Energy Technology

Generation, Conversion, Storage, Distribution

Accepted Article
Title: Flexible Lead-Free BaTiO3/PDMS/C Composite Nanogenerators as
Piezoelectric Energy Harvester

Authors: Cuixian Luo, Sihuan Hu, Mengjie Xia, Pengwei Li, Jie Hu, Gang Li,
Huabei Jiang, and Wendong Zhang

This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication of the
final Version of Record (VoR). This work is currently citable by using the Digital
Object Identifier (DOI) given below. The VoR will be published online in Early
View as soon as possible and may be different to this Accepted Article as a
result of editing. Readers should obtain the VoR from the journal website shown
below when it is published to ensure accuracy of information. The authors are
responsible for the content of this Accepted Article.

To be cited as: Energy Technol. 10.1002/ente.201700756

Link to VoR: http://dx.doi.org/10.1002/ente.201700756

www.entechnol.de
Energy Technology 10.1002/ente.201700756

FULL PAPER
Flexible Lead-Free BaTiO3/PDMS/C Composite Nanogenerators as
Piezoelectric Energy Harvester
Cuixian Luo[a], Sihuan Hu[a], Mengjie Xia[a], Pengwei Li*[a], Jie Hu[a], Gang Li[a], Huabei Jiang[b],
Wendong Zhang[a]
A novel approach to develop high performance flexible piezoelectric when the C content of PNGs is 3.2 wt%.The generated electric energy
nanogenerators (PNGs) by employing lead-free BaTiO3/PDMS/C can be effectively stored by the energy storage capacitor (47μF) and
composite thin film has been proposed, among which lead-free BaTiO3 successfully used to light up a commercial red light-emitting diode
nanoparticles (NPs) has been successfully fabricated by a facile (LED). These results show that BaTiO3/PDMS/C composite is a
modified (nano-scale precursors) solid phase method. The synthesized promising candidate for large-scale lead-free piezoelectric
BaTiO3/PDMS/C composite PNGs exhibits an output voltage of ∼7.43

Accepted Manuscript
nanogenerator applications.
V by periodically beating from a vibrator, which is increased by 143%
compared to the PNGs without C doping. Meanwhile, the maximum
power could reach up to ∼7.92μW with the load resistance of 2MΩ

