Polymer 283 (2023) 126179

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Polymer
journal homepage: www.elsevier.com/locate/polymer

A review on electrospun PVDF-based nanocomposites: Recent trends and

developments in energy harvesting and sensing applications
Sreelakshmi Moozhiyil Purushothaman a, Maïté Fernandes Tronco a, Bicy Kottathodi a, b,
Isabelle Royaud a, Marc Ponçot a, Nandakumar Kalarikkal b, Sabu Thomas b, Didier Rouxel a, *
a
Université de Lorraine, CNRS, IJL, F-54000, Nancy, France
b
International and Interuniversity Centre for Nanoscience and Nanotechnology, Mahatma Gandhi University, Kerala, India

A R T I C L E I N F O A B S T R A C T

Keywords: Modern-day requirements for efficient, eco-friendly, and self-powered devices have resulted in a growing interest
PVDF-Nanocomposites in piezoelectric polymers among the scientific community. Polyvinylidene fluoride (PVDF) is an excellent
Electrospinning electroactive polymer that is flexible, with high mechanical strength, thermal stability, and biocompatibility. The
Piezoelectricity
relatively low cost and easiness to be fabricated into thin pliable films made PVDF one of the most studied
Triboelectricity
polymers for the development of nanogenerators and wearable sensors. The piezoelectric properties and
Hybrid nanogenerators
therefore the energy harvesting and sensing capabilities of PVDF are distinct characteristics of its electroactive
polar phases, especially the β phase. Hence, several PVDF-based nanocomposites that could achieve a high β
phase fraction have been widely explored. Electrospinning is one of the best methods for manufacturing such
PVDF-based nanocomposite films. This article, therefore, highlights essential information about different elec­
trospinning parameters which help to enhance the β phase in PVDF. The review then progresses into the recent
developments and technological advances of electrospun PVDF-based nanocomposite devices in energy har­
vesting and sensing applications. The piezo-, pyro-, and triboelectric properties of PVDF allow the fabrication of
conventional and hybrid nanogenerators. The later can harvest energy simultaneously from multiple sources,
sense various fluctuations in their surroundings, and transmit the acquired data immediately when integrated
with Bluetooth or wireless devices. They are fine models of self-powered, portable, multifunctional, and sus­
tainable engineering. Finally, a peek into the other possible applications of electrospun PVDF-nanocomposite
fibers is also made. Overall, the review aims to illustrate the innovative research and developments of PVDF
fiber-based devices and the relevance and prospects they hold as future green sources of energy.

1. Introduction Quartz is a well-known piezoelectric material and was one of the first
to be identified [1]. Some of the later materials include zinc oxide (ZnO),
Technological advances and rising global energy consumption have barium titanate (BaTiO3), and lead zirconate titanate (Pb(ZrTi)O3)
turned wireless and self-powered devices into one of the requirements of (PZT) [2–4]. These ceramic materials possess high piezoelectric co­
the 21st century. Compactness, flexibility, durability, portability, and efficients and high electroactive potential but have poor flexibility and a
the ability to be integrated with other devices are other features ex­ high-cost preparation process. Their toxicity also questions their suit­
pected of such modern devices. A possible solution to satisfy all the ability as ideal clean and green sources of energy [5,6]. Hence, it became
aforementioned requirements is the use of electroactive materials. necessary to investigate another class of piezoelectric materials: poly­
Hence, a wide variety of piezoelectric, pyroelectric, and triboelectric mers. Polymers are flexible, with enhanced mechanical strength, and are
materials have been explored for the development of energy harvesters lightweight, affordable, and biocompatible [7–10]. Many piezoelectric
and self-powered sensors. The ability of these materials to electrically polymers are available, whether synthetic such as polyvinylidene fluo­
respond to the omnipresent energy sources of mechanical vibrations and ride (PVDF), polyamides, and polyL-lactic acid (PLLA) [11,12], or nat­
heat makes them exceptionally suitable for sustainable energy ural like cellulose, keratin, collagen, or chitin [13]. Among these, PVDF
harvesting. is one of the most explored and efficient piezoelectric polymers, which

* Corresponding author.
E-mail address: [email protected] (D. Rouxel).

https://doi.org/10.1016/j.polymer.2023.126179
Received 17 February 2023; Received in revised form 9 June 2023; Accepted 28 June 2023
Available online 10 July 2023
0032-3861/© 2023 Elsevier Ltd. All rights reserved.
S.M. Purushothaman et al. Polymer 283 (2023) 126179

also exhibits pyroelectric and triboelectric properties. The outstanding 1.1. Fundamentals of PVDF
properties of this fluoro-polymer lead to its frequent selection for the
development of energy generators and sensors. This claim is statistically PVDF (–CH2–CF2–)n is a semicrystalline thermoplastic homopolymer
justified by the increasing number of publications on topics such as [15,16]. It is a promising electroactive polymer with wide frequency
“PVDF”, “PVDF- Energy harvesting”, “PVDF-Electrospinning” and responses, exceptional sensitivity, high piezoelectric coefficient, high
“PVDF-Electrospinning-Energy harvesting” (as obtained from the Web dipole moment in the polar phases, and high thermal stability [17–25].
of Science core database of the Université de Lorraine, France, https:// Depending on the different processing parameters and post-treatments,
www-webofscience-com.bases-doc.univ-lorraine.fr/wos/bci/analyze-re PVDF is found to exist in five different crystalline phases (α, β, γ, δ, and ε)
sults/ac23749a-4a75-4103-8d9a-160d7ffa07de-9034f4bb). This article [26]. The three principle phases are represented in Fig. 2. In general,
provides a brief description of PVDF and explores a wide variety of PVDF crystallizes in the non-polar α phase and is commonly obtained by
PVDF-based nanocomposites. Because of the increasing use of electro­ crystallization from the melt. The polymer chains adopt a
spinning to manufacture PVDF films, it also details the effect of various trans-gauche-trans-gauche (TGTG) conformation, which is the thermo­
electrospinning parameters on PVDF. The review then focuses on the dynamically favorable form of PVDF due to the minimal steric strains
energy harvesting applications of electrospun PVDF and explains the [27–29]. Uni- or bi-axial stretching [30,31], poling under a high electric
recent trends and technological advances in the field of piezoelectric, field [31,32], pressure quenching [33], or sample fabrication techniques
pyroelectric, and triboelectric nanogenerators and sensors. Moreover, a such as electrospinning [34,35] or spin coating [36] align the polymer
new and emerging technology for energy harvesting, the hybrid nano­ chains in the all-trans (TTTT) conformation called the β phase (also
generators, is also detailed. These devices can simultaneously harvest referred to as phase I) [29]. In this phase, the dipole moments of C–F and
energy using the piezo, -pyro, and triboelectric properties of PVDF and C–H bonds add up so that an effective dipole moment develops in the
sense various fluctuations in the surrounding environment. When inte­ direction perpendicular to the carbon backbone. Hence, as the highly
grated with wireless data-transmitting devices, they have the potential polar phase of PVDF, the β phase is the most widely studied [37–39]. A
to become a true example of portable, multipurpose, multifunctional, semipolar polymorph of PVDF known as the γ phase is obtained by
and sustainable engineering. The inspiration behind this paper is to annealing at high temperature and pressure, slow melting, and recrys­
highlight the potential of electrospun PVDF films, with a focus on these tallization from different solvents or using different surfactants. In the γ
devices, and inspire their integration as innovative sustainable sources phase, the polymer chains take a TTTGTTTG or T3GT3G conformation
of energy. To the best of our knowledge, there are no recent reviews that [15,40]. Often, the β phase and γ phases are together called the elec­
focus on all the above-mentioned types of nanogenerators together, and troactive phases of PVDF. The δ phase of PVDF is the polar analog of the
the wide variety of energy sources they could detect as sensors or use in α phase. The ε phase is the antipolar analog of the γ phase. The δ phase
the process of energy harvesting. In addition, a brief overview of other can be obtained through the transition of the α phase with apparently no
applications of such films is also presented. The current review is also change in the chain conformation, and by the application of electric
significant as a good reference for the scientific community to look fields near 1 MV/cm at room temperature. At high temperatures, the δ
forward to the real-life applications and perhaps the commercialization phase easily transforms into a mixture of polymorphs in which small
of PVDF-based multifunctional devices as depicted in Fig. 1. amounts of the ε phase are obtained along with a higher amount of the γ

Fig. 1. Schematic visualization of the futuristic possible applications of PVDF-based multi-modes single piezoelectric nanogenerator devices (MSPNG) (reproduced
with permission from Ref. [14]).

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S.M. Purushothaman et al. Polymer 283 (2023) 126179

Fig. 2. Schematic representation of the α, β and γ phase of PVDF.

phase. [26,41–43]. corresponding to (020), (110), (021) and (200) reflections [43,66–69].
The content of the three principle crystalline phases in PVDF is The peak at 20.6ο due to the sum of the diffraction in the (110) and (200)
commonly investigated using Fourier Transform Infrared Spectroscopy planes and another one near 36.5ο due to (020) reflections are the
(FT-IR). From the FT-IR spectra, the α phase can be identified from the characteristic peaks of the β phase [61,66,69–73]. The characteristic
bands at 1423, 1383, 1214, 1146, 976, 854, 796, 764, 615, and 532 peaks of the γ phase occur around 18.5 ο, 20.3 ο, and 39.0 ο because of
cm− 1 [44–50]. The characteristic band of the β phase which is not the diffraction from the (020), (110/101), and (211) planes [66,67,70,
composed of other crystal modifications occurs at 1275 cm− 1, and the 74–76]. By curve deconvolution of the XRD spectra, the overall degree
bands at 510 and 841 cm− 1, though initially considered to be charac­ of crystallinity (χC), as well as crystallinity of β (χCβ) and γ (χCβ) phases
teristic of the β phase, are characteristic of both the β and γ phases. The can be calculated using the following equations:
characteristic bands of the γ phase occur at 813 cm− 1, 833 cm− 1, and ∑
ACR
1232 cm− 1 [37,44,45,48,51–65]. Apart from identifying the presence of χC = ∑ ∑ ∗ 100%
ACR + Aamr
different crystalline phases from the band positions, the fraction of the
electroactive (EA) phases and α phase can be estimated as follows: ∑
Aβ
⎛ ⎞ χ Cβ = χ C ∗ ∑ ∑
Aβ + Aγ
⎜ AEA ⎟
FEA = ⎜
⎝K840
⎟ ∗ 100 %
⎠
∑
∗ A 763 + A EA
Aγ
K763 χ Cγ = χ C ∗ ∑ ∑
Aβ + Aγ

F(α) = 100 − FEA % where, ΣAcr and ΣAamr represent the summation of the total integral
areas of crystalline diffraction peaks and amorphous halo, respectively;
where F represents the fraction of the corresponding phase; AEA and A763 ΣAβ and ΣAγ are the area under crystalline β− and γ− peaks, respectively
are the absorbance values at 840 and 763 cm− 1, respectively; K840 and [77].
K763 are the absorption coefficients at the respective wave numbers and The determination of the fraction of each crystalline phase is
are equal to 7.7x104 and 6.1 × 104 cm2 mol− 1, respectively. important as the electroactive response of PVDF is determined by the
Furthermore, the individual fraction of β and γ phases can be esti­ content of the electroactive polar phases, especially the β phase. This
mated as follows: fraction can vary under the influence of the electric field, temperature,
( ) or mechanical stress [30,38,45,77,78]. Considering the electric prop­
ΔHβ’
F(β) = FEA ∗ erties of PVDF is helpful to further understand the reasons behind this. In
ΔHβ’ + ΔHγ’
PVDF each monomer unit has an electric dipole moment directed
( ) perpendicular to the carbon backbone. Each monomer unit has a dipole
ΔHγ’ moment of 8.10− 30 Cm in the β phase and 5.10− 30 Cm in the α phase.
F(γ) = FEA ∗
ΔHβ’ + ΔHγ’ However, as these monomer units crystallize in anti-parallel orientation,
the net dipole moment becomes zero in the α phase [79–83]. Dipole
where ΔHβ’ and ΔHγ’ are the height differences (absorbance differences) moments of PVDF can be permanently aligned to acquire considerable
between the 1275 cm− 1 peak and the nearest valley of 1260 cm− 1, and remnant polarization by the application of a high electric field, with or
the 1234 cm− 1 peak and the near valley of 1225 cm− 1, respectively without applying temperature. Though polarization can take place upon
[66]. heating, thus allowing the chains to rotate more easily [84], the appli­
X-ray diffraction (XRD) studies can also be used to distinguish the cation of higher temperatures can cause depolarization of the PVDF
different phases in PVDF. XRD patterns show characteristic peaks of the samples. The thermal depolarization of PVDF was studied by Eberle and
α phase at 18.4ο and 20.0ο and two weak peaks at 26.6ο and 35.9ο Eisenmenger using a mechanically stretched and poled PVDF film with a

