Research Article

www.acsami.org

Flexible Lead-Free BiFeO3/PDMS-Based Nanogenerator as

Piezoelectric Energy Harvester
Xiaohu Ren, Huiqing Fan,* Yuwei Zhao, and Zhiyong Liu
State Key Laboratory of Solidification Processing, School of Materials Science and Engineering, Northwestern Polytechnical
University, Xi’an 710072, China
*
S Supporting Information
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ABSTRACT: Perovskite ferroelectric BiFeO3 has been extensively researched in many application fields, but has rarely been
investigated for the energy conversion of tiny mechanical motions in electricity in spite of its large theoretical remnant
polarization. Here we demonstrate the fabrication of a flexible piezoelectric nanogenerator based on BiFeO3 nanoparticles (NPs),
which were synthesized using a sol−gel process. The BiFeO3 NPs−PDMS composite device exhibits an output open circuit
voltage of ∼3 V and short circuit current of ∼250 nA under repeated hand pressing. The output generation mechanism from the
PNG is discussed on the basis of the alignment of electric dipoles in the composite film. It is demonstrated that the output power
from the PNG can directly drive the light-emitting diode (LED) and charge capacitor. These results demonstrate that BiFeO3
nanomaterials have the potential for large-scale lead-free piezoelectric nanogenerator applications.
KEYWORDS: nanogenerator, lead-free, BiFeO3, piezoelectricity, composites

1. INTRODUCTION investigated and applied extensively as piezoelectric materials

Power generation based on fossil energy has faced many critical
problems such as a shortage of resources and environmental
pollution, which is expected to be aggravated over several years
in the future.1 In order to mitigate this tendency, making use of
various renewable energy resources has attracted increasing
attention.2 Especially, small-scale energy harvesting approaches
by converting environmental energy such as solar,3,4 thermal,5,6
and biomechanical energy7−9 into power have been extensively
researched to realize self-powering electronic devices.10−12
Among these methods, a piezoelectric nanogenerator (PNG) is
seen as a viable and promising approach for its relatively smaller
influences from external conditions.13
Up to now, various types of PNGs based on non-
centrosymmetric oxides such as ZnO,14,15 PZT,16,17 and
BaTiO313,18 have been reported for energy harvesting
applications. ZnO has received meaningful attention for NGs
because of its unique noncentrosymmetric structure, but its
intrinsically low piezoelectric coefficient effects further
improves device performances.19 Furthermore, ferroelectric
perovskites exhibit a high polarization and piezoelectric
coefficient; especially, the Pb-based perovskites have always
candidates.20,21 However, with consideration of the toxicity of
lead, lead-free materials would be more ecofriendly for
extensive applications.22 Among the lead-free perovskites,
much attention has been paid to BiFeO3 due to its unique
crystalline structure and characteristics. However, the studies of
BiFeO3 are mainly focused on the multiferroic property,23 ion
conduction,24 photovoltaic effect,25 electromagnetic proper-
ties,26 and magnetic properties.27 It is known that the energy
harvesting performances of piezoelectric materials are closely
related to their piezoelectric coefficient (d33 ∝ εPr).28 Thus, the
larger remnant polarization (Pr) of materials is desirable for
enhancing the performance of PNG devices. Ravindran et al.29
reported their theoretical studies using density functional
theory, predicting a large spontaneous polarization of about 90
μC/cm2 along the [111] direction, which is larger than that of
other materials such as ZnO (Pr ∼ 5 μC/cm2),30 KNbO3 (Pr ∼
23 μC/cm2),31 LiTaO3 (Pr ∼ 32 μC/cm2),32 AgNbO3 (Pr ∼ 52
Received: April 15, 2016
Accepted: September 9, 2016
Published: September 9, 2016

