Nano Energy 32 (2017) 542–550

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Reduced graphene-oxide acting as electron-trapping sites in the friction MARK

layer for giant triboelectric enhancement
⁎
Chaoxing Wu1, Tae Whan Kim ,1, Hwan Young Choi
Department of Electronic and Computer Engineering, Hanyang University, Seoul 04763, Republic of Korea

A R T I C L E I N F O A BS T RAC T

Keywords: The continuously seeking of approaches for enhancing the output of triboelectric nanogenerators (TENGs) has
Reduced graphene oxide always been the goal of researchers attempting to harvest mechanical energy efficiently. Here a novel
Triboelectric nanogenerators methodology for enhancing the output performance of the TENG by introducing electron traps into the
Triboelectric enhancement common friction layer has been firstly developed. For this purpose, reduced graphene oxide (rGO) embedded in
Electron-trapping
the friction layer has been used as electron traps. Because the triboelectric electrons generated on the surface of
Nanocomposites
a polyimide layer can be efficiently captured and stored in rGO sheets due to the interaction between the rGO
sheets and the polyimide layer, the loss of triboelectric electrons can be suppressed. The maximum output
power density of a vertical contact-separation mode TENG containing rGO sheets reached 6.3 W/m2, which was
30 times larger than that of a device without rGO sheets. We also showed that the output performance of the
lateral sliding-mode TENG, which is the other fundamental working mode of the TENG, can be enhanced due to
the advantage of additional electron trapping in the friction layer, indicating that the concept demonstrated in
this work holds potential for providing significant enhancements in next-generation triboelectric devices.

1. Introduction
Recently, triboelectric nanogenerators (TENGs), which can directly
translate mechanical energy into electrical energy, have been exten-
sively developed due to their high energy-conversion efficiency, low
cost, simple structure, flexibility, and abundant choices of materials
[1–3]. Energy harvesting from broadband mechanical energy sources,
such as body motions, vibrations, wind flows, and ocean waves, by
using TENGs has been demonstrated [4–12]. However, the perfor-
mances of TENGs, including the output performance and the endur-
ance, must be significantly improved through a rational design before
the TENGs can act as practical, green power sources for large-scale
application [13–15].
The output performances of TENGs rely highly on the efficiencies of
the processes for triboelectric charge generation and for separating
positive and negative charges. On the basis of the working principle,
two routes can be typically considered for enhancing the outputs of
TENGs. Appropriate friction materials with markedly different pola-
rities can be used to increase the density of charge generated during the
friction process [16–18]. The building of friction layers with a surface
micro-/nano-structure and a nanoscale surface modification can also
greatly increase the triboelectric charge density [19–24]. Furthermore,
the surface charge density can be enhanced by injecting ionized air
[25]. Moreover, multi-layer integrations can increase the total number
of electrons and simultaneously maximize the instantaneous output
power [26,27]. As for the second route, effective separation of positive
and negative charges is dominantly attributed to the design of the
device's structure. Thus, novel structures, such as the linear grating
structure, the rolling structure, and the planar structure, have been
demonstrated to enhance the performances of the TENGs [28–30].
Even though various efforts have been committed, methods for
integrating mature, robust technologies and cutting edge designs so
as to enhance the performances of TENGs are still needed if these
devices are to have future, large-scale applications.
Note that the electrons in the friction layer serve as an electrostatic
induction source for the TENG's electricity generation process.
Actually, once the triboelectric electrons are generated, the electron
density on the surface of the friction layer will decrease gradually [31].
Thus, the loss of triboelectric electrons could decrease the potential
difference between the two electrodes of the TENG. Here, we propose a
superior methodology for enhancing the output performance of the
TENG by introducing electron traps into the common friction layer. For
that purpose, as electron traps we use reduced graphene oxide (rGO)
embedded in the friction layer. A derivative of graphene, rGO consists

⁎
Corresponding author.
E-mail address: twk@hanyang.ac.kr (T.W. Kim).
1
Both authors contributed equally to this work.