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S.M. Purushothaman et al. Polymer 283 (2023) 126179

high fraction of β phase [85]. The β-PVDF which has high spontaneous of the fillers can also affect PVDF-filler interaction. For example, Fu et al.
polarization also exhibits the maximum ferroelectric response, highest demonstrated this dependence by studying PVDF-BaTiO3 spherical
remnant polarization, and coercive field [86–89]. In the study of Eberle nanoparticles (BTNPs) and PVDF-BaTiO3 nanorods (BTNRs) composites
and Eisenmenger, it was observed that with increased heating temper­ [116]. The higher interfacial area of the BTNRs/PVDF composite
ature, the remnant polarization of the PVDF film decreased slowly from compared to the BTNPs/PVDF nanocomposites was found to enhance
5.4 μC/cm2 at 20◦ C and tended to zero at 180◦ C. Even after cooling the interface polarization in the first configuration. Mendes et al., from
down to 20◦ C, the values did not increase considerably except for an studies on PVDF-BaTiO3 composite films, concluded that smaller
anomaly at 180◦ C. As the electroactive behavior of PVDF is associated nanoparticles act as nucleating agents for the β phase of PVDF during
with its absence of a centre of symmetry, high dielectric constant, and polymer phase crystallization. Larger particles, due to the reduced
also the polarization of the material, depolarization of the film will relative interaction area for a given volume concentration, can cause
significantly lower all its electroactive properties [82,90–92]. defect formation [117]. Apart from the type of fillers used, the proper­
Though well-known as a potential dielectric material, extensive ties of the nanocomposite will also depend on its filler dispersion, lattice
studies on the electroactive behavior of PVDF leaped with the discovery matching, processing conditions, and, importantly, the relative fraction
of piezoelectricity in PVDF by Kawai in 1969 [93]. The value of piezo­ of the fillers. Every researcher chooses the most adequate fraction of
electric coefficients, such as d33 and d31 are often used to evaluate the fillers by studying the different films they prepared based on prior as­
piezoelectric properties of PVDF. Typically, PVDF exhibits d31 values sumptions. This can be clearly understood from every research article
between 8 to 22 pC/N and d33 values between -24 to –34 pC/N. How­ illustrating the wide variety of applications of PVDF-based
ever, these values can be significantly tailored through the modification nanocomposites.
of the polymer processing conditions, heat treatments, poling under Very often, the primary intention behind the addition of fillers in the
high electric field, nano-confinement, formation of blends, formation of PVDF matrix is to increase the fraction of β phase, and piezoelectric
nanocomposites by the addition of fillers, electrospinning and creation coefficients in the case of piezoelectric applications. Indeed, the pres­
of porous structures [94–97]. The discovery and detailed studies on the ence of nanofillers was observed to reduce the nucleation energy barrier
piezoelectricity in PVDF later lead to the exploration of the pyroelectric and thus enhance the crystallization rate and the degree of crystallinity
properties of PVDF which are related to the ferroelectric phase content of PVDF [94]. For example, Thakur et al. observed that, by introducing
of PVDF. The pyroelectric coefficient (p) of PVDF is typically observed to ZnO NPs into a PVDF matrix, the β-phase content increased up to 84%
be between 0.27 × 10− 4 and 0.357 × 10− 4 C/m2 K. However, the py­ (0.85 vol% of ZnO) and the piezoelectric coefficient d33 increased to 50
roelectric properties are also tunable like the piezoelectric properties pC/N from 22.3 pC/N at 50 Hz [118]. The addition of fillers to PVDF can
[98–100]. enhance its other properties as well, such as in the study of Elizalde et al.
Here, they focused on altering the hydrophobicity and wettability of
1.2. PVDF based nanocomposites PVDF through the addition of chitosan. Similarly, Zhou focused on
increasing the thermal conductivity of PVDF by adding core–­
There are different manufacturing methods to modify the properties shell-structured aluminum (Al) particles [119], while Ram et al. were
of PVDF like copolymerization, blending, and addition of nanofillers. working on both the thermal and electrical conductivity of PVDF-carbon
Compared to copolymers and blends, PVDF-based nanocomposites black nanocomposite films [120]. The addition of such high electric
allow them to obtain distinct physicochemical properties that are conductivity fillers to PVDF increases the overall conductivity of
otherwise difficult to tune. This is due to the higher surface-to-volume PVDF-nanocomposite films, which also increases the d33 coefficient at
ratio and subsequent higher contact area of the fillers with the poly­ lower concentrations of the fillers. It also leads to significant changes in
mer matrix. The commonly used fillers can be classified as inorganic, the breakdown field, charge transport, charge distribution, and electric
organic, or bio-fillers, carbon-based fillers, and hybrid fillers. A few energy density of the material. In the case of highly conductive fillers, a
examples of inorganic fillers include metal nanoparticles like gold [55] drastic decrease in breakdown strength may occur due to high con­
or palladium [45], metal salts such as CaCl2, BaCl2 [101], several ferrites ductivity that limits the improvement of the piezoelectric performance
such as ZnFe2O4 [102], CoFe2O4 [103], and carbon-based materials like of PVDF nanocomposites. The addition of fillers with high dielectric
carbon nanotubes, graphene or graphene oxide [77,104]. Examples of constants can significantly increase the dielectric permittivity of PVDF.
organic include nanocellulose, chitin, and chitosan [105–107], and However, on attaining the percolation threshold, the output of the
hybrid fillers include organometallic compounds, combination of fillers piezoelectric devices is found to reduce drastically. The composites can
like multi-walled carbon nanotubes (MWCNT)-Cloisite 30B hybrid also suffer from an abrupt variant in the dielectric loss. Sometimes, high
nanoparticles and titanium dioxide (TiO2) nanoparticles-graphene oxide filler loading might be necessary to achieve high dielectric permittivity,
(GO) [108–110]. which weakens the processability, flexibility, and mechanical perfor­
The selection of the fillers is often made to improve (or alter) the mance of the composites. Hence, there exists a certain threshold to
properties of the matrix and is specific to the final application of the provide an optimal balance [95,96,121–123]. Similar to increasing the
polymer nanocomposite. However, a few of the basic properties to be conductivity of an insulator like PVDF, It is possible to impart other
considered are the chemical composition, shape, size, and aspect ratio of properties to the polymer nanocomposite that the polymer alone
the fillers [111–113]. The synergic effect of the nanofillers is generally initially does not possess. For example, Durga Prasad, by the addition of
due to the interaction of the electronegative fluorine atom with the ferromagnetic fillers like ZnFe2O4 and CoFe2O4 into ferroelectric PVDF,
electropositive metal atom in a metallic compound or the positive sur­ made multiferroic films [102,103].
face charge of the fillers. It sometimes can be due to the interaction of With time, the number of fillers used with PVDF has increased
the electropositive hydrogen atom with the effective negative surface considerably and their effect on the properties of PVDF is becoming very
charge of the fillers. But in the case of fillers like nanocellulose, a specific. Thus, a list addressing every filler and its applications will be
hydrogen bond is formed between the fluorine atoms of PVDF and quite long. However, it was attempted to cover a majority of the recent
hydrogen atoms of the filler [45,114]. Karan et al. suggested that in the ones in different sections of the review.
case of composite fillers such as aluminum oxides decorated reduced
graphene oxide (AlO-rGO) sheets, β-phase nucleation can occur through 2. Manufacturing of PVDF films
stress-induced polarization, in addition to surface charge-induced po­
larization. Here, external mechanical forces build a potential in the With advances in the field of material manufacturing, a variety of
AlO-rGO nanosheets which aligns the PVDF dipoles in the direction of techniques are used for the fabrication of PVDF films. Solvent casting
the applied force [115]. Just like the filler composition, the morphology [124,125] and spin coating [126,127] are some of the simplest

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S.M. Purushothaman et al. Polymer 283 (2023) 126179