© 2016 American Chemical Society 26190 DOI: 10.1021/acsami.6b04497

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μC/cm2),33 NaNbO3 (Pr ∼ 40 μC/cm2),34 and ZnSnO3 (Pr ∼
59 μC/cm2).35 Although BiFeO3 with the R3c space group
exhibits large spontaneous polarization, it has not been as
extensively investigated as other lead-free perovskite materials
in piezoelectric applications. The one reason is the large
difficulty of preparing single-phase BiFeO3 bulk;36 another
main reason is the problem of the high electrical conductivity of
BiFeO3, which not only limits its applicability, but makes it
difficult to investigate its basic ferroelectric and piezoelectric
properties. However, the pure phase BiFeO3 nanoparticles are
easier to synthesize compared to bulk due to a low preparation
temperature. In addition, compositing oxide nanoparticles with
polymer matrix can overcome the difficulty in the poling
process due to low electrical resistance. Therefore, it is
significant to research the energy harvesting performance of a
composite based on BiFeO3 nanoparticles and its practical
application in PNG.
Here, we report a flexible PNG based on the composite film
obtained by dispersing BiFeO3 nanoparticles (NPs) in a PDMS
matrix. The BiFeO3 NPs were synthesized by a convenient sol−
gel method, and the composite thin film was prepared by the
spin-coating process. In the PNG, BiFeO3 NPs act as power
generation sources and the PDMS acts as flexible matrix. With
the impact from a human hand, the output voltage and current
of the fabricated PNG were measured. A stable output voltage
of around 3 V and current density of 0.12 μA/cm2 are obtained.
The generating power can instantly light a commercial light-
emitting diode (LED). Besides, the capacitor charging
capability of the PNG demonstrates that it might be an
alternative candidate as a piezoelectric energy transformer. In
addition, it is low-cost and simple and has the potential for
large-scale fabrication for the approach we report here.
2. EXPERIMENTAL SECTION
2.1. Synthesis of BiFeO3 Nanoparticles. BiFeO3 nanoparticles
were synthesized via a previously reported sol−gel method,27 using
bismuth nitrate pentahydrate, iron nitrate nonahydrate, acetic acid,
ethylene glycol, and citric acid as starting ingredients. Initially,
stoichiometric bismuth nitrate and iron nitrate were, respectively,
dissolved in acetic acid and ethylene glycol. Then, the two solutions
were mixed together after stirring for 30 min, after which the citric acid
monohydrate solution was added. The mixture was stirred constantly
at 80 °C until a yellow-brown sol was obtained by volatilization of the
excess solvent. After the sol was dried at 100 °C, the obtained gel was
preheated to 400 °C to remove residual oxynitride and hydrocarbon
impurities. After being further calcined at 600 °C for 2 h, the BiFeO3
nanoparticles were finally obtained.
2.2. Fabrication of PNG. The PNG fabrication process can be
described as the following. At first, the polydimethylsiloxane (PDMS;
Sylgard 184, Dow Corning Corp., Auburn, MI) solution was prepared
by adding curing agents to base (where weight ratio of PDMS and
curing agent = 10:1), and then the synthesized BiFeO3 NPs were
dispersed into the PDMS at various concentrations of 10, 20, 30, and
40 wt %. Next, the mixture is spin-casted onto an Al electrode with a
spinning rate of 500 rpm for 30 s and then cured at 70 °C for 10 min.
Thereafter, another Al electrode was pasted to the top surface of a
BiFeO3−PDMS composite film directly and fully cured. Further, the
two electrodes were both pasted onto the PET substrate. Finally, the
PNG device was poled using an applied electric field of 200 kV/cm for
10 h at 150 °C.
2.3. Characterization. Structural and crystallographic character-
izations of the synthesized BiFeO3 NPs were performed via using X-
ray diffraction (XRD; X’Pert PRO MPD, Philips, Eindhoven,
Netherlands) with Cu Kα radiation (λ = 1.54 Å). The morphologies
of BiFeO3 NPs and structure of composites were observed by field
emission scanning electron microscopy (FESEM; Supra 55, Zeiss,
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Research Article
Germany). The output voltage and current from the PNGs under
repeated hand impact were measured by a digital oscilloscope and a
source measurement unit (2410 SMU, Keithley, Beaverton, OR),
respectively. Ferroelectric and piezoelectric characteristics were
investigated by piezoelectric force microscopy (PFM; Dimension
Icon, Bruker, Santa Barbara, CA).
3. RESULTS AND DISCUSSION
The XRD Rietveld refinements for BiFeO3 were performed by
using the GSAS-EXPGUI program to characterize structure of
the prepared BiFeO3 nanoparticles at room temperature.37 The
XRD pattern for BiFeO3 is shown in Figure 1a, which was well-
fit by the rhombohedral structure with R3c symmetry.
Figure 1. Structural and morphology of BiFeO3 NPs. (a) Rietveld
refinement analysis of XRD spectra of BiFeO3. (b) FE-SEM image
showing the crystalline surface morphology of BiFeO3 NPs. (c) Crystal
structure of BiFeO3.
Figure 1b shows an FE-SEM image of BiFeO3, exhibiting a
spherical shape with homogeneous particle sizes of about 100
nm. The summary of crystal data and R factors is listed in Table
S1 (Supporting Information). The final factors, Rwp, Rp, and χ2,
are 6.92%, 5.05%, and 2.73. Table 1 lists the atomic
occupancies, coordinates, as well as isotropic thermal
parameters of BiFeO3 at room temperature. To understand
the crystallographic structure of BiFeO3, a rhombohedral unit
cell of BiFeO3 is depicted in Figure 1c on the basis of the
refined result. It is observed that the crystal possesses a
perovskite structure with high distortion and rhombohedral
symmetry. In the ideal cubic perovskite structure, the oxygen
ions would occupy the face-centered sites. However, the low
tolerance factor of BiFeO3 indicates that the Bi ion may be
difficult to stabilize in the high-symmetry position of the cubic
perovskite structure due to lattice mismatch between the
cations.29 Therefore, as shown in Figure 1c, a lattice distortion
arises by the displacement of FeO6 octahedra along the [111]rho
direction of the rhombohedral unit cell to reduce the lattice
mismatch and enhance stability, which leads to off-centering of
Fe3+ in the lattice thereby forming strong spontaneous
polarization. Thus, a piezoelectric nanogenerator (PNG)
fabricated based on BiFeO3 NPs is expected.
For BiFeO3 with the R3c space group, atomic displacements
along the c axis ([001]hex direction) from the corresponding
locations in the hexagonal structure cause ferroelectric
spontaneous polarization (Ps). In light of the atomic displace-
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Table 1. Atomic Coordinates, Occupancies, and Isotropic Thermal Parameters of BiFeO3