http://dx.doi.org/10.1016/j.nanoen.2016.12.035
Received 3 November 2016; Received in revised form 5 December 2016; Accepted 18 December 2016
Available online 09 January 2017
2211-2855/ © 2017 Elsevier Ltd. All rights reserved.
C. Wu et al.
Fig. 1. Device structure. (a) Illustration of the vertical contact-separation mode TENG with a PI:rGO film. The right panel shows a schematic diagram of electron transfer from the PI
layer to the rGO sheets. (b) Optical image of the vertical contact-separation mode TENG. The inset presents an optical image of the separated PI:GO layer. (c) SEM images of the PI:rGO
layer. The inset presents an SEM image of the PI (Kapton)/PI:rGO/PI stacked layer.
of a hexagonal carbon network with both sp2- and sp3-hybridized
carbon atoms bearing hydroxyl and epoxide functional groups on basal
planes [32]. Tailoring the functional groups of rGO can modify
extensively its electronic structural and chemical properties, enabling
it to have various applications. Especially, we have illustrated in our
previous work that rGO can efficiently capture external electrons with
nonvolatile electron-trapping properties due to its unique electronic
and morphologic properties [33–35]. In the case of a vertical contact-
separation mode TENG with a polyimide (PI) flat film as a friction
layer, by employing rGO as electron traps we showed that the
maximum power density of the TENG with rGO reached 6.3 W/m2,
which was 30 times larger than that of the device without rGO. In
addition to rGO being applied in vertical contact-separation mode
TENGs, we have shown that its introduction into the friction layer can
enhance the performance of lateral sliding-mode TENGs, which proves
that the strategy for enhancing the output performance of a TENG by
introducing electron traps into the friction layer can be widely applied
in the field of TENGs and triboelectric devices.
2. Experimental section
2.1. Preparation of the polyamide acid (PAA) and the PAA:GO
solutions
The GO used in this experiment was prepared from purified natural
graphite by using the modified Hummers method. PI, from a PAA
precursor, was prepared by dissolving polyamic acid in dimethylforma-
mide (DMF), which consisted of 287.5 mg of p-phenylenediamine (PDA)
and 781.25 mg of biphenyltetracarboxylic dianhydride (BPDA) dissolved
in 500 mL of DMF solvent. For the preparation of the PAA: GO mixture,
GO sheets were added into the PAA precursor, followed by ultrasonication
for 1 h. The GO sheets were uniformly dispersed in the PAA precursor.
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Nano Energy 32 (2017) 542–550
2.2. Fabrication of TENG
To fabricate the negative friction layer of the TENG, An Al film,
acting as an electrode, was deposited on the surface of a glass substrate
by using thermal evaporation. The PAA: GO film was deposited on the
surface of the PI (Kapton) film by using the spin-coating method and
was baked at 135 °C for 30 min to evaporate the solvent. Then, another
PAA layer was spin-coated onto the surface of the as-prepared PAA: GO
layer. After the amination treatment at 400 °C for 2 h, the GO sheets
were reduced to rGO sheets, and the PI: rGO hybrid layer was obtained.
Then, the PI (Kapton)/PI: rGO/PI stacked layer adhered to the surface
of the as-fabricated Al electrode. The positive friction layer was
composed of a glass substrate with a piece of Al foil affixed to its
surface. The positive friction layer was supported by a spring of 10 mm
in thickness, which served as a spacer for the TENG. The active size of
the TENG was 1.5 cm×2.5 cm. For the lateral-sliding mode TENG, the
positive and the negative parts were kept parallel to each other. The Al
surface on the top plate and the surface of the friction layer on the
bottom plate were in intimate contact.
2.3. Characterization and electrical measurement
Scanning electron microscopy (SEM, NOVA nanoSEM 450) was
used to investigate the distribution of graphene-oxide sheets embedded
in the PI layer. Fluorescence spectra of the PI and the PI: rGO films
were obtained by using a HITACHI F-4600 fluorescence spectro-
photometer. Fourier-transform infrared spectroscopy (FTIR) spectra
of PI and PI: rGO were measured with a NICOLET 360 spectro-
photometer. An oscilloscope (Tektronix TDS2024C) and a current
meter (Keithley 2400) were used for measuring the output voltage
and the current of the TENG. The capacitance-voltage (C-V) cures were
measured by using a Keithley 4200SCS unit.
C. Wu et al. Nano Energy 32 (2017) 542–550