Introduction
With the rapid development of sustainable and renewable energy and K0.5Na0.5Nb0.995Mn0.005O3), which could obtain a maximum output
generation technologies, high performance nanogenerators have been voltages and current densities of 2.2 V and 0.12 μA/cm2. Shin [29]
exploring during recent years [1-6]. Among which piezoelectric reported high-performance flexible NGs based on a composite thin
nanostructures-based nanogenerators (NGs) show superior advantages film, composed of hemispherically aggregated BaTiO3 NPs and poly-
because of their distinctive high power density, relatively smaller size, (vinylidene fluoride-co-hexafluoropropene) P(VDF-HFP), exhibiting
easy fabrication design, long cycle life and the environmentally high electrical output up to∼5 V and ∼750 nA by cyclic measurement
friendly characteristic [7-8]. Originally, ZnO nanowire arrays have been under bending stage. Park [30] reported the nanocomposite generator
used to fabricate such piezoelectric NGs due to their unique (NCG) achieving a simple, low-cost, and large area fabrication based
piezoelectric properties [9-10]. However, considering the relatively low on BaTiO3 NPs synthesized via a hydrothermal reaction and graphitic
piezoelectric coefficient of ZnO, it is desirable to design NGs made by carbons (such as single-walled and multi-walled carbon nanotubes and
perovskite materials with large piezoelectric coefficients such as reduced graphene oxide), which repeatedly generated an open-circuit
BaTiO3, Pb(Zr,Ti)O3 (PZT) and Pb(Mg,Nb)O3-PbTiO3 (PMN-PT)[11]. voltage (Voc) of ∼3.0 V and a short-circuit current signal of 300 nA.
Unfortunately, the component lead in PZT and PMN-PT has the Indeed, the electrical output of composite nanogenerator has
concern of toxic effect toward human health and environmental significantly increased. Whereas, the non-uniform distribution of
problems. Consequently, BaTiO3 has drawn significant attentions due conductive materials or their aggregation into large clusters can
to its non-polluting, simple and convenient preparation and low cost [12- decrease the effective surface area of fillers particles per unit volume,
14]
. resulting in a lower dielectric permittivity [31]. Consequently, the choice
In contrast to its strong merits, the application of BaTiO3 films for of fillers and their mass ratio, as well as the effective surface area
flexible energy harvesting devices has been limited by its inherent would have great potential for high-power nanogenerators and large-
fragility property [15-17]. In order to solve the fragile problems of the output signal sensors with lightweight, flexibility, and low cost.
PNGs, silk fibroin, polyvinylidene fluoride (PVDF) and polydimethyl In this paper, we fabricated the high-performance flexible PNGs
siloxane (PDMS) are widely used as a matrix in the pure piezoelectric based on the composite film obtained by dispersing BaTiO3 NPs and
NPs [18-22]. It can be found that piezoelectric nanocomposites composed BaTiO3/C in a PDMS matrix. With the impact from the concentration
of piezoelectric NPs and flexible polymers have demonstrated of the synthesized and commercial BaTiO3 NPs, the thickness of the
remarkable flexibility towards flexible devices and wearable composite thin film and the concentration of the acetylene black, the
applications [23-27]. For Example, Kim [28] reported the silk fibroin-based output voltage and current of the fabricated PNGs have been measured
biodegradable piezoelectric composite nanogenerators using lead-free and analyzed. Under periodic external mechanical deformation by
ferroelectric nanoparticles (BaTiO3, ZnSnO3, Bi0.5 (Na0.82K0.18)0.5TiO3, beating from mechanical vibrator, electric signals are repeatedly
generated from the PNGs device and stored to operate a commercial
red LED.
[a] Cuixian Luo, Sihuan Hu, Mengjie Xia, Pengwei Li*, Jie Hu, Gang Li,
Huabei Jiang, Wendong Zhang
Micro Nano System Research Center of College of Information
Engineering and Key Lab of Advanced Transducers and Intelligent
Control System of the Ministry of Education, Taiyuan University of
Results and Discussion
Technology.
No.79, Yingze West Street, Taiyuan, Shanxi 030024, China Fig. 1a shows the SEM image of BaTiO3 powders sintered at
E-mail: [email protected] 1350 °C and the average particle size is about 1.2 ± 0.6 μm. The Ɛr, Pr,
[b] Huabei Jiang and d33 of BaTiO3 at sintered temperature (1350 ºC) in our previous
University of South Florida
ENB 343J, 4202 E. Fowler Ave. Tampa, FL 33620, USA paper are 3533, 16.24 μC/cm2 and 420 pC/N, respectively, as shown in
Table S1. From the XRD pattern it can be seen that the BaTiO3
nanocrystals have a typical perovskite-type tetragonal structure

This article is protected by copyright. All rights reserved.

Energy Technology 10.1002/ente.201700756

FULL PAPER

(JCPDS-ICDD File No. 05-0626) with no diffraction peaks from any composite generator improves 1.4%-5.1% and its stability is better.
other impurities, as shown in Fig. 1b. The schematics of the PNG The reason of which could be attributed to the uniform size of BaTiO3
fabricating process are shown in Fig. 1c. The process contains four NPs prepared by nano-scale precursors in composite piezoelectric
main steps, including spin-coating, curing, peel-off and packaging, and matrix and the piezoelectric performance shows stable and reliable.
the detailed information of the fabrication process is described in the
Experimental Section. The practical image in the top right corner of
Fig. 1c shows the bend of the PNGs by human fingers, confirming its
suitability in flexible and embedded electronics.

Accepted Manuscript
Fig. 2. The output performance for BaTiO3/PDMS composite PNGs: (a) The
output voltage for PNGs with 10, 20, 30 and 40 wt % BaTiO3 NPs
concentration; (b) The output current for PNGs with different concentration of
BaTiO3 NPs (10, 20, 30 and 40 wt %).

The output performance for different film thickness BaTiO3/PDMS

composite PNGs is shown in Fig. S3. It is clearly evident that with the
film thickness of composite PNGs becoming thicker and thicker (60-
240 μm), the output voltage of PNGs rises to 3.61V. This behavior
occurs because the quantity of BaTiO3 NPs in unit area increases.
Based on the study above, every aspect such as electrical output,
flexibility, and craftsmanship should be taken into account
compromised. Therefore, the optimal parameters of PNGs with 30 wt %
BaTiO3 NPs concentration and the film thickness of 180 μm have been
Fig. 1. (a) SEM pictures of the surface of BaTiO3 powders sintered at 1350 °C; chosen in the next study (Table S2 and S3).
(b) XRD patterns of the BaTiO3 powders with 1350°C sintered temperature; (c)
Schematic diagrams of the BaTiO3/PDMS/C composite nanogenerators
fabricating process.