techniques to obtain films, while melt spinning [128,129] and electro­ decreased with an increase in concentration [154]. Baji also suggests
spinning are employed for fiber production. Hot-pressing and extrusion that thinner fibers formed at lower concentrations will have higher β
are also used for the production of PVDF films [39,130,131]. The latest phase content [155].
addition to this list is an electric poling-assisted additive manufacturing In a similar study, Costa et al. suggested that adding a more volatile
(EPAM), which is a 3D printing process that incorporates electric poling, solvent (like acetone) to polar solvents like dimethylformamide (DMF)
and allows simultaneous printing and poling of 3D free-form single lowers the surface tension and increases the net evaporation rate of the
structures [132,133]. solvents, thereby affecting the relative fraction of phases [156]. It also
Among these, one of the most promising techniques is electro­ lowers the viscosity, α phase content, and formation of beads in PVDF
spinning. It is used to produce highly oriented 2D nanofibrous films of fibers. However, too much acetone will speed up evaporation exces­
PVDF with a high fraction of β phase without any post-treatment. The sively and the solution may solidify at the tip of the needle [153,157,
general trend observed within the literature about PVDF is the rapidly 158]. Gee et al. studied the effects of different solvents on the electro­
growing number of publications on electrospun PVDF films. This un­ spinning of PVDF. They used solvents like DMF, dimethyl sulfoxide
derlines that electrospinning is considered one of the best methods for (DMSO), and N-methyl-2-pyrrolidone (NMP) with a 6:4 vol ratio with
manufacturing PVDF. Hence, this section proposes to discuss the prep­ acetone. They found DMF: acetone 6:4 v/v% to be the best combination
aration of electrospun PVDF nanofibers. to increase the fraction of β phase [159]. This solvent combination is
often found in other works [108] but the ratio may vary from one to
2.1. Electrospinning: basic principles and process another. For example, Saha et al. suggested 7:3 [160] as the best ratio
while 4:6 was preferred by Jiyong [161].
Electrospinning involves producing smooth and continuous fibers of
different polymers with diameters down to the range of nanometers 2.2.2. Effect of voltage
[134]. A viscoelastic jet derived from a polymer solution or melt is The applied voltage plays an irreplaceable role in altering the
submitted through uniaxial stretching under the application of a high properties of PVDF fibers, especially the formation of the β phase. The
voltage. In general, an electrospinning setup consists of a high-voltage fiber diameter is found to decrease and the fraction of β phase to increase
power supply, a spinneret, and a collector. When a high voltage is with the increase of voltage. The excessive increase in voltage will result
applied, the charge is induced at the surface of the polymer solution and in the beading and eventually the breaking of the fibers [153,161,162].
as a result, a mutual charge repulsion opposing the cohesion and surface This is clearly understood from the observation of Gade et al. [154]. A
tension of the solution starts to develop. As the voltage increases, and slightly different suggestion was put forward by Andrew and Clarke.
because of the increasing charge repulsion, the solution droplets elon­ They claim that the applied voltage has much less effect on the fraction
gate into a conical shape called the Taylor cone. At a critical value of the of β phase for a less viscous solution and affects the solution with higher
voltage, the repulsive electric force overcomes the surface tension of the viscosity as mentioned above [163].
solution, and a charged jet of the polymer solution is ejected from the tip
of the Taylor cone. As the jet extends, the solvent evaporates which 2.2.3. Effect of tip to collector distance (TCD)
results in its stretching and thinning. The TCD affects the evaporation of the solvent and electric field in­
The electrospinning process is influenced by a set of different pa­ tensity. As the TCD increases, the β phase content increases at first and
rameters. These parameters are classified into three sets: the solution then decreases, hence the most preferred TCD being between 10 to 20
parameters, process parameters, and ambient parameters. The solution cm [153,164]. Shao et al. reported that at a constant voltage, the average
parameters include the type of material/polymer and solvents used, fiber diameter decreases with an increase in the TCD [165]. The studies
solution concentration, viscosity, conductivity, and surface tension. The of Motamedi et al. also support this observation [166]. Zaarour et al.
process parameters include applied voltage, tip-to-collector distance reported that the pore size of porous fibers, groove size of grooved fibers,
(TCD), flow rate, spinneret choice, and the type of collector. Humidity and roughness of rough fibers increased with an increase in the TCD
and room temperature are the ambient parameters. Each of these pa­ [167].
rameters is chosen carefully to achieve efficient electrospinning
[135–148]. 2.2.4. Effect of flow rate
Finding the critical flow rate is necessary for the electrospinning of
2.2. Electrospinning of PVDF PVDF. Lower flow rates will cause a vacuum inside the needle, while at
higher flow rates some polymer may deposit at the tip. A lower flow rate
To ensure the formation of PVDF fibers, optimization of the various is preferred to ensure enough time to stretch and polarize the jet and the
sets of parameters plays an important and decisive role. solvents to evaporate [153,164]. In general, the diameter of the PVDF
fiber is found to increase with the increase in the flow rate [166,167]. On
2.2.1. Effect of solvents and solution viscosity the contrary, Ghafari et al. did not find such sensitivity or change in fiber
The molecular weight, concentration of PVDF, and solvents used are diameter with a change in flow rate [168]. Gade et al. observed that fiber
the solution parameters that allow more tuning options over other pa­ diameter increased with flow rate, but β-phase content decreased from
rameters like viscosity, polarity, vapor pressure, and surface tension. An 92.5% at a flow rate of 2 ml/h to 85.5% at 8 ml/h [154]. Lei et al. re­
increase in the molecular weight of PVDF increases the viscosity of the ported the formation of the γ phase at a flow rate of 2000 μL/h at 30οC,
solution. A more viscous solution will take longer to reach the collector and the formation of the α phase at 50οC [169].
and so the jet stretches more under the applied voltage and solvents
evaporate better, enhancing the β phase content. Hence, higher molec­ 2.2.5. Effect of collector type
ular weight PVDF fibers generally have better piezoelectric and me­ The fraction of the β phase was found to improve as a static collector
chanical properties [149,150]. This was confirmed by the studies of was replaced with a rotating one due to the additional stretching force.
Magniez et al. [151] and Zaarour et al. [152]. The weight percentage of Fu et al. observed that the fraction of β phase increased to 93.2% at a
PVDF also has a similar effect on the viscosity of the solution. With the speed of 2000 rpm for the rotating drum [150]. Along with the increase
increase in concentration, the uniformity and fraction of the β phase in β phase content, a decrease in fiber diameter is also observed with an
increase at first due to the improved stretching effects. If it increases increase in collector speed. However, an increase beyond an optimum
beyond a critical limit, the solution becomes highly viscous and harder value will result in wider, non-uniform, or broken fibers [153,154,158,
to stretch. As a result, the fraction of the β phase decreases [153]. 166]. Zaarour et al. reported that by increasing the rotation speed of the
Justifying this claim, Gade et al. reported that the β phase content drum collector, the macropores of the fiber changed into elliptical

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S.M. Purushothaman et al. Polymer 283 (2023) 126179

shapes, grooves deepened, and roughness increased [167]. Thus, the surface morphology of the fibers. Szewczyk et al. observed that fibers
collector speed has an intermediate optimum value which gives the best spun at a relative humidity of 30% (PVDF-30) had a smooth surface and
fibers. an average diameter of 0.92 μm while those spun at a relative humidity
of 60% (PVDF-60) had a wrinkled surface and larger average diameter of
2.2.6. Effect of temperature and humidity 1.68 μm [172]. Zaarour et al. observed that smooth fibers were formed at
The increase in the ambient temperature increases the solvent 5% relative humidity, and macroporous, rough, and grooved fibers were
volatilization rate and reduces the surface tension and viscosity of the produced at higher relative humidity [173]. Studies found that the
PVDF solution, thereby affecting the fiber morphology and fraction of β relative humidity must not be increased beyond a critical value as this
phase [153]. Huang et al. reported that with an increase in temperature, will inhibit the evaporation of solvents and hinder the electrospinning
more uniform fibers with lesser beading were formed [170]. As the process [153,164,174].
temperature increases, fiber diameter decreases but beading may occur. From the above discussions, the conclusion reached is that for every
Mohamadi and Sanjani reported that with the temperature set to 40◦ C, parameter there is an intermediate optimum value that gives the best
the growth of the γ phase was seen. It was accounted for by the increase fibers. Furthermore, as all of these parameters are somewhat interre­
in thermal energy causing the rotation of the CF2 group [171]. The lated and interdependent, varying one can vary the previously obtained
relative humidity also affects solvent volatility and thus alters the optimum value of another parameter [174–176]. Once the optimum

Fig. 3. Schematic representation of (a) the process of electrospinning of PVDF, and (b) the parameters which affect it along with the subsequent change in crys­
talline phase.

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parameters have been found, electrospinning becomes a reliable way to positive triboelectric layer through an external circuit. As the separation
produce PVDF fibers with a high electroactive phase fraction. Mechan­ between the layers increases, an electrostatic equilibrium is reached and
ical stretching and electrical poling are the most common methods to the electron flow stops. When the two layers are again driven towards
induce the β phase in PVDF. Electrospinning is the only technique that each other, the electrostatic equilibrium is again broken and the elec­
offers both of these methods within the process itself. The high voltage trons flow back in the opposite direction, thus reducing the number of
applied and the high drawing of the jet during electrospinning produce induced charges. Finally, all the induced charges are neutralized when
an in situ poling and stretching effect, and thereby induce preferred the layers come in contact [187–189]. Interestingly, in PVDF-based
dipole orientation and all trans conformation in the electrospun PVDF devices, piezoelectric, pyroelectric, and triboelectric effects can act
fibers. The fraction of the β phase found in electrospun samples can be as complementary to enhance the overall output performance and func­
high as 99% [177,178]. The electrospinning process of PVDF, the pa­ tionality of the device. This principle forms the basis of hybrid energy
rameters which affect it, and the subsequent change in the crystalline harvesting. For example, during the simultaneous application of pres­
phase are schematically shown in Fig. 3. After acknowledging the ad­ sure and heating, the piezoelectric output under the heated condition is
vantages of electrospinning for the manufacturing of electroactive PVDF observed to be higher due to thermal strain coupled with the piezo­
nanofibers, the coming section of the review will present the recent electric effect. Similarly, the pyroelectric output improves upon
developments and applications in which they can be of use. increasing the stretching elongation of the device due to
mechanical-strain-induced pyroelectric output [190]. Even when
3. Applications of electrospun PVDF- nanocomposites considering the application of external forces without heating, there still
exists a complementary method to enhance the output of the devices
The previous sections showed the interesting microcrystalline through coupled mechanisms of piezoelectric and triboelectric energy
properties that can be achieved by PVDF fibers when the optimum harvesting. Indeed, when an external force is applied, the deformation of
electrospinning parameters are used. The next section will attempt to material can occur simultaneously with contact friction, thus allowing
give an overview of the various application of such electrospun PVDF the complete exploitation of the applied mechanical energy. At first,
fibers. when the triboelectric layers are brought toward each other, triboelec­
tric charges develop due to interface friction. As the application of
3.1. Energy harvesting and sensing external force continues, a piezoelectric potential is also generated due
to the deformation of the PVDF film. Then, there is a current flow in the
PVDF is an excellent electroactive material with high sensitivity, circuit to balance the piezoelectric potential. As the external force is
flexibility, biocompatibility, and non-toxicity. Compared to other removed, the PVDF film recovers from compression and the piezoelec­
manufacturing processes of PVDF, electrospun nanofibers are reported tric potential disappears. With the triboelectric layers separating from
to possess the highest β phase content, high surface area, and surface each other, an internal triboelectric potential develops resulting in a
charge production. Hence, they are one of the most ideal candidates to current flow in the circuit [191]. Fig. 4 summarizes the principles of
harness the otherwise lost mechanical and thermal energy. The interest piezoelectric, pyroelectric, and triboelectric energy generation in
shown in research for such materials is made apparent by the great ef­ PVDF-based devices. The following sections will discuss their architec­
forts to develop PVDF-based novel energy harvesting devices or self- ture and applications.
powered sensors. The different energy harvesting mechanisms in
PVDF-based devices can be explained as follows. 3.1.1. Piezoelectric nanogenerators and sensors
Under stress or other stimulations like change in temperature, The elemental structure of a piezoelectric nanogenerator (PENG) or
deformation of the crystals, and rotation of dipoles occur within the sensor consists of four parts. The piezoelectric material is the active layer
crystalline phase of PVDF films. This forces a change in the dipole and is primarily responsible for the entire process of energy harvesting
density of the film and causes the electric charges within the film to be and sensing upon the application of pressure. The piezoelectric material
out of equilibrium. Thus, the result is the variation of the electrostatic- is sandwiched between suitable electrodes connected to the external
induced charge density of the electrodes fixed on either side of the circuit. The entire PENG is wrapped in suitable materials like poly­
film, inducing a voltage and current flow in the external circuit. Once dimethylsiloxane (PDMS) to protect it from damage from continuous use
the stimulation is removed, the accumulated free charges flow back, and exposure to different environments [192,193]. It is worth consid­
resulting in a reverse electrical signal in the external circuit. When the ering some of the recent PENGs, and innovations in their structure,
external stimulation is completely removed, the device returns to its output, and high-performance applications. The CsPbBr3-PVDF PENG
initial condition. The production of an electrical output by PVDF films in based on in situ growth of CsPbBr3 nanocrystals in PVDF matrix fabri­
response to applied pressure forms the foundation of piezoelectric en­ cated by Chen et al. for mechanical energy harvesting and motion
ergy harvesting. Pyroelectric energy harvesting is based on the response sensing is a relevant example [194]. They used a one-step technique in
of the PVDF films to temperature [179–184]. Because of its unique which the solutions containing CsPbBr3 precursors and PVDF was
electroactive properties, electrospun PVDF is an effective dielectric electrospun to produce the nanocomposite fibers. The PENG gave a
material for triboelectric energy harvesting as well [185]. In triboelec­ maximum piezoelectric output voltage of 103 V and a current density of
tric energy generation, it is the charge transfer due to contact electrifi­ 170 μAcm− 2. The fabrication of the flexible PENG, it’s structure,
cation and electrostatic induction that is responsible for the production cross-section, and energy harvesting during walking is schematically
of the electrical output. This electrostatic induction arises from the illustrated in Fig. 5. Sengupta et al. developed another motion sensor and
friction of two different layers with different electro affinities, namely PENG using PVDF− polycarbazole nanofibers which were suitable for
the positive triboelectric layer (losing electrons) and negative tribo­ biosensing and bioactuation [195]. The PENG generated an open-circuit
electric layer (gaining electrons) which develop positive and negative voltage (Voc) of 2V under a pressure of 0.24 MPa and had a stable
charge respectively when subjected to pressure [185,186]. PVDF, response in the frequency range of 1 to 7 Hz. In the study conducted by
especially in the β phase, can act as an excellent negative triboelectric Amith et al., the addition of Cloisite-30B nanoclay into PVDF was found
layer that efficiently traps the electrons. This is made possible because of to strengthen the β phase and piezoelectric response of electrospun
its high spontaneous polarization, high electronegativity, and high PVDF fibers. In this study, the authors reported the PVDF/Cloisite-30B
surface charge density. When the two triboelectric layers come in con­ nanofiber composite to produce an output voltage of 4.74 V when
tact, they develop opposite charges and as they move away an electrical actuated at 1500 rpm [196]. Ramasamy et al. presented a rare result in
potential difference will begin to develop. This creates a flow of elec­ which oleylamine functionalized boron nitride nanosheets (OLABN)
trons from the electrode of the PVDF layer to the electrode of the incorporated PVDF nanofibres with a high fraction of ~92% of γ–phase

