Nano-Structures & Nano-Objects 12 (2017) 174–181

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Nano-Structures & Nano-Objects

journal homepage: www.elsevier.com/locate/nanoso

Piezo devices using poly(vinylidene fluoride)/reduced graphene oxide

hybrid for energy harvesting
Chandan Kumar a , Anupama Gaur b , Sanjay Kumar Rai a , Pralay Maiti b, *
a
School of Biomedical Engineering, Indian Institute of Technology (Banaras Hindu University), Varanasi 221005, India
b
School of Materials Science and Technology, Indian Institute of Technology (Banaras Hindu University), Varanasi 221005, India

graphical abstract

article info a b s t r a c t
Article history: Harvesting of energy, the continuous human effort throughout history, or reclaim energy from mechanical
Received 1 August 2017 stress is presented in this work. Reduced graphene oxide, homogeneously dispersed in poly(vinylidene
Received in revised form 16 September fluoride), induces the electroactive phases in the polar polymer. Good dispersion arising from better inter-
2017
actions between 2-D nanofiller and polymer chain is revealed through transmission electron microscopy
Accepted 12 October 2017
and spectroscopic measurement. The induction of electroactive phases in polymer in the presence of
nanofiller has been confirmed through structural, spectroscopy and thermal studies. Electroactive phases
Keywords:
PVDF is confirmed through FTIR peaks at 840 cm−1 for β/γ phase and 884 cm−1 band for γ -peak in nanohybrid
Piezoelectricity against 796, 876 and 975 cm−1 absorption peaks for α -phase in pure PVDF. Morphological alteration (both
Device surface and bulk) reaffirms the change of phases in the nanohybrid vis-à-vis pure polymer. Quantification
Energy harvesting of different phases has been made, in the presence of varying content of graphene, which is directly
reflected in their properties. Greater mechanical and thermal stability of the nanohybrid help promoting
this class of hybrid material for device application. Devices have been fabricated to understand the
piezoelectric responses from the hybrid materials and output electrical signals (both voltage and current)
are measured under mechanical stress applied from a motor driven mechanical setup. Both output voltage
and current significantly increase either with greater applied load or graphene content in hybrid primarily
due to higher strain produce or better induction of piezo phase, respectively. Moderately high electrical
power density up to 14 µW/cm3 is measured from the device made of the hybrid material, suitable for a
number of low power consuming electronic self-power devices and wireless sensors.
© 2017 Elsevier B.V. All rights reserved.

* Corresponding author.
E-mail address: pmaiti.mst@itbhu.ac.in (P. Maiti).

https://doi.org/10.1016/j.nanoso.2017.10.006
2352-507X/© 2017 Elsevier B.V. All rights reserved.
 C. Kumar et al. / Nano-Structures & Nano-Objects 12 (2017) 174–181
1. Introduction
Poor power density of primary batteries is amongst the core
issues of the leading pacemaker manufacturer over the years since
its inception where conventional power sources are not a good fit
either for medical ground or durability until lithium battery with
high energy density was introduced [1–3]. A pacemaker produces
electric impulses that are considerably more powerful than the
stimulus itself. During cardiac contraction, a small fraction of the
energy is released which can be reused as pulse energy, turning the
receiver, i.e., the patient into his supplier. This idea started with the
quest for powering medical implants from the human body itself.
Advancement in micro-fabrication and ultra low-power electron-
ics techniques are now empowering a large range of miniaturized
implantable systems for sensing, health monitoring and deficiency
treatments [4,5]. Nanodevices and nanosystems usually function at
a very low power which falls in the vicinity of nW to µW. Thus, if
a small portion of such mechanical vibration could be converted
into electrical energy which should be enough to energize low-
power biomedical devices [6]. Mechanical or vibrational stress is
one of the most abundant energies available in our surroundings
that can be reprocessed. It can be from a moving object, a vibrating
structure or vibration induced by water flow or air. Mechanical
waste energies are commonly harvested through vibration-to-
electricity conversion [6–8]. Waste energy harvesting is primarily
recognized for low power generations, so its main applications
are for low-power electronic devices only. However, the latest ad-
vancement in the field of energy harvesting is also useful for large
scale applications [9]. Vibration-to-electricity conversion can be
achieved by three simple transduction principles, including elec-
tromagnetic [10–12], electrostatic [13], and piezoelectric [14,15]
transductions.