The relationship between BaTiO3 concentration and its output

performance was studied, as shown in Fig. 2. Output voltages around
0.69, 1.75, 3.45, and 6.33 V from the PNGs, for BaTiO3 NPs fractions
of 10, 20, 30, and 40 wt %, respectively, can be obtained (Fig. 2a). It
can be seen that the output voltage gradually increases with the content
of BaTiO3 NPs increasing up to 40 wt %, and gains a maximum output
voltage of around 6.33 V. Similar to the Fig. 2a, a difference of current
peak values about 0.466, 1.241, 2.42 and 4.19 μA could be observed
when the concentration of BaTiO3 NPs proportionally increases from
10 wt % to 40 wt %. It can be explained that the BaTiO3 NPs are well
distributed in PDMS matrix except for slight agglomeration and the
density of BaTiO3 NPs becomes large with rising concentration of
BaTiO3 (From SEM image of Fig. 2a), which makes the voltage grow
further.
Typical time-dependent output voltages and current measured for the Fig. 3. The output performance for BaTiO3/PDMS/C composite PNGs: (a) The
output voltage for PNGs with different C contents (0, 1.6, 2.4, 3.2, 4.0 and 4.8
various concentrations of commercial BaTiO3 NPs during cyclic
wt %); (b) Dependence of generated voltage, current and power on the C
beating and the releasing process are shown in Fig. S2. The voltage contents of composite PNGs; (c) AC conductivity at 1 kHz of PNGs with
(and the current) of BaTiO3/PDMS composite PNGs (fabricated by the different C contents (0.0-4.8 wt%); (d) The output voltage and power under
commercial BaTiO3 NPs) increases from 0.61 V to 6.02 V (and 0.41 different external loads of the PNGs with the C content of 3.2 wt%.
μA-4.03 μA) with the concentration of commercial BaTiO3 NPs
fractions varying from 10 wt % to 40 wt %. Compared with the output
performance of PNGs (fabricated by the commercial BaTiO3 NPs), the Time-dependent output voltages measured for the various C
output voltage and the output current of synthesized BaTiO3/PDMS concentrations of PNGs (30 wt % BaTiO3 NPs) during cyclic beating

This article is protected by copyright. All rights reserved.

Energy Technology 10.1002/ente.201700756

FULL PAPER

process is shown in Fig. 3. Output voltages about 3.05, 3.49, 5.01, 7.43, are examined also at room temperature, as shown in Fig. 4b. It can be
3.67 and 0.33 V from the PNGs, for C fractions of 0, 1.6, 2.4, 3.2, 4.0 found that the Pr value of BaTiO3/PDMS/C composite (7.5 μC/cm2) is
and 4.8 wt %, respectively, can be obtained (Fig. 3a). It can be found about two times of BaTiO3/PDMS composite without C (3.5 μC/cm2).
that the voltage increases from 3.05 V (C, 0 wt %) to 7.43 V (C, 3.2 The reason of which may be ascribed to the change of domain
wt %) firstly, then falls to 0.33 V (C, 4.8 wt %).The output current and structures of BaTiO3/PDMS composite with C addition [34].
the output power have a similar trend as the output voltage for varying It is known that the energy harvesting performances of piezoelectric
C content, as shown in Fig. 3b. The maximum power of 7.92 μW can materials are closely related to their piezoelectric coefficient d33 values,
be obtained with the load resistance of 2MΩ when the C contents of which can be expressed as:
composite PNGs reach up to 3.2%. Compared to the other works d33 =2Q11 0 r Pr (1)
(different materials doped BaTiO3 NPs), the output performance of our where Ɛ0 = 8.854 × 10−12 F/m is the permittivity of vacuum, and Q11
work improves obviously (Table 1). In Fig. 3c, it can be found that the (0.05-0.1m4/C2) is the electrostrictive constant of the paraelectric phase
conductivity goes rise when the concentration of C in mixture increase. [35]
. Based on the formula and the experiment results (Fig. 4), the d33
The output power of the PNG (C: 3.2 wt%) is calculated by measuring values of BaTiO3/PDMS/C and BaTiO3/PDMS composites are

