Accepted Manuscript

Full Length Article

Enhanced piezoelectric output of the PVDF-TrFE/ZnO flexible piezoelectric

nanogenerator by surface modification

Jie Li, Chunmao Zhao, Kai Xia, Xi Liu, Dong Li, Jing Han

PII: S0169-4332(18)32410-3
DOI: https://doi.org/10.1016/j.apsusc.2018.08.266
Reference: APSUSC 40303

To appear in: Applied Surface Science

Received Date: 29 May 2018

Revised Date: 4 August 2018
Accepted Date: 31 August 2018

Please cite this article as: J. Li, C. Zhao, K. Xia, X. Liu, D. Li, J. Han, Enhanced piezoelectric output of the PVDF-
TrFE/ZnO flexible piezoelectric nanogenerator by surface modification, Applied Surface Science (2018), doi:
https://doi.org/10.1016/j.apsusc.2018.08.266

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 Enhanced piezoelectric output of the PVDF-TrFE/ZnO flexible
piezoelectric nanogenerator by surface modification

Jie Lia, 1, *, Chunmao Zhaoa, 1, Kai Xiaa, Xi Liua, Dong Lib, Jing Hanb

a School of Materials Science and Engineering, North University of China, Taiyuan 030051, China

b School of Mechatronic Engineering, North University of China, Taiyuan 030051, China

Declarations of interest: none

*
Corresponding author. Tel.: +86-0351-3559885.

E-mail address: ajiestar@nuc.edu.cn (Jie Li)

1
Contributed equally and should be treated as the co-first author.

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Abstract: In this paper, ZnO nano-particles (NPs) were modified by adding a dispersant
(n-propylamine, PA) and a silane coupling agent (1H, 2H, 1H, 2H, Perfluorooctyltriethylsilane,
PFOES) simultaneously. Further, the PVDF-TrFE/modified ZnO composite films with high
crystallinity and large specific surface area were prepared, which acted as the active layer of the
piezoelectric nanogenerator (PENG). Four species of films, pure PVDF-TrFE, PVDF-TrFE/ZnO,
PVDF-TrFE/ZnO@PA and PVDF-TrFE/ZnO@PA@PFOES were marked P-0-0-0, P-Z-0-0,
P-Z-P-0 and P-Z-P-P, respectively. The crystalline phases of the films were determined by Fourier
infrared spectroscopy (FT-IR) and wide-angle X-ray diffraction (WXRD). Scanning electron
microscope (SEM), Laser scanning confocal microscope (LSCM), Atomic force microscope (AFM)
and water contact angle (WCA) measurements were employed to analyze the surface morphology
of the films. The thermal properties of the materials were characterized with a differential scanning
calorimeter (DSC). From the FTIR spectra and WXRD pattern, it was notable that the modified ZnO
NPs promoted the crystallization of β-phase. The results showed that the crystallinity of P-Z-P-P
was increased by 36.12% compared to P-0-0-0. Combined with the results of SEM, LSCM and
AFM, it can be concluded from WCA that modified ZnO NPs can increase the specific surface area
of the film. The piezoelectric strain constant d33 value of P-Z-P-P film was 73.5% higher than that
of P-0-0-0 film, and the output voltage value of ITO/P-Z-P-P/Au PENG increased 24.4% than that
of ITO/P-0-0-0/Au PENG. After 1000 cycles of testing, the output voltage of the ITO/P-Z-P-P/Au
PENG has been maintained at 2.40 V, indicating that the generator exhibited the high mechanical
endurance. By clarifying the mechanism of surface modification, it can be concluded that enhanced
piezoelectric output of the PENG is contributed to both higher β-phase content and larger charge
collecting area by surface modification.

