Current Applied Physics 32 (2021) 50–58

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Current Applied Physics

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

A flexible piezoelectric-triboelectric hybrid nanogenerator in one structure

with dual doping enhancement effects
Xiude Yang a, b, Ping Li a, b, Bo Wu a, b, Hongwei Li a, Guangdong Zhou c, *
a
School of Physics and Electronic Science, Zunyi Normal College, Zunyi, 563002, China
b
Guizhou Key Laboratory for Advanced Materials and Technologies of Clean Energy, Zunyi, 563002, China
c
School of Materials and Energy, Southwest University, Chongqing, 400715, China

A R T I C L E I N F O A B S T R A C T

Keywords: For achieving more effective mechanical energy conversion, based on low-cost and flexible polydimethylsiloxane
Piezoelectric-triboelectric (PDMS) and polyvinylidene fluoride (PVDF) polymer film as triboelectric and piezoelectric function layer
Hybrid nanogenerator respectively, a polymer-based hybrid piezoelectric-triboelectric nanogenerator (PT-NG) with a structure of Al/
PDMS
PVDF/Cu-PDMS/indium tin oxide (ITO)/polyethylene terephthalate (PET) has been demonstrated. The device
PVDF
has realized the simultaneous triboelectric and piezoelectric conversions in one structure. In addition, when
PDMS and PVDF are further modified by graphene quantum dot (GQD) and titanium dioxide (TiO2) nano­
particles respectively, both triboelectric and piezoelectric outputs of the modified device are greatly enhanced
synchronously. The experimental results have indicated that the increase of triboelectric output is due to the
improvement of dielectric properties of PDMS film doped with conductive GQDs as well as the enhancement of
the effective contact caused by the change of PDMS surface microstructure. While the promotion of piezoelectric
output is mainly attributed to the fact that PVDF film after TiO2 modification induces more polarized β phase
with a polarization-free process. Accordingly, the modified device converts mechanical energy into electricity
more effectively, which shows a promising prospect in the fields of flexibility display, electronic skin, wearable
electronic products and self-powered sensors.

1. Introduction
As the rapid development of the big data and the internet of things
(IOTs), traditional batteries, such as the nickel metal hydride battery
and lithium battery are no longer suitable to drive the worldwide sensor
network that will emerge in near future. So, it is very urgent to develop a
widely distributed mobile micro/nano energy. Triboelectric nano­
generator (TNG) can use triboelectrification effect to convert mechani­
cal energy from external environment (e.g. wind, water, vibrating, etc.)
or organism (e.g. pulse, heartbeat, acoustic wave, etc.) into electricity.
Therefore, it has been considered to be an ideal choice to realize
distributed and self-powered micro/nano energy since invented in 2012.
However, the limited output of a single TNG is a main bottleneck
restricting its practical application. In order to acquire more effective
energy conversion, studies on hybrid TNGs involving multiple mecha­
nisms of energy conversion have attracted much attention recently. As
with the multi-layer design of TNGs, the combination between piezo­
electric and triboelectric effect is also an important way to effectively
convert mechanical energy into electric energy. For this reason, many
recent hybrid PT-NGs have been reported and mostly realized a good
performance [1–6,7,8]. Among these devices, PDMS as triboelectric
layer and PVDF as piezoelectric layer are employed popularly. This is
because that PDMS owns a larger electron affinity and is negatively
charged easily during contact-friction process. Similarly, PVDF has
excellent piezoelectric properties [3,4] and is often used in piezoelectric
nanogenerator (PNG). In addition, both PDMS and PVDF films have the
advantages of good stability, flexibility, transparency, non-toxicity, low
cost and easy preparation.
For further improving the output of hybrid PT-NGs, many composite
methods have been demonstrated on PDMS and PVDF films respectively
by filling a certain amount of functional nanoparticles in their pre­
cursors during preparation process [9–12]. For PDMS, it has been found
that when the carbon nano-materials, such as graphite [12], carbon
nanotubes [4,5] and graphene sheets [11] are added into PDMS elas­
tomer, the dispersed conductive nanoparticles can greatly improve the
dielectric properties of PDMS film, so that the output of device is

