.; Lusiola, T.; Kozielski, L.; Clemens, F. Investigation of electromechanical properties on 3-D
printed piezoelectric composite scaffold structures. Materials 2021, 14, 5927. [CrossRef] [PubMed]
123. Li, J.; Yang, F.; Long, Y.; Dong, Y.; Wang, Y.; Wang, X. Bulk ferroelectric metamaterial with enhanced piezoelectric and biomimetic
mechanical properties from additive manufacturing. ACS Nano 2021, 15, 14903–14914. [CrossRef]
124. Wang, L.; Zhang, J.; Li, G.; Ge, X.; Teng, M.; Li, Y. Dielectric relaxation behavior of PVDF-based composites filled with different
nanofillers. Acta Mater. Compos. Sin. 2014, 31, 880–887.
125. Hong, S.; Lee, J.; Kim, K.; Choi, S. Electrospun Poly L-Lactic Acid Nanofiber Webs Presenting Enhanced Piezoelectric Properties.
Polymers 2024, 16, 347. [CrossRef]
Micromachines 2024, 15, 982 48 of 49

126. Yang, X.; Li, H.; Fang, B.; Zhang, S.; Lu, X.; Ding, J. Enhancing piezoelectricity of low-temperature-sintered PZT-BNZ ceramics by
pulse poling. J. Mater. Sci. Mater. Electron. 2024, 35, 611. [CrossRef]
127. Tian, G.; Deng, W.; Da, X.; Yang, T.; Zhang, B.; Ren, X.; Lan, B.; Zhong, S.; Jin, L.; Zhang, H.; et al. Dielectric micro-capacitance for
enhancing piezoelectricity via aligning MXene sheets in composites. Cell Rep. Phys. Sci. 2022, 3, 100814. [CrossRef]
128. Thirumalasetty, A.; Pamula, S.; Krishnan, T.; Khade, V.; Sharief, P.; Venkata, S.; Adiraj, S.; Wuppulluri, M. Energy storage and
catalytic behaviour of cmWave assisted BZT and flexible electrospun BZT fibers for energy harvesting applications. Sci. Rep. 2024,
14, 2650. [CrossRef]
129. Verma, K.; Sharma, R. A flexible piezoelectric generator based on KNN/PVDF composite films: Role of KNN concentration on
the piezoelectric performance of generator. Chin. J. Phys. 2023, 84, 198–215. [CrossRef]
130. Fathollahzadeh, V.; Khodaei, M. Enhanced piezoelectric response of PVDF by incorporating of BaTiO3 nanoparticles and surface
treatment. J. Mater. Sci. Mater. Electron. 2024, 35, 107. [CrossRef]
131. Silakaew, K.; Saijingwong, W.; Meeporn, K.; Maensiri, S.; Thongbai, P. Effects of processing methods on dielectric properties of
BaTiO3 /poly (vinylidene fluoride) nanocomposites. Microelectron. Eng. 2015, 146, 1–5. [CrossRef]
132. Mo, X. Progress and Opportunities of Underwater Transducers in China. Bull. Chin. Acad. Sci. 2019, 34, 272–282.
133. Wen, X.; Sun, Y.; Shen, Y. Research on underwater acoustic communication system of micro-unmanned underwater vehicle.
Foreign Electron. Meas. Technol. 2022, 41, 76–82.
134. Su, J.; Wang, H. Research on high sensitivity integrated transmit and receive hydroacoustic transducer. Phys. Scr. 2023, 98, 125028.
[CrossRef]
135. Wang, J.; Zhong, C.; Hao, S.; Lv, N.; Wang, L. Design of planar array transducers based on connected 1–3 piezoelectric composites.
Micromachines 2021, 12, 1417. [CrossRef]
136. Wang, L.; Dong, T.; Qin, L.; Wang, G. Fabrication and Performance of Piezoelectric Composite with Multi-elements. Piezoelectrics
Acoustooptics 2010, 32, 433–436.