Keywords: PVDF-TrFE, Nano-ZnO, Surface modification, Perfluorooctyltriethylsilane,

n-Propylamine

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1. Introduction

In 1969, Japanese scholar Kawai [1] for the first time reported a strongly piezoelectric activity
of ferroelectric polymer Polyvinylidene fluoride (PVDF). PVDF, a semi-crystalline polymer, is
widely used in many applications such as electro acoustic transducer, pressure sensor and
ferroelectric random access memory etc [2, 3]. There are five crystal forms of PVDF, which called
α-, β-, γ-, δ- and ε-phases [4]. The most common α-phase is non-polar, while the γ- and δ-phase are
weakly polar. Strongly polar β-phase displays the best piezoelectric and ferroelectric properties, as a
result that PVDF with high β-phase content is the most broadly used piezoelectric polymer in many
flexible electromechanical systems [5]. Therefore, PVDF will exhibit superior piezoelectric
performance when the content of β-phase is relatively high [6, 7]. Studies have shown that the
addition of Trifluoroethyline (TrFE) in PVDF can promote the formation of β-phase due to the
steric hindrance effect. What's more worth mentioning is that β-phase is formed mainly when
PVDF-TrFE is under various molding processes. Based on the characteristic, PVDF-TrFE has been
paid attention by many researchers, and the range of applications has been expanded [8-11].
Recently, ZnO-based nano-particles (NPs) have been regarded as a next-generation
piezoelectric material due to their inherent piezoelectricity [12]. A potential method for improving
piezoelectric performance is to introduce nano-ZnO into composites. In fact, ZnO has already been
added to PVDF [13, 14], PVDF-TrFE [15] and PSS/PVA [16] polymer matrices for enhancing
piezoelectricity. M.S.S. Bafqi et al.[10] prepared the PVDF/ZnO composite using electrospinning
technique in order to have the benefit of piezoelectric properties and the electrical output of
composite samples was improved as high as 1.1 V compared with 0.351 V for the pure PVDF
samples. Compared with ordinary ZnO, nano-ZnO has larger specific surface area, so it can produce
many effects such as volume effect and quantum effect etc [17, 18]. ZnO NPs are mainly used as a
nucleating agent and is more conducive to the formation of β-phase after adding nano-ZnO to
PVDF-TrFE. Unfortunately, it is easy for ZnO NPs to aggregate with each other owing to the higher
surface activity and larger surface area. In addition, PVDF-TrFE is usually high-viscosity system in
DMF solution. It causes the poor dispersion of inorganic particles in polymer matrix. Therefore, the
key to prepare PVDF-TrFE/ZnO composite film is to solve the immiscibility between the polymer

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and ZnO NPs. To the best of our knowledge, the surface modification of ZnO NPs is an effective
strategy to improve the interfacial compatibility between the NPs and the polymer matrix.
The method adopted in this paper is to add a dispersant (n-propylamine, PA) and a silane
coupling agent (1H, 2H, 1H, 2H, Perfluorooctyltriethylsilane, PFOES) to nano-ZnO system at the
same time, and the ZnO NPs are surface-treated by the synergistic modification of two agents. The
addition of PA is a non-reactive treatment that can reduce the surface energy of the NPs and
improve the dispersion of the particles, while it does not improve the interfacial binding between
the particles and matrix. PFOES can interact with the NPs to enhance the interfacial bonding
between ZnO and PVDF-TrFE to help ZnO disperse better. Therefore, our goal is to use the
modified PVDF-TrFE/ZnO composite film as an active layer of the simple piezoelectric
nanogenerator (PENG) to obtain the higher piezoelectric output.
Further, the possible mechanism of surface modification was clarified. Modified nano-ZnO has
a smaller dispersed particle size. Adding the modified ZnO NPs in the PVDF-TrFE matrix not only
facilitates the crystallization of the composite film, but also contributes to increasing the specific
surface area of the composite film [17, 19-21]. Larger charge collecting area and higher β-phase
content can be employed to enhance the PVDF-TrFE piezoelectric output. Fig.1a is a schematic
view of a sandwich-type flexible PENG. When pressure is applied to the generator, it can be
converted into electrical signals. The PENGs we prepared can collect the energy generated by the
human body during exercise and convert it into electrical energy to charge the electronic devices.
They are potential candidates for the wearable flexible electronic applications.