3. Results and discussion
3.1. Structure of the TENG with electron traps
A schematic view of a vertical contact-separation mode TENG with
an electron-trapping layer is shown in Fig. 1a. The bottom part of the
TENG is made of a glass substrate onto which an Al electrode and a
negative friction layer with a PI (Kapton)/PI: rGO/PI stacked structure
are deposited (Fig. S1). A cross-sectional SEM image of the friction
layer is shown in the inset of Fig. 1c. The top part of the TENG is made
of a glass substrate onto which an Al electrode is deposited. The top PI
layer in the friction layer acts as the negative friction material and can
capture electrons from the top Al electrode during the triboelectrifica-
tion process. A PI: rGO layer, which provides electron-trapping sites,
exists under the top PI layer. The PI/PI: rGO stacked layer is deposited
on a PI (Kapton) film. A photograph of the TENG with electron traps
and with an active size of 1.5 cm×2.5 cm is presented in Fig. 1b, and
the detailed fundamental electricity generation mechanism of the
contact-separation mode triboelectric generator is illustrated. A tribo-
electric dipole layer induces a potential difference between the electro-
des in a contact or a separation process, which causes the free electrons
to flow across the external load to countervail the field produced by the
triboelectric charges.
In order to achieve a uniform distribution of rGO sheets in the PI
layer, we functionalized GO sheets coupled with PAA and were able to
achieve good, stable dispersion in a PAA solution (Fig. S2). The inset of
Fig. 1b shows a photograph of the separated PI: rGO film. Because of
the functional GO sheets with PAA, the PI: rGO layer can be
conveniently fabricated by using spin-coating and subsequent imidiza-
tion [33]. The introduction of the rGO sheets does not affect the
chemical structure of PI, and the degrees of imidization of the PI film
from both the PAA precursors and the GO-PAA precursors are
identical, as confirmed from the FTIR spectra (Fig. S3). Cross-sectional
SEM images of the PI: rGO film show that the rGO sheets can be
uniformly dispersed in the PI film by using a solution method, as
shown in Fig. 1c.
3.2. Performance improvement and mechanism
Four TENGs were fabricated to investigate the effect of the
introduction of rGO sheets on the TENGs’ performances. In these four
devices, the negative friction layers were Kapton film (inset of Fig. 2a),
Kapton film/PI film (inset of Fig. 2e), Kapton film/PI: rGO film (inset
of Fig. 2i), and Kapton film/PI: rGO film/PI film (inset of Fig. 2m). The
different negative friction layers used in this work shared a positive
friction layer part for the purpose of facilitating comparisons. The
typical open-circuit voltages of the TENGs with the four kinds of
negative friction layers are shown in Fig. 2. Some remarkable key
phenomena are observed based on the measurements: (1) For the
TENG with a Kapton/PI: rGO/PI stacked structure, about 40 contact-
separation cycles are needed to achieve a stable voltage output, which is
less than the number of cycles needed by the other three TENGs

Fig. 2. Open-circuit voltages of TENGs with different friction layers. (a)-(d) Activation process (a) and open-circuit voltages of the TENG using a Kapton film as a friction layer under
operation frequencies of 0.2 (b), 1 (c) and 7 (d) Hz. (e)-(h) Activation process (e) and open-circuit voltages of the TENG using a Kapton/PI stacked film as a friction layer under operation
frequencies of 0.2 (f), 1 (g) and 7 (h) Hz. (i)–(l) Activation process (i) and open-circuit voltages of the TENG using a Kapton/PI:rGO stacked film as a friction layer under operation
frequencies of 0.2 (j), 1 (k) and 7 (l) Hz. (m)–(p), Activation process (m) and open-circuit voltages of the TENG using a Kapton/PI:rGO/PI stacked film as a friction layer under operation
frequencies of 0.2 (n), 1 (o) and 7 (p) Hz.