* Corresponding author.
E-mail address: zhougd@swu.edu.cn (G. Zhou).

https://doi.org/10.1016/j.cap.2021.09.003
Received 5 May 2021; Received in revised form 13 August 2021; Accepted 2 September 2021
Available online 30 September 2021
1567-1739/© 2021 Korean Physical Society. Published by Elsevier B.V. All rights reserved.
X. Yang et al. Current Applied Physics 32 (2021) 50–58

increased with increase of device capacitance [10–12]. Compared with 2. The preparation of PT-NG
above carbon materials, GQDs not only have the same excellent con­
ductivity, but also better strength, lighter mass and smaller grains. 2.1. Materials
Moreover, GQD in PDMS base has a better dispersion, which is more
beneficial to improve the properties of PDMS films. But, there is no Flexible ITO/PET substrate was bought from Xiangcheng Ltd
relevant report on PDMS modified by GQD for use in TNG. For PVDF (China). Ethanol and acetone cleaning agents were bought from Sichuan
with molecular formula of (C2H2F2)n, there are α, β, γ and δ crystal Chemical Industry Corp (China). PVDF powder, TiO2 with the particle
structures generally [13,14]. Among these structures, the PVDF usually size of ~50 nm and purity of 99.8%, N,N-dimethylformide (DMF) were
obtained after high temperature melting is mostly composed of purchased from Sigma-Aldrich (American). GQD with the transverse
non-polarized α phase; γ phase is required in the application of tran­ size of 5–15 nm, thickness of 1–2 nm and purity of 99.9% was purchased
sistor; only the polarized β phase with full trans-backbone structure, from Shenzhen Nano Technology Ltd (China). PDMS containing curing
where H and F atoms are distributed on both sides of C atoms, is the most agent was bought from Dow Corning (American). Cu tape, Al tape, Cu
useful crystal phase to realize semiconductor energy devices. wire, light emitting diode (LED) and capacitor were commercial prod­
Commonly, for achieving a good piezoelectric behavior of PVDF, ucts from online retail stores.
polarizing sample in an external electric field is an effective approach,
but a high-energy consumption process requiring a high voltage up to
2.2. Device structure and preparation process
~kV magnitude, a high temperature above room temperature and a
certain time. Therefore, to obtain more β phase in PVDF film, many
The preparation of the modified device is identical with the reference
composite methods have been extensively studied without the need of
device except doping procedure. Here, we take the modified PDMS:
the post polarization [15–20]. For example, the synthetic copolymer P
GQD/PVDF:TiO2 device as an example. The whole preparation process
(VDF-TrFE) contains more β phase, and the addition of graphene oxide
is shown in Fig. 1.
[13], carbon nanotubes [14], and ZnO nanoparticles [3] into PVDF
precursor can produce a higher proportion β phase in PVDF. Besides, it
2.2.1. The preparation of PDMS:GQD film
has been reported that by adding TiO2 nanoparticles in PVDF matrix
200 μL toluene was firstly poured into the glass bottle of 10 mg GQD
with the aid of homemade temperature control device [15,21,22], PVDF
for uniform dispersion, subsequently mixed and stirred with 3 g PDMS
films with a higher β phase can also be prepared through spin-coating
elastomer until toluene solvent volatilized completely. Then, 0.3 g
method. However, this method has not been applied to PNG or TNG
curing agent was added into the PDMS base. After degassing, 350 μL
so far.
PDMS precursor was spin-coated on a clean ITO substrate (1.8cm × 1.8
Therefore, with piezoelectric and triboelectric combination, we
cm) at 1000 rpm for 50 s, later placed into a vacuum oven at 80 ◦ C for 2 h
firstly assembled a polymer-based hybrid PT-NG with the structure of
to solidify into a film.
Al/PVDF/Cu-PDMS/ITO/PET, based on low-cost and flexible PDMS and
PVDF polymer film as triboelectric and piezoelectric layer respectively,
2.2.2. The preparation of PVDF:TiO2 film
and realize simultaneous triboelectric and piezoelectric conversions in
At first, 1 g PVDF powder was added to 5 g DMF solvent, then stirred
the same device structure. Further, we modified PDMS by doping GQD
strongly with 0.1 g TiO2 nanoparticles for 6 h until evenly dispersed.
and added TiO2 nanoparticles under room temperature to regulate the
Meanwhile, the cleaned glass (1.8 cm × 1.8 cm) was heated in advance
growth of PVDF crystal, and prepared the modified device consisting of
on a hotplate with temperature of 60 ◦ C, that is the most appropriate
Al/PVDF:TiO2/Cu-PDMS:GQD/ITO/PET. Compared with the reference
temperature to prepare more proportion β phase of PVDF in our
device, the modified device has obtained an obvious dual enhancement
experiment. Secondly, 350 μL DMF solution of PVDF was spin-coated on
effects in triboelectric and piezoelectric output. In this paper, the
above heated glass at 1500 rpm for 35 s, then sintered in a vacuum oven
working process, principle and output enhancement mechanism of PT-
at 120 ◦ C for 4 h to form a compact PVDF:TiO2 film. Lastly, peeling
NG are also discussed in detail.
PVDF:TiO2 film off glass substrate, a very thin Au layer was sprayed on
its front and back surfaces, which is very important to enhance the