2. Experimental

2.1. Materials

PVDF-TrFE of composition 80/20 mol% was purchased from Beijing Aipu slong Technology
Co., Ltd. The average molecular weight of PVDF-TrFE was 300,000. ZnO NPs (the particle size =
30±10 nm, Mw = 81.37) were purchased from Aladdin Industrial Corporation. PFOES
(C14H19F13O3Si, Mw = 510.36) was obtained from Beijing bailingwei Technology Co., Ltd.PA
(CH3CH2CH2NH2, Mw = 59.11) was supplied from Aladdin Industrial Corporation. The flexible
substrate Indium tin oxide-Polyethylene naphthalate (ITO-PEN) was obtained from Southern China
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Xiangcheng Technology Co., Ltd., Shenzhen. The square resistance and thickness of ITO are 6-8 Ω
and 0.125 mm, respectively.

2.2. Preparation of ZnO@PA@PFOES NPs

0.3 g nano-ZnO was dissolved with 10ml acetone, following PA and PFOES added to the
solution. The dosages of PA and PFOES were 4 wt% and 1 wt% of nano-ZnO, respectively. At room
temperature, the uniform nano-ZnO solution was obtained by ultrasonic mixing (Ultrasonic
Cleaners, KQ-50B). Ultrasound produces huge shock waves and micro jets near the surface of
particles, which could weaken the surface energy of these particles and prevent particles form
agglomeration effectively.

2.3. Preparation of PVDF-TrFE/modified ZnO composite films

3 g PVDF-TrFE was dissolved in 10 ml DMF and stirred magnetically (Collecting

Thermostatic Heating Magnetic Stirrers, DF-101S) under ambient temperature for 60 min to obtain
a clear and homogenous solution. The ZnO NPs dispersion was injected into the PVDF-TrFE
solution. The ZnO content was 10 wt% of PVDF-TrFE. The mixture was stirred magnetically for 60
min and ultrasonically stirred for 30 min to obtain a pale yellow gel. Additionally, it has been found
that shear effect can accelerate crystallization and induce the formation of abundant crystalline
forms simultaneously [22]. Because the spin-coating effect is equivalent to shearing, we use spin
coater (KW-4A) to prepare composite films. The spin-coating parameters were 500 r/min×18 s (low
gear) and 2000 r/min×60 s (high gear), and the number of spin-coating layers was three. Then, the
composite films with ITO-PEN were placed in vacuum oven (-0.09 MPa) and annealed at 140°C for
1 h. At 140°C, the copolymer segments move more easily and promote crystallization. Four kinds
of films, pure PVDF-TrFE, PVDF-TrFE/ZnO, PVDF-TrFE/ZnO@PA and
PVDF-TrFE/ZnO@PA@PFOES, which were prepared under the same preparation conditions, were
marked P-0-0-0, P-Z-0-0, P-Z-P-0 and P-Z-P-P, respectively. As shown in Fig.1b, it could be seen
that the P-Z-P-P film had a very high transparency, providing opportunities for wearable
applications that require transparency. The P-0-0-0, P-Z-0-0 and P-Z-P-0 films were also the
transparent films. The thickness of the P-Z-P-P film was determined from the SEM image of the

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cross-section (Fig.1c), approximately 22 μm.

2.4. Preparation of PENGs

3 μm of gold was sputtered as the upper electrode surface, which resulted in a typical sandwich
structure generator. On the upper and lower electrode surfaces, the pins were staggered, and the
electrodes were pulled out. After packaging, a simple flexible PENG was obtained (Fig.1d). PENGs
that made with four active layers were marked ITO/P-0-0-0/Au PENG, ITO/P-Z-0-0/Au PENG,
ITO/P-Z-P-0/Au PENG, and ITO/P-Z-P-P/Au PENG, respectively. As can be seen from Fig.1e, the
prepared device was particularly flexible.

Fig.1 (a) The structure schematic of the PENG. (b) Image showing the optical transmittance of the P-Z-P-P

composite film. (c) Side-view SEM image of the ITO/P-Z-P-P/Au PENG. (d) Digital image of the

ITO/P-Z-P-P/Au PENG and (e) the flexibility of the ITO/P-Z-P-P/Au PENG.