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S.M. Purushothaman et al. Polymer 283 (2023) 126179

Fig. 4. Schematic representation of the principles of (a) piezoelectric, pyroelectric, and (b) triboelectric energy generation.

was used as the active material for energy harvesting and sensing [197]. Shivalingappa et al. used silver nanoparticles as fillers with PVDF to
The piezoelectric device developed from these fibers was able to detect a fabricate a sensitive PENG [200], and Ongun et al. experimented with
minimum force of 0.1 N and light up a 4V light-emitting diode (LED) silver-doped zinc oxide nanoparticles [201]. The PENG of Shivalingappa
upon finger tapping with the aid of a simple amplifier. A combination of et al. could trigger a burglar alarm when the pressure on the PENG was
ZnSnO3–MoS2 was used by Muduli et al. as fillers with PVDF to develop a high enough to produce an output greater than 0.4 V. The device of
PENG for biomechanical energy harvesting. Here, a 1 μF capacitor Ongun’s group had the potential to be used within flexible, portable
charged from the device was able to power a calculator with stability electronic systems, and wearable gadgets. Similarly, Hasanzadeh et al.
[198]. To explore the possibilities of another transition metal-based added ZnO nanoparticles along with graphene (graphene-ZnO nano­
filler, Zhao et al. developed a highly sensitive pressure sensor based on composite) into PVDF fibers and found that an applied force of 1 N
flexible piezoelectric MXene/PVDF hybrid film [199]. They reported produced a peak-to-peak voltage (Vpp) of 840 mV. This was significantly
that with only 0.4 wt% MXene, the piezoelectric coefficient d33 of higher than the outputs of the pristine PVDF and PVDF/ZnO nanofibers
MXene/PVDF hybrid film reached values as high as 43 pC/N. The sensor which were 640 mV and 710 mV respectively [202]. Another
gave a stable output for 10,000 s. A combination of BiCl3 and ZnO was graphene-based filler incorporated PVDF nanofibres was developed
used by Zhang et al. as a filler to obtain PVDF/BiCl3/ZnO composite using COOH-functionalized graphene nanosheet and talc nanosheet by
fibers with a high β phase content of 92% [184]. The piezoelectric sensor Shetty et al. [203]. As they could obtain a power density of 1.72 μW/cm2
developed from these fibers and simple aluminum foil electrodes gave a when a pressure of 0.4 MPa was imparted, the authors suggested this
maximum Voc of 3 V and 0.6 V for elbow and knee bending, and material as a promising candidate for the fabrication of portable and
stretching between specific angles. This signals the applicability of the flexible electronic devices. Electrospun PVDF films with Y-doped ZnO
device as a wearable sensor for detecting vital signals such as breathing, fillers and a very high F(β) of 98% were fabricated by Yi et al. thus
heartbeats, and hand movements post-stroke or traumatic brain injury. combining the flexibility of PVDF and high piezoelectricity of Y-doped

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S.M. Purushothaman et al. Polymer 283 (2023) 126179

Fig. 5. a) Preparation of precursor solution of CsPbBr3@PVDF for in situ growth method. b) Preparation of precursor solution of CsPbBr3@PVDF for two-step growth
method. c) Schematic diagram of the fabrication of the flexible PENG. d) Schematic diagram of the PENG structure. e) Cross section of the PENG based on in situ
growth method. f) Display of energy collection during walking (reproduced with permission from Ref. [194]).

ZnO [204]. The PENG gave an output voltage of ~8 V under continuous of the final piezoelectric yarn increased with the thickness of the PVDF
punching for a trial lasting over 1100 s at 0.8 Hz. It could also charge a layer. Bai et al. also used a distinct method by creating PVDF nanofiber
capacitor of 5 μF to ~2.8 V or ~3.7 V in 50 s by walking or running. array films via a combination of electrospinning and cutting methods
The possibility of using fillers derived from biological sources was [208]. The PVDF nanofiber films were stacked layer by layer along the
explored by Ponnan et al. by using magnesiochromite nanocrystalline same direction and compressed to get an oriented nanofiber bulk. It was
powder synthesized from egg shell membrane and incorporating it in then cut to obtain the PVDF nanofiber array film having dense vertical
PVDF nanofibers [205]. This PENG could provide stable output for over alignment as shown in Fig. 7. From the power output of two such par­
750 cycles and could charge a 10 μF capacitor within 643 s. Exploring allelly connected PENG, 12 LEDs could be lit without storage devices.
the possibilities of different fillers, and using a different electrospinning A bit different from the conventional fabrication methods, Du et al.
technique was done by Wang et al. [206]. In Wang’s study, an all-organic used a laminating method to develop multilayered porous composite
and core-shell structured silk fibroin/PVDF nanofibers were fabricated fibers-based piezoelectric nanogenerators [209]. The laminating process
using a coaxial electrospinning strategy. The ability of the device to was beneficial as it increased the possibility of stressing every fiber by
generate distinct output voltage for different movements of the human reducing the porosity of the fiber film. For this, they layered fiber
body was used for the development of a sensor in a human-machine membranes of PZT incorporated PVDF fibers along the same direction
interactive interface. This was demonstrated by making a smart car and compressed them together. The output of the PENG was found to
move forward, backward, and turn around by punching, tapping, and increase with the increase in thickness, and an output voltage as high as
bending respectively (Fig. 6.). A wearable piezoelectric device based on 92 V was obtained from a 500 μm thick film. Another example of
yarns and fabrics was woven by Xue et al. using a highly integrated innovative design is the piezo-organic e-skin sensor (POESS) fabricated
PVDF/conductive nylon core-sheath structure [207]. In this study, a by Maity et al. through an all-organic strategy. Here, metal-free, high­
dense PVDF fibrous coating was electrospun on the outer surface of a ly-conductive, flexible, and biocompatible spongy electrodes were used
conductive nylon yarn which functioned as one of the electrodes. The instead of conventional electrodes [210]. Such an organic
same nylon yarn was braided on top of the PVDF-coated nylon yarn via a electrode-piezoelectric stack was developed by polymerization of ani­
2D braiding technology to function as the second electrode. The output line monomer by vapor phase polymerization using FeCl3⋅6H2O

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S.M. Purushothaman et al. Polymer 283 (2023) 126179

Fig. 6. (a) SEM image and (b) TEM image of SF/PVDF nanofibers. (c) Schematic diagram of the structure of the piezoelectric device based on SF/PVDF nanofibers.
(d) The sensor attached on the hand bending at various angles and the corresponding piezoelectric responses. (e) The interacting process between human motion and
a smart toy car. The smart toy car moved towards different directions when (f) punching, (g) tapping, and (h) bending motion were applied on the SF/PVDF
piezoelectric sensor (reproduced with permission from Ref. [206]).

containing PVDF. The POESS was then attached to the human body for extra layer of PVDF nanofibers was electrospun onto this yarn to fix the
self-powered physiological signal monitoring such as wrist bending, silver nanoparticles. Finally, a plain weave fabric was made with
neck stretching, throat movements, phonation recognition, and pulse nanofiber yarns through a traditional textile weaving technique. Here,
measurement. An all-fiber piezoelectric nanogenerator (A-PNG) was the core layer of silver-plated nylon yarn acted as the inner electrode and
designed by Mahanty et al. by using 0.5 wt% ZnO nanoparticles rein­ the other electrode was a metal electrode clip clamped to the outer
forced electrospun PVDF nanofibers as the active layer [211]. In this surface of the PVDF nanofiber film. The sensor was fabricated by
study, copper–nickel plate interlocked conducting micro-fiber-based encapsulating this yarn in PDMS and had good response behavior which
polyester fabric was used as electrodes. Owing to its reliable piezo­ increased with the increase of effective contact area and applied weight.
electric response and skin conformable functionality, the A-PNG was Similar to the advances made in manufacturing methods, researchers
attached to the throat, wrists, fingers, and knees for vocal cord move­ came up with advanced and novel applications for the different piezo­
ment monitoring, pulse monitoring, remote health care monitoring, electric devices they fabricated. Yen et al. demonstrated that a dynamic
sports activities, and related movements analysis respectively. The de­ soft sensing element made using AgNO3/PVDF composite fibers could be
vice was also used as a weight monitoring sensor which could give the used for accurate diagnosis and treatment [213]. The device could
weight of a person weighting between 45 and 80 kg. A core-shell type of detect the tremors produced in the biceps muscles and was beneficial in
PVDF yarn was developed by Li et al., with a silver-plated nylon yarn as detecting muscle tremors after high-intensity training to obtain infor­
the core [212]. Li’s group used TiO2 as fillers and silver nanoparticles as mation regarding the changes in the symptoms of fasciculation.
an extra coating on top of the electrospun PVDF@TiO2 nanofibers. An Furthermore, Li et al. fabricated a wearable and implantable biomedical

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S.M. Purushothaman et al. Polymer 283 (2023) 126179

Fig. 7. (A) Processing and structure of PVDF nanofiber array film and nanogenerator. a) Schematic procedure of the preparation of the PVDF nanofiber array film. b,
c) Schematic diagram and digital photograph of nanogenerator based on PVDF nanofiber array film. d) SEM image of PVDF nanofiber array film. (B) a) Digital
photograph of the test system. b,c) Output voltage curve features of the piezoelectric nanogenerator based on the nanofiber array film with a thickness of 2.3 mm and
schematic diagram of working mechanism during one impact cycle, respectively (reproduced with permission from Ref. [208]).