137. Lu, Z.; Gao, G. Research Progress in PVDF Piezoelectric Composites and Their Applications. Micronanoelectric Technol. 2023,
60, 1356–1365.
138. Lin, X. Investigations on the Design, Characterization and Applications of Flexible Pressure Sensor Based on Piezoelectric
Composite. Ph.D. Thesis, Guangdong University of Technology, Guangzhou, China, May 2021.
139. Wen, D.; Sun, D.; Huang, P.; Huang, W.; Su, M.; Wang, Y.; Han, M.; Kim, B.; Brugger, J.; Zhang, H.; et al. Recent progress in silk
fibroin-based flexible electronics. Microsyst. Nanoeng. 2021, 7, 35. [CrossRef] [PubMed]
140. Tian, G.; Deng, W.; Yang, T.; Zhang, J.; Xu, T.; Xiong, D.; Lan, B.; Wang, S.; Sun, Y.; Ao, Y.; et al. Hierarchical Piezoelectric
Composites for Noninvasive Continuous Cardiovascular Monitoring. Adv. Mater. 2024, 36, 2313612. [CrossRef] [PubMed]
141. Huang, Y.; Chen, S.; Li, Y.; Lin, Q.; Wu, Y.; Shi, Q. Flexible piezoelectric sensor based on PAN/MXene/PDA@ ZnO composite film
for human health and motion detection with fast response and highly sensitive. Chem. Eng. J. 2024, 488, 150997. [CrossRef]
142. Wang, X.; Yang, B.; Liu, J.; Zhu, Y.; Yang, C.; He, Q. A flexible triboelectric-piezoelectric hybrid nanogenerator based on P
(VDF-TrFE) nanofibers and PDMS/MWCNT for wearable devices. Sci. Rep. 2016, 6, 36409. [CrossRef]
143. Chen, T.; Wei, Q.; Ma, Y.; Tang, Y.; Ma, L.; Deng, S.; Xu, B. Multifunctional Electronic Skins for Ultra-Sensitive Strain, Temperature,
Humidity Sensing, and Energy Harvesting. Nano Energy 2024, 127, 109752. [CrossRef]
144. Ren, Y.; Gao, G. Research and Development of Sensors in the Field of Pulse Diagnosis. China Ceram. 2023, 59, 1–15.
145. Khanbareh, H.; De Boom, K.; Schelen, B.; Scharff, R.; Wang, C.; Zwaag, S.; Groen, P. Large area and flexible micro-porous
piezoelectric materials for soft robotic skin. Sens. Actuators A Phys. 2017, 263, 554–562. [CrossRef]
146. Liu, Y.; Zheng, H.; Zhao, L.; Liu, S.; Yao, K.; Li, D.; Yiu, C.; Gao, S.; Avila, R.; Chirarattananon, P.; et al. Electronic skin from
high-throughput fabrication of intrinsically stretchable lead zirconate titanate elastomer. Research 2020, 2020, 1085417. [CrossRef]
147. Wu, Z.; Dai, Y.; Zeng, Y. Intelligent robot-assisted fracture reduction system for the treatment of unstable pelvic fractures. J.
Orthop. Surg. Res. 2024, 19, 271. [CrossRef] [PubMed]
148. Li, J.; Ke, Y.; Xie, J. Design of Intelligent Inspection Robot System Based on Multi- source Perception. Microcomput. Appl. 2024, 40,
15–18+22.
149. Zhou, Y.; Zhao, X.; Xu, J.; Chen, G.; Tat, T.; Li, J.; Chen, J. A multimodal magnetoelastic artificial skin for underwater haptic
sensing. Sci. Adv. 2024, 10, eadj8567. [CrossRef] [PubMed]
150. Lin, L.; Guo, J.; Liu, L. Multi-scene application of intelligent inspection robot based on computer vision in power plant. Sci. Rep.