Amongst the three stated principles, piezoelectric transduction
has acknowledged more interest among scientists because of its
high power storage capacity and no requirement of external power
sources [6,9]. Another benefit over other devices is from its micro-
scale fabrication, smooth deposition techniques for thin or thick-
films of piezoelectric materials especially polymers [14,16–18].
Various methods have been adopted to alter the configuration
of energy harvesting device, like changing the electrode pattern,
adding pre-stress to maximize the coupling and applied strain of
the material, modification of piezoelectric materials, changing the
poling and stress direction and tuning the resonant frequency of
the device to get an efficient output. Recent research focuses on
improving the effectiveness of power harvesting through various
piezoelectric materials [8]. Piezoceramics are vulnerable to high
frequency because it develops fatigue crack growth when exposed
to cyclic loading [19] leading to a search for tough polymeric
materials. Various techniques exist for harvesting energy which
includes the use of electromagnetic induction [11], electrostatic
generation [13], dielectric elastomers [20], and piezoelectric ma-
terials. However, piezoelectric materials have stood out because
of their ability to direct conversion of applied mechanical energy
into useful electric energy and the simplicity at which they can
be electromechanically coupled to an external system. Another
advantage of piezoelectric materials is their capacity to withstand
a large amount of mechanical strain which makes them an appro-
priate candidate for power harvesting applications. Approximately
18 µW of power is produced when a pressure produced by a
68 kg weighing human coupled with 500 k load put under the
normal walking condition, showing good correlation between the
analytical model and experimental data [21].
The need for creating miniaturized, self-powered devices grows
with the recent advancement in electronics and computer tech-
nology. Some micro scale chips require very less power for its
operation which can be provided by the energy generated from
175
micro-scale piezoelectric power harvesters. The size of sensor, the
cost of batteries and its cost of replacement can be minimized
by integrating power harvesting technology with the wireless
sensors [8]. To harvest mechanical energy and to achieve better
conversion to electrical energy requires a system that would ef-
ficiently couple mechanical vibration or motion to a transduction
mechanism.
PVDF films have electroactive properties like, piezoelectricity,
pyroelectricity, ferroelectricity etc. which make them a remarkable
candidate for energy harvesting applications [22]. Recently, PVDF
found its increased application enormously in many fields such as
in sensors, actuators, biomedicine, nonvolatile memory, nanogen-
erators and energy harvesting [22–25]. PVDF crystallizes generally
in four types of phases namely, α , β , γ and δ . The piezoelectric
properties are exhibited by the β and γ -phases [26]. The γ -phase
has a higher piezoelectric coefficient than the β -phase, but the β -
phase is found to be more polar [27,28]. γ -phase is more thermally
stable than β -phase because of higher melting point making it
appropriate for the fabrication of a thermally stable and long-
lasting device [29]. However, to use PVDF in piezoelectric energy
harvesting applications, many limitations have come up such as
the nucleation of the γ and β -phases, mechanical stretching under
electric field which makes it difficult for the generation of the
batch production in the industry for device applications. Therefore,
the best alternate method is to add filler into the PVDF matrix
to make a nanohybrid. For improving the functionalities of PVDF,
nanofillers have been used for stabilizing the γ /β -polymorphs,
thus making the PVDF based nanohybrid as an improved material
for piezoelectric energy harvesting. Some research groups have
attempted to maximize the harvesting performance by stabilizing
electroactive phases by a combination of PVDF with fillers such as
graphene [30] MWCNTs [31], CTAB [32], graphene–CuS [33], nan-
oclay [34], graphene–ZnO [35], PMMA-RGO [36] and ferrite [37].