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Fig. 3. Electron-tapping mechanism analysis. (a) Excitation (left) and emission (right) spectra of the PI film and the PI:rGO film. (b) Absorption spectra of the PI film and the PI:rGO
film. (c) C-V curves of the Al/p-Si/PI/PI:rGO/PI/Al device. The inset presents a schematic of the device used for the C-V measurements. (d) Flat-band voltage shift (ΔVfb) under diverse
applied voltages. (e), (f) Schematic diagram of the energy bands for the floating-gate MIS device under zero bias (e) and under negative bias (f).
(Figs. 2a, 2e, 2i, and 2m). (2) The output voltage at a frequency of 7 Hz
for the TENG with a PI: rGO layer is as large as 90 V (Fig. 2p), which is
almost three times higher than those of the TENGs without a PI: rGO
layer (Figs. 2d and 2h). (3) The output voltage of the TENG with a
Kapton/PI: rGO/PI stacked structure is independent of the operation
frequency (Figs. 2n-2p). However, the output voltages for the other
three TENGs increase with increasing operation frequency. (4) The
device performance of the TENG with the Kapton/PI: rGO stacked
structure is much lower in comparison with that of the device with a
Kapton/PI: rGO/PI stacked structure.
In order to explore the improvement in the TENG's performances
by the introduction of the rGO sheets, firstly we use a fluorescence
method to study the aggregation structures consisting of intermolecu-
lar charge-transfer (CT) complexes. The excitation (left) and the
emission (right) spectra of the PI film and the PI: rGO film are shown
in Fig. 3a. The fluorescence excitation at 361 nm for the PI: rGO film is
stronger than that of the PI film. According to the literature [36,37], the
excitation peak around 361 nm and its corresponding fluorescence
peak around 500 nm are assigned to a locally-excited transition that
occurs at the dianhydride moiety followed by energy transfer to the
excited CT state. The enhancement in the excitation of the PI: rGO
nanocomposites shows that the rGO sheets can promote the charge
transfer process, in which electrons are transferred from the electron-
donating diamine to the electron-accepting rGO sheets (charge trans-
fer) and are then captured in the rGO sheets (charge trapping), as
schematically shown in the right panel of Fig. 1a. The absorption
spectra of the PI film and the PI: rGO film were further measured to
clarify the nature of the electron transfer from PI to rGO. The relatively
small energy gaps of the CT transitions are well known to displace the
absorption edges of PI films to longer wavelengths (λ > 400 nm, visible
region), which is essentially the reason for the orange-to-brown colors
of fully aromatic PI films [38]. The absorption peak in the visible
wavelength region shifts from 544(PI film) to 572 nm (PI: rGO film)
due to the introduction of rGO, as shown in Fig. 3b. The red shift in the
absorption spectrum indicates that rGO can reduce the energy gaps of
the CT transitions in PI, which can originate from electron transfer
from the electron-donating diamine to the electron-accepting rGO
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sheet [33].
In order to further experimentally confirm the electron transfer and
trapping effects, we fabricated a floating-gate metal-insulator-semi-
conductor (MIS) device, in which the PI: rGO nanocomposites were
inserted as a charge-storage region in the middle of the PI insulator
layer. The effect of trapping and detrapping charge carriers in the rGO
sheets can be directly detected by measuring the capacitance of the MIS
device. A schematic diagram of the fabricated floating-gate MIS with an
Al/p-Si/PI/PI: rGO/PI/Al structure is shown in the inset of Fig. 3c. The
C-V curves for the device were measured at 5 MHz to investigate its
electrical characteristics. The C-V measurements were conducted by
applying voltage sweeps with different negative maximum voltages
from −1 to −9 V. The C-V curves showed behaviors similar to those of a
typical p-Si-based MIS with charge-trapping regions. Finally, the C-V
hysteresis windows are seen to expand with increasing negative
maximum bias, indicative of increased capture of carriers. A clockwise
hysteresis is clearly observed in the C-V characteristics, indicative of
the existence of sites occupied by carriers [39]. The presence of such
sites is attributed to the electron-trapping effect of the rGO sheets
embedded in the PI layer.
The flat-band voltage shifts (ΔVfb) under diverse applied voltages
are presented in Fig. 3d. The magnitude of the Vfb shift is strongly
related to the number of carriers trapped in the rGO layer. The charge
density Q that accumulates in the PI: rGO layers can be estimated from
the equation of Q =ΔVfb·d0·C0/x, where ΔVfb is the flat-band shift in the
C-V curves, d0 is the thickness of the active layer, C0 is the capacitance
of the dielectric stack layer, and x is the location of the rGO layer [40].
The average density of captured electrons under a negative bias can be
estimated to increase from to 3.8×10−3 to 2.8×10−2 C/m2 with
increasing negative applied voltage from −1 to −8 V. The C-V
characteristics can be described by using the dominant electron
transport mechanisms. A schematic diagram of the energy bands for
our floating-gate MIS device are presented in Figs. 3e and 3f. When the
voltage applied to the top electrode is zero, no charge is trapped in the
rGO trapping layer (Fig. 3e). When negative applied voltages are
applied to the top Al electrode, electrons are injected from the Fermi
level of the Al electrode to the lowest unoccupied molecular orbital
C. Wu et al. Nano Energy 32 (2017) 542–550