Fig. 1. The preparation flowchart of PT-NG.

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X. Yang et al.
electrical contact between the piezoelectric layer and electrodes to
improve the accuracy of experimental results.
2.2.3. Assembly of device
The device consists of two parts: the upper friction layer is PET/ITO/
PDMS:GQD; the lower friction layer is Cu/PVDF:TiO2/Al, that also
contains a PVDF piezoelectric component. The two parts were glued to
the bottoms of two acrylic plates respectively, and then four homoge­
neous springs were installed face to face in the four corners of acrylic
plates. Hereto, the entire assembly process was completed. Under the
trigger of external force, the vibration of springs can make the two
friction layers continuously contact and separate which constitutes a
triboelectric component. In this structure, the triboelectric and piezo­
electric components can work at the same time, thus realizing the syn­
chronous transformations of piezoelectric and triboelectric output with
the same mechanical energy.
2.3. Characterization
The surface morphology of PDMS and PVDF films before and after
modification were observed by SEM (JSM-6510LV). The crystal patterns
of TiO2, PVDF and PVDF:TiO2 films were characterized by XRD (SHI­
MADZU, XRD-7000), and subsequently were further verified with the
FTIR (THERMO NICOLET 6700). The dielectric properties of PDMS and
PDMS:GQD films were tested by using the impedance analyzer (KEY­
SIGHT E4980AL). Electrical output (e.g., the output voltage, current and
power) for both the reference device and the modified device were
measured by using an oscilloscope (Agilent DSO-3102 a) with a total
input impedance of 10 MΩ in series an adjustable resistance box.
Commercial LED and capacitor were used to assess the actual output
capability of device. During the measurement, the acrylic plates at the
top and bottom of device were fixed on the stator and actuator of a linear
motor (WMUA512075-06-D) respectively. For the convenience of
comparison, the vibration amplitude of 3 mm and frequency of 5 Hz
were set under the device operation.
3. Results and discussion
3.1. The working principle of PT-NG
Fig. 2(a) is the schematic diagram of the as-prepared PT-NG, which
works under the contact-separation mode. It can be seen that the device
is integrated into a spring structure, which has shown an excellent
Fig. 2. (a) The schematic diagram of PT-NG; (b)–(e) The working principle of PT-NG in a cycle.
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Current Applied Physics 32 (2021) 50–58
contact/separation synchronism for harvesting mechanical energy [20].
The friction layer located above the spring is both a PNG component and
a friction layer for a TNG component. Below the spring is another fric­
tion layer for TNG component. In working process, the Cu sheet is the
common output electrode of two components, so that triboelectric and
piezoelectric conversion can be realized simultaneously as the spring
vibrates.
Fig. 2(b–e) illustrate the working principle of PT-NG in a cycle. When
four springs are in initial state, no charge is generated on surface of
PDMS and Cu electrode. When the contact-friction occurs under vertical
external force, PDMS surface acquires electrons easy with negative
charges, while Cu surface losses electrons with positive charges. It
should be emphasized that PDMS has so good insulation that the surface
charges can be maintained for a long time. Fig. 2(b) shows that the
spring is completely compressed under external force, and the friction
layers of TNG component are just in the close physical contact. In
addition to triboelectric charges, PNG component is deformed under
pressure and generates negative piezoelectric polarization charges on
the upper surface of PVDF and positive polarization charges on the lower
surface. Due to electrostatic equilibrium, no charge flows between the
electrodes in two components. When the external force is released, the
elastic potential energy stored in the spring will make device return to its
original state. As PVDF layer is affected by the opposite strain when
compressed, the piezoelectric potential between upper and lower sur­
faces is opposite to that shown in Fig. 2(b). As shown in Fig. 2(c),
electrons will be transferred from Al to Cu electrode in PNG component.
At the same time, the Cu foil is separated from PMDS film, and the
change of space electric field causes electrons in TNG component to flow
from ITO to Cu electrode until they recover the original state (Fig. 2(d)).
So, its output current experiences a rapid decrease to 0 after reaching the
peak value. As shown in Fig. 2(e), on the contrary, once compression
force is applied, PNG component returns to the piezoelectric charge
distribution again similar to that shown in Fig. 2(b), thus generating the
piezoelectric output opposite to that released by external force. In