The choice of materials for energy harvesting is a significant step
in order to achieve high efficiencies. The efficiency can be improved
by increasing the value of electromechanical coupling factor (k)
and mechanical quality factor (QM ) which are the inherent prop-
erties of the piezoelectric materials [17].
Herein, we introduce a facile method to find the piezoelec-
tricity of light weight, low-cost and flexible reduced graphene
oxide/PVDF nanohybrid prepared through solution route. The
nanohybrid films have shown very good piezo sensitivity against
the repetitive load or external pressure. Reduced graphene oxide
has been chosen as conducting fillers because of their large surface
area, high aspect ratio, superior mechanical, electrical and ther-
mal properties [38]. Owing to its high aspect ratio and excellent
electrical conductivity, it is likely to form a microcapacitor if two
or more graphene sheets have a compact parallel structure in the
hybrid, isolated by a layer of the polymer [39]. Device has been
fabricated using the hybrid piezo material and electrical output is
measured under applied stress, and finally demonstrated the effect
of mechanical stress to produce electricity from waste mechanical
sources.
2. Experimental
2.1. Materials
Poly(vinylidene fluoride) (Sigma Aldrich), graphite flakes
(Sigma Aldrich, USA), sodium nitrate and potassium perman-
ganate, Sulphuric acid (H2 SO4 ), hydrogen peroxide, hydrazine hy-
drate, dimethyl formamide were purchased from Merck, Mumbai
and were used as received.
176 C. Kumar et al. / Nano-Structures & Nano-Objects 12 (2017) 174–181
2.2. Preparation of nanofiller
Reduced graphene oxide is used as nanofiller, which is obtained
from reduction of graphene oxide. Graphene oxide is prepared
from graphite powder using modified Hummer’s method [40,41].
In this method, 10 gm of graphite powder is mixed with 230 ml of
sulphuric acid. These ingredients are mixed in a one litre jar which
is kept in an ice bath so that temperature ∼0 ◦ C can be maintained
as a safety measure. While maintaining the stirring condition, 30
gm of KMnO4 is added gradually, so that temperature should not
exceed 20 ◦ C. After that ice bath is removed and the mixture is
stirred for 30 min at room temperature. 1.5 l of water is added
slowly that increases the temperature up to 98 ◦ C and stirred for
15 min. This mixture is further diluted to 500 ml of warm water
and treated with 3% of hydrogen peroxide to reduce the residual
permanganate and manganese oxides, after which the suspension
turns into bright yellow colour. The suspension was filtered and
washed with warm water repeatedly afterwards. It was collected
by centrifugation and drying in an oven. To prepare the reduced
graphene oxide, 100 mg graphene oxide was dispersed in 100 ml
of water at 100 ◦ C and 32.1 m mol hydrazine hydrate was added
to the dispersion and allowed stirring for 24 h. The dispersion was
filtered and washed with distilled water followed by drying. The
obtained reduced graphene oxide power is termed as ‘RGO’.
2.3. Preparation of nanohybrid
For nanohybrid preparation, dimethyl formamide (DMF) is used
as a solvent. Hybrids with different weight fractions of RGO are
prepared. The solution of PVDF powder was prepared in DMF at
60 ◦ C and RGO is dispersed in DMF separately through sonication.
Both the prepared solutions are mixed and are allowed for stirring
for 2 h. The mixture is poured into a petri dish for air drying
followed by drying under vacuum for overnight. Henceforth, pure
PVDF and the prepared nanohybrids are termed as P, PG 0.1, PG 0.5
and PG 1.0 having 0, 0.1, 0.5 and 1.0 wt.% of RGO with respect to
polymer weight, respectively.
2.4. Sample preparation
Samples are prepared through compression moulding tech-
nique. Pure PVDF and prepared nanohybrids are moulded into 100
µm films using compression moulding machine (S.D. instruments).