(LUMO) level of PI and are then captured in the rGO sheets (Fig. 3f). inactivity. (4) The existence of rGO sheets on the surface of the TENG
The capture of electrons in the rGO layer will cause an accumulation of with a Kapton/PI: rGO stacked structure reduces the contact area
holes in the PI/p-Si interface, resulting in an increase in the value of between the PI material and the Al electrode (Fig. S4) and further
the capacitance. The capture of electrons in the rGO sheets and the decreases the density of generated triboelectric electrons. Therefore,
ensuing induction of positive charge accumulation in the floating-gate the performance of the device with a Kapton/PI: rGO stacked structure
MIS are similar to the operating principles of our TENG with electron- deteriorates in comparison with that of the device with a Kapton/PI:
trapping sites. rGO/PI stacked structure.
As well known, the value of open-circuit voltage of TENG is
proportional to the density of electron σ; i.e, V = σ·x(t)/ε, where V is
3.3. Friction layer optimization and electrical output performance
the open-circuit voltage, x(t) is the gap between the electrodes at time t,
and ε is the permittivity [41]. However, both the drift process caused by
We first optimized the PI (Kapton) film/PI: rGO film/PI film
electric field and the diffusion process caused by the concentration
stacked layer by changing the thickness of the PI: rGO film. As the
gradient of electrons will result in the loss of triboelectric electrons.
PI: rGO film becomes thicker, more triboelectric electrons can be
Moreover, the loss of the surface triboelectric electrons can come from
captured. The open-circuit voltage of the TENG with a 180-nm-PI: GO
the recombination with adsorbing positively-charged ions or particles
layer was 90 V (Fig. 2p) and increased with increasing thickness of the
from air. As a result, the performance of typical TENGs can deteriorate
PI: rGO film (Fig. 4a-c). As the thickness of the PI: rGO film was
with decreasing density of triboelectric electrons. The mechanism for
increased to 6.5 µm, the open-circuit voltage increased to 150 V
the dramatic increase in the open-circuit voltage output of the TENG
(Fig. 4c). Furthermore, the concentration of the rGO sheets in the PI
with PI: rGO films is attributed to efficient electron capture in the PI:
layer was increased while keeping the PI: rGO film's thickness at
rGO layer. The remarkable key phenomena observed in Fig. 2 can be
6.5 µm (Fig. 4d-f). The value of the open-circuit voltage was found to
explained as follows: (1) The rGO sheets embedded in the PI layer can
increase with increasing concentration of rGO sheets. When the mass
efficiently capture the triboelectric electrons. The recombination be-
fraction of the rGO sheets in the PI: rGO film was about 20.0 wt%, the
tween electrons and positive charges is suppressed. As a result, a higher
maximum open-circuit output voltage was as large as 190 V, which was
density and a higher voltage output of triboelectric electrons can be
almost seven times larger than that of the devices without an electron-
achieved. (2) A stable voltage output can be established quickly for the
trapping layer. However, the open-circuit voltage dramatically de-
fresh TENG with a PI: rGO layer due to efficient suppression of the
creased to 50 V when the mass fraction of rGO sheets reached about
recombination of negative electron charge with positive charge.
28.9 wt%. A possible reason is that rGO sheets might connect together
However, more contact-separation cycles for the fresh TENG without
at high concentrations, and the connected rGO layers in the bottom of
a PI: rGO layer are necessary to generate a sufficient number of
the PI: rGO film might screen the internal electric field. The electric-
triboelectric electrons, which might result from the recombination
field screening effect can suppress the induction of positive charges in
between triboelectric electrons and positive charges adsorbed on the
the bottom Al electrode. As a result, the potential difference between
surface. (3) The electron density under low operation frequencies is
the electrodes induced by the triboelectric dipole layer might be
almost the same as that under high operation frequencies due to the
decreased.
efficient storage of triboelectric electrons in the friction layer. As a
We have characterized the dependences of the output voltage and
result, while the output voltages of the TENG with a PI: GO layer are
current (under a frequency of 7 Hz) on the load resistance for the
almost independent of the operation frequency, those of the TENG
optimized TENG with a PI: rGO layer and for the TENG without a PI:
without a PI: rGO layer decrease with decreasing operation frequency.
rGO layer, as shown in Fig. 5a. The electrical outputs of both TENGs
This might result from the recombination between triboelectric elec-
depend on matching the resistance of the load. While the instantaneous
trons and positive charges, including induced positive charges and
currents dropped with increasing load resistance, the voltages rose. The
positive charges adsorbed on the surface, during a long period of
resulting instantaneous power densities on the load were calculated, as

