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Comparative evaluation of piezoelectric response

of electrospun PVDF (polyvinilydine fluoride)
nanofiber with various additives for energy
scavenging application

F. Mokhtari, M. Shamshirsaz, M. Latifi & S. Asadi

To cite this article: F. Mokhtari, M. Shamshirsaz, M. Latifi & S. Asadi (2017) Comparative
evaluation of piezoelectric response of electrospun PVDF (polyvinilydine fluoride) nanofiber with
various additives for energy scavenging application, The Journal of The Textile Institute, 108:6,
906-914, DOI: 10.1080/00405000.2016.1202091

To link to this article: https://doi.org/10.1080/00405000.2016.1202091

Published online: 14 Jul 2016.

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The Journal of The Textile Institute, 2017
VOL. 108, NO. 6, 906–914
http://dx.doi.org/10.1080/00405000.2016.1202091

Comparative evaluation of piezoelectric response of electrospun PVDF

(polyvinilydine fluoride) nanofiber with various additives for energy scavenging
application
F. Mokhtaria, M. Shamshirsazb, M. Latifia and S. Asadib,c
a
Textile Engineering Department, Textile Excellence & Research Centers, Amirkabir University of Technology, Tehran, Iran; b New Technologies Research
Center, Amirkabir University of Technology, Tehran, Iran; c Mechanical Engineering Department, Amirkabir University of Technology, Tehran, Iran

ABSTRACT ARTICLE HISTORY

Energy harvesting using piezoelectric nanomaterial provides an opportunity for advancement toward self- Received 22 December 2015
powered electronics. The fabrication complexity and limited power output of these nano/micro generators Accepted 12 June 2016
have hindered these advancements. This paper introduced a flexible and light weight nanogenerator
KEYWORDS
package that was obtained by variety of additives (ZnO, CNT, LiCl, PANI) and try to have comparisons Electrospun PVDF nanofiber;
between them to choose appropriate one base on final application. Performances of these additives piezoelectric; energy
were evaluated using Fourier Transform Infrared, Scanning Electron Microscopy, Impedance analyzer, harvesting; additive; low
and traction-compression machine. The excitation method is based on low velocity impact test by falling velocity impact test
down a ball on samples. Results show that for all additives there is a direct connection between β phase
formation and output voltage. CNT nanoparticles lead to have more β Phase formation and higher output
voltage (0.9 V) for electrospun web with 230 μm thickness. The results imply promising applications, as an
enhanced efficiency energy-scavenging interface, for various wearable self-powered electrical devices and
systems.

Introduction
Every day, the world produces carbon dioxide that is released
to the earth’s atmosphere which is the main cause of global
warming. One answer to this phenomenon is tapping most of
the renewable resources of the earth and using growing techno-
logical awareness to create less pollution. Self-powering system
with the capability of harvesting energy from the environment
is an attractive option for this purpose. Piezoelectric materials
are one of the most important materials used to harvest energy
and many studies have been done on this subject. Polyvinylidene
Fluoride (PVDF) is the commercial piezoelectric polymer that
exhibits the highest piezo, pyro, and ferroelectric activities with
great potentials for various device applications (Yee, Kotaki, Liu,
& Lu, 2007). There are at least four crystalline phases in PVDF
named α, β, γ, and δ phase. Among them, the β-phase has all
the dipolar moments pointing to the same direction and has the
best piezoelectric responses. The α-phase is the common form
and most stable one in the commercial PVDF that is formed by
the simple crystallization process upon cooling from the melt
under quiescent conditions (Mokhtari, Latifi, & Shamshirsaz,
2015). In order to achieve high performances of piezoelectric
devices, a high content of the β phase in PVDF material is
desired (Lovinger, 1983). Conventional piezoelectric materials,
which are usually in the form of thin films, have low efficiency
in responding to slight mechanical forces (Bafqi, Bagherzadeh,
& Latifi, 2015). Many researchers used the electrospinning pro-
cess to improve PVDF properties by converting α phase to β
phase which is responsible for piezoelectric properties of PVDF
(Greeshma, Balaji, Nayak, & Jayakumar, 2009; Huang, Zhang,
Kotaki, & Ramakrishna, 2003; Lee, Collins, & Arinzeh, 2011;
Mohammadi, Yousefi, & Bellah, 2007; Seoul, Kim, & Baek, 2003).
The main reason for getting the β phase from the PVDF nano-
fibers goes back to the physical and electrostatic forces applied
to the polymer droplet due to the electrospinning process. When
a droplet of the solution is subjected to an electric field, the high
applied voltage leads the drop into an elongated cone. This pro-
cess makes use of fluid applied charges to provide a stretching
force to a collector which is a potential gradient. This mecha-
nism ensures the fiber polarization and the morphological and
crystalline structure of the fibers changes and the β phase forms
within the structure of the fibers. Different approaches can be
joining to the electrospinning process to improve PVDF abil-
ity for more output voltage. These approaches can be divided
into three main groups: adding additive to polymer solutions
(NaCl, LiCl, KCl, BTEAC, CNTs, ZnO, …), processing condition
(thickness variations, substrate type, different collection meth-
ods, …), and post treatment (e.g. drawing, annealing, poling,
and etc.). Although the feasibility of harvesting the energy from
the piezoelectric nanofibers is investigated in the literature, the
direct effect of these approaches on piezoelectric response should
be scrutinized (Mokhtari et al., 2015). Varieties of electrospun