From these films, samples of 60 × 15 × 0.01 mm3 and 1 × 1 cm2
dimensions are cut for various characterizations.
2.5. Device fabrication
Nanohybrid of the dimension of 1 × 1 cm2 is taken and a
conducting layer of silver is applied on both sides in order to
make the contact between the charge generated on the surface of
composite and the respective electrodes. Devices using both pure
PVDF and its nanohybrid are made by coating conducting layer
having efficient area of 0.7 × 0.7 cm2 of sample size. Electrodes are
attached to these samples using conductive adhesive for further
measurements.
2.6. Characterization
Transmission Electron Microscopy (TEM) was done to observe
the nanoscale dispersion of RGO in the polymer matrix. TEM im-
ages were obtained using FEI Tecnai 20 twin model.
Tensile tests are performed using Instron universal testing ma-
chine. Rectangular samples are used for the measurement. A strain
rate of 5 mm/min is selected to record the data up to total breakage
of the samples.
Fourier transform infrared spectroscopy (FTIR) is performed in
the reflectance mode at room temperature from 650 to 3500 cm−1
using Nicolet 5700 instrument having resolution of 6 cm−1 .
UV–visible spectrophotometer (Jassco V650, Japan) operating
in spectral range of 200 to 900 nm is used to take the spectra of
the samples.
X-ray diffraction analysis is used to study the structure of pure
PVDF and nanohybrids. XRD patterns of the samples are measured
using a Rigaku miniflex 600 X-ray diffractometer operating under
a voltage of 40 kV and a current of 15 mA using Cu Kα Radiation
(λ = 1.54 Å) at the scan rate of 3 ◦ /min at room temperature.
Polarized optical microscopy (POM) is used to investigate the
morphology, after suitably crystallize thin films of pure poly-
mer and nanohybrids using polarized optical microscope (Leitz,
Biomed).
The surface morphology of pure PVDF and its nanohybrids are
obtained from scanning electron microscopy (SEM) (SUPRA 40,
Zeiss). Film samples are gold coated by mean of sputtering before
observation in SEM.
Raman spectroscopy is done using Renishaw InVia Raman Mi-
croscope at laser power 5% of 100 mW using solid state diode laser
of wavelength 532 nm and integration time of 50 s.
The melting temperature of pure PVDF and its nanohybrids are
determined using differential scanning calorimeter (Mettler 832).
The peak temperature and enthalpy of fusion are measured from
the endotherms of the peak position and its area under the curve.
DSC is calibrated using indium before use. The samples are taken
in a platinum pan and are heated up to 250 ◦ C at a scan rate of
10◦ /min.
Thermo gravimetric analysis (TGA) is done using Mettler Toledo
system to study thermal stability of pure PVDF and its nanohybrid.
The degradation temperature is calculated from the temperature
corresponding to 5% of weight loss.
Surface morphology of samples is also measured using AFM
NTEGRA Prima, NT-MDT. AFM in contact mode is used to determine
the surface roughness and height profile of pure PVDF and its
nanohybrid samples.
Power Measurement: Power is calculated from the output volt-
age and current from the respective devices under applied stress.
For voltage and current measurement, an electromechanical setup
with the motor driven pulley is installed, a fixed weight is attached
to one end and the other end is attached to a motor. The load strikes
the samples and the output is recorded as voltage and/or current.
Voltage is measured using Nvis 102CT digital storage oscilloscope
and the current is measured using Agilent 34410A 61/2 Digit Mul-
timeter.
3. Results and discussion
3.1. Graphene induced electroactive phase in polymer
Reduced graphene oxide has been dispersed homogeneously
in PVDF matrix as observed through transmission electron micro-
scope with graphene platelet dimension of 10–15 nm (Fig. 1a). The
dispersion is very uniform and distributed throughout the matrix
presumably due to greater dipolar interactions between functional
groups present in graphene layers and dipoles in PVDF chains.