Fig. 4. Optimization of the PI:GO film. (a)–(c) Open-circuit voltages of the TENGs with a PI:rGO film, in which the thickness of the PI:rGO film was increased from 2.8 to 6.5 µm. (d)–
(f) Open-circuit voltages of the TENGs with a PI:rGO film, in which the concentration of rGO sheets in the PI:rGO film was increased from 16.8 to 28.9 wt% while keeping the thickness
of the PI:rGO film constant at 6.5 µm.

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Fig. 5. Performances of the TENGs. (a) Dependence of the output voltage and the current density on the external loading resistance. (b) Dependence of the output power density on the
external loading resistance. (c) Rectified open-circuit voltage of the optimized TENG with a PI:rGO film. (d) Charging processes using the TENGs. (e) Enlarged view of the details in (d).
The inset presents the rectified voltage output of the TENG with a PI:rGO layer during a single press-release process. (f) Calculated accumulative charge produced by the TENGs. (g), (h)
Photographs of 100 green LEDs directly driven by the TENG with a PI:rGO film in the press process (g) and the release process (h). (i), (j) Photographs of 100 green LEDs and 100 red
LEDs directly driven by the TENG with a PI:rGO film in the press process (i) and the release process (j).

Fig. 6. Application in sliding TENGs. (a) Illustration of the sliding TENG with a PI:rGO layer. (b) Open-circuit voltage of the sliding TENG with a PI:rGO layer. (c) Open-circuit voltage
of the sliding TENG without a PI:rGO layer. (d) Dependence of the output power density on the external loading resistance. (e) Charging processes when using sliding TENGs. (f)
Calculated the accumulative charges produced by the sliding TENGs.