2.5. Characterization

The crystalline phases of the films were determined by Fourier infrared spectroscopy (FT-IR,
German Bruker-TENSOR27) and Wide-angle X-ray diffraction (WXRD, Diffraction meter
D/max-rB). Scanning electron microscope (SEM, JEM-6510), Laser scanning confocal microscope
(LSCM, LEXTOLS4100) and Atomic force microscope (AFM, Bruker dimension) were used to
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study the surface morphology of the films and analyze the dispersion of ZnO NPs in the composite
films. To complement the SEM, LSCM and AFM datas, the dispersion of nano-ZnO was indirectly
determined using water contact angle (WCA), which was conducted by Contact Angle Meter
(JY-82B) with a 5-μL droplet of distilled water. The average values of WCA were obtained by
measuring the same sample at five different areas at room temperature. The thermal properties of
the materials were characterized with a differential scanning calorimeter (DSC, METTLER
TOLEDO DSC 3). All of the samples were initially heated up to 195°C (kept at this temperature for
5 min) and cooled down to 25°C. The rate was 5 degrees/minute. And then the above process was
repeated once. Both the heating and cooling rates were set to 5°C/min. The ZJ-3AN quasi-static d33
meter (Acoustics Institute, Chinese Academy of Sciences) was used to compare the piezoelectric
constant d33 of the composite films after modification with that of untreated composite films. The
time dependence of output voltage of the PENGs was detected by the KDL-02/02L impact hammer
(5 times per sample) under ambient temperature. Finally, the cantilever beam exciter was used to
test the V-t loops of the devices after 1000 cycles of vibration.

3. Results and discussion

3.1. Crystalline phases of the films

Fig.2a-b illustrated the FT-IR spectra of four kinds of composites films. Particularly, the
vibrational bands such as those occurring at 840 and 880 cm-1 are of more interest. The 840 cm-1
band, which relates to stretching of CF2 and C-C bonds, corresponds to the ferroelectric phase
(β-phase). While the 880 cm-1 band, which could be ascribed to the rocking of C-C skeleton
vibration, corresponds to non-polar α-phase [23]. The content of α-phase and β-phase is usually
determined by the area ratio of 840 cm-1 band and 880 cm-1 band. Evaluation of the electroactive
β-phase content (F(β)) in the samples is executed using Lambert–Beer law,

(1)

Here, Aα and Aβ are the absorbance intensities at 880 cm−1 and 840 cm−1, Kβ = 7.7×104 cm2 mol−1
(the absorption coefficient at 840 cm−1) and Kα = 6.1×104 cm2 mol−1 (the absorption coefficient at
880 cm−1 [24-26]. From Fig.2a, it can be concluded that the evaluation of P-0-0-0 and P-Z-0-0 are
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29.4% and 3.16%, respectively (Fig.2d). In fact, the F(β) of the composite film added with
unmodified ZnO NPs decreased significantly since the added nano-ZnO was agglomerated and did
not function as a nucleating agent. In other words, unmodified ZnO NPs could be viewed as
impurities in films. It was noteworthy that the polar hydroxyl groups (–OH) were introduced after
adding ZnO to the film. The peak at 3400 cm-1 was the characteristic band of the group –OH, as can
be seen from Fig.2a. These hydroxyls groups can make it easier to react chemically with PFOES
and produce physical interactions with PA.
Fig.2b showed the FT-IR spectra of the P-Z-P-0 and P-Z-P-P films. It was obvious that the
band at 3437 cm-1was not a single hydroxyl peak. A fitted band of the hydroxyl band (derived from
ZnO and PFOES) and amino band (derived from PA) can be seen through the data-fitting graph
(Fig.2c). From the calculation, the evaluated F(β) values of P-Z-P-0 and P-Z-P-P were 27.1% and
38.7%, respectively (Fig.2d). After adding PFOES, the intensity of the characteristic band at 3437
cm-1 in the composite film became smaller, while the β-phase content was opposite. It indicated that
there was a dehydration reaction between PFOES and hydroxyl groups on the surface of ZnO and a
part of hydroxyl groups –OH was consumed. On account of the dehydration reaction, ZnO was well
dispersed in the matrix, better acting as a nucleating agent [15].
Fig.2e was the WXRD pattern of the P-0-0-0, P-Z-0-0, P-Z-P-0, P-Z-P-P films. The WXRD
spectrum of pure PVDF-TrFE film consisted of the shoulder peak of polar β-phase at 2θ=19.6° [27].
Unlike to P-0-0-0 film, there were additional diffraction peaks in the WXRD spectra of other
composite films at 2θ=31.9°(100), 34.5°(002) and 36.3°(101), which agreed with the characteristic
peaks of nano-ZnO [28, 29]. Apparently, compared with the pure PVDF-TrFE film, the weakening
of the peak at 2θ=19.6° indicated that unmodified ZnO NPs had the serious agglomeration
phenomenon. When only PA was added to composite film, the β-phase content to some extent
increased and was higher than that of P-Z-0-0. It revealed that the modification of PA played a
certain role in the dispersion of nano-ZnO. The most significant aspect of the WXRD spectrum was
that the P-Z-P-P film had the highest content of β-phase in all of four films, which demonstrated
that the introduction of PA and PFOES promoted the β-phase crystallization of PVDF. Combined
with FT-IR data, it can be confirmed that the use of PA and PFOES as nano-ZnO modifiers achieved
the desired effect in the article.
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Fig.2 (a) FT-IR spectra of the P-0-0-0 and P-Z-0-0 films (room-in view of FT-IR spectra from 1000 cm-1 to 700