Accepted Manuscript
the output voltage across a load resistance (Fig. 3d). The output voltage calculated as 15.3 pC/N and 5.4 pC/N, respectively [36-37]. These results
is steadily increased as the value of the load resistance is increased and indicate that the d33 of BaTiO3/PDMS composite with C doped
become saturated at 10MΩ load resistance. From these results, the increases by 183%, which can be ascended to the increment of Ɛr and
maximum output power is calculated to be about 7.92 μW at 2 MΩ Pr values. In addition, it can be explained that the addition of acetylene
load resistance. These good results with the addition of acetylene black black make the free electron less prone to recombination in composite
can be well explained by percolation theory [32]. PDMS, BaTiO3 and C material, resulting in a greater quantum yield of piezoelectric electrons
are usually considered as non-conductive phase, piezoelectric phase [38-39]
.
and conductive phase, respectively. The piezoelectric effect of BaTiO3
NPs plays a fundamental role in terms of piezoelectric property.
Dispersing conductive acetylene black into the nonconductive matrix Table 1 Output comparison of piezoelectric nanogenerators in bending
mode.
(PDMS) can form conductive composites. The electrical conductivity
of a composite is strongly dependent on the mass fraction of the Output Active
Active
Form area Ref.
conductive phase (acetylene black). At low mass fractions, the Material Voltage Current
(cm2)
conductivity remains very close to the conductivity of the pure matrix (V) (μA)
(PDMS/ BaTiO3). As the conductive C increases in the matrix, the BaTiO3 Thin film 1 0.16 0.82 [8]
PDMS, BaTiO3 and C have significant synergistic action and the
piezoelectricity of the composite film rises rapidly. If the threshold of BaTiO3+PVC Composite 0.9 0.01 N.A. [26]
the certain mass fraction is exceeded, the whole piezoelectric
BaTiO3+CNT
composite film is transformed into conductor with the rapid increasing Composite 3 0.3 1.3*1.3 [28]
+PDMS
of conductivity; and then the piezoelectricity goes down continuously
and the piezoelectricity of the composite film ultimately disappears [33]. BaTiO3+P(VD
Composite 5 0.75 4 [29]
F-HFP)

BaTiO3+C This
Composite 13.5 5.13 2*2
+PDMS work

To test the feasibility of the practical application of the PNGs, the

BaTiO3/PDMS/C composite PNGs are directly connected with the
rectifier bridge and energy storage capacitor (47 μF). A schematic
circuit diagram is displayed in Fig. 5a. The energy storage capacitor
collects energy from the BaTiO3/PDMS/C composite PNGs to supply
of the commercial red LED by a control switch S. The output voltage
on capacitor is reach up to the threshold value, then the switch S is
Fig. 4. The parameter measurement of BaTiO3/PDMS composite with C and
closed to the B and the red LED is instantly lit. The commercial red
without C: (a) Dielectric spectrum of BaTiO3/PDMS composite with C and
without C; (b) The polarization-electric filed hysteresis loops (P-E) of LED has been lighted, as shown in Fig. 5b. Fig. 5c presents the
BaTiO3/PDMS composite with C and without C. rectification output voltage results of the PNGs through the rectifier
bridge. Fig. 5d shows the curve of the charge and discharge for energy
storage capacitor. During the testing process, the working cycle time of
Fig. 4a shows the Ɛr of BaTiO3/PDMS composite with C and without energy storage capacitor is 330 s. The above result indicates that the
C from 0.1 kHz to 1 M at room temperature. The Ɛr of these two PNGs can be seen as a promising power source device for tiny energy
samples are all remaining a constant, which respectively are 87±4 of harvesting applications and self-powering electronic devices.
BaTiO3/PDMS and 115±2 for BaTiO3/PDMS/C composite. Apparently,
the dielectric constant of BaTiO3/PDMS/C composite is much higher,
which could be explained that the addition of acetylene black increases
the capacitance value of the composite, and leads to the increment of
the dielectric constant further. Electric hysteresis loops of the samples

This article is protected by copyright. All rights reserved.

Energy Technology 10.1002/ente.201700756

FULL PAPER

in the inset shows that the Vpp of the open-circuit voltage is about 13.5
V. The generated potential does not appear to change significantly after
4000 cycles, which indicates that the device is very stable.