CONTACT  F. Mokhtari  mokhtari.fatemeh2@gmail.com

© 2016 The Textile Institute
 The Journal of The Textile Institute   907

piezoelectric packages are offered with challenges of more pie- researchers so it would be a big challenge that which one is the
zoelectric output with special structures (Kang et al., 2015; Zeng best additive in the same condition.
et al., 2013). In the case of adding additive to the polymer solu- In order to achieve this desire, a one-step and cost-effective
tions, researchers have been investigating the addition of additives nanogenerator package fabricated and subjected to impact
such as inorganic salts (NaCl, KBr, KCl), organic salts (BTEAC,), test by dropping a ball on samples. The output voltages of
and CNTs on fiber morphology for PVDF solutions. For example, electrospun samples as a performance factor of the nano-
Jalili show the effect of CNTs addition on the strain-sensing per- generators were measured. Indeed, effect of each additive on
formance of electrospun PVDF. When the proportion of CNTs β phase formation evaluated by Fourier Transform Infrared
in the composite was increased, the response generated by the Spectroscopy (FTIR). Also the influence of these additives
sensor increased drastically to as much as 35 times from 2.4 to on tensile strength and impedance of electrospun webs
84.5 mV for 0.05 wt % of the nanotubes in comparison to the considered.
response obtained from the plain sensor (Ramaratnam & Jalili,
2006). Zeng et al. set four PVDF/NaNbO3 nanofiber nonwoven
Experimental
fabrics sandwiched between two electrically conducting knitted
fabric electrodes, which consistently produced a peak open-cir- Materials
cuit voltage of 3.4 V and a peak current of 4.4 μA in a cyclic
PVDF pellets (from Sigma-Aldrich) with molecular weight of
compression test (Zeng et al., 2013). Pyridiniumformate (PF),
534,000(g/mol) are utilized for experimental tests. The solvents
an organic salt in the range of 2 to 10% (v/v) was added to the
used in this work were ‘N-Ndimethylformamide’ (DMF, Merck
solutions of 8.5% (w/v) PS/MEH-PPV. Results of SEM image for
Chem. Co.) and acetone (Merck Chem. Co.). The additives are
different range of PF salt show that the sizes of the beads were
lithium chloride as inorganic salt additive (LiCl, Merck Chem.
found to decrease when the concentrations of PF were 8 and 10%
Co.), commercial ZnO nanopowder (US Research nanomate-
(v/v) (Wutticharoenmongkol, Supaphol, Srikhirin, Kerdcharoen,
rials Inc.), with average particle size of ~20  nm, poly aniline
& Osotchan, 1881). Lin et al. in solution of polyacrylonitrile
emeraldine base with molecular weight of 50,000 g/mol (from
(PAN)/platinum (II) used Pt salt for electrospinning. The average
Sigma-Aldrich), carbon nanotubes with 0.7–1.1  nm diameter
nanofiber diameter increased slightly when the Pt salt concen-
(from Sigma-Aldrich). All the materials were used without fur-
tration increased from 0 to 2.0 wt%. However, when the Pt salt
ther purification.
concentration increased to 3.0 wt%, the average fiber diameter
decreased to 293  nm. In another word at low Pt salt concen-
trations, the addition of Pt salt increased the fiber diameter Solution preparation
because of the predominant influence of the increasing solution
In order to evaluate the effect of different additives on the β
viscosity. However, the fiber diameter decreased at higher Pt salt
phase formation and consequently improvement in piezoelectric
concentrations because of the decreased solution viscosity and
response variety of solutions prepared. To evaluate direct effect
increased solution conductivity (Lin et al., 2010). LiCl also used
of additive on piezoelectric response tried to keep processing
in PVDF membrane which resulted in enhancement of porosity
parameters constant. The maximum amount of additive was
(Khosravi, Ghaee, & Mansourpoor, 2014). Li et al. in order to
added to the solutions till they had the capability for electros-
obtain desired pore structure in membrane obtained by solution
pinning process. The processing set up adjacent to have uniform
of poly(p-phenyleneterephtalamide) (PPTA)/PVDF used LiCl. It
and non-bead structure for electrospun fibers.
was found that, by increasing LiCl content, a porous membrane
structure with long finger-like pores was formed (Li, Shi, Zhang,
Liu, & Liu, 1846). When PVDF film is filled with LiCl, results PVDF-LiCl solution
show that by increasing the content of LiCl, the films surface
Dimethylformamide(DMF)/acetone was used as solvent with a
become rough with some small aggregates, but the particles
ratio of 6/4 (v/v) for PVDF/solvent concentration 16%(w/w).
were well distributed in the entire surface region (Elashmawi,
PVDF was first dissolved in DMF and the PVDF/DMF solution
2008). About 16 wt% of PAA (from pyromelliticdianhydride
is stirred for 1 h at 60 °C (Figure 1). The additive LiCl was used
and 4,4-oxydianiline) in NMP with 5 wt% LiCl as additive pro-
after drying in a vacuum oven for approximately 24 h at a tem-
vided the membrane a completely macrovoid-free. By increasing
perature of 120 °C. LiCl with concentrations 0.00133 wt% was
LiCl concentration in the casting solution, membrane porosity
added into the solution. Finally, acetone is added because of its
increased and pore size decreased (Lee, Won, Lee, & Kang, 2002).
high evaporation rate and the solution is stirred again for 24 h
The main aim of this study is to have comparative evaluation