cm-1). (b) FT-IR spectra of the P-Z-P-0 and P-Z-P-P films (room-in view of FT-IR spectra from 1000 cm-1 to 700

cm-1). (c) Fitting diagram of the peak at 3437 cm-1 in the figure 2(b). (d) The evaluation F(β) of the P-0-0-0,

P-Z-0-0, P-Z-P-0, P-Z-P-P films, respectively. (e) WXRD patterns of the P-0-0-0, P-Z-0-0, P-Z-P-0, P-Z-P-P films,

respectively. (f) The WCA of the above four films.

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3.2. Morphology and WAC of the films

The SEM, LSCM and AFM images (Fig.3) more intuitively exhibited the effect of surface
modification by PA and PFOES on ZnO NPs. It can be seen from the SEM images that the films
prepared by the spin-coating method were of a dense type, which was also verified by combining
the sectional views of the P-Z-P-P film (Fig.1c). As shown in the SEM and LSCM images,
aggregated ZnO NPs in PVDF-TrFE (Fig.3b) were easily observed and the cluster size of
unmodified ZnO was about 700 nm. After the modification of ZnO NPs by PA, the agglomeration
of ZnO NPs in the film was significantly weakened (Fig.3c). The ZnO NPs treated by PA and
PFOES were more uniformly dispersed in the film (Fig.3d) and had a particle size of approximately
200 nm. The surface roughness values (Ra) of the four films obtained by AFM were 20.9 nm, 27.6
nm, 28.2 nm and 38.6 nm, respectively. It could be concluded that uniformly dispersed ZnO
increased the surface roughness of the P-Z-P-P film. Thus, a larger charge collection area was
obtained.

Fig.3 SEM, LSCM and AFM images (top-down) of the P-0-0-0(a), P-Z-0-0(b), P-Z-P-0 (c), P-Z-P-P (d) films,

respectively.

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 Further, the dispersion of nano-ZnO was indirectly determined using WCA measurements.
Before the experiments, the samples needed to be washed and dried several times to keep the
surface clean and smooth. Fig.2f was the graph of water contact angles of these films. The WCA of
pure PVDF-TrFE film was 75.67°, which could be attributed to the compactness of the surface
structure of the film prepared in this paper (the SEM image in Fig.3a). The WCA of three other
PVDF-TrFE/ZnO composite films increased from 82.18° to 110.49°, because the specific surface
area of the film increased after adding ZnO NPs. Combined with the results of SEM, LSCM and
AFM it can be concluded from Fig.2f that the agglomeration of ZnO@PA@PFOES NPs in the
matrix were significantly reduced compared to the unmodified ZnO. On the surface of the film, the
uniformly dispersed particles caused the increased specific surface area of the film. Therefore, the
P-Z-P-P film had the largest WCA value among the three composite films [30-39].