addition, as the two friction layers approach each other, the triboelectric
charges will lead to a decrease of space electric field, which will induce
electrons in the external circuit of TNG to return from Cu to ITO elec­
trode until complete compression.
3.2. The output performance of PT-NG
3.2.1. Output voltage and current
For the reference device and the modified device, the output voltage
X. Yang et al.
Fig. 3. Voc of PT-NGs. (a) Triboelectric output of the reference device; (b) Piezoelectric output of the reference device; (c) Triboelectric output of the modified device;
(d) Piezoelectric outputs of the modified device.
(Fig. 3) and current (Fig. 4) of triboelectric and piezoelectric compo­
nents were obtained. From corresponding insets, it can be seen that
there is an obvious difference between their output waveforms. The
output value of triboelectric part is larger, but the full width at half
maximum (FWHM) is narrower; while the output value of piezoelectric
part is smaller, but the FWHM is larger. This is consistent with the re­
ported literatures [1–4], indicating that the as-prepared device achieves
the conversion of triboelectric and piezoelectric mechanism simulta­
neously in one structure.
For output voltage of triboelectric component as shown in Fig. 3(a)
(c), the peak open-circuit voltage (Voc) of the reference device can be
directly read out to be 52 V. However, the Voc of the modified device is
increased to 105 V with an increase of 102%, indicating that GQD
modification in PDMS plays an effective role in enhancing the tribo­
electric output. For output voltage of piezoelectric component as shown
in Fig. 3(b)(d), we observe that the peak Voc of the reference device is
only 8.7 V, while the Voc of the modified device is increased to 14.3 V
with an increase of 64%, showing that TiO2 modification in PVDF im­
proves the piezoelectric output. Under the frequency of 5 Hz and
amplitude of 3 mm, a stability test for the modified device was carried
out for about 5000 cycles. The Voc values for both triboelectric and
piezoelectric components have no obvious attenuation.
As shown in Fig. 4, compared to the reference device without
modification, the output short circuit current (ISC) of the triboelectric
part for the modified device is increased from 13.9 μA to 18.1 μA;
similarly, ISC of the piezoelectric part is also increased from 3.7 μA to 5.1
μA. In terms the contrast of Voc and Isc, the effectiveness of GQD and
TiO2 double-doped modification on the triboelectric and piezoelectric
output enhancement of the modified device has been confirmed.
3.2.2. Output capacity to load resistance
In addition, we further tested the output capacity of two devices with
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Current Applied Physics 32 (2021) 50–58
different load resistances ranging from 10 kΩ to 100 MΩ, as shown in
Fig. 5. It can be seen that with increase of resistance, both triboelectric
and piezoelectric components show a constant increase in output
voltage, but a constant decrease in output current. We can observe that
the maximum triboelectric peak voltage and current of the reference
device are 54 V and 17.3 μA, respectively. The modified device can reach
88 V and 19.5 μA, respectively, particularly the maximum output power
of triboelectric part is increased from 224.7 μW to 343.5 μW, and the
output power of piezoelectric component also increases from 20.8 μW to
43.2 μW. As compared to the previous ZnO-PVDF/PTFE based hybrid
device reported by N. Khare et al. [3], the triboelectric and piezoelectric
Voc are increased to 1.59 and 1.19 times respectively, especially the
triboelectric power density is 4.2 times greater than the maximum
hybrid output power. Besides, both triboelectric and piezoelectric power
show a higher output than the proposed P(VDF-TrFE)-PDMS/MWCNT
device with the values of 98.568 μW and 9.747 μW respectively by X.
Wang et al. [5]. The above results have shown that adding GQD and TiO2
to PDMS triboelectric film and PVDF piezoelectric film, respectively,
improves the output of triboelectric and piezoelectric conversions,
achieving a commendable performance.
3.2.3. Output capacity to LED and capacitor
Finally, we evaluated the output capability of two devices to com­
mercial LED and capacitor after rectification, which is very necessary to
investigate the practical application potential. As shown in Fig. 6(a–e),
the piezoelectric output of the reference device can lit up 7 white LEDs
(Fig. 6(b)), while the number of LEDs that can be lit by the modified
device is increased to be 9 (Fig. 6(c)). Also, Fig. 6(d)(e) show the situ­
ations that the triboelectric outputs in series 50 LEDs when the reference
device and the modified device are working, respectively. It is observed
that the reference device can only lit up a part of 50 LEDs and the
brightness is weak. However, the modified device can completely lit up
X. Yang et al. Current Applied Physics 32 (2021) 50–58