at room temperature.
on output efficiency of a flexible nanogenerator through combi-
nation of a piezo-polymer (PVDF) with different additives (LiCl,
PANI, ZnO, and CNT). PVDF-ZnO solution
Since PVDF is a semiconducting polymer, PVDF webs need
additives in their structure to be able to transfer the accumulated PVDF solution was prepared on 16% (w/w) with DMF/ ace-
static charge. Therefore, PANI used as conductive polymer, CNT tone solvent mixture with a ratio of 6/4 (v/v) then an appropri-
as a semiconductive nanoparticle filler, ZnO as a semiconductor ate amount of ZnO nanopowder (18%wt) was added and then
nanoparticle with piezoelectric properties, and LiCl as a salt sonicated for 20  min (Cycle: 0.5, Amplitude: 60). Afterward,
with high ionic properties. Also these additives used a lot by solutions were stirred at 60 °C for approximately 15 min again.
908    F. Mokhtari et al.
Figure 1. PVDF/LiCl Solution preparation for electrospinnig process.
Finally, white homogeneous solution was obtained and used for
electrospinning.
PVDF-PANI solution
To create conductivity in PANI, camphor sulfonic acid used
with ratio (2/3 = Pani/camphorsulfonic acid). These two addi-
tives solved in DMF for 24 h (green color solution) and then
added to PVDF/acetone solution (16%wt) which was stirred
for 1 h at 60 °C. Next, solutions were stirred again for 15 min
without heat.
PVDF-CNT solution
An appropriate amount of CNT was added to specific vol-
ume of DMF and then sonicated for 25  min (Cycle: 0.5,
Amplitude:
( 60) then ) this solution was added to main solution of
PVDF/ Acetone
DMF
= 46 in 16 wt% by this method different concen-
tration of CNT can be prepared. The whole solution was stirred
for 30 min at 60 °C. As it was explained before to assess effect
of additive on piezoelectric response tried to keep processing
parameters constant, and added the maximum amount of addi-
tives (Table 1) to have uniform fibers at the same electrospinning
conditions.
Preparation of PVDF/additive nanofibers mat
Electrospinning of nanofibers was performed in a horizontal
electrospinning setup. It consists of a syringe positioned hori-
zontally with its needle (22-gage stainless steel), a precisely
controlled syringe pump, a high voltage power supply capable
of 0–25 kV (Gamma High Voltage Research), and a grounded
collector. The solutions were injected into the needle at a
constant rate with a syringe pump (KD Scientific, USA). A
cylindrical drum collector (outer diameter 26 cm) wrapped
with aluminum foil as the collector. Depends on different
additive the distance between the needle tip and the collec-
tor was set, and rotational speed of collector was 180  rpm.
The entire electrospinning fiber formation process is carried
out at room temperature. The process of electrospinning was
continued for certain duration until the desired thickness of
Table 1. Additive concentrations for electrospinning process.
Additive ZnO LiCl CNT
Concentration (wt%) 18 0.00133 0.005
Table 2. Process parameters employed during the electrospinning process.
PVDF Concentra- Voltage Distance Flow rate Volumetric ratio
tion (wt%) (kV) (cm) (ml/h) (Acetone/DMF)
16 20 20 0.3 4/6
the non-woven fabric was obtained. In all the experiments,
the electrospun films had a thickness of 230 μm. Descriptions
of the samples with different parameters involved in the elec-
trospinning process are given in Table 2.
Fabrication of power generator samples
In this part, an attempt was made to explore the possibility
of utilizing a fabrication scheme for developing a one-step
and cost-effective electrospun nanofiber-based electrical
power generator to evaluate the piezoelectric response of the
samples. In order to fabricate a nanofibrous power generator,
aluminum foil was used as a collector plate. A small piece of
PVDF nanofiber mat (3 × 1.5 cm, and thickness 230 μm) was
used as an active layer and sandwiched between two alumi-
num foils. Because of sharp edge of aluminum foil, a paper
frame set between two layers of aluminum foil to avoid web
surface scratching. Due to good conductivity, two copper
strips are set on both sides of the aluminum foils by silver
paste and wires were soldered onto them to connect to the
Pico Scope. The entire generator device was fully packaged
with epoxy resin to enhance mechanical robustness and pro-
tect it from dust and water(Figure 2).
Characterization
FT-IR spectra of PVDF/additives nanofiber webs were
recorded by a Spectrometer (model: NEXUS 670, Nicolet Co.)
over a range of 400–4000  cm−1. The fibers morphology was
characterized using a scanning electron microscope (SEM,
model:XL30,PHILIPS Co.). All samples were gold coated
(Bal-tec SCD50 sputter coater). The fiber diameter was
measured using image processing software (ImageJ, National
Institutes of Health, USA). The tensile tests are carried out on
a traction-compression machine Instron 5566. The traction
loading ramp was applied with the rate of 1 mm/min. Samples’
thicknesses were measured with OSK (Ogawa seikico.LTD).
The measuring thickness for each sample was performed to
measure thickness from 10 points of the sample. Impedance and
the electrical conductivity of the fabricated composites were
also evaluated by Keithley instruments. Electrical response of
samples was measured using an impedance analyzer made in
Aims Lab (http://aims.aut.ac.ir) at room temperature.
PANI
0.001
Figure 2. Schematic structure of nanogenerator package.