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C. Wu et al.
shown in Fig. 5b. The power density of the optimized TENG with a PI:
rGO layer reached a maximum value of 6.3 W/m2 at a resistance of
approximately 5 MΩ. This maximum power density of the TENG with a
PI: rGO layer is 30 times larger than that of the TENG without a PI:
rGO layer.
The electricity generated by using TENGs needs to be stored in an
energy-storage device before powering electronic devices. The total
amount of charge, rather than the peak current, acts as the key factor
for efficiently charging an energy-storage device. When TENGs are
used to charge energy-storage devices, the AC signals need to be
rectified before being connected to the load. As shown in Fig. 5c, the
output voltage can be rectified by using a rectifier bridge circuit (Fig.
S5). After the rectification of the output signals, the TENGs can be used
to charge capacitors. As shown in Fig. 5d, a 0.22-μF capacitor was
charged by using a TENG with a PI: rGO layer under an operation
frequency of 7 Hz. The capacitor was charged to 6 V in merely 7 s,
which is a gigantic enhancement compared to the work using a TENG
without a PI: rGO layer. (Fig. 5e shows an enhancement of the details
shown in Fig. 5d.) Both the press and the release operations can charge
the capacitor because the output signals are rectified. The voltage of the
capacitor charged by using an optimized TENG with a PI: rGO layer
can be increased by 0.32 V in each press process, which is almost the
same as that in the release process. However, each press or release
process can only result in a voltage increase of about 0.1 V for a TENG
without a PI: rGO layer. We further calculated the accumulated charge
produced by using the TENGs. For an optimized TENG with a PI: rGO
layer, the total amount of stored charge provided by a press-release
cycle reached approximately 0.16 μC, which was much larger than that
(0.05 μC) produced by using a TENG without a PI: rGO layer, as shown
in Fig. 5f.
In order to demonstrate the capability for using TENGs, in
principle, as a direct power source, we assembled arrays of commercial
multicolor light-emitting diode (LED) bulbs in series to fabricate LED
panels. The optimized TENG with a PI: rGO layer served as a direct
power source for the LEDs. Triggered by pressing and releasing, the
TENG generated current pulses, instantaneously lighting up 200 LED
bulbs (Figs. 5g-5h). Every press and release process was capable of
simultaneously lighting up the 200 LEDs (Video S1 and S2).
Supplementary material related to this article can be found online
at doi:10.1016/j.nanoen.2016.12.035.
3.4. Extended application in lateral sliding-mode TENGs
The above-demonstrated enhanced performance of TENGs due to
the insertion of electron-trapping sites was based on the vertical
contact-separation mode. Note that another fundamental working
mode based on sliding electrification between two surfaces can over-
come the limitations of the vertical contact-separation mode, and can
expand significantly the applicability of TENGs for diverse forms of
mechanical motions [42,43]. In this part, we showed that the introduc-
tion of electron-trapping sites, in this case PI: rGO nanocomposites,
could enhance the performance of the lateral-sliding mode TENG. The
schematic structure of a lateral sliding-mode TENG with a PI: rGO
layer is presented in Fig. 6a, in which the two plates are kept parallel to
each other. The Al surface on the top plate and the friction-layer
surface on the bottom plate are in intimate contact. Driven by
mechanical motion, the two plates slide against each other with the
contact area changing periodically.
The detailed power-generation mechanism for a lateral sliding-
mode TENG has been illustrated in previous reports [42,43]. The open-
circuit voltage of the TENG using a PI (Kapton)/PI: rGO/PI stacked
layer as a friction layer is shown in Fig. 6b. The structure of the stacked
friction is the same as that mentioned in Fig. 5. The value of the output
voltage for the TENG with a PI: rGO layer is three times larger than
that of the TENG without a PI: rGO layer (Fig. 6c). Furthermore, the
power density of the device with a PI: rGO layer reached a maximum
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Nano Energy 32 (2017) 542–550
value of 0.3 W/m2 at a resistance of about 10 MΩ, as shown in Fig. 6d.
That maximum power density was 9 times larger than that of the TENG
without a PI: rGO layer. A 0.22-μF capacitor was charged by using a