Fig. 4. Isc of PT-NGs. (a) Triboelectric output of the reference device; (b) Piezoelectric output of the reference device; (c) Triboelectric output of the modified device;
(d) Piezoelectric outputs of the modified device.

Fig. 5. Output of two devices to different load resistance. (a) Triboelectric output of the reference device; (b) The piezoelectric output of the reference device; (c)
Triboelectric output of modified device; (d) Piezoelectric outputs of the modified device.

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Fig. 6. Output capacity to commercial electron components. (a) Output rectification circuit of triboelectric and piezoelectric output of PT-NG; (b) Triboelectric
output of the reference device; (c) The piezoelectric output of the reference device; (d) Triboelectric output of the modified device; (e) Piezoelectric output of the
modified device. (f) Charging test with a capacitor (TNG represents the triboelectric output; PNG represents the piezoelectric output).

the same 50 LEDs and the brightness is very strong. Likewise, the output
of two devices shows the same variation trend when charging a 1 μF
capacitor, as shown in Fig. 6(f). The piezoelectric output of the reference
device makes the voltage of capacitor reach 0.65 V within 50 s, while the
modified device increases to 0.73 V within the same time. Especially,
triboelectric improvement of the modified device is obvious. The
charging voltage of capacitor is greatly increased from 1.2 V to 1.9 V
within 50 s. These results have further confirmed that the dual
enhancement effects of triboelectric and piezoelectric output are real­
ized by the dual doping modifications.
3.3. Output enhancement mechanism of the modified device
3.3.1. Triboelectric part
In order to investigate the source of triboelectric and piezoelectric
output enhancement of the modified device, the properties of PDMS and
PVDF polymer films before and after modification were compared.
Fig. 7(a)(c) are photographs of PDMS and PDMS:GQD films obtained
respectively by spin-coating on ITO/PET substrate. The thickness is
about ~50 μm observed with a high power optical microscope. It can be
seen that the modified PDMS film still maintains a good flexibility.
Moreover, the addition of GQD does not significantly affect its trans­
parency. The SEM images in Fig. 7(b)(d) show that the surface of PDMS
has a zigzag and wrinkled pattern, after adding GQD, the drape pattern
on surface of PDMS basically disappears and micro-nano structure
pattern becomes more refined.
Fig. 8 shows the comparison of dielectric constant and dielectric loss
of PDMS and PDMS:GQD films obtained by impedance analyzer. It is
found that after addition of GQD, the permittivity of PDMS film is
significantly increased, while the dielectric loss is decreased to a certain
extent. It is obvious that doping GQD greatly improves the dielectric
properties of PDMS film, which can be interpreted as follows:
In term of the dielectric percolation theory model of the conductive
particle/polymer matrix composite films, the effective permittivity of
the system can be expressed as [23,24]:

Fig. 7. (a)(c) Photographs of PDMS films before and after adopting GQD, respectively; (b)(d) The SEM images of PDMS film surface before and after adopting GQD,
respectively.