atom site x y z 100Uiso (Å2) occupancy
Bi 6a 0 0 0.00117(15) 0.0202(2) 1
Fe 6a 0 0 0.22217(18) 0.0196(8) 1
O 18b 0.4448(13) 0.0133(11) 0.95256(28) 0.0024(2) 1

ments in the unit cell, the total Ps of displacement-type
ferroelectrics can be calculated by Shimakawa’s mode38
mi × Δxi × Q ie
Ps = ∑ aluminum (Al) foil as electrodes on a polyethylene
i
V terephthalate (PET) substrate. The detailed information
Here, mi, V, Δxi, and Qie represent the site multiplicity, unit cell
volume, and atomic displacement along the c axis direction
from the corresponding location in the symmetric structure and
the ionic charge of the ith corresponding ion, respectively.
According to the crystallographic data obtained from refine-
ment (Table 1 and Table S1), the ion displacements along the c
axis direction and the contributions of each ion to the total Ps of
BiFeO3 are shown in Figure 2. The calculated Ps is 22.76 μC/
cm2, which is consistent with some experimental result reported
previously.39,40
Figure 2. Ion displacement and contribution to the total spontaneous
polarization (Ps) of each ion in BiFeO3.
The schematics of the PNG fabricating process are shown in
Figure 3a. The PNGs were fabricated by covering the top and
bottom surfaces of BiFeO3 NPs-PDMS nanocomposite with
about the fabrication process is described in the Experimental
Section. The optical image in Figure 3b shows the bend by
human fingers, confirming its suitability in flexible and
embedded electronics. Figure 3c exhibits cross-sectional SEM
image of PNG that is composed of a composite film and two
metal electrodes, indicating that the composite film is about
100 μm thick. A magnified cross-sectional SEM image shown in
Figure 3d suggests that the BiFeO3 nanoparticles were well-
distributed in PDMS matrix by and large except for slight
agglomeration. Random orientation of BiFeO3 nanoparticles
inside PDMS will result in the electric dipoles being randomly
aligned between the two electrodes before electric poling.
The generated voltage and current outputs of the poled PNG
during the periodic vertical pressing and releasing process were
measured, respectively. The open circuit voltage and short
circuit current of PNG (40 wt % of BiFeO3 NPs concentration)
under repeating impact are shown in Figure 4a,d, respectively.
An open circuit voltage of around 3 V and a short circuit
current of around 250 nA are clearly seen. Table 2 shows that
BiFeO3 NPs mixed with PDMS in the present work exhibit
output performance comparable to that of other piezoelectric
nanogenerators. In order to verify that the output electric signal
was purely resourced from the piezoelectric phenomenon of
PNG, switching-polarity tests were carried out. As shown in
Figure 4a,b, when the PNG is forward connected to a
measurement device, a positive voltage generated can be
detected under compressed conditions. While under a reverse
connection, an opposite output voltage signal is measured. It is