Conclusions

In summary, we have demonstrated a flexible lead-free

BaTiO3/PDMS/C composite PNGs, which can yield high and steady
electrical outputs during periodic mechanical beating process.
Acetylene carbon black is employed as the conductive phase in the
BaTiO3/PDMS composite to regulate the Ɛr and Pr values (or the
domain structure) of the sample, thus serving as the possible origin of

Accepted Manuscript
their comparative piezoelectric activities. The output power generated
from the composite film PNGs with an embedded BaTiO3 NPs
concentration of 30 wt% and C concentration of 3.2 wt% could
produce a maximum output voltage of 7.43 V and easily light up a
commercial red LED by energy storage capacitor. BaTiO3/PDMS/C
Fig. 5. The performance measurement of BaTiO3/PDMS/C composite PNGs:
(a) Circuit schematic of LED driving and capacitor charging; (b) Driving the red
composite PNGs exhibit a good performance enhancement and
LED by output power from beating; (c) Rectified output voltage of the PNGs; (d) advantages such as easy fabrication, biocompatibility and
The voltage across energy storage capacitor by periodic lighting the red LED. environmentally friendly, which can be potentially adopted as a
valuable flexible power supply for realizing self-powered electronics.

Two kinds of BaTiO3/PDMS/C composite films (A: 2.4 wt % C

Experimental Section
concentration; B: 3.2 wt % C concentration) are measured by series
connection (the upper left corner schematic in Fig. S4) to verify the
linear superposition of obtained signal came from the piezoelectricity 1. Synthesis of BaTiO3 NPs
of composite film. In Fig. S4, it can be observed that the output voltage
of BaTiO3/PDMS/C composite film by series connection is BaTiO3 NPs were synthesized via the conventional solid-state
approximately equal to the voltage superposition of every reaction technique [40-41], using TiO2 nanoparticles prepared by a typical
BaTiO3/PDMS/C composite film. liquid phase method and BaCO3 nanopowder. In a typical procedure,
the raw materials were weighed according to the stoichiometric ratio
and ball-milled with absolute ethyl alcohol for 12 h on a planetary ball
mill. The milled mixture was dried at 80°C for 12 h, and then calcined
at 1350°C for 4 h.

2. Fabrication of BaTiO3/PDMS/C composite thin film

The BaTiO3/PDMS/C composite thin film 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 (weight ratio of PDMS and curing
agent = 10:1), and then the synthesized BaTiO3 NPs (30 wt %) and the
C (Acetylene carbon black (about 30nm，in Fig S5), 0, 1.6, 2.4, 3.2,
4.0, 4.8 wt %) were dispersed into the PDMS. Next, the mixture was
spin-coated onto a Si wafer piece (2cm*2cm) with a spinning rate of
1000 rpm for 30 s (obtain the film thickness of about 180 μm) and then
cured at 80 °C for 1 h. The cured composite thin film with BaTiO3
clusters was peeled off from the Si substrate. Thereafter, the
piezoelectric PNGs device was poled 100 °C while applying the
electric field of 30 kV/mm for 20 h. Finally, the Cu electrodes was
Fig. 6. The output potential recorded during the stability test for 4000 cycling
times. The inset shows the magnified output signals. pasted to the top and bottom surface of a BaTiO3/PDMS/C composite
film directly and fully cured. Further, the two electrodes were both
Long-term stability test is conducted to confirm the mechanical packaged with the PDMS.
reliable and endurance of the NGs. Measurements of more than 4000
cycling times are demonstrated in Fig. 6. The magnified output signal 3. Characterization

This article is protected by copyright. All rights reserved.