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X. Yang et al.
Fig. 8. Dielectric constant and dielectric loss of PDMS and PDMS:GQD films,
respectively.
( )
ε = εm (pc − p)− β
thisequation should numberas 3− 1 inmanuscript.
(3–4)
Here, εm is the dielectric constant of polymer matrix, p and pc are the
volume fraction and the critical volume fraction (namely, percolation
threshold) of the filler respectively, β is a constant related to the material
properties, microstructure and insulator-conductor interface. Accord­
ingly, under the p≤pc condition, the dielectric constant of PDMS film
increases with increase of GQD filler. Unexpectedly, the dielectric loss of
PDMS films does not undergo an increase due to the uniform distribution
of GQD particles in PDMS substrate without forming circuit channels.
Based on above comparison of surface morphology and dielectric
properties of PDMS films before and after modification, we believe that
the improvement of triboelectric output of the modified device mainly
comes from the following two reasons:
Firstly, after adding GQD to PDMS precursor, the mechanical
dispersion between GQD and PDMS substrate will finally improve the
surface microstructure of PDMS film, thus enhancing the triboelectric
effect.
The second is that the dielectric properties of PDMS polymer sub­
strate are optimized by addition of conductive GQD nanoparticles,
resulting in more polarized tribo-charges on the surface during contact
friction process. This is because that triboelectric output voltage V is
given by the following formula [12]:
( )
σ0 x(t) Q d
V= − + x(t) The number of equation should display as 3 − 2
ε0 Aε0 εr
Where σ0 is friction charge density generated on the surface of PDMS
film, which can be regarded as a constant; ε0 is the vacuum dielectric
permittivity; εr is the relative dielectric constant of PDMS film; Q is the
amount of charge transferred between two electrodes of triboelectric
output in half a cycle; A and d are the surface area and thickness of
PDMS dielectric film, respectively; x is the distance between two friction
layers. In the open circuit condition, there is no charge transfer in the
external circuit, therefore, the Voc can be expressed as [10]:
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Current Applied Physics 32 (2021) 50–58
( )
σ0 x(t)
Voc = This equation should number as 3 − 3 (3-2)
ε0
For contact-separation mode TNG, the friction charge density σ0 is
determined by device capacitance C, which can be obtained from the
following formula [12]:
( )
εr
Cmax = ε0 A⋅ This equation should number as 3 − 4 (3-3)
deff
Where deff is the effective thickness of dielectric PDMS film. The pre­
vious results [9–12] have shown that the εr /deff value of PDMS film is
directly proportional to Voc. When conductive GQD particles are added
to PDMS substrate, on one hand, the dielectric properties of PDMS film
are significantly improved; On the other hand, a large number of
micro-capacitors are formed by GQD particles in PDMS substrate, thus
reducing the effective thickness of PDMS dielectric film. As a result, the
εr /deff ratio of PDMS film increases significantly, leading to an effective
increase in capacitance of device. Therefore, Voc of triboelectric part is
significantly enhanced, which is consistent with previous studies on the
similar TNG devices with PDMS films [9–12].
3.3.2. Piezoelectric part
Likewise, from pictures of PVDF and PVDF:TiO2 films as shown in
Fig. 9(a)(b), addition of TiO2 nanoparticles does not affect the good