2024, 14, 10657. [CrossRef] [PubMed]
151. Li, T.; Wei, Z.; Jin, F.; Yuan, Y.; Zheng, W.; Qian, L.; Wang, H.; Hua, L.; Ma, J.; Zhang, H.; et al. Soft ferroelectret ultrasound receiver
for targeted peripheral neuromodulation. Nat. Commun. 2023, 14, 8386. [CrossRef] [PubMed]
152. Wang, A.; Ma, X.; Yang, Y.; Shi, G.; Han, L.; Hu, X.; Shi, R.; Yan, J.; Guo, Q.; Zhao, Y. Biophysical-driven piezoelectric and aligned
nanofibrous scaffold promotes bone regeneration by re-establishing physiological electrical microenvironment. Nano Res. 2024,
1–18. [CrossRef]
153. Chen, Y.; Feng, P.; Zhong, G.; Liu, J.; Jiang, B.; Harn, Y.; Zhao, D.; Lin, Z.; Zhang, Q.; Shen, Q. Piezoelectric nanogenerators enabled
neuromodulation rescued dopaminergic neuron loss in Parkinson’s disease. Nano Energy 2024, 121, 109187. [CrossRef]
154. Tian, G.; Deng, W.; Gao, Y.; Xiong, D.; Yan, C.; He, X.; Yang, T.; Jin, L.; Chu, X.; Zhang, H.; et al. Rich lamellar crystal
baklava-structured PZT/PVDF piezoelectric sensor toward individual table tennis training. Nano Energy 2019, 59, 574–581.
[CrossRef]
Micromachines 2024, 15, 982 49 of 49

155. Yamashita, T.; Kobayashi, T. Smart table tennis racket using a rubber mounted ultrathin piezoelectric sensor array. Sens. Mater.
2021, 33, 1081–1089. [CrossRef]
156. Guan, Y.; Bai, M.; Li, Q.; Li, W.; Liu, G.; Liu, C.; Chen, Y.; Lin, Y.; Hui, Y.; Wei, R. A plantar wearable pressure sensor based on
hybrid lead zirconate-titanate/microfibrillated cellulose piezoelectric composite films for human health monitoring. Lab Chip
2022, 22, 2376–2391. [CrossRef]
157. Gao, X.; Zheng, M.; Lv, H.; Zhang, Y.; Zhu, M.; Hou, Y. Ultrahigh sensitive flexible sensor based on textured piezoelectric
composites for preventing sports injuries. Compos. Sci. Technol. 2022, 229, 109693. [CrossRef]
158. Zeng, W.; Deng, W.; Yang, T.; Wang, S.; Sun, Y.; Zhang, J.; Ren, X.; Jin, L.; Tang, L.; Yang, W. Gradient CNT/PVDF piezoelectric
composite with enhanced force-electric coupling for soccer training. Nano Res. 2023, 16, 11312–11319. [CrossRef]
159. Zhang, J.; Zhang, Y.; Yang, J.; Wang, X. Beyond Color Boundaries: Pioneering Developments in Cholesteric Liquid Crystal
Photonic Actuators. Micromachines 2024, 15, 808. [CrossRef]
160. Wang, C.; Li, X.; Hu, H.; Zhang, L.; Huang, Z.; Lin, M.; Zhang, Z.; Yin, Z.; Huang, B.; Gong, H.; et al. Monitoring of the central
blood pressure waveform via a conformal ultrasonic device. Nat. Biomed. Eng. 2018, 2, 687–695. [CrossRef] [PubMed]
161. Jiang, L.; Lu, G.; Zeng, Y.; Sun, Y.; Kang, H.; Burford, J.; Gong, C.; Humayun, M.; Chen, Y.; Zhou, Q. Flexible ultrasound-induced
retinal stimulating piezo-arrays for biomimetic visual prostheses. Nat. Commun. 2022, 13, 3853. [CrossRef]
162. Wang, Q.; Zhang, Y.; Xue, H.; Zeng, Y.; Lu, G.; Fan, H.; Jiang, L.; Wu, J. Lead-free dual-frequency ultrasound implants for wireless,
biphasic deep brain stimulation. Nat. Commun. 2024, 15, 4017. [CrossRef]

Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual
author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to
people or property resulting from any ideas, methods, instructions or products referred to in the content.