Figure 3. (a) Schematic diagrams of the PNG fabricating process. (b) Photograph of the BiFeO3−PDMS composite film bent by fingers. (c) The
cross-sectional SEM image of the PNG device. (d) The magnified cross-sectional SEM image of the BiFeO3−PDMS composite film with 40 wt %
BiFeO3 NPs.

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Figure 4. (a) Open circuit voltage of the PNG in the forward connection. (b) Open circuit voltage of the PNG in the reverse connection. (c)
Enlarged view for one cycle of output voltage under forward connection. (d) The short circuit current of the PNG during the periodic pressing and
releasing motions.

Table 2. Output Performance Comparison of Piezoelectric PNG, which proves that the output is associated with
Nanogenerators ferroelectricity of BiFeO3−PDMS composite. So the poling
process is an indispensable step to improve the output
output performance
capability of the PNG. The PFM measurement was used to
current/ investigate the piezoelectricity of the BiFeO3−PDMS compo-
piezoelectric filler matrix voltage current density ref
site film containing 40 wt % BiFeO3 NPs. Figure 5a,b shows the
PZT nanowires PDMS 6V 50 nA 17
PZT microsphere PDMS 6V 0.2 μA/cm2 43
BaTiO3 nanowires PVC 1.9 V 24 nA 44
BaTiO3 nanoparticles PDMS 3V 0.3 μA 41
+ CNT
NaNbO3 nanowires PDMS 3.2 V 16 nA/cm2 42
LiNbO3 nanowires PDMS 0.46 V 9.11 nA/ 45
4.64 nA/cm2
BiFeO3 nanoparticles PDMS 3V 0.25 μA/ this work
0.12 μA/cm2