3.3. Thermal analysis of the samples

For the most part, the crystallization behaviors of PVDF-TrFE were affected after the addition
of ZnO NPs. The melting behavior (a) and crystallization behavior (b) of the four samples were
shown in Fig.4. The second heating curves were displayed in Fig.4a. There were both peaks
appeared in the melting process of the four samples. One peak at 92.82 ± 0.96°C originated from
the ferroelectric to paraelectric phase transition (Curie transition), and another peak at 152.45 ±
1.04°C was caused by the existence of PVDF-TrFE crystalline phases [40]. The specific melting
temperature (Tm) and the melting enthalpy (ΔHm) were displayed in Table 1. The crystallinity (Xc)
has been calculated according to equation, Xc=ΔHm/ΔH100%, (where, ΔH100%=38 J/g, the melting
enthalpy of 100% crystalline PVDF-TrFE) [40-43]. By calculation, the crystallinity of the P-0-0-0,
P-Z-0-0, P-Z-P-0, and P-Z-P-P samples was 54.76%, 47.73%, 61.63% and 74.55%, respectively.
The crystallinity of the P-Z-0-0 sample was reduced compared to the P-0-0-0 sample because ZnO
acts as impurity in the sample. The crystallinity of the P-Z-P-0 sample obtained by modifying of
ZnO with PA increased to 61.63%. After PA and PFOES treated ZnO NPs, the crystallinity of the
P-Z-P-P sample reached 74.55%.

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 Fig.4 The melting (a) and cooling (b) curves of the above four samples.

Fig.4b showed the crystallization behaviors of the samples after second heating, which can be
seen four samples possessed two peaks at 129.65 ± 1.45°C and 87.96 ± 0.56°C, resulting from the
crystallization and the paraelectric to ferroelectric phase transition, respectively. As can be seen
from Table 1, compared with P-0-0-0, these values of Tm, Tc, and Xc of P-Z-P-P increased by 1.67°,
1.95°C and 36.12%, respectively. The above results, correlated with both crystallization and
morphological studies, strongly demonstrated the surface modification method for nano-ZnO by
adding PA and PFOES in the study was very effective. This was of great help to the piezoelectric
output of the flexible PVDF-TrFE/ZnO PENG.
Table 1 Melting and crystallization behavior parameters of the samples

Sample Tm (℃) Tc (℃) ΔHm(J/g) Xc (%)

P-0-0-0 151.82 129.15 20.81 54.76

P-Z-0-0 151.41 128.19 18.14 47.73

P-Z-P-0 152.66 130.33 23.42 61.63

P-Z-P-P 153.49 131.10 28.33 74.55

3.4. Piezoelectric strain constants of composite films and piezoelectric output of PENGs

The d33 values of the four prepared films were measured with a ZJ-3AN quasi-static d33 meter.
The average d33 value of each film was listed in Table 2, and its corresponding change curve could
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be observed from Fig.5a. These ZnO@PA@PFOES particles were uniformly dispersed in the
PVDF-TrFE matrix and acted as a heterogeneous nucleating agent, greatly improving the
crystallinity of PVDF-TrFE. The average d33 value of P-Z-P-P film was ~34.7 pC/N, which was
improved by 73.5% in comparison with that of pure PVDF-TrFE film (~20.0 pC/N).
Table 2 The piezoelectric strain constant of the films

Sample d33 (pC/N)

P-0-0-0 20.0 ± 2.7

P-Z-0-0 14.8 ± 1.9

P-Z-P-0 25.3 ± 1.9

P-Z-P-P 34.7± 2.4

Fig.5 (a) The piezoelectric strain constant d33 of the P-0-0-0, P-Z-0-0, P-Z-P-0, P-Z-P-P films, respectively. (b)

Time-dependent open-circuit voltage of the ITO/P-0-0-0/Au, ITO/P-Z-0-0/Au, ITO/P-Z-P-0/Au, ITO/P-Z-P-P/Au

PENGs, respectively. (c) Magnified view of the open-circuit voltage output signals (highlighted red in (b)). (d)

The piezoelectric output average value of PENGs. (e) Open-circuit voltage of the ITO/P-Z-P-P/Au PENG loading

during stability testing. (f) Magnified view of the open-circuit voltage output signals (highlighted red in (e)).