lateral sliding-mode TENG under an operating frequency of 8 Hz, the
results are shown in Fig. 6e. The capacitor was charged to 4.5 V in
merely 5 s, which was a gigantic enhancement in comparison with that
obtained using the TENG without a PI: rGO layer. The accumulated
charges produced by the two kinds of TENGs were calculated. For the
TENG with a PI: rGO layer, the total stored charge provided by a
sliding outward-inward cycle reached approximately 0.1 μC, which was
much larger than that (0.01 μC) produced by using the devices without
a PI: rGO layer, as shown in Fig. 6f.
This study proposes a frontier direction in device structure design,
material selection, and fabrication process for next-generation tribo-
electric devices. The basic concept demonstrated in this work can be
extended to other TENG configurations, such as disk-TENGs
[13,23,30], multilayered-TENGs [26,27], spiral-interdigitated elec-
trode-TENGs [11], and electricity-generating clothes [5], that are
applicable to harvesting multiple forms of ambient mechanical energy.
The concept of introducing electron-trapping sites can also be used to
increase the sensitivity of self-powered motion sensors based on
triboelectrics [6,44,45]. Furthermore, this work can expand the choice
of the triboelectric material to nanocomposites, which should provide
further ways to enhance the performances of TENGs. Nanomaterials,
including quantum dots (zero-dimensional), nanowires (one-dimen-
sional), nanosheets (two-dimensional) and three-dimensional macro-
structures, and their nanocomposites can be considered for use to
provide electron-trapping sites in TENGs.
4. Conclusions
In summary, we have demonstrated a novel methodology for
dramatically enhancing TENG performance by introducing electron-
trapping sites, in this case rGO sheets, into the friction layer. The
dramatic increase in the electrical output of the TENG with a PI: rGO
films is attributed to efficient electron capture in the PI: rGO layer,
which can suppress recombination between triboelectric electrons and
positive charges and increase the electron density in the friction layer.
The maximum power density of the optimized vertical contact-separa-
tion mode TENG with a PI: rGO layer reached 6.3 W/m2, which was 30
times as large as that of the TENG without a PI: rGO layer. The TENG
with a PI: rGO layer drives a larger amount of charge through the
external load in each cycle, which is more efficient in charging an
energy-storage device and allows the direct lighting of hundreds of
LEDs. We also showed that the introduction of electron-trapping sites
in the friction layer could enhance the performance of a lateral sliding-
mode TENG.
Acknowledgements
T.W.K. acknowledges Prof. Z. L. Wang at the Georgia Institute of
Technology for valuable discussion about and helpful comments on this
manuscript. This research was supported by the Basic Science Research
Program through the National Research Foundation of Korea (NRF)
funded by the Ministry of Education, Science and Technology
(2016R1A2A1A05005502). C. W. is supported by the Korea Research
Fellowship (KRF) Program through the National Research Foundation
of Korea funded by the Ministry of Science, ICT and Future Planning
(2015H1D3A1062276).
Appendix B. Supplementary material
Supplementary data associated with this article can be found in the
online version at http://doi:10.1016/j.nanoen.2016.12.035.
C. Wu et al.
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Dr. Chaoxing Wu received his B. S. and Ph.D. degree
from School of Physics and Information Engineering,
Fuzhou University, China, in 2009 and 2015. He is
currently working a postdoctoral research fellow in
Hanyang University, Korea, since 2015. His current re-
search interest is the flexible & wearable smart electronics
based on low-dimensional nanomaterials.
Prof. Taewhan Kim received Ph.D. degree in
Department of Physics from State University of New York
at Buffalo in 1989. He is the HYU Distinguished Professor
in Department of Electronic Engineering at Hanyang
University. His current interests are focused on the fabri-
cation of next-generation nonvolatile memory devices,
organic light-emitting devices, solar cells, and nanogenera-
tors.
C. Wu et al. Nano Energy 32 (2017) 542–550

Hwan Young Choi received his B. S. degree in Chung-

Ang University, Korea, in 2015. Currently, he is studying
for a M. S. degree in Hanyang University, Korea. His
current research interests include triboelectric generators
and nanoscale electronics.

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