indicated that the detected outputs are the true electric signals
produced from PNG strained by compressing motions.41
Figure 4c exhibits an enlarged graph of the single voltage
pulse. A difference of voltage peak values between compressed
and released conditions is observed, which can be attributed to
the difference of the strain rate in the process of applying and
releasing the stress on the PNG.42 In addition, there are two
opposite responses in the release process for one cycle. The
former one generates when the surface recovers to its initial
position after press releasing, and the latter one can be ascribed
to reverse strain due to elasticity of the BiFeO3−PDMS
composite.
To confirm the contribution of BiFeO3 NPs within PNG, the
PNG with pure PDMS was measured under the same test
conditions. The result is shown in Figure S1 of Supporting
Information. It is observed that the output voltage of pure
PDMS PNG is much smaller than the outputs of PNG with
BiFeO3 NPs. It works out that the high output of PNG is
mainly attributed to addition of BiFeO3 NPs. Furthermore, to
research the importance of the poling process, a comparative
trial of the PNG without poling was carried out. Figure S2 in
Supporting Information suggests that the output voltage of the
unpoled PNG is about 100 mV and smaller than the poled
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Figure 5. (a) Phase and (b) amplitude hysteresis loop of BiFeO3−
PDMS composite film with 40 wt % BiFeO3 NPs.
piezoelectric/ferroelectric response phase and amplitude,
respectively, under application of direct-current (dc) bias
voltage. Before measurement, two layers of Au film were
coated on top and bottom surfaces of the sample to eliminate
the effect of electrostatic cantilever−sample interaction.46 The
piezoelectric response amplitude (nm) was calculated by
dividing the measured amplitude (mV) with the cantilever
sensitivity (0.00934 V/nm for the tip). The difference of phase
ΔΦ (Figure 5a) between the opposite signals is around 180°,
meaning a 180° domain switching of the permanent polar-
ization, and a classic butterfly shaped amplitude loop (Figure
5b) corresponds to the strain−voltage (S−V) phenomenon of
piezoelectric materials. Those results indicate a nonlinear
characteristic of the composite film as expected from the strong
piezoelectricity of the component materials.47
In Figure 6, we schematically show the work mechanism of
the PNG device. Initially, without any electric poling, electric
dipoles within the BiFeO3 NPs randomly align in the PDMS
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Figure 6. (a) Dipoles in BiFeO3 NPs randomly align before the poling process. (b)After poling, the dipoles in BiFeO3 NPs will align in one direction
along the electric field. (c) When the compressive force is applied on the PNG, a piezoelectric potential is generated. (d) As the compressive force is
released, the accumulated electrons flow back along the opposite direction. (e) After returning to original state, a reverse piezoelectric potential is
produced from tensile strain due to good elasticity of PDMS.

Figure 7. (a) Time-dependent output voltage for PNGs with 0−40% BiFeO3 NP concentration. (b) The variation of open circuit voltage and
COMSOL simulation results from distribution of piezoelectric potential for PNGs with different BiFeO3 contents.