Good dispersion of nanosheets is a prerequisite to improve the
properties of the hybrid materials especially to induce structural
or morphological alterations. XRD pattern of pure PVDF shows
peaks at 17.6◦ , 18.5◦ and 19.9◦ corresponding to α -phase (TGTG)
while these peaks are going to diminish in nanohybrid with the
appearance of a new peak at 20.5◦ , indication of the formation of
polar β -phase (TTTT) of the matrix polymer (Fig. 1b). Overall, the
intensity of the β -peak increases with graphene content and the
quantification of different phases have been calculated from the
 C. Kumar et al. / Nano-Structures & Nano-Objects 12 (2017) 174–181
Fig. 1. (a) Transmission electron micrograph showing the dispersion of RGO in PVDF matrix (PG 1.0); (b) X-ray-diffraction patterns showing structural changes in nanohybrids
as compared to pure PVDF; (c) Phase fraction of indicated samples as measured from the deconvoluted patterns; (d) FTIR spectrum of indicated sample showing different
phases by the vertical lines; (e) UV–visible spectrum of indicated samples; and (f) DSC thermograms of indicate samples.
deconvolution of various peaks and is presented in Fig. 1c showing
greater electroactive phase in higher graphene content nanohybrid
against meagre amount present in pure PVDF. This is to mention
that the XRD peaks at 19.2◦ and 20.0◦ are to be assigned due to
distorted β - or γ -phase (TTTG) which is also considered as one of
the electroactive phases of PVDF [42]. The deconvoluted graphs for
pure PVDF and PG 1.0 are shown in supplementary Figure S1. The
induction of electroactive phases is also confirmed through FTIR
peaks at 840 cm−1 for β/γ phase and 884 cm−1 band for γ -peak in
nanohybrid against 796, 876 and 975 cm−1 absorption peaks for α -
phase in pure PVDF (Fig. 1d) [43,44]. Other β -phase peaks at 1173
and 1274 cm−1 along with decreasing α -phase peak intensity with
higher graphene content hybrid auxiliary support the formation
of piezoelectric phase in PVDF matrix induced by the reduced
graphene (supplementary Figure S1). The induction of β -phase by
graphene moiety is primarily due to better interaction between
the two components and is verified from the red shift of the UV
absorption peak at 250 nm in PG 0.1 to 257 nm peak for PG 1.0 (Fig.
1e). Pure PVDF does not show any absorption band in the range
studied here (inset figure). Further, the melting behaviour of PVDF
and its nanohybrid has been shown in Fig. 1f indicating higher
melting temperature of nanohybrid as compared pure PVDF. Pure
PVDF shows melting peak at 161.3 ◦ C which has been shifted to
a higher melting temperature of 166.6 ◦ C for nanohybrid (PG 1.0)
due to the presence of γ -phase. The order of melting temperature
of different phases of PVDF is β < α < γ [45]. Both β and γ phases
are present in PG 0.5 while β phase increases with increasing the
filler content as compared to γ -phase. Hence, PG 1.0 has lower
melting temperature than PG 0.5. Moreover, one lower melting
peak at 156–158 ◦ C for nanohybrids indicate the presence of β -
phase. However, the induction of electroactive β - and γ -phase in
nanohybrid by reduced graphene oxide is evident from the thermal
measurement which is also commensurate from the results of XRD
and FTIR studies.
177
3.2. Properties and morphology: phase variation
Stress–strain curves for pure PVDF and PG 0.5 are presented
in Fig. 2a showing higher elongation of break for nanohybrid as
compared to pure PVDF. Comparable modulus is noticed for both
the samples while toughness, area under the curve, increases sig-
nificantly to 5.7 J/cm3 from its value of 1.9 J/cm3 for pure PVDF.
Hence, mechanical strength enhances in nanohybrid in presence of
minute quantity of graphene. Thermal stability of nanohybrid has
also increased as evident from the higher degradation temperature
of nanohybrid (453.0 ◦ C) vis-à-vis pure PVDF (429.6 ◦ C) (Fig. 2b).