Tensile test
For tensile testing, electrospun samples were produced and kept
in a desiccator for 24 h. The Instron 5566 machine was used for
tensile testing of the web samples using a 50 N load cell. The ten-
sile test set up followed by Choia method (Kima, Ahnb, Leeb, &
Choic, 2011). The load was set to zero and then the machine was
started and the sample stretched at a rate of 1 mm/min until the
sample ruptured. A load is applied in order to produce elongation
and then the load-elongation data were digitally stored. Figure 3
depicts a typical tensile test of electrospun samples.
Impact test setup
The nanogenerator samples after fabrication were subjected to
the impact testing process in order to enhance the effect of the
additives on the piezoelectric performance. Different methods
are used to excite and harvest energy from nanogenerators of
piezoelectric polymers (Lin et al., 2010; Wutticharoenmongkol
et al., 1881). The excitation of the piezoelectric package was per-
formed by evaluating the effect of drop weight impact on the
output voltage and tracing the falling trend (Figure 4). A steel ball
(15 mm in diameter, 12 g in weight) was dropped from a height
of 20 cm through a steel guide pipe there by applying impact
on the piezoelectric electrospun web. The electrical response
of piezoelectric properties to applied stress was displayed in an
oscilloscope (Pico Scope4224). In all the methods, two electrodes
were used on the top and bottom surface of the electrospun mat.
The voltage difference between the two adjacent electrodes was
thereby induced due to this separation of charge. To protect
samples from damage caused by repetitive impacts and also to
Figure 3. Web tensile tester with a sample mounted on it.
The Journal of The Textile Institute   909
Figure 4. Schematic drawing of the impact testing for evaluation of piezoelectric
response of samples.
excite and obtain voltage from whole active areas of samples,
an aluminum sheet placed on samples during impact test and
whole system (samples and aluminum sheet) fixed with a paper
tape on a rigid surface.
Results and discussion
Additives concentration effect on fiber diameter
Different additive may have changed solution properties. These
materials for example carry charge for increasing solution con-
ductivity and bending instability. Charge carriers such as salts
or conductive particles leads to increase solution conductivities
which can have two different effects such as changing the flow rate
and increasing net charge density on fiber formation and diam-
eter (Satapathy, Pawar, Gupta, & Varma, 2011). Furthermore,
additives have this ability to affect interactions in solution and
affect fiber diameter and morphology (Heikkilä, 2008). Additives
may also interact with solvent, with polymer or with both. The
electrospinnability of the solution may also change as a result
of these interactions (Qin, Yang, Li, & Wang, 2007). As can be
seen from Figure 5 all additives lead to decrease fibers diameter,
the least fiber diameter in comparison with electrospun pure
PVDF fiber is related to PVDF/LiCl electrospun fibers (504 nm)
and after that with great difference PVDF/PANI electrospun
fibers (1154  nm) has the greatest fiber diameter. PVDF/CNT
and PVDF/ZnO electrospun fibers with diameters of 1448 and
1424 are in the same range. The electrical conductivity of CNTs
depending on the arrangement of atoms varied. So by increasing
CNTs concentration in composite structure, a conductive net-
work will be formed while this formation in nanofiber is more
difficult because the arrangement of CNTs in nanofiber can be
in a form that there isn’t any connection between them (Wang,
Yao, Chang, & Chen, 2012). PANI promoted the formation of
conductive bridges between the nanofibers which eliminated air
resistance between the fibers. X-ray spectroscopy of these bridges
showed high content of nitrogen which comes from the amine
groups of polyaniline. In any case this property leads to better
transferring charge in PVDF and better piezoelectric properties
(Haghi & Akbari, 2007). Also this conductivity can explain the
finer diameter for PVDF/PANI in comparison with PVDF/CNT
electrospun fiber because conductive particles in electrical field
of electrospinning process was affected more by the field and
910    F. Mokhtari et al.
Figure 5.  SEM of electrospun fibers with different additives and their diametser
distribution: (a) Pure PVDF, (b) CNT, (c) PANI, (d) ZnO, (e) LiCl.
leads to finer fiber as a result of more tension. By adding ZnO
nanoparticles to the polymer solution, since ZnO is a semicon-
ductor particle, the dielectric constant of the solution decreases
and resulting effects on instability of the whip and charge density
in the Taylor cone led to an increase in nanofibers diameter. ZnO
nanoparticles also reduced the critical voltage for electrospinning
(Bafqi et al., 2015). But in this paper the optimum value for ZnO
concentration is defined (18 wt%) which leads to reducing fiber
diameter in comparison with pure PVDF.
Adding soluble LiCl salt to the polymer solution which sepa-
rated into equal numbers of positive and negative ions increases
the electrical conductivity of the solution by increasing the num-
ber of ions per unit volume. During electrospinning, when an
external electrical field is applied to the solution, the positive and
negative ions in the polymer fluid tend to move in opposite direc-
tions. Negative ions are forced toward the positive electrode, and
positive ions are forced toward the negative electrode, in which
stretching and elongation are the results of this phenomenon as
mentioned above. An inorganic LiCl salt into the spinning solu-
tions helps to increase the conductivity of the solutions consid-
erably which results in a reduced possibility for bead formation.
The increased conductivity of the solution in the electrostatic
field of the spinning zone results in greater bending instability.
According to the previous research and finding, the viscosity of
the polymer solutions increases with increasing LiCl content.
By adding more LiCl in comparison with optimum value, high
viscosity leads to bending instability of the jet and consequently,
a decrease in the drawing forces of the spinning zone occurs. The
increase in viscosity arises from strong LiCl–solvent interaction
and probably from those between Li+ and an electron donor
group of PVDF, which leads to the formation of macromolecular
fluctuating networks (Mokhtari, Shamshirsaz, & Latifi, 2015).
Fourier Transform Infrared Spectroscopy (FTIR) Analysis
Crystal structure of produced nano composite materials was
investigated through FTIR spectroscopy. The FTIR spectrum
of the nanofiber mats demonstrates vibration peaks at 840 and
764  cm−1 which are typical vibration characteristics of the β
crystalline phase according to the previous researches and find-
ings. Figure 6 shows the FTIR absorbance spectra for the PVDF/
Additives electrospun webs. FTIR spectra of the samples show
peaks for α-phase (TGTG−) at 482 and 511 cm−1 (CF2 bend-
ing), 610 cm−1 (CF2 bending and skeletal bending), 1073 cm−1
(CH2 wagging) (Lee, Won, Lee, & Kang, 2002), and peaks at
840 and 1,280 cm−1, which are typical vibration characteristics
of the β crystalline phase (Gheibi, Bagherzadeh, Merati, & Latifi,
2014). Regards to the importance of β phase in piezoelectric
properties, different methods are used to improve this phase.
One of the common methods is to drawing PVDF nanofibers
with α phase in longitudes direction in temperature of 50–100 °C.
Electrospinning leads that molecular chains with high orienta-
tion because of shear force be alongside each other, so expect
more β phase formation during electrospinning process (Bafqi
et al., 2015). In this paper, different additives assessed to improve
β phase formation in addition to electrospinning process.
Although some researchers show that adding PANI and CNT
Figure 6. FTIR absorption spectra of PVDF electrospun web with different additives:
(a) Pure PVDF, (b) ZnO (c) LiCl, (d) CNT, (e) PANI.
 The Journal of The Textile Institute   911