sensor from electrospun core/shell PVDF/dopamine nanofibers [214]. generated a maximum output voltage of 17.45 mV and electrical power
The device was attached to the diaphragm and around the femoral ar­ of 0.40 μW under a resistive load of 750 KΩ, at a low-level magnetic field
tery of mice and could indicate the inhibition of respiration and loos­ frequency of 50 Hz. A novel PENG-sensor-photodetector was fabricated
ening of the peripheral arterial walls under the effect of anesthesia by a by Mondal et al. using a composite of all-inorganic cesium lead bromide
change in Vpp. Such a piezoelectric sensor offers great potential for the (CsPbBr3) perovskite rod and PVDF nanofiber [217]. The device is a
early assessment and prevention of cardiovascular diseases, respiratory potential vibration sensor for mobiles, air blower, and regular table fan
disorders, and other pressure-related acute and chronic diseases. It could with an output power of 4.24 mW and durability over 4 months. Simi­
also be employed to harvest energy from biological deformations such as larly, Yang et al. used reduced graphene oxide incorporated PVDF fibers
heartbeats and lung movements, and used to produce electrical stimu­ and developed a PENG for motion and air leakage detection that pro­
lation for tissue repair and disease treatment (Fig. 8.). A PVDF-based duced an output of 200 nA and 150 nA respectively [218]. A type of
piezoelectric device was also used as a human-machine interface in self-supporting smart air filter was developed by He et al. from elec­
Zhao’s study [215]. They fabricated a matrix motion sensor by arran­ trospun PZT/PVDF nanofibers for the harvesting of wind energy along
ging several small motion sensors from PVDF/ZnO hybrid material. The with air filtering [219]. The energy harvested was then used to inhibit
individual ones were used to detect various movements like finger and bacterial growth. The energy harvester was designed to be a multi­
foot pressing. With the one with a two-dimensionally arranged set of functional device by sputtering a series of square gold particle layers
devices, an NAO robot could be moved and turned according to the over the fibers and using two metal meshes on either side as electrodes.
walking directions of a person. The gold particle layer acted as a volatile organic compound sensing
Sources other than motion or mechanical deformation can be used to area in which resistance increases as cracks were formed. The formation
initiate the piezoelectric response of the PENGs. Demirci et al. studied of cracks is due to the swelling of the underlying PZT/PVDF fibers as
the piezoelectric and magnetoelectric energy harvesting capability of a they absorb ethanol vapors. The cracks were healed after the evapora­
device fabricated from PVDF/NiFe2O4 fibers [216]. The device was tion of ethanol and thus the conductivity of the sensing element was
found to be able to harvest the magnetic fields from the coil of a kettle. It restored. Mousa et al. fabricated PVDF-cellulose nanocrystal

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S.M. Purushothaman et al. Polymer 283 (2023) 126179

Fig. 8. (A) SEM image of PVDF/DA nanofibers (NFs) showing their uniform sizes with average diameters of 260 ± 80 nm. (B) Surface topography of a single PVDF/
DA NF and pure PVDF NF. (C) In vivo applications of PVDF/DA NF-based sensors. a) Schematic of the PVDF/DA NF-based sensor implantation for recording subtle
mechanical pressure changes in vivo. b) Surgical images of the implanted PVDF/DA NF-based sensors attached on the diaphragm membrane in the abdominal cavity
(top) and onto the femoral artery (bottom). c) Piezoelectric voltage signals induced by diaphragm motions and blood pulsing when the mouse was at different
physiological states. State i: anesthesia; state ii: overdose anesthesia; state ii: continuous overdose anesthesia (for diaphragm: agonal respiratory; for femoral artery:
articulo mortis). d) Respiratory rate and arterial pulse of the mouse at different physiological states measured by a clinical vital signs monitor. e) Piezoelectric signals
from femoral artery showing three typical BCG pulse waveforms of the Ps, Pi, and Pd. f) BCG values of IJ interval and Tr of a reflected wave from the hand periphery
obtained from (e). g) Comparison of the femoral AIx and DAI among different physiological states, where AIx (%) was defined as (Ps − Pi)/Ps and DAI was defined as
Pd/Ps (reproduced with permission from Ref. [214]).

membranes, that were used to make oil-wastewater separation and change in humidity into electric power. Considering real-life applica­
self-powered sensors [220]. With their higher water flux and oil rejec­ tions, it was able to harvest energy from moisture changes in human
tion properties, they hold potential for future exploration, based on the breath, palm (based on its motion towards and away from the film) and
energy harvesting from flowing droplets. Li et al. manufactured poly­ also mental sweating. Thus, the device could be a candidate for human
vinyl alcohol (PVA)-wrapped dopamine/polyvinylidene fluoride healthcare monitoring too. Another similar example is the study of Lu
shell/core nanofibers and used them as a two-in-one humidity et al. [222]. They developed a PENG using 3D-Tb-modified (BaCa) (ZrTi)
actuator-driven piezoelectric generator [221]. The ability of PVA to O3 (BCZT)-PVDF core/shell nanofibrous membrane for microenergy
spontaneously form hydrogen bonds with water molecules under harvesting from mechanical motion, acoustic waves and wind. The
ambient humidity and anisotropical swelling allowed it to produce PENG could achieve 12–28 V as output voltage with wind speeds of 5 to
mechanical deformation within the PVDF fibers and thereby convert a 14 m/s. Hence, it holds the potential to be used as a commercial digital

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S.M. Purushothaman et al. Polymer 283 (2023) 126179

temperature-humidity meter powered by wind energy. is expected to possess a high pyroelectric coefficient as well so that it
Acoustic waves are another interesting source for stimulating the responds well to changes in temperature. The electrodes and protective
piezoelectric effect in PVDF nanofibers. Mahanty et al. designed a highly coatings are chosen in such a way that along with performing their
sensitive all-fiber acousto- and piezo-electric nanogenerator (AAPNG) normal functions, they contribute to the process of heat transfer to the
with MgCl2⋅6H2O added PVDF nanofibers [223]. The AAPNG is a highly active layer [226,227]. In this section, the different structures and
sensitive device that generated an open circuit output voltage of 2 and 3 methods used by researchers to maximize the pyroelectric output and to
V at sound pressure levels (SPL) of 80 and 120 dB respectively. Because widen the practical applications of the device will be explored.
of its improved sensitivity to SPL, the AAPNG could be used as a noise Wu et al. developed an infrared-driven non-contact pyroelectric
detector and possibly as a self-powering microphone for sound generator based on electrospun tungsten oxide incorporated PVDF
recording. Another motion monitor and acoustic energy harvester with nanofibrous membrane (PVDF/WO2.72) with improved Near Infrared
high-potential electronic skin applications were developed by Roy et al. (NIR) absorption and photothermal conversion ability [228]. They
[224]. They used naphthylamine bridging a [Cd(II)-μ-I4] designed the generator using two types of electrodes to maximize the
two-dimensional metal− organic framework-reinforced PVDF composite heat transfer and the pyroelectric output. Ni–Cu conductive fabric sub­
nanofibers mat to fabricate this flexible and sensitive composite piezo­ strates were used as the bottom electrodes on which the PVDF nano­
electric nanogenerator. When the composite fibers were used for fibers were directly electrospun. The top electrode was an L-shaped
acoustic energy harvesting, the architecture of the device became conductive carbon nanotube (CNT) sheet that partially covered the
slightly different from the conventional way. In this case, the nanofiber nanofibrous membrane, thus allowing maximum heat transfer (Fig. 9.).
mat was sandwiched in between two samples of indium tin oxide coated The as-prepared pyroelectric generator with 7 wt% WO2.72 was sub­
on a poly(ethylene terephthalate) (PET) sheet, with one circular hole of jected to NIR radiations, and the temperature rapidly increased to
1 cm diameter cut on each PET film. The hole allowed nanofibers to 107.1 ◦ C after 60 s. Meanwhile, the maximum output voltage could
directly experience the sound vibrations. The as-prepared acoustic reach 1.5 V and remained stable during multiple cycles (Fig. 10.). The
nanogenerator gave an open-circuit voltage of 6 V at a sound wave outputs suggested that the device could also be used as an efficient
frequency of 120 Hz and 110 dB SPL. A piezoelectric acoustic detector temperature sensor. Employing cesium tungsten bronze (Cs0⋅33WO3)
with a frequency resolution better than 0.1 Hz was developed by Xu et al. incorporated screen-printed serpentine electrodes (SRE) and Cs0⋅33WO3
[225]. For this PVDF membrane, a soft pad and a metal plate were put in incorporated PVDF nanofibers Gokana et al. developed a potential py­
sequence on a metal and pushed into the grooves of a metal template. roelectric nanogenerator to harvest solar energy [229]. Compromising
The PVDF film was then peeled off to obtain a wave-shaped nanofiber between the heat transfer rate and resistance of the electrode, and
membrane. The device thus produced clear-cut and comparatively considering the pyroelectric output of the devices made, the SRE which
higher responses to sounds of different frequencies and SPL. Based on covers 54% of the PVDF film was found to be a suitable electrode. The
the above results and the fact that every human being’s voice has a pyroelectric nanogenerator made from this electrode and 7 wt% of
unique characteristic frequency spectrum, the potential of the device to Cs0⋅33WO3 added PVDF films could power a liquid crystal display (LCD)
recognize individuals, words, musical notes or animal sounds were and four light-emitting diodes through capacitor charging. Along with
demonstrated by human trials and sounds from a computer played via a demonstrating the pyroelectric application of PVDF, the study demon­
loudspeaker. strates how the engineering of electrode structure plays a crucial role in
the final output.
3.1.2. Pyroelectric nanogenerators and sensors
The structure of a pyroelectric nanogenerator based on PVDF films is 3.1.3. Triboelectric nanogenerators and sensors
similar to that of a PENG. In this case, the film with high β phase content Triboelectric nanogenerators (TENG) possess two active layers. As

Fig. 9. (a) SEM and (b) TEM images of electrospun PVDF/WO2.72 nanofibrous membranes, (c) Schematic illustrations of pyroelectric measurement (reproduced
with permission from Ref. [228]).

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S.M. Purushothaman et al. Polymer 283 (2023) 126179

Fig. 10. (a) Temperature variation over time, (b) corresponding differential curve, (c) output voltage and (d) output current of WO2.72-free PVDF and 7 wt% PVDF/
WO2.72 pyroelectric composites (reproduced with permission from Ref. [228]).

mentioned earlier, a PVDF nanofiber-based membrane acts as the triboelectric energy harvesting performance [235]. An electrospun
triboelectric negative layer, and aluminum films, copper films, or nylon Nylon 6/6 nanofibrous membrane acted as the positive triboelectric
are commonly used as positive triboelectric layers. The separation be­ membrane. The fabricated TENG-energy storage device could success­
tween these active layers is maintained using spacers, binding yarns, or fully power 120 commercial LEDS under gentle tapping. It could charge
transition layers which are often made of polyimide (PI) films, Kapton a 10 μF capacitor up to 2.25 V within 31 s and a 22 μF capacitor up to
films, etc. The electrodes and connection lead further to complete the 2.25 V within 50 s to turn on a sports watch for 5 s and operate a hy­
TENG. There are four representative modes of operation of TENGs, grometer sensor, respectively. This device was further used as a
among which the most common is the vertical separation mode. In this self-powered foot motion sensor, which automatically controls the lights
mode, the layer on which pressure is applied will come in contact with on the steps as one moves over the stair (Fig. 11.). Another PVDF-nylon
the other, and a transfer of charges occurs. As the pressure is released the TENG was developed by Sun et al. [236]. Herein they doped MoS2/CNTs
layers attain the initial separation with the help of the spacers. In the in PVDF to produce TENG that could give an open-circuit voltage
lateral sliding mode, one triboelectric layer is made to slide over the reaching 300 V, and short-circuit current (Isc) of ~11.5 μA when the
other to produce charge separation. In the single-electrode mode charge thickness of PVDF nanofibers was 0.08 mm and MoS2/CNT concentra­
transfer occurs as the surfaces of the triboelectric polymer fibers are tion was 0.3 wt%. It gave a Vpp of ~50 V, 90 V, and 100 V when worn
brought to contact with the electrode. The fourth mode is the free- while walking, or running. Similar to the above, the large difference in
standing mode which is accomplished by arranging the triboelectric triboelectric polarity of PVDF and nylon membranes encouraged Li et al.
layers with electrodes attached to them underneath another frictional to structure a wearable, flexible, and lightweight TENG from these
layer. The approaching and departing of the frictional layer from the [237]. By attaching the TENG to various keys of a keyboard, an output
electrodes build an unbalanced charge distribution resulting in the flow voltage of 8 V is obtained while typing and elbow bending produced 10
of electrons between the electrodes [230–234]. As the performance of V.
TENGs strongly depends on surface properties, their fabrication should Huang et al. developed an all-fiber-structured TENG as an energy
focus on improving the effective contact area and minimizing the change harvester and self-powered human motion monitor [238]. Here, ethyl
in surface properties with time under friction exposure and environ­ cellulose co-electrospun with polyamide 6 was used as the triboelectric
mental conditions. Accordingly, great efforts have been made to develop positive material, and electrospun PVDF nanofibers with MXene sheet
robust TENGs. In this section of the review, some of the recent attempts were used as the triboelectric negative material. This device could
in the case of PVDF-based TENGs will be explored, and the development charge capacitors of varying capacitance and power 180 commercial
of highly durable TENGs will be discussed. LEDs. The motion monitoring ability of the TENG was confirmed from
Bhatta et al. proposed the use of MXene (Ti3C2Tx) functionalized the output of the sensor detecting walking, hand clapping, and moving
PVDF composite nanofiber as a negative triboelectric layer for of arms. A TENG with ultrahigh outputs which reached 1502 V and