flexibility of PVDF film, but the transparency is reduced to some extent.
The thickness is also observed to be ~50 μm. Similar to PDMS film,
PVDF surface has a stripe of folded shape pattern. It is noted that after
adding an appropriate amount of TiO2 nanoparticles, the folded pattern
completely disappears and the surface becomes very flat, meanwhile,
the nano-scale TiO2 particles can be detected and are evenly distributed
in PVDF film generally, as shown in Fig. 9(c)(d).
To verify whether the method of spin-coating/annealing with doping
TiO2 nanoparticles promoted the formation of more β phase in PVDF
film, we used XRD to compare PVDF:TiO2 composite film with PVDF
powder and PVDF film obtained by the same way, as shown in Fig. 10(a).
For PVDF powder, it can be clearly seen that the intensity peaks of 18.3◦ ,
20◦ , 26.6◦ , 33◦ , 36.5◦ and 38.9◦ are all corresponding to the diffraction
characteristic peaks of α phase, indicating that PVDF powder mainly
exists in the stable α phase, which is consistent with previous reports
[13–16]. The PVDF film prepared by dissolving PVDF powder with DMF
solvent shows the β phase diffraction peak at 20.5◦ , but still retains the
characteristic peak of 36.5◦ and 38.9◦ of α phase, indicating that the use
of DMF polar-solvent and spin coating-annealing plays a positive role in
promoting the generation of β phase. For PVDF:TiO2 composite film, it is
found that in addition to the diffraction peak of anatase TiO2 at 25.4◦ ,
38.0◦ and 48.0◦ , the diffraction peaks of α phase of PVDF disappear
completely and the β phase diffraction peak of PVDF at 20.5◦ still re­
( )
(3-1)
tains. Therefore, it could be considered that PVDF is almost presented in
the single β phase, indicating that the intervention of TiO2 further in­
duces the transformation of PVDF crystals from α to β phase.
Previous studies have shown that different crystal structures of PVDF
present different FTIR absorption characteristic peaks [19]. In order to
further verify the promotion effect of DMF solvent and TiO2 nano­
particle on polarization β phase of PVDF film, we tested the FTIR ab­
sorption spectra of PVDF film obtained under the above conditions, as
shown in Fig. 10(b). For PVDF powder, the absorption peaks at 762
cm− 1, 795 cm− 1, 854 cm− 1, 975 cm− 1 and 1210 cm− 1 of wave numbers
X. Yang et al.
Fig. 9. (a)(b) Photographs of PVDF films before and after TiO2 modification, respectively; (c)(d) Surface SEM images of PVDF films before and after TiO2 modi­
fication, respectively.
Fig. 10. (a) XRD pattern of PVDF films before and after modification with TiO2 nanoparticles; (b) FTIR absorption of PVDF films before and after modification with
TiO2 nanoparticles.
are observed to correspond to the characteristic peaks of α phase. Only a
weak absorption peak of β phase is also found at 840 cm− 1, which has
confirm the fact that PVDF powder is mainly composed of α phase. The
PVDF film obtained by solvent dissolution in DMF and
spin-coating/annealing are similar to above results characterized by
XRD. Except for the absorption peak at 762 cm− 1, the other absorption
peaks of α phase are eliminated, while the absorption intensity of β
phase at 840 cm− 1 is significantly enhanced. Different from XRD char­
acterization, we have found the presence of γ phase in the absorption
spectrum. After addition of TiO2 nanoparticles still by using DMF sol­
vent, spin-coating/annealing method, the absorption peak of α phase
completely disappear, and PVDF film is mainly composed of β phase
co-existed with γ phase. However, after addition of TiO2, the ratio of the