Table 3. Comparison of β phase crystallization of samples for different additive by Sorayani et al. show that at approximately the same adding
FTIR test.
15%wt of ZnO leads to decrease in β phase formation. It may be
f(β) (%)
because of the existence of semiconductor particle of ZnO in pol-
Absorbance Intensity Sample
ymer solution which leads to decrease in dielectric constant and
A764 A840
disturbing electrospinning process. On the other side, presence
66.66 0.143 0.36 PANI+PVDF
81.5 0.00626 0.031 ZnO+PVDF of nanoparticles in the solution without changing in electros-
96.53 0.0119 0.39 CNT+PVDF pinning parameters, leads to nonuniform distribution of tension
95 0.0117 0.271 LiCl+PVDF because of critical voltage and the conditions necessary for the
86.9 0.0305 0.2 Pure PVDF
formation of β phase disrupts. So that is why need to adjusting
appropriate applied voltage or electrospinning distance (Bafqi
et al., 2015). To determine β phase crystallization in each sample,
absorbance peaks related to the α and β phase in wavenumbers
764 and 840 cm−1 are evaluated. The β phase crystallization is
calculated from Equation 1. Here, Aα and Aβ are absorbance for
the α and β phase, respectively. Xα and Xβ are the degree of crys-
tallization for the α and β phase (Mokhtari et al., 2015).