Energy Technology 10.1002/ente.201700756

FULL PAPER

The crystal structures and morphologies of the as-prepared samples H. Park, K. H. Lee, Y. S. Kang, J. H. Park, H. Jung, W. R. Yu, S. G. Doo,
were studied by using X-ray diffraction (XRD, Rigaku Co., Tokyo, ACS Nano. 2016, 10, 2617-2627.
[15] K. I. Park, S. B. Bae, S. H. Yang, H. I. Lee, K. Lee, S. J. Lee, Nanoscale.
Japan) techniques and scanning electron microscopy (SEM, SU-3500,
2014, 6, 8962-8968.
Hitachi, Japan). The performance of composite thin films was analyzed [16] Y. L. Zhao, Q. L. Liao, G. J. Zhang, Z. Zhang, Q. J. Liang, X. Q. Liao, Y.
by using LCR tester (E4980AL, Agilent, USA) and ferroelectric Zhang, Nano Energy. 2015, 11, 719-727.
analyzer (TF-1000, aixACCT, Germany). BaTiO3/PDMS/C composite [17] X. L. Chen, J. Y Shao, N. L. An, X. M. Li, H. M. Tian, C, Xua, Y. C. Ding, J.
films was polarized at 80 °C in silicon oil under 30 kV/mm for 2 h Mater. Chem. C, 2015, 3, 11806.
(High voltage polarization device, ET2673D-4, Entai Co., China). The [18] S. Y. Xu, Y. W. Yeh, G. Poirier, M. C. McAlpine, R. A. Register, N. Yao,
output voltage and current from the BaTiO3/PDMS/C composite thin Nano Lett. 2013, 13, 2393-2398.
[19] Z. H. Lin, Y. Yang, J. M. Wu, Y. Liu, F. Zhang, Z. L. Wang, J. Phys. Chem.
films were measured by a digital oscilloscope (33522A, Agilent, USA)
Lett. 2012, 3, 3599-3604.
and a source measurement unit (2400 SMU, Keithley, USA), [20] S. Siddiquia, D. I. Kima, L. T. Duya, M. T. Nguyena, S. Muhammadb, W.
respectively (The detailed testing process is described in the Fig. S1). S. Yoonb, N. E. Lee, Nano Energy. 2015, 15, 177-185.
The beating for PNGs was provided by a shaker (ESS-025, Dongling [21] X. L Chen, X. M. Li, J. Y. Shao, N. L. An, H. M. Tian, C. Wang, T. Y. Han,