The degradation temperature is calculated from the temperature
corresponding to the weight loss of 5%. Change of surface and bulk
morphology in presence of graphene has been observed through
optical and atomic force microscopy. Spherulitic pattern of pure
PVDF, signatory of α -phase, has changed completely in nanohybrid
and the birefringence less dark patches along with tiny spherulite
of γ -phase appear in presence of graphene sheets in the polymer
matrix as noticed through optical images under polarized light (Fig.
2c). This is worthy to mention that β -phase does not exhibit any
birefringence while the size of γ -phase spherulite become very
less as compared to α -phase spherulites. The structural alteration
due to the presence of graphene, as observed in XRD and DSC
studies, is also reflected in bulk morphology. Surface topography
has been observed through AFM suggesting relatively smooth sur-
face in pure PVDF against roughening of surface in presence of
graphene as evidenced from the height profile of the AFM images
(Fig. 2d). The average roughness of the surface gradually increases
with filler concentration in the nanohybrid samples as compared to
pure PVDF. This increase in roughness is due to the addition of two
dimensional nanofiller in PVDF matrix. However, piezoelectric β -
phase, induced by graphene, enhances the mechanical and thermal
stability of nanohybrid and morphology also suggests the forma-
tion of the electroactive phases. Surface morphology as observed
through SEM has been presented in Supplementary Figure S3. The
structural changes in GO and RGO is also shown through Raman
178 C. Kumar et al. / Nano-Structures & Nano-Objects 12 (2017) 174–181
Fig. 2. (a) Stress–strain curve for pure PVDF and its indicated nanohybrid; (b) TGA thermograms comparing degradation temperature of PVDF and its nanohybrids; (c)
Polarizing optical micrographs of pure PVDF and PG 0.5, and (d) AFM images of PVDF and its nanohybrids and their corresponding height profiles (bottom profiles).
spectroscopy (Supplementary Figure S4). GO shows the G and D
bands at 1596 and 1345 cm−1 which have been shifted to 1580 and
1348 cm−1 , respectively, in RGO with the increased D/G intensity
ratio of 1.18 as compared to GO (0.78). This change shows the
decrease in average size of sp2 domains after the reduction of
exfoliated GO [46].
3.3. Energy harvesting using hybrid piezoelectric:
Over 90% piezoelectric phase is measured for nanohybrid (PG
1.0) against meagre amount in pure PVDF leading to the use of
this novel hybrid material for energy harvesting purpose under
applied stress. A laboratory made motor driven arrangement has
been made which provides load impact on the material without
making direct human contact with it as shown in Fig. 3a. Different
predetermined load has been applied to various filler content
nanohybrids by keeping all other parameters, such as height from
which the load falls and frequency of striking, same in all the ex-
periments. The basis of this study is to show the strain dependency
on the piezoelectricity in terms of power generation. The electric
response or the energy harvesting capability of the piezoelectric
hybrid films are tested by using a mechanical arrangement. Fig. 3b
illustrates electric pulse signals in the form of voltage generated
from the device using PG 0.1 and PG 1.0 with an excitation load
of 500 gm showing higher voltage output (±0.45 V) of the device
containing greater graphene content nanohybrid (PG 1.0). One
single strike generates the electrical signal continuously for 0.2 s
as shown by the shredded area. To understand the effect of load
on piezoelectricity, various loads are subjected to the same device
showing varying voltage generation and higher output voltage is
obtained from greater load (Fig. 3c). Output voltage for the devices
using PVDF and its nanohybrid as a function of load is shown in Fig.
3d clearly indicating higher voltage for nanohybrid having higher
graphene content. Initially, the output voltage increases steadily
with increasing load while it levels off at higher load. However,
pure PVDF exhibits meagre increase in voltage under impulse
load against significant increment of output voltage is noticed
for nanohybrid arising from their piezoelectricity. The maximum
output voltage obtained with 1% of filler content and upon impact
load of 500 gm is ± 0.45 V, which is nearly five times greater than
that of pure PVDF. To the best of our knowledge, this output voltage
is higher than the reported for RGO/PVDF systems where electric
poling and direct contact with the device was not applied [47]. To
understand the durability and repeatability of the devices, con-
tinuously exerted load is applied to the devices with a particular
frequency and output of four such representative and consecutive
strikes are shown in Fig. 3e. As the mechanical load is subjected to
the nanohybrid it undergoes under some strain which results in the
generation of electric dipoles as a phenomenon of piezoelectricity.