Figure 7.  Typical tensile stress–strain curves of electrospun PVDF web with
different additives: (a) LiCl, (b) PANI, (c) CNT, (d) ZnO, (e) Pure PVDF.
have no effect in crystalline phase but nuclear effect of these
additives can lead to increase crystalline content or by decreas-
ing in crystalline growing rate can lead to decrease. In any case
effect of different additive on crystalline content followed by
their concentration in polymer solution (Hattori, Kanaoka, &
Ohigashi, 2016). As can be obtained from Table 3 adding CNT
in comparison with pure PVDF leads to decreasing α phase
and increase in β phase. This improvement only can be seen in
samples containing CNT and LiCl. Although, it may be possi-
ble that by changing electrospinning parameters and optimizing
PANI and ZnO concentration, improvement happened in these
two samples but, here by constant electrospinning condition no
improvement happed in β phase formation.
X𝛽 A𝛽
f (𝛽) = × 100 = × 100. (1)
X𝛽 + X𝛼 1.26A𝛼 + A𝛽
Tensile test for electrospun PVDF web contain different
additives
Different additives lead to changes in mechanical properties of
electrospun PVDF fiber. Adding 3%wt of CNT to the polymer
solution lead to increase tensile modulus and tensile strength 32
and 28%, respectively (Bafqi et al., 2015). Considerable change
can be seen by adding PANI in young modulus increasing and
decreasing in elongation at break (Baji, Mai, & Wong, 2015).
In another case by adding more PANI to the polymer solution,
tensile strength increase from 40 MPa for pure PVDF to 50 and
55 MPa for 12 and 22.4% PANI. Also young modulus increase
from 1.2 Gpa to 1.5 Gpa (Merlini et al., 2015). Here the highest
tensile strength related to ZnO (Figure 7), however, this does
not mean that the sample has better piezoelectric properties.
Regards to this note that if the purpose for piezoelectric sample
production is energy harvesting from body movement under
different tensile force so it is better to consider elongation at
break that is reprehensive for samples elastic ability. As can be