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S.M. Purushothaman et al. Polymer 283 (2023) 126179

Fig. 11. Application and demonstrations of the TENG. (a) Schematic diagram of the TENG with rectifier circuit, photograph of more than 120 LEDs arranged in series
connections, and photograph of the corresponding LEDs turned ON from the TENG upon simple hand tapping motion. (b) Charging and discharging characteristics
curves of the capacitors utilized to operate a commercial sport watch (insert shows the turned ON condition hygrometer). (c) Charging and discharging charac­
teristics curves of the capacitors utilized to operate a thermohygrometer sensor from the TENG under gentle hand tapping motion (insert shows the turned ON
condition of thermohygrometer sensor) (d) Schematic illustration of the TENG utilized as a self-powered footstep motion sensor. (e) Photograph of (i) fabricated
TENG utilized as self-powered foot motion sensor, (ii) sensor data processing and controlling circuitry, (iii) sensor and LED arrangements over the steps, and (iv),
real-time step lights control application demonstration. (f) Durability test voltage waveform of TENG at 6 Hz input frequency. (reproduced with permission
from Ref. [235]).

50.61 μA, was fabricated by Sun et al. [239]. For this, the friction layers vertical-separation TENG. Under a constant tapping of 10 N force and 2
were manufactured by growing triangular cone-structured polyaniline Hz frequency, a maximum root-mean-square (RMS) power output of 72
(PANI) nanofibers vertically on PI substrates and electrospinning PVDF nW at a 400M Ω resistance could be obtained. The ability of the tribo­
on PI substrates. The micro/nanostructure obtained during electro­ electric yarn (in single electrode mode) to generate voltage curves with
spinning provided a rough surface which enhanced the generation of distinct peaks, peak width, and peak amplitude portrays it as a wearable
surface charges during the friction process. This TENG with stable motion, haptic, and force sensor. Sun et al. developed a wearable,
output for over 50,000 cycles and 12,000 s at a frequency of 5Hz was washable, and air-permeable TEN sensor which is also waterproof
later used to form self-powered electrostatic manipulation systems and [242]. Electrospun PA66/MWCNT nanofiber film, conductive fabric
to reciprocate the movement of macro-charged droplets. In a study electrode, and waterproof and breathable cotton fabric were sewn
conducted by Zhang et al., an electrospun PVDF nanofibrous layer was together to act as the triboelectric positive layer. Electrospun PVDF
put to aid the energy harvesting from a flexible triboelectric generator nanofiber film was sewn together to act as the waterproof, breathable
integrated with a high-efficiency energy storage unit [240]. This device fabric and the triboelectric negative layer. It could power 160 LEDs by
gave a Voc of 560 V and Isc of 1.30 μA, respectively. itself and be combined with clothes to harvest the energy from hand,
Busolo et al. focused on improving the robustness of the TENG along shoulder, or arm movement (49 V and 36 V, respectively). Tests revealed
with improving its energy harvesting potential [241]. For this, a con­ that the TENG has consistent output over 10,000 cycles of pressure
ducting CNT yarn electrode was placed as a rotating collector which was stimulation and 2–6 h of washing. By weaving Si3N4 doped PVDF and
coated with PVDF fibers by electrospinning. For the energy harvesting polyurethane nanofiber core-spun yarns into a double-layer fabric, Tao
study, the as-prepared yarn was cyclically tapped against a Nylon 6 film et al. developed a flexible, wearable, washable, and highly durable
sputter-coated with gold on its non-contact side to form the TENG [243]. Herein they used a four-needle conjugated electrospinning

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S.M. Purushothaman et al. Polymer 283 (2023) 126179

technique with copper fibers as the conductive core yarns. Later these In the framework of research during the Covid-19 pandemic, He et al.
yarns were woven into two plain fabrics using textile weaving tech­ developed a respiration monitoring triboelectric nanogenerator (RM-
nology and were sewn into a double-layer fabric by using nylon yarn. TENG) The RM-TENG could be attached to a mask to be used as a
The output of the TENG depended on the fabric area and pressing fre­ convenient, smart, changeable, and self-powered mask filter [245]. It
quency. The TENG was also successful in producing output signals with could successfully monitor respiratory parameters, such as respiratory
varying amplitudes and rates corresponding to the difference in the way rate (RR), inhalation time (tin), exhalation time (tex), and their ratio
of finger tapping. Thus, it was established that the TENG could clearly (IER=tin/tex) with good accuracy. Looking into the architecture of
distinguish between various forces and frequencies and hence be used RM-TENG, polyacrylonitrile, and PVDF electrospun nanofiber mat
for human motion monitoring, intelligent textiles, etc. Adding to the list functioned as the triboelectric layers, to which conductive aluminum
the highly durable TENGs, Cheng et al. developed a flexible, and fabrics (with and without holes) were attached as electrodes. A minia­
self-healing ionic liquid elastomer-based triboelectric generator [244]. ture printed circuit board was attached to collect and transmit the data.
Herein, an electrospun PVDF/PU nanofibrous membrane was used as Fig. 12 Represents the signal wave forms and real-time RR and IER
the triboelectric layer and was integrated on the CNTs-doped ionic response of RM-TENG during walking and running when the mask was
liquid elastomer (ILC) electrodes by autonomous adhesion. This me­ attached to RM-TENG. A novel approach in which a single self-powered
chanical damage-resistance TENG with a stable output after five device could simultaneously generate power from wave motion, sense,
cutting-healing cycles is a promising wearable bioelectronic device for and wirelessly transmit wave information was put forward by Bhatta et
human healthcare detection and human-machine interaction. al. [246]. The TENG had a composite nanofiber of 2D MXene/PVDF and

Fig. 12. (A) SEM image of PAN-NFM (insert is the photograph of the PAN-NFM); (b) SEM image of PVDF-NFM (insert is the photograph of the PVDF-NFM); (c) Water
contact angle on flat PAN-NFM; (d) Water contact angle on flat PVDF-NFM. (e)Schematic illustration of the RM-TENG. (B) (a) Photo of the subject walking on the
treadmill with a mask attached to the RM-TENG. (b) The enlarged mask attached to the RM-TENG. (c) The signal waveforms recorded by the RM-TENG after the
subject walked/ran on the treadmill at various speeds. (d) The real-time RR and IER obtained from the RM-TENG after the subject walked/ran on the treadmill at
various speeds (only 20 s of data recording for each test is displayed for the clear peaks and frequencies). (reproduced with permission from Ref. [245]).

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S.M. Purushothaman et al. Polymer 283 (2023) 126179

Nylon 6/6 as the triboelectric layers and a custom-fabricated ferro­ sensing. The sensor units could also be arranged as e-skin sensor arrays
magnetic composite film of iron-silicon chromium (FeSiCr)/PDMS that can distinguish the contour of physical objects. It was finally able to
attached on top of it. A magnetic ball within an ellipsoid body of the track the real-time touch movements visually which could operate small
device rotated distinctly according to different wave parameters which robots, artificial prosthetics, etc.
caused actuation in the TENG, therefore producing an output that was Similarly, Ghosh et al. developed an all-organic stretchable energy
characteristic of the wave. An entire Bluetooth signal processing cir­ harvester with electrodes made of a xylitol-added poly(3,4-ethyl­
cuitry was powered from a capacitor (1 F, 5.5 V) charged for 124.5 min enedioxythiophene): poly(4-styrenesulfonate) film [190].
to 4.1 V using the device. Continuous data transmission was possible PANI-reinforced PVDF nanofibers were the piezo and pyro-active ma­
from the Bluetooth circuitry for 31.25 s and stopped as the capacitor terial and PDMS coating acted as the protective layer. The device pro­
voltage dropped below 3.75 V. Apart from using TENG as sensors, Yang duced maximum pyro- and piezoelectric power outputs of 3 μW/m2 and
et al. used electrospun nylon-PVDF nanofiber-based TENG for water/oil 31 μW/cm2 respectively under periodic thermal and mechanical oscil­
(W/O) emulsion separation [247]. In this case, the TENG was used to lations. It was also attached to a philtrum to demonstrate its
charge parallel electrodes to produce an asymmetric alternating voltage breath-sensing functionality and a peak-to-peak voltage of ~555 mV
output of 2500 V for W/O emulsion separation. Under the action of was obtained corresponding to the temperature fluctuation from 298 to
electric field force the demulsification, coalescence, and sedimentation 304 K during inhalation and exhalation. By producing a positive pyro­
of droplets occurred and visible free water appeared at the bottom of the electric output peak as a hot object approached, and a negative pyro­
container. After 30 min of being subjected to the asymmetric AC electric electric output as it moved away (vice versa in the case of a cold object),
field powered by TENG, the moisture content reduced from 5 wt% to the device demonstrated its purpose as a temperature sensor. It was also
0.15 wt% in the W/O emulsion. The separation efficiency increased with integrated into a smartphone to warrant the applicability of this sensor
an increase in the output voltage of the TENG and working time. towards wireless human-machine interfacing point-of-care diagnostic
Furthermore, a sandwich-like TENG was designed to harvest wind en­ devices (Fig. 13). Xia et al. developed a flexible, multi-site tactile and
ergy and demonstrate W/O emulsion separation from natural energy thermal sensor (MTTS) using PVDF nanofibers as the active material,
sources. In this case, PVDF nanofibers served as the flexible vibration etched copper wire polyimide film as the top electrode, and aluminum
layer, and nylon nanofibers as the bound layer, an output voltage of electrode array as the bottom one [251]. By arranging several of these
1400 V was produced at a triggering frequency of 28 Hz driven by the sensors into a 2-D array the group successfully employed it for spatial
wind with a speed of 8 m/s. This was then used to power four parallel mapping and recording of the 2-D motion trajectory of an object. The
electrodes which produced an asymmetric AC electric field. After 30 min output voltage and current from each sensor of the array were recorded
of use, the device was able to lower the moisture content in a 500 ml as the mapping of the external pressure and thermal stimulus from the
W/O emulsion from 10 wt% to 0.18 wt%. This high efficiency, along object. The piezoelectric and pyroelectric components were extracted
with the low cost and safety of the TENG qualifies it for industrial from the composite output through the mapping relationship between
wastewater treatment. the signals. The simultaneous pressure and temperature mapping of the
human palm and foot were performed using the device and the results
3.1.4. Hybrid nanogenerators and sensors showed very few errors from the actual pressure and temperature. The
Hybrid nanogenerators are devices that combine piezoelectric, py­ study demonstrated that integration of the MTTS with a wireless sensing
roelectric, or triboelectric mechanisms for efficient and advanced energy system can have extraordinary potential in human behavior detection,
harvesting and sensing applications. They are manufactured to maxi­ disability aids, thermoelectric distribution detection, etc. In addition to
mize the output from both mechanisms without one suppressing the the nucleation of the β phase, Li et al. explored the possibility of
other [191,248]. A few of the recent attempts at developing such novel enhancing the piezoelectric and triboelectric effects in PVDF fibers
devices, their structure, and fascinating real-time applications are dis­ through the addition of fillers [252]. In the study, by simply adding
cussed in this section. carbon-coated zinc oxide (ZnO@C) nanoparticles, they demonstrated
Mahanty et al. developed an interesting all-fiber pyro- and piezo­ that the piezoelectricity improved due to the nucleation of the β phase
electric nanogenerator (PPNG) healthcare monitor and sensor [249]. and the triboelectricity improved due to the shift in surface potential.
Herein, MWCNT-incorporated electrospun PVDF nanofibers were used The device made from 5% ZnO@C/PVDF nanofibers showed a very high
by them as the active layer along with an interlocked conducting output voltage of 37 V and 39 V as PENG and TENG respectively. It was
micro-fiber-based electrode to fabricate this device. This PPNG, with an then put to test as a motion sensor and was successful in producing
ultra-fast response time of ~10 m s, also had a high electrical throughput characteristic outputs for different arm movements and also detecting
and produced an output voltage of ~35 V under repeated finger tapping. even slight vibrations, with an output voltage of 0.1 V.
The PPNG was even capable of harvesting large temperature fluctua­ A piezo-tribo hybrid nanogenerator for efficient acoustic harvesting
tions of ~14.30 K as well as sensing thermal fluctuations as low as ~5.4 was fabricated by Yu et al. from nanoporous PVDF hollow fiber and
K. The device also exhibited different and characteristic responses for PDMS valve (PHVAH) [253]. The hollow PVDF fibrous membrane was
different biomechanical signals such as wrist and palm movements, obtained by removing the polyethylene glycol (PEG) in the PVDF/PEG
pulse rate, or vocal cord vibrations. Thus, the PPNG could be used as a fiber prepared by coaxial electrospinning. Then, by immersing this
biomedical sensor capable of monitoring body temperature as well as membrane in the diluted PDMS, the PDMS valve structure which can
body movements. This possibility was further demonstrated by inte­ mimic the eardrum could be formed between the hollow fibers. To
grating the PPNG with a Bluetooth module or Wi-Fi module connected to facilitate the direct contact of sound waves with the fibers, iron meshes
smartphones, for wireless healthcare monitoring. With a slightly more were placed on both sides of the membranes as electrodes. As the
complex architecture, Wang et al. fabricated an all-in-one electronic skin membrane deformed due to sound waves a piezoelectric output was
textile for both temperature and pressure sensing [250]. The tempera­ generated along with a triboelectric output due to the rubbing of the
ture sensing layer was made up of flexible thermal-resistance carbon PVDF hollow fibers with the PDMS valves and iron meshes (Fig. 14.).
nanofibers with localized graphitic structures while PVDF/ZnO nano­ The optimum output of the acoustic harvester from the combined piezo
fibrous membrane acted as the pressure sensing layer. The change in and triboelectric effects was equal to 105.5 V under the sound stimu­
resistance as the temperature changes allowed the e-skin to detect lation of 117.6 dB and 150 Hz. PHVAH showed high sensitivity, wide
temperature accurately. Practical pressure sensing applications were frequency response (70 to 1500 Hz), stability, and flexibility and thus,
demonstrated by sensitive weight identification, finger touch pressing, could be used for real-time detection of sound changes and further
and human carotid pulse capture. Expiratory air temperature moni­ harvesting of acoustic energy. In the study of Niu et al. on nylon-6/PVDF
toring depicted the potential of the e-skin in real-time temperature single-layer nanofibers, the device was fabricated so that it behaves like