Fig. 3f clearly shows when there is no load applied on to sample
the net dipoles inside the nanohybrid cancel each other resulting
very less or zero potential but when it is subjected to stress,
dipoles align themselves resulting some net potential difference
across the material [48]. These devices generate a stable and equal
voltage irrespective of the number of strikes for a particular load
while voltage output increases with load. The equal output voltage
can be attributed to the uniformity of the piezoelectric phase in
the hybrid while greater electrical output from higher graphene
content device is due to the larger electroactive phase present in
the nanohybrid. Further, the response time remains same (0.2 s)
 C. Kumar et al. / Nano-Structures & Nano-Objects 12 (2017) 174–181 179

Fig. 3. (a) Schematic of electromechanical arrangement to measure piezo responses from the device; (b) Generation of voltage from single strike showing the duration of
piezo responses of indicated specimens (shredded section); (c) Output voltage from the devices made of indicated samples at three varying indicated loads showing higher
response from higher load; (d) Voltage output as a function of applied load comparing pure PVDF and its indicated nanohybrids; (e) voltage vs. time graph with multiple
strikes showing the durability and repeatability of the devices; and (f) Schematic model showing the piezoelectric effect under loading condition for energy harvesting.

for all the strikes as crystal deformation occur for that time period
and subsequently the device return to its original structure and is
ready for the next cycle to show its piezoelectricity. Moreover, the
output voltage improves with the increase in load as larger strain
generates from greater load which induce more piezoelectricity in
the devices.
Electrical signal in terms of short circuit current from the piezo
devices are shown in Fig. 4a and the current gradually increase
with the graphene content primarily due to greater piezo phase
as discussed earlier. The maximum short circuit current from the
device reaches up to 50 and 150 nA using the nanohybrid of PG
0.1 and PG 1.0, respectively, under a load of 500 gm. Further, the
output currents under varying load are shown in Fig. 4b indicating
systematic increment of current with increasing load. On applying
the mechanical stress, nanohybrid device experiences strain which
deform the molecular structure of the electroactive material pro-
ducing charges which freely move towards the electrodes result-
ing electrical responses from the piezo devices. Higher graphene
content and larger load produce more charges, and thereby greater
electrical responses are obtained from the respective devices aris-
ing from their greater piezoelectric phases. Graphene oxide net-
work helps transporting those charges towards the electrodes in
addition to its electroactive phase nucleating effect. The genera-
tion of power from the devices under the application of different
loads is shown in the bar diagram (Fig. 4c) measuring maximum
power delivered of 14 µW/cm3 under a load of 500 gm using PG
1.0 nanohybrid for the fabrication of the device. Power density
systematically increases with graphene content for a fixed load
180 C. Kumar et al. / Nano-Structures & Nano-Objects 12 (2017) 174–181
Fig. 4. (a) Output current from the devices made of indicated specimens under the application of 500 gm load showing response time by shredded area; (b) Output current
from the device made of PG 1.0 under indicated varying load; and (c) power density of the devices made of PG 0.1, PG 0.5 and PG 1.0 under three different loads.
while it enhances with increasing load for any particular hybrid.