Figure 8. Impedance of electrospun PVDF fibers with different additives in different frequency: (a) ZnO, (b) LiCl, (c) Pure PVDF, (d) CNT, (e) PANI.
912    F. Mokhtari et al.
Figure 9. Piezoelectric response of electrospun PVDF webs with different additives: (a) CNT, (b) LiCl, (c) Pure, (d) ZnO, (e) PANI.
seen, samples related to PANI and LiCl as additive in this respect
are more significant.
There is no special article that reports the effect of LiCl on
the modulus of electrospun PVDF/LiCl fibers. The mechanical
behavior of PVDF membranes is closely linked to crystalline
morphology, which depends strongly on the crystallization
process. Different crystalline morphologies lead to great differ-
ences in the crystalline phase and the amorphous–crystalline
interfacial region (Heikkilä, 2008). Previous research shows that
the solution additive exerts a great influence on the elongation
at break of the electrospun PVDF webs. The PVDF web shows
typical ductile behavior with 5.3 ± 0.2% of elongation at break,
while the tensile strength and Young modulus are 0.3 ± 0.1 and
2.3 ± 0.1 MPa, respectively. The elongation at break for the sam-
ple containing LiCl increased four times more than pure PVDF.
LiCl leads to greater elongation in electrospun PVDF fibers, and
it can be explained with the thinner fiber diameter and porous
structure obtained by salt additive (Mokhtari et al., 2015). This