Fig.5b-f was the time dependence of output voltage of the PENGs. Above all, Fig.5b-c were

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V-t curves measured by a KDL-02/02L impact hammer striking a flexible generator. The pressure of
each tap was a fixed value, and the sensitivity was 4 pC/mV. Fig.5c was the magnified view of the
open-circuit voltage output signals (highlighted red in Fig.5b), which showed a single signal of the
compressing and releasing process after the impact hammer striking the PENG. The average values
of the output voltages of the ITO/P-0-0-0/Au PENG, ITO/P-Z-0-0/Au PENG, ITO/P-Z-P-0/Au
PENG and ITO/P-Z-P-P/Au PENG was 2.13V, 2.07V, 2.30V and 2.65V, respectively (Fig.5d). The
average value of the output voltage of the ITO/P-Z-P-P/Au PENG was 24.4% higher than that of
the ITO/P-0-0-0/Au PENG. Also, Table 3 summarized the d33 values and peak voltage of
PVDF-based nano-generators in our study and other reports. It can be seen that surface modification
of ZnO NPs by PA and PFOES was beneficial to the piezoelectric output of the PENG.
Finally, the anti-fatigue test of the ITO/P-Z-P-P/Au PENG was performed by means of an Izod
exciter. After 1000 cycles, the output voltage of the flexible generator remained at 2.40 V (Fig.5e-f).
The stable voltage output suggested that this flexible PENG had high mechanical fatigue resistance,
which can expand its application range and service life.
Table 3 Summary of PVDF-based nano-generators in our study and other reported studies.

Active material Modification Form d33(pC/N) Peak Voltage (V) Ref.

PVDF —— Thin film 2 [44]

PVDF/graphene PFOES Thin film 39.8 [3]

PVDF-TrFE —— Thin film 4 [45]

PVDF-TrFE —— Nanowires 0.4 [46]

PVDF/PVDF-TrFE —— Thin film 27.3 [11]

PVDF-TrFE/AgNPs —— Thin film 0.02 [47]

PVDF-TrFE/AgNWs —— Thin film 0.06 [47]

PVDF-TrFE/BaTiO3 —— Nanofibers 5 [48]

PVDF-TrFE/BaTiO3 (3-aminopropyl)triethoxysilane Nanofibers 1.1 [10]

PVDF-TrFE/ZnO —— Thin film 19 [17]

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 PVDF-TrFE/ZnO organo-silane coated Thin film 19 [17]

PVDF-TrFE/ZnO acetylacetonate Thin film 20 [17]

PVDF-TrFE/ZnO PA/PFOES Thin film 34.7 2.65

3.5.Possible mechanism of surface modification

In this article, we mainly investigated the synergistic effect between PFOES and PA to enhance
the dispersion of ZnO NPs in the matrix. Through the comparison of the microscopic and
macroscopic properties at the front, it can be concluded that the agglomeration of ZnO NPs
modified by PFOES and PA in the matrix PVDF-TrFE had been improved. The possible
modification mechanism was shown in the Scheme.1, which illustrated the reaction among ZnO,
PA and PFOES during modification. The intermolecular forces between amino group of PA and
hydroxyl on the surface of nano-ZnO played an important role in the dispersion of nano-ZnO
(Scheme.1a). Scheme.1b was the two-step hydrolysis process of PFOES. The hydrolyzed PFOES
covalently interacted with ZnO@PA and underwent the dehydration reaction (Scheme.1c).
Unmodified ZnO NPs were easy to aggregate due to the higher surface activity and larger surface
area. After adding the modified ZnO@PA@PFOES NPs to the polymer PVDF-TrFE matrix, there
were the intermolecular forces (hydrogen bonds or van der Waals forces) between the perfluorinated
segments in PFOES and the PVDF-TrFE segments, which was easier to the dispersion of ZnO in
the matrix [3, 30, 49].