absorption peak at 840 cm− 1 to the absorption peak at 875 cm− 1 is
slightly increased, indicating that TiO2 nanoparticles could induce the
conversion of PVDF from α to β phase. Obviously, the results obtained by
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Current Applied Physics 32 (2021) 50–58
FTIR and XRD are basically mutually verified. To sum up, on the basis of
DMF solvent and spin-coating/annealing at room temperature, adding
TiO2 nanoparticles in PVDF polymer substrate can effectively induce the
formation and transformation of PVDF from α to β phase, realizing PVDF
film with more β polarized phase.
Based on above contrasts of PVDF surface morphology and phase
structure before and after modification, we believe that the increase of
piezoelectric output mainly comes from PVDF polymer substrate mixed
with the suitable amount of TiO2 nanoparticles so as to own more pro­
portion β phase, making the piezoelectric output larger than that before
modification. Of course, DMF organic polar-solvent, spin-coating and
annealing together play a positive role in promoting the formation of
PVDF from α to β phase. In addition, whether the improved surface
smoothness of PVDF film obtained after TiO2 addition also promotes the
piezoelectric output remains to be further verified [25,26].
X. Yang et al.
4. Conclusion
In order to effectively convert mechanical energy, the reference de­
vice with a structure of Al/PVDF/Cu-PDMS/ITO/PET has been designed
and assembled by using low-cost flexible PDMS and PVDF polymer films
as triboelectric and piezoelectric functional layers, respectively. The
device works in the contact-separation mode and realizes the simulta­
neous conversion of triboelectric and piezoelectric mechanism, there­
fore, the same mechanical energy can be converted into electrical energy
more effectively. More importantly, through the modification of PDMS
triboelectric and PVDF piezoelectric films by GQD and TiO2 functional
nanoparticles respectively, a dual enhancement of triboelectric and
piezoelectric output is achieved synchronously. According to charac­
terization results, the increase of triboelectric output of the modified
device mainly comes from the improvement of dielectric properties of
PDMS film doped with conductive GQD and the change of surface
microstructure, which enhances the effective contact between friction
layers. However, the enhancement of piezoelectric output of the modi­
fied device is mainly attributed to the formation of a more proportional
polarization β phase after TiO2 addition. In short, this study not only
puts forward a new way to improve dielectric properties of PDMS
polymer film by doping GQD, but also explores preliminarily a new
technology to prepare PVDF film with more proportion β phase under
room temperature. Thus, the modified device has realized a dual
enhancement of triboelectric and piezoelectric output synchronously.
Additionally, due to its low cost, simple preparation, flexibility and
biocompatibility, our device would show a good application prospect in
the fields of flexibility display, electronic skin, wearable electronic
products and self-powered sensors.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
We gratefully acknowledge to the financial support from Natural
Science Foundation of Technology Department (QKHPTRC[2018]5784-
01), First-Class Discipline ([2018] 216), and Key Laboratory Project at
Institutions of Higher Education in Guizhou Province (QJHKY[2019]
055).
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