The devices show the linear relationship of the output voltage with
exerted mechanical force and thus, can be used as a nanogenerator
to harvest energy from body motion [49]. The amplitude of the
voltage output depends on the amount of the strain imposed on
the surface of the nanohybrid, higher mechanical deformations led
to higher output as larger strains provide more mechanical energy
available for conversion into electrical energy [50]. A complete
video has been presented in supplementary video VS1 showing
the device fabrication and power generation from the device using
hand press or under walking condition. Hence, RGO/PVDF nanohy-
brid can find its application as a polymer based flexible nanogen-
erator which can harvest biomechanical energy from the human
body, thus, possess a world of possibilities in health monitoring
systems. Energy harvesting systems have been developed using
PVDF and different polymers/composites with similar or other
methods. Some interesting data using PVDF thin film having area of
2× 0.4 cm2 produces an output of 2 V and 0.3 µA [51], P(VDF-TrFE)
nanocomposite provides voltage output of 0.3 V and current 0.4
µA [52] and P(VDF-TrFE)/ BaTiO3 composite generates a maximum
voltage of 5.02 V by finger pressing [49].
Now, it is pertinent to understand the structure, property and
performance of the piezo material to devices. PVDF molecule
has –CF2 –/–CH2 – dipoles which actively bind with the opposite
charge present on RGO surfaces, thus, promoting the nucleation
and stabilization of the piezoelectric polar phases (both β - and γ -
phases) through surface charge induced polarization [47]. As the
external pressure or strain is applied on to the electroactive phases,
molecular structures of PVDF/RGO nanohybrid get distorted lead-
ing to an effective enhancement in the responses by switching
the distorted structure to a stable one, or vice versa. Further, the
potential developed in the RGO nanosheets upon application of
external mechanical load accelerate the alignment of the PVDF
dipole slightly more, along with the usual stress induced polar-
ization [53]. The potential difference thus developed across the
surface accelerates the electron flow in the external circuit, which
can be observed as output voltage and current. As a result, the
nanohybrid film provides an improved output voltage together
with the energy harvesting ability. The combined effect of surface
charge induced polarization and stress without any external elec-
tric field makes the dipoles of the PVDF molecules self-polarized,
causing the formation of a self-powered flexible PVDF piezoelectric
energy harvester.
4. Conclusion
Reduced graphene oxide is dispersed in PVDF through solu-
tion route to prepare nanohybrids with varying graphene content.
Graphene induces the electroactive phases in PVDF, presumably
due to dipolar interaction, whose extent depends on the amount
of graphene in polymer matrix. Both the electroactive phases (β -
and γ -phase) are identified using XRD, FTIR and DSC studies and
are quantified from the deconvoluted patterns showing higher β -
and γ -phase in higher graphene content nanohybrid. The mor-
phology has been transformed into mesh-like and rough surface in
nanohybrid against spherulitic and smooth surface in pure PVDF
as observed through AFM and polarized optical images. Nanohy-
brids exhibit higher mechanical strength (higher toughness) and
thermal stability (higher degradation temperature) as compared to
pure PVDF, indicating better material for device application with
greater flexibility. Devices have been fabricated using PVDF and its
nanohybrid and piezo responses are measured from the devices.
Higher output voltage and current have been measured from the
devices made of nanohybrid and under greater mechanical stress.
Power generation is calculated from the electrical output signals
showing 14 µW/cm3 from the device made of 1 wt.% graphene
nanohybrid indicating a linear relationship with applied stress
up to certain value. Thus, nanohybrids are highly piezoelectric
and suitable for energy harvesters for self-powered nanogener-
ator under mechanical stress. The long standing stability of the
nanohybrid device has been demonstrated (over 2000 cycles under
high stress) along with mechanical strength as confirmed through
tensile test and thereby confirms its reciprocating mechanical
stimulation and it provides consistent results over a long period
and finally designed to make an actual device for nanogenerator
under shoe sole.
Acknowledgements
CK acknowledges the Institute for his teaching assistantship.
Authors also acknowledge Prof. S. Jit of IIT (BHU) for the measure-
ment of current and Prof. Ranjan K. Singh, Department of Physics,
Institute of Science, BHU for Raman Spectroscopy measurement.
Appendix A. Supplementary data
Supplementary material related to this article can be found
online at https://doi.org/10.1016/j.nanoso.2017.10.006.
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