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 Scheme.1 Illustration of the reaction among ZnO, PA and PFOES

Larger charge collecting area and higher β-phase content can be employed to enhance the
PVDF-TrFE piezoelectric output. The crystallinity of the films was confirmed by FT-IR, XRD, and
DSC measurements, which indicated that P-Z-P-P film maintained high crystallinity. Through SEM
and WCA testing, it brought to light a conclusion that the modified ZnO NPs remained smaller size
and were uniformly dispersed in the matrix. As a result, a composite film having larger specific
surface area was obtained. When strain was applied to the film, the electric charges were generated,
which generated a potential difference across the piezoelectric film [15, 44]. Based on the pure
PVDF-TrFE film with a small specific surface area, the potential difference of P-0-0-0 film was also
relatively low. Although the addition of non-modified NPs increased the surface roughness of the
film, ZnO acted as an impurity in the film, resulting in a decrease in the crystallinity of the film.
With regard to the influence of the piezoelectric output, low crystallinity became the dominant
factor. Therefore, its piezoelectric output was decreased relative to pure film. The
ZnO@PA@PFOES NPs can result in higher β-phase content and larger charge collection area.
These two predominant conditions leaded to an increase in the potential difference of the film,

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thereby enhancing the piezoelectric output (Scheme.2). This was consistent with the previous
piezoelectric output test results.

Scheme.2 Schematic diagram of charge accumulation on the surface of P-0-0-0, P-Z-0-0 and P-Z-P-P films.

4. Conclusions

Our goal is to obtain the good dispersion of nano-ZnO in the PVDF-TrFE by using PA and
PFOES as the modifiers simultaneously. It was worth noting that evenly dispersed ZnO can increase
the specific surface area of the film and β-phase content of PVDF-TrFE, which was beneficial to the
piezoelectric output of the PENG. Pure PVDF-TrFE and PVDF-TrFE/ZnO composite films were
prepared by a simple and effective spin coating method. From the FT-IR diagram, it can be
concluded that the nano-ZnO surface has a large amount of hydroxyl. These functional hydroxyls
groups can react chemically with PFOTS and produce physical interactions with PA. Other result
from FT-IR was that ZnO@PA@PFOES NPs promoted the crystallization of β-phase of
PVDF-TrFE, which agreed with WXRD pattern. From the heating curves of the samples, the
crystallinity of P-Z-P-P was increased by 36.12% compared to P-0-0-0. Combined with the results
of SEM, LSCM and AFM, it can be concluded from WCA that modified ZnO NPs can increase the
specific surface area of the film. The average d33 value of P-Z-P-P film was ~34.7 pC/N, which was

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improved by 73.5% in comparison with that of pure PVDF-TrFE film (~20.0 pC/N). The average
value of the output voltage of the ITO/P-Z-P-P/Au PENG was 2.65 V, which was 24.4% higher than
that of the ITO/P-0-0-0/Au PENG (2.13 V). After 1000 cycles of testing, the output voltage of the
self-made simple ITO/P-Z-P-P/Au PENG had been maintained at 2.40 V, indicating that the
generator exhibited the high mechanical endurance and provided a potential possibility in flexible,
smart devices.

Acknowledgments

This work was supported by International Scientific and Technological Cooperation Project of
Shanxi Province (grant number 201703D421007); Science and Technology Project of Shanxi
Province (grant number 2015031007-4); Scientific Research Project of North University of China
(grant number 2017010); and Undergraduate Innovation and Entrepreneurship Training Project of
North University of China.

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Highlights:
1. PA and PFOES were introduced for the modification of nano-ZnO simultaneously.
2. The dispersion of ZnO@PA@PFOES in PVDF-TrFE was improved compared to pristine ZnO.
3. ZnO@PA@PFOES can increase the specific surface area and β-phase content of films.
4. The modified ZnO was beneficial to the piezoelectric outputs of the PENG.

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