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S.M. Purushothaman et al. Polymer 283 (2023) 126179

Fig. 13. a) Schematics of (i) wireless arterial pulse monitoring, (ii) epidermal–dermal layer of the human skin, and (iii) developed all-organic epidermal sensor. (b)
Three-dimensional (3-D) design and optical images of the all-organic nanoharvester possessing bending (i), folding (ii), and twisting (iii) abilities and composed of
(iv) flexible PEDOT:PSS/Xyl electrode manufactured from (v) the PEDOT:PSS/Xyl gel. (c) Schematic of electrospinning used for fabrication of (i) ESPVPANI nanowire
mat possessing (ii) excellent flexibility and (iii) conformability to human skin, (d) Fourier transform infrared (FT-IR) spectra, (e) high-resolution transmission
electron microscopy (HR-TEM) image, (f) cross-sectional field emission scanning electron microscopy (FE-SEM) image of the all-organic nanoharvester, (g)
stress–strain curves, where the inset shows an optical image of the all-organic nanoharvester (without poly(dimethylsiloxane) (PDMS) encapsulation) loaded with a
tensile force based on a hanging mass of 100 g, and (h) resistance change and corresponding strain gauge factor of the PEDOT:PSS/Xyl electrode under a range of
compressive forces and strains. The inset shows the force versus strain graph up to 0.6% strain. (reproduced with permission from Ref. [190]).

an assembly of many small PENGs and TENGs [254]. Here, the small nanofibers. The device was completed with the addition of
number of nylon-6 nanofibers incorporated into the PVDF fibrous matrix stainless-steel mesh electrodes and produced a peak voltage output of
by co-electrospinning acted as a dopant to form macro dipoles. This 201.4 V under a sound wave of frequency 230 Hz, 118 dB SPL. The
improved the charge transport from the dielectric layer to the external practical application of the device was put to test by using it to charge
electrodes and also caused an endogenous triboelectric effect with PVDF batteries and capacitors, light LEDs, and power an electronic watch, and

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S.M. Purushothaman et al. Polymer 283 (2023) 126179

Fig. 14. (A)Structure illustration and mechanism diagram of PHVAH driven by sound: (a) Initial equilibrium state. (b) PVDF hollow fiber and polydimethylsiloxane
valve (PHV) membrane deformed by sound waves. (c) Membrane recovers from the deformation. (d) PHV membrane deformed by sound waves in the opposite
direction. (e) Membrane recovers from the deformation again. (B) (a) Schematic diagram of the realization from sound to electricity with the fabricated PHVAH. (b)
Morphology of single PVDF hollow fiber (PH) fiber. (c) Morphology of PH fibers. (d) Morphology of PVDF fiber with PDMS valves. (e) X-ray diffraction (XRD)
pictures of PVDF powder and PVDF fiber prepared by coaxial electrospinning. (f) Optimal output voltage of PHVAH under a sound stimulus of 117.6 dB and 150 Hz.
(g) Optimal output current of PHVAH under a sound stimulus of 117.6 dB and 150 Hz. (h) Fourier-transform infrared spectra (FTIR) images of PVDF powder and
PVDF fiber. (i) Output voltages of PVDF acoustic harvester (AH), PHAH, and PHVAH under a sound stimulus of 117.6 dB and 150 Hz. (j) Output currents of PVDFAH,
PHAH, and PHVAH under a sound stimulus of 117.6 dB and 150 Hz. (reproduced with permission from Ref. [253]).

an electric torch. The charge of capacitors when the device was kept in a PVDF, the architecture, and a wide variety of non-conventional energy
noisy workshop with a hammer sounds further justified its applicability. generation techniques.
Based on the above-mentioned research works it is clearly under­
stood that electrospun PVDF films are high potential candidates for 3.2. Other applications
different types of nanogenerators and sensors. The study also reveals
different types of fillers which contribute to the electroactive response of The applications of PVDF or electrospun PVDF nanofibers are not

19
S.M. Purushothaman et al. Polymer 283 (2023) 126179

limited to energy harvesting. Over time, both PVDF and electrospun demonstrated that electrospun PVDF fibers with lanthanide (Ln) doped
PVDF nanofibers created their own space in several fields from material ZnO nanoparticles (Ln=Sm, La, Er) as fillers could be developed into
science to biology and medicine. Along with the intensive study on the membranes for adsorption and photocatalytic degradation of dyes and
polymer, great efforts are being taken to develop novel devices from it organic pollutants [260]. When put to test for the degradation of
for various applications. methylene blue (MB) and rhodamine B (RhB) the PVDF/ZnO: La mem­
Because of the biocompatibility, non-degradable nature, and low brane showed color removal efficiency of 96.33% and 93.36% respec­
fiber diameter of electrospun PVDF nanofibers, Klapstova et al used it as tively. By using ultrathin PVDF fibers with high surface area, smaller
glaucoma drainage implants by mixing it with polyethyleneoxide (PEO) pores, and rough surface, Yang et al. developed a high-efficiency coa­
[255]. Meanwhile, Agueda et al. used PVDF nanofibers for renal tissue lescence membrane [261]. The membrane, with poor oleophilicity
regeneration [256]. Along with biocompatibility, minimal cellular and under water, efficiently separated different types of emulsions which
tissue response, and chemical inertness, the possibility of producing indicated its applicability to clean different oil wastewaters. A
uniform fibers with larger pore sizes was the reason for them to choose multi-functional fiber membrane for sewage treatment and desalination
PVDF nanofibers. By soaking PVDF nanofibers in benzocaine and its was developed by Tessema et al. from cesium tungsten oxide/graphitic
complex with β-cyclodextrin (benzocaine-β-cyclodextrin or BNC:β-CD) carbon nitride (Cs0⋅32WO3@g-C3N4) hybrids doped PVDF nanofibers
Rajamohan et al. developed a drug delivery system of BNC and [262]. The multifunctionality of the membrane could be attributed to
BNC:β-CD [257] (Fig. 15 (a).). the hydrophobicity of PVDF. Organic dyes like 4-nitro phenol and
PVDF nanofibers are also extensively used for the fabrication of tetracycline were also efficiently removed by the membrane making it a
different filters. Because of their filtration efficiency, small pore size, and suitable candidate for practical waste water treatment in the future
large surface-to-volume ratio, Victor et al. used PVDF-titanium nanotube (Fig. 15 (b).).
fibers to develop an antibacterial filter media [258]. In the future, this Electrospun PVDF fibers, because of their electrochemical stability,
filter could be used for filtration of other microbes, facemasks, and mechanical strength, and flexibility can be used for battery applications
industrial-scale air filters. Wang et al. also used electrospun PVDF [263]. A self-standing electrolyte membrane was created by Makh­
membrane to produce air filters that out-performed commercial masks looghiazad et al. from triisobutyl(methyl)phosphonium bis(fluo­
by capturing up to 99.9% of coronavirus aerosols [259]. Pascariu et al. rosulfonyl)imide ([P1i444][FSI]) OIPC mixed with 20 mol% of NaFSI or

Fig. 15. (a) Schematic procedure for drug release from PVDF nanofibrous membranes (reproduced with permission from Ref. [257]), (b) Schematic illustration of
salt resistance hydrophobic CSxWO3@g-C3N4/PVDF fiber membranes (reproduced with permission from Ref. [262]), Schematic electromagnetic interference
shielding mechanisms for the dip-coated and spray-coated PVDF/AgNW hybrid membranes (reproduced with permission from Ref. [265]).”