elongation is related to the application of the PVDF/LiCl web
in energy harvesting and smart textile which is preferable when
placed under repeated bending formation.
Impedance and output voltage analysis for electrospun
PVDF nanogenerators with different additives
Impedance of samples in different frequency measured and pre-
sented in Figure 8. Since PANI is a conductive polymer, it has less
electrical resistance. Pure PVDF, CNT, and LiCl have almost the
same impedance and adding these additives has no significant
effect on resistance. The specific concentration for these additives
may be less than the minimum required value to change the
resistance of samples. Also the major parts for internal resistance
of samples related to cupper electrodes and aluminum foil that
resistance of electrospun webs may be affected by them which
are not measurable. As can be seen from Figure 8 the maximum
impedance related to ZnO because of its semiconductor nano-
particles that lead to increase internal resistance.
Measuring output voltage is the most important method to
analyze piezoelectric response of nanogenerators. The piezoe-
lectric output depends on the thickness of samples, dimension,
method of excitation, and additives because of these reasons the
output voltage reported by researchers are different with each
other. Here, samples were excited by dropping a ball from height
20 cm as described. As illustrated in Figure 9, there is a relation
between β phase formation and output voltage generated by sam-
ples. The maximum output voltage is related to CNT (0.9  V)
and the minimum value assigned to PANI (0.46 V). As it was
expected from Table 3 the maximum β phase is related to CNT
too. The assortment for output voltage base on different additive
is CNT>LiCl>Pure PVDF>ZnO>PANI. These approaches about
CNT confirm Jalili’s finding about evaluation effect of CNT on
piezoelectric response of PVDF fiber. The generated voltage was
2.4 mV for pure PVDF while this output voltage for sample con-
tained 0.01% CNT is nearly two times more than pure PVDF.
The CNT-based piezo polymer composites demonstrated an
increase in strain-sensing ability (as measured by voltage across
the sensor) by 35 times from 2.4 to 84.5mV for only 0.05 wt%
of the nanotubes (Ramaratnam & Jalili, 2006).
Conclusion
Uniform nanofiber composites from PVDF were produced with
different additives. The electrospinning conditions kept con-
stant to just evaluate the effect of additives (LiCl, PANI, CNT,
ZnO). Influence of each additive assessed on tensile strength,
impedance, output voltage, β phase formation, and fiber diam-
eter. Stress–strain curve shows that electrospun web of PVDF/
ZnO has higher tensile strength in comparison with pure PVDF
electrospun web, although higher elongation at break is related
to PVDF/LiCl web. The less electrical resistance is for PANI
and more is for ZnO. The β phase formation is directly related
to output voltage of nanogenerator. CNT and PANI have the
maximum and minimum β phase formation and output voltage.
The biggest sensitivity of the voltage response is about 39.1 V/J
for the thickness 230 μm. Different Additives in polymer solu-
tion needless PVDF electrospun webs for post treatment process
in case of energy harvesting application. Adding LiCl to the
The Journal of The Textile Institute   913
polymer solution leads to have finer fiber diameter (504 nm)
in comparison with ZnO and CNT which have highest fiber
diameter (~1430 nm). The finer fiber diameter for PVDF/LiCl
leads to spider connection between fibers and this be the reason
for high elongation at break. Regards to the final application
each of these additives can be used for smart textile, PVDF/
LiCl because of its high elongation at break and output voltage
is recommended.
Disclosure statement
No potential conflict of interest was reported by the authors.
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