matrix between the two electrodes (Figure 6a). When an
electrical field is applied on the PNG, the dipoles within
BiFeO3 NPs tend toward aligning along the applied electric-
field direction as depicted in Figure 6b. If no external force on
the device is applied, no electric signal will be detected due to
the device remaining in an equilibrium state. Further, when the
PNG suffers a vertical compressive force, a change of total
polarization of the composite is generated due to the
compressive strain, which results in a piezoelectric potential
between the top and bottom electrodes. In such a way, external
free charges will move to and accumulate at the electrodes to
screen the piezoelectric potential. During this process an output
signal can be detected from the PNG (Figure 6c). When the
vertical applied mechanical force is released, the vertical strain
and piezoelectric potential between the two electrodes of the
PNG disappear. The accumulated charges transport back in a
reverse direction, and a negative electric signal is generated
(Figure 6d). After the first return to the original state, a small
tensile strain will be produced due to good elasticity of the
PDMS matrix, resulting in a reverse piezoelectric potential. To
screen the piezoelectric potential, the motion and accumulation
of free charges happen again as shown in Figure 6e. So a weak
negative electric signal can be detected. As discussed above,
output pulse signals from the PNG device are obtained during
continuous application and release of the external compressive
force.
In order to study the influence of BiFeO3 NPs concentration
on the output capability of the PNG, a series of PNGs were
fabricated on the basis of BiFeO3−PDMS composites with
various mass fraction of BiFeO3 NPs (10, 20, 30, and 40 wt %).
26194
To select a suitable electric poling process, we measured the
output performance of the PNGs with different BiFeO3 NP
contents polarized by various poling times, which are shown in
Figure S3 of Supporting Information. Finally, we poled each
PNG by applying an electric field of 2 kV for 10 h at 150 °C.
Typical time-dependent output voltages measured for the
various PNGs during cyclic pressing and the releasing process
are shown in Figure 7a. Output voltages around 0.2, 0.7, 1.5,
and 3 V from the PNGs, for BiFeO3 NPs fractions of 10, 20, 30,
and 40 wt %, respectively, can be obtained. We can see that the
output voltage gradually increases with increasing content of
BiFeO3 NPs up to 40 wt %, and gains a maximum output
voltage of around 3 V. Further, we simulated the distribution of
induced piezoelectric potential in vertically stressed PNGs
based on BiFeO3 NPs by using COMSOL multiphysics
software for finite element calculations, by which piezoelectric
potential distribution in PNGs with different amounts of
piezoelectric particles dispersed in matrix were calculated,
respectively. Differences of the piezoelectric potential were
clarified by color code, as a compressive stress of 10 kPa was
applied to the BiFeO3−PDMS composite. It can be found that
the piezoelectric potential difference between two electrodes of
the PNGs increases linearly with an increasing amount of
piezoelectric particles, as shown in Figure 7b. For comparison,
the experimentally obtained output voltages from the PNGs
with different concentration of BiFeO3 particles are also
depicted in Figure 7b. It is found that the tendency of output
voltages obtained experimentally is consistent with the
simulated result.
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ACS Applied Materials & Interfaces
To test the feasibility of the practical application of the PNG,
the PNG is directly connected with two commercial LEDs in
parallel but opposite directions without any storage units (a
schematic circuit diagram is displayed in Figure 8a). When the
Figure 8. (a) Circuit schematic of LED driving and capacitor charging;
the switch is connected to “A” first to drive the LED by ac output
generated by the PNG, and then connected to “B” to charge the
capacitor. (b) The red and green LEDs were driven successively by
output generated from hand pressing and releasing. (c) Rectified
output voltage of the PNG. (d) The capability of the capacitor
charging from the PNG by periodic pressing.
PNG is impacted by hand, the red LED is instantly lit, and the
green LED is lit by reverse output after release as shown in
Figure 8b and the Supporting Information video file. Then, a
typical rectifier was employed in order to convert the generated
ac to dc output. Figure 8c shows the output voltage signal
rectified. To test the capacitor’s charging capability from the
PNG, the capacitors of 1.0, 2.2, and 4.7 μF were charged by the
rectified output with the PNG, respectively; the concerning
transient response is exhibited in Figure 8d. It is observed that
the charging voltages increased gradually and eventually
reached the maximum value of 1.26, 1.68, and 2.58 V within
55, 170, and 527s, respectively. The above result indicates that
the PNG can be seen as a promising power source device for
tiny energy harvesting applications48,49 and self-powering
electronic devices.50,51 Moreover, in order to prove the stability
of the PNG, a durability test was carried out over 1000 cycles.
As shown in Figure 9, no degradation in the output
performance is observed even after 1000 cycles. The
Figure 9. Durability test of the PNG. The inset shows an enlarged
view of the open circuit voltage signal in the durability test process.
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Research Article
BiFeO3−PDMS-based nanogenerator shows exceptionally
durable and reliable energy harvesting performance.
4. CONCLUSION
In summary, BiFeO3 nanoparticles were synthesized via a sol−
gel method. We have also fabricated a flexible piezoelectric
nanogenerator based on BiFeO3 NPs−PDMS composite
structure for scavenging mechanical energy. The output voltage
and current of the PNG reached up to ∼3 V and ∼300 nA
which corresponds to a current density of ∼0.12 μA/cm2 under
repeating hand impacting. The single output pulse generated
from the PNG can light up a commercial LED directly. It is
concluded that the BiFeO3 nanoparticle is a valuable candidate
for energy harvesting application.
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsami.6b04497.
Video showing the powering up of the LED (AVI)
Refined crystal data for BiFeO3, output voltage generated
from the PNG without BiFeO3 NPs, output voltage
generated from the PNG before the poling process, and
output voltage of the PNGs with different BiFeO3 NPs
contents polarized by various poling times (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: hqfan3@163.com. Fax: +86-29-8849 2642. Phone:
+86-29-8849 4463.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work was supported by the National Natural Science
Foundation (51672220), the 111 Program (B08040) of MOE,
the Xi’an Science and Technology Foundation (CXY1510-2),
the Fundamental Research Funds for the Central Universities
(3102014JGY01004) of China.
■
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26197 DOI: 10.1021/acsami.6b04497

ACS Appl. Mater. Interfaces 2016, 8, 26190−26197