20
S.M. Purushothaman et al. Polymer 283 (2023) 126179

NaTFSI and combined with electrospun PVDF membranes. The PVDF project administration, funding acquisition
nanofibers, along with providing structural support, interacted with
NaTFSI-doped electrolytes and thus made them more conductive and
superior to several other fiber-based electrolytes in Na metal batteries. Declaration of competing interest
Similarly, Barbosa et al. used electrospun PVDF fibers as separators for
lithium-ion batteries [264]. In this case, the ionic conductivity of the The authors declare that they have no known competing financial
PVDF fibers was enhanced by the addition of ionic liquids sharing the interests or personal relationships that could have appeared to influence
same anion, but different cations. By improving the electrical conduc­ the work reported in this paper.
tivity of PVDF nanofibers, it became suitable for electromagnetic
interference (EMI) shielding. Qian et al. used electrospun porous PVDF Data availability
nanofibers and developed an efficient lightweight EMI shielding mem­
brane by dip-coating silver nanowires (AgNWs) onto it [265]. The No data was used for the research described in the article.
AgNWs reached well into the pores of the PVDF fibers and increased the
electrical conductivity of the fibers by forming 3D AgNW networks. This Acknowledgments
also resulted in the multiple reflections of the EM wave (Fig. 15 (c).).
Ann Rose et al. also used electrospun PVDF fibers for EMI shielding The authors of the work would like to thank Indo-French Centre for
[266]. Here they added graphene as the filler to improve electrical the Promotion of Advanced Research/Centre Franco-Indien pour la
conductivity and by increasing its concentration, the EMI shielding Promotion de la Recherche Avancée (IFCPAR/CEFIPRA), French Na­
property increased. Thus, PVDF can play an important role in reducing tional Centre for Scientific Research (Centre national de la recherche
the growing radiation pollution as well. scientifique, CNRS) and Lorraine University of Excellence for the
support.
4. Conclusions
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S.M. Purushothaman et al. Polymer 283 (2023) 126179

[258] F.S. Victor, V. Kugarajah, M. Bangaru, S. Ranjan, S. Dharmalingam, Electrospun Isabelle Royaud who is a University lecturer in Polymer physics
nanofibers of polyvinylidene fluoride incorporated with titanium nanotubes for and Polymer science since 1990 joined the University of Lor­
purifying air with bacterial contamination, Environ. Sci. Pollut. Res. 28 (2021) raine in 2011 after beginning her career in the University of
37520–37533, https://doi.org/10.1007/s11356-021-13202-3. Lyon. She has obtained her PhD in Polymer Properties from
[259] Shuai, D. Development of Electrospun Nanofibrous Filters for Controlling University of Southampton – UK on “Conformation and crys­
Coronavirus Aerosols. vol. 17. tallinity in Polymers: A study using novel Raman techniques” in
[260] P. Pascariu, C. Cojocaru, P. Samoila, N. Olaru, A. Bele, A. Airinei, Novel 1989 then she has obtained her HDR on “Study of the influence
electrospun membranes based on PVDF fibers embedding lanthanide doped ZnO of ageing on molecular mobility of polymers”, (University of
for adsorption and photocatalytic degradation of dye organic pollutants, Mater. Lyon 1/IMP-Engineering of Polymer Material) in 2000. From
Res. Bull. 141 (2021), 111376, https://doi.org/10.1016/j. 2011 and up to now, she is a Professor at University of Lorraine
materresbull.2021.111376. (EEIGM: European School of Material Science and Engineering,
[261] Y. Yang, L. Li, Q. Zhang, W. Chen, S. Lin, Z. Wang, W. Li, Enhanced coalescence Nancy, France) and a Researcher at Institut Jean Lamour UMR
separation of oil-in-water emulsions using electrospun PVDF nanofibers, Chin. J. CNRS 7198 (Nancy, France). She is a specialist of relationship
Chem. Eng. 38 (2021) 76–83, https://doi.org/10.1016/j.cjche.2020.08.037. architecture/morphology/dielectric, viscoelastic and vibrational properties of polymers.
[262] A.A. Tessema, C.-M. Wu, K.G. Motora, S. Naseem, Highly-efficient and salt- Her scientific production is composed of 81 Publications, 2 book chapters, 1 patent, 13
resistant CsxWO3@g-C3N4/PVDF fiber membranes for interfacial water invited lectures in International Conferences, 180 Communications; 89 oral (International
evaporation, desalination, and sewage treatment, Compos. Sci. Technol. 211 Conferences: 50); 91 posters (International Conferences: 62), and 18 invited seminars. Her
(2021), 108865, https://doi.org/10.1016/j.compscitech.2021.108865. research activities deal with the following subjects:
[263] K. Bicy, A.B. Gueye, D. Rouxel, N. Kalarikkal, S. Thomas, Lithium-ion battery
separators based on electrospun PVDF: a review, Surface. Interfac. 31 (2022), - Polymer physic properties for synthetic polymers and biopolymers.
101977, https://doi.org/10.1016/j.surfin.2022.101977.
[264] J.C. Barbosa, D.M. Correia, R. Gonçalves, V. de Zea Bermudez, M.M. Silva, - Relations between architecture/morphology and mechanical, elec­
S. Lanceros-Mendez, C.M. Costa, Enhanced ionic conductivity in poly(vinylidene trical, vibrational properties of polymer and multimaterials.
fluoride) electrospun separator membranes blended with different ionic liquids - Influence of ageing and morphology on molecular mobility and
for lithium ion batteries, J. Colloid Interface Sci. 582 (2021) 376–386, https://
doi.org/10.1016/j.jcis.2020.08.046. relaxational phenomena in polymer materials.
[265] J. Qian, Z.-M. Zhang, R.-Y. Bao, Z.-Y. Liu, M.-B. Yang, W. Yang, Lightweight poly - Molecular mobility at the interfaces of nanostructured systems.
(vinylidene fluoride)/silver nanowires hybrid membrane with different - in situ monitoring of plastic deformation in polymers at different
conductive network structure for electromagnetic interference shielding, Polym.
Compos. 42 (2021) 522–531, https://doi.org/10.1002/pc.25844.
scales using vibrational techniques, videometric tensile test, syn­
[266] A. Rose, P.A. F, P.K. S Mural, A.M. Chandran, A Carbon Doped Electrospun Nano chrotron radiation and broadband dielectric analysis.
Fibre for Effective Emi Shielding, Social Science Research Network, Rochester,
NY, 2021.
Marc Ponçot obtained his PhD in 2009 at the Institut National
Polytechnique de Lorraine as part of a CIFRE grant with Ace­
Sreelakshmi Moozhiyil Purushothaman obtained her MS.c.in lorMital on the development and characterization of metal/
Physics in 2021 from School of pure and applied physics, polymer composites for the automotive sector. In 2011, he was
Mahatma Gandhi University, Kerala, India. She subsequently appointed Associate Professor at the Ecole Nationale Supérieure
started her Ph.D. at Insitut Jean Lamour, University of Lorraine, des Mines de Nancy, University of Lorraine. He carries out his
Nancy, France, under the supervision of Prof. Didier Rouxel and research at the Institut Jean Lamour within the Physics, Me­
Prof. Isabelle Royaud. Her research works focuses on the elab­ chanics and Plasticity team in the field of polymers and com­
oration and microstructure-property relations studies of poly­ posites, elaboration-microstructure-property relations. Since
mer nanocomposites and the development of polymer-based 2019, he has received his Habilitation à Diriger les Recherches
nanogenerators and sensors. (HDR).

Nandakumar Kalarikkal received his Ph. D in Semiconductor

Physics from Cochin University of Science & Technology, Ker­
Maïté Fernandes Tronco is a doctoral student at Institut Jean ala, India. In 1994, he joined the School of Pure and Applied
Lamour, University of Lorraine, Nancy, France. Under the Physics, Mahatma Gandhi University, Kerala, India as a Lecturer
guidance of Prof. Didier Rouxel and Dr. Marc Ponçot she studies and at present is a Senior Professor at the school. Prof. Kalar­
piezoelectric polymers, polymer-nanocomposites, their micro­ ikkal also functioned as the Director of the School of Pure and
structure, properties and their potential in energy harvesting Applied Physics and the International and Inter University
and sensing. She had completed her degree in Materials Engi­ Centre for Nanoscience and Nanotechnology, at Mahatma
neering from École Européenne d’Ingénieurs en Génie des Gandhi University. His presence among the academic commu­
Matériaux (EEIGM), Nancy, France. nity is strengthened by the various other recognitions he
received, which include Professor@Lorraine, University of
Lorraine, Nancy, France, CNRS Professor, Institute of Light
Matter, Claud-Bernard Lyon University, Lyon, France, Visiting
Professor, Stockholm University, Sweden, Guest Scientist, Leibniz-Institut fur Polymer­
forschung Dresden, Germany, and Visiting Fellow, Jawaharlal Nehru Centre for Advanced
Scientific Research, Bangalore, India The research activities of his group are highly
interdisciplinary in nature to address issues related to Energy, Water, Food, Health and
Environment securities in including the syntheses, characterization, and applications of
Bicy Kottathodi obtained her Ph.D from Mahatma Gandhi Uni­ various Nanomaterials, LASER Plasma, Ion irradiation effects on various novel materials
versity, Kerala, India in 2020. The doctoral research work and phase transitions. Through various national and international projects, he could
focused on the fabrication of microporous polymer nano­ contribute to scientific research by co-authoring more than 260 publications, 16 book
composite membranes for lithium ion battery separator appli­ chapters, and editing 32 books. He has an h-index of 50 with more than 8500 citations.
cation. She received junior research fellowship in Chemistry Recently, he was awarded the Fulbright-Nehru Academic and Professional Excellence
from Council of Scientific and Industrial Research (CSIR), India Fellowship.
in 2013. Her research interests are, polymer blends and nano­
composites, lithium-ion battery, piezoelectric polymers, energy
harvesting and storage, biopolymers etc. She has participated
several national and international conferences and worked at
Institute Jean Lamour, University of Lorraine, Nancy France, as
a part of her PhD. Currently she is working as a teacher.

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S.M. Purushothaman et al. Polymer 283 (2023) 126179

Sabu Thomas is the Vice-Chancellor of Mahatma Gandhi Uni­ Didier Rouxel was born in Lyon, France, in 1965. He received
versity, Kottayam, Kerala, India. He is also a Professor of Poly­ the Engineer degree from the École Supérieure des Sciences et
mer Science and Engineering at the School of Chemical Sciences, Techniques de l’Ingénieur de Nancy, Nancy, France, and the Ph.
and also the Director of School of Energy Materials and the D. degree in material sciences and engineering from the Uni­
founder Director of International and Inter-University Centre for versity of Nancy I, Nancy, France, in 1993. Since 2013, he has
Nanoscience and Nanotechnology, Mahatma Gandhi University. been the Leader of the “Micro and NanoSystems” Group of the
He obtained in Ph. D in Polymer Science and Engineering in Institut Jean Lamour, Nancy, France. He is currently a Full
1987, Indian Institute of Technology, Kharagpur, India. His Professor of the University of Lorraine, Lorraine, France, and the
research interests include polymer nanocomposites, polymer Institut Jean Lamour of Nancy, Nancy, France. His research in­
blends, fiber filled polymer composites, polymer nano­ terests include physical chemistry of surfaces and thin films,
composites for electronic applications, green bio­ quasicrystal surfaces, and more recently on Brillouin spectros­
nanotechnological and nanobiomedical sciences, dual porous copy for elastic properties of polymeric materials, polymer
nanocomposite scaffolds for tissue engineering, recyclability and nanocomposites, nanomaterials and piezoelectric materials.
reuse of waste plastics and rubbers, etc. Prof. Thomas has authored around 1200 peer Prof. Rouxel has been involved in the spectroscopic analysis of inorganics and is vastly
reviewed publications, edited and co-authored 150 books and holds four patents. experienced in the analysis of polymer nanocomposite systems by almost all spectroscopic
Furthermore, he has received a number of national and international awards, including techniques. His current areas of interest include the development of electrospun polymer
Docteur Honoris Causa from University of Southern Brittany, and University of Lorraine, nanocomposite materials and of micro-devices based on piezoelectric polymers, for
France, Fellowship of the Royal Society of Chemistry, MRSI award, CRSI award, the example acoustic microsensor for surgery, energy harvesting device, etc. He has written
Distinguished Professorship award form Josef Stefan Institute, Slovenia, Kairali Life time more than 150 publications, including more than 100 in international journals, 14 book
Research Award 2021 b y Kerala Government and was also honoured as the Foreign Fellow chapters, 8 books edited and more than 200 communications.
of the European Academy of Sciences (EurASc). The H index of Professor Thomas is 132
and has a citations of more than 83,000.

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