Accepted Manuscript
vibration test instrument Co., Ltd., China). L. Wang, B.H. Lu, Small. 2017, 13, 1604245.
[22] X. L. Chen, H. M. Tian, X. M. Li, J. Y. Shao, Y. C. Ding, N. L. An, Y. P.
Zhou, Nanoscale. 2015, 7, 11536.
[23] M. Lee, C.Y. Chen, S. Wang, S. N. Cha, Y. J. Park, J. M. Kim, L. J. Chou,
Acknowledgements Z. L. Wang, Adv. Mater. 2012, 24, 1759-1764.
[24] M. Zhang, T. Gao, J. S. Wang, J. J. Liao, Y. Q. Qiu, H. Xue, Z. Shi, Z. X.
This work was supported by National Natural Science Foundation of Xiong, L. F. Chen, Nano Energy. 2015, 11, 510-517.
China (Grant Nos. 51205276 and 61474079), China Postdoctoral [25] R. Ding, X. L. Zhang, G. Chen, H. L. Wang, R. Kishorb, J. X. Xiao, F. Gao,
K. Y Zeng, X. D. Chen, X. W. Sun, Y. J. Zheng, Nano Energy. 2017, 37,
Science Foundation (Grant No. 2013T60268), Science and Technology
126-135.
Major Project of the Shanxi Science and Technology Department
[26] U. Aqoob, A.S.M. I. ddin, G. S. Chung, Appl. Surf. Sci. 2017, 405, 420-
(Grant No. 20121101004), Shanxi Province Science Foundation (Grant 426.
Nos. 2015021092 and 2016011039), Special talents in Shanxi Province [27] X. Chen, S. Y. Xu, N. Yao, Y. Shi, Nano Lett. 2010, 10, 2133-2137.
(Grant No. 201605D211020), Scientifc & Technological Innovation [28] K. N. Kima, J. Chuna, S. A. Chaeb, C. W. Ahnb, I. W. Kimb, S. W. Kimc,
Programs of Higher Education Institutions in Shanxi (Grant No. Z. L. Wang, J. M. Baik, Nano Energy. 2015, 14, 87-94.
2016136), Graduate Student Education Innovation Project in Shanxi [29] S. H. Shin, Y. H. Kim, M. H. Lee, J.Y. Jung, J. Nah, ACS Nano. 2014, 8,
2766-2773.
(Grant No. 2017BY049 and 2017SY021) and China Scholarship
[30] K. I. Park, M. Lee, Y. Liu, S. Moon, G. T. Hwang, G. Zhu, J. E. Kim, S. O.
Council (CSC) (Grant No. 201706930003) .
Kim, D. K. Kim, Z. L. Wang, K. J. Lee, Adv. Mater. 2012, 24, 2999-3004.
[31] Y. Jin, N. Xia, R. A. Gerhardt, Nano Energy. 2016, 30, 407-416.
Keywords: piezoelectric nanogenerator; lead-free; BaTiO3/PDMS/C [32] C.Y. Li, E. T. Thostenson, T. W. Chou, Compos. Sci. Technol. 2008, 68
composite; energy harvesting 1227-1249.
[33] C. Seoul, Y. T. Kim, C. K. Baek, J. Polym. Sci. Pol. Chem. 2003, 41,
1572-1577.
[34] Y. M. You, W. Q. Liao, D. W. Zhao, H. Y. Ye, Y. Zhang,Q. H. Zhou, X. H.
References Niu, J. L. Wang, P. F. Li,D. W. Fu, Z. M. Wang, S. Gao, K. L. Yang, J. M.
Liu, J. Y. Li, Y. F. Yan,R. G. Xiong, Science. 2017, 357, 306-309.
[1] S. H. Shin, Y. H. Kim, M. H. Lee, J. Y. Jung, J. H. Seol, J. Nah, ACS [35] A. L. Kholkin, N. A. Pertsev, A.V. Goltsev, Springer US, 2008, 17-38.
Nano. 2014, 8, 10844-10850. [36] J. L. Zhang, P. F. Ji, Y. Q. Wu, X. Zhao, Y. Q. Tan, C. L. Wang, Appl. Phys.
[2] X. D. Wang, J. H. Song, J. Liu, Z. L. Wang, Science. 2007, 316, 102-105. Lett. 2014, 104, 222909.
[3] K. I. Park, J. H. Son, G. T. Hwang, C. K. Jeong, J. Ryu, M. Koo, I. Choi, S. [37] G. H. Haertling, J. Am. Ceram. Soc. 1999, 82, 797.
H. Lee, M. Byun, Z. L. Wang, K. J. Lee, Adv. Mater. 2014, 26, 2514-2520. [38] S. Barrau, P. Demont, A. Peigney, C. Laurent, C. Lacabanne,
[4] Y. Qin, X. D. Wang, Z. L. Wang, Nature. 2008, 451, 809-813. Macromolecules, 2003, 36, 5187-5194.
[5] Y. Chena, Y. Zhanga, L. Zhang, F. Ding, O. G. Schmidt, Nano Energy. [39] A. K. Jonscher, Nature, 1977, 267, 673-679.
2017, 31, 239-246. [40] S. H. Hu, C. X. Luo, P. W. Li, J. Hu, G. Li, H. B. Jiang, W. D. Zhang, J.
[6] R. Dinga, X. Zhang, G. Chen, H. Wang, R. Kishorb, J. Xiao, F. Gao, K. Mater. Sci: Mater. Electron. 2017, 28, 9322-9327.
Zeng, X. Chen, X. W. Sune, Y. Zheng, Nano Energy. 2017, 37, 126-135. [41] J. Yan, Y. G. Jeong, Compos. Sci. Technol. 2017, 144, 1-10.
[7] J. H. Song, J. Zhou, Z. L. Wang, Nano Lett. 2006, 6, 1656-1662.
[8] K. I. Park, S. Xu, Y. Liu, G. T. Hwang, S. J. L. Kang, Z. L. Wang, K. J. Lee,
Nano Lett. 2010, 10, 4939-4943.
[9] G. Zhu, R. S. Yang, S. H.Wang, Z. L. Wang, Nano Lett. 2010, 10, 3151-
3155.
[10] W. L. Deng, B.B. Zhang, L. Jin, Y. Q. Chen, W. J. Chu, H. T. Zhang, M.
H. Zhu, W. Q. Yang, Nanotechnology. 2017, 28, 135401.
[11] F. R. Fan, W.Tang, Z. L. Wang, Advanced Materials. 2016, 28, 4283-
4305.
[12] C. K. Jeong, I. Kim, K. I. Park, M. H. Oh, H. Paik, G. T. Hwang, K. No, Y.
S. Nam, K. J. Lee, ACS Nano. 2013, 7, 11016-11025.
[13] J. Yan, Y. G. Jeong, ACS Appl. Mater. Inter. 2016, 8, 15700-15709.
[14] B. S. Lee, J. Yoon, C. Jung, D. Y. Kim, S. Y. Jeon, K. H. Kim, J. H. Park,

This article is protected by copyright. All rights reserved.

Energy Technology 10.1002/ente.201700756

FULL PAPER

Accepted Manuscript

This article is protected by copyright. All rights reserved.