micromachines

Article
Wearable Woven Triboelectric Nanogenerator
Utilizing Electrospun PVDF Nanofibers for
Mechanical Energy Harvesting
Muhammad Omar Shaikh 1 , Yu-Bin Huang 2 , Cheng-Chien Wang 3 and
Cheng-Hsin Chuang 1, *
1 Institute of Medical Science and Technology, National Sun Yat-sen University, Kaohsiung 80424, Taiwan
2 Department of Mechanical Engineering, Southern Taiwan University of Science and Technology,
Tainan 71005, Taiwan
3 Department of Chemical and Materials Engineering, Southern Taiwan University of Science and Technology,
Tainan 71005, Taiwan
* Corresponding author: [email protected]; Tel.: +886-7525-2000 (ext. 5785)




Received: 8 June 2019; Accepted: 29 June 2019; Published: 30 June 2019


Abstract: Several wearable devices have already been commercialized and are likely to open up
a new life pattern for consumers. However, the limited energy capacity and lifetime have made
batteries the bottleneck in wearable technology. Thus, there have been growing efforts in the area of
self-powered wearables that harvest ambient mechanical energy directly from surroundings. Herein,
we demonstrate a woven triboelectric nanogenerator (WTENG) utilizing electrospun Polyvinylidene
fluoride (PVDF) nanofibers and commercial nylon cloth to effectively harvest mechanical energy
from human motion. The PVDF nanofibers were fabricated using a highly scalable multi-nozzle
far-field centrifugal electrospinning protocol. We have also doped the PVDF nanofibers with small
amounts of multi-walled carbon nanotubes (MWCNT) to improve their triboelectric performance by
facilitating the growth of crystalline β-phase with a high net dipole moment that results in enhanced
surface charge density during contact electrification. The electrical output of the WTENG was
characterized under a range of applied forces and frequencies. The WTENG can be triggered by
various free-standing triboelectric layers and reaches a high output voltage and current of about 14 V
and 0.7 µA, respectively, for the size dimensions 6 × 6 cm. To demonstrate the potential applications
and feasibility for harvesting energy from human motion, we have integrated the WTENG into
human clothing and as a floor mat (or potential energy generating shoe). The proposed triboelectric
nanogenerator (TENG) shows promise for a range of power generation applications and self-powered
wearable devices.

Keywords: triboelectric nanogenerator; energy harvesting; human motion; self-powered wearables;

electrospinning; polyvinylidene fluoride

1. Introduction
In recent years, there has been a shift towards “wearable electronics” to meet the requirements of
modern living such as motion tracking, physical health monitoring and artificial skin sensors among
others [1–7]. These wearable electronics are likely to open up new applications and can be integrated
with currently existing wearables like wristwatches [8] and eyeglasses [9]. One common drawback
of these wearables is that they all need to be powered by rechargeable batteries, which limit their
lifetime and sustainability [10,11]. Furthermore, it almost becomes impossible to replace or recharge
these batteries due to their distributed nature over multiple devices. Thus, there have been growing
efforts to make these wearable electronics “self-powered” and sustainable by directly harnessing

Micromachines 2019, 10, 438; doi:10.3390/mi10070438 www.mdpi.com/journal/micromachines

Micromachines 2019, 10, 438 2 of 13

energy from human motion. Since human activity is based on mechanical movement, harnessing this
ubiquitous source of biomechanical energy represents the most reliable strategy to generate power for
wearables [12–14].
To date, several approaches have been proposed to harvest mechanical energy and convert it into
useful electrical energy, which includes electrostatic [15], piezoelectric [16] and triboelectric [17] among
others. Among the various approaches, triboelectric nanogenerators or triboelectric nanogenerators
(TENGs) have gained significant research interest due to merits like a wide choice of materials and
nanogenerator designs, low cost, high efficiency, robustness, flexibility and being environmentally
friendly [15–22]. TENGs can harvest energy from ambient mechanical motion like vibration, rotation,
expansion and contraction and are based on contact electrification and electrostatic induction arising
from the friction of two materials that have different affinities for electrons [23,24]. Several materials
have been employed as dissimilar triboelectric surfaces and a larger difference in the electron affinity of
the two materials results in higher output performance of the TENG. Until now, a range of applications
have been successfully demonstrated for TENGs based on the relative position change between two
dissimilar triboelectric materials, such as shoe insole to harvest energy from human walking [25],
smart clothing for harvesting energy from human motion [26] and harvesting high altitude wind
energy [27] among others. The output performance of TENGs has improved significantly in recent
years owing to novel designs and materials optimization. However, while TENGs based on micro and
nanopatterned silicone and other polymeric films have demonstrated energy harvesting capability for
a range of applications, they are not ideal materials for direct integration with regular clothing due
to issues associated with washability and air permeability. Consequently, there has been a growing
trend to develop smart textiles based on fibers that provide excellent deformability, breathability and
washability while enabling easy and direct incorporation into everyday clothing [28–30].
Herein, we have developed a woven structured TENG (WTENG) based on freestanding
triboelectric mode utilizing polyvinylidene fluoride (PVDF) nanofibers (as the electronegative material)
woven together with a commercial nylon cloth (as the electropositive material) to harvest energy
from human motion. PVDF is an attractive non-reactive polymeric material with unique electroactive
properties, low acoustic impedance and flexibility, thus making it an effective dielectric for triboelectric
applications [31]. The PVDF nanofibers are fabricated using a low cost and scalable centrifugal
electrospinning process and have small structural features that significantly increase the surface area on
contact, thus resulting in an amplified response. Furthermore, these fibers have also been doped with
varying concentrations of multi-walled carbon nanotubes (MWCNT) which have shown to increase
the overall triboelectric charge generation. The proposed WTENG does not utilize any nanostructured
patterning, thus resulting in increased reliability over its lifetime and ease of fabrication. At first,
the working principle is analyzed followed by testing it under different contact conditions to observe
the electrical output. Finally, the WTENG is applied to harvest different forms of mechanical energy
from human motion such as movement of arms and walking.

2. Materials and Methods

2.1. Fabrication of PVDF Nanofibers

The PVDF nanofibers were fabricated using a far-field centrifugal electrospinning (CE) protocol
where the synergistic effect of the centrifugal drawing force and the conventional electrical force results
in nanofibers with improved yields [32]. The schematic of the CE setup is shown in Figure 1 and
the aim was to enable scalable mass manufacturing of nanofibers. First, the spinning solution was
prepared by adding 7 wt. % semi crystalline PVDF powder (Mw ~534,000 by GPC, Sigma-Aldrich,
St. Louis, MO, USA) in a solution of Dimethylformamide (DMF) and Tetrahydrofuran (THF) where the
ratio of DMF to THF was 39:1. The PVDF powder was completely dissolved by heating the solution at
50 ◦ C for 1 h under constant magnetic stirring. The addition of THF reduces the boiling point of the
solution, which aids in evaporation during electrospinning, thus resulting in improved fiber formation.
Micromachines 2019, 10, 438 3 of 13
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fiberCE
The formation. The CE
setup consists setup
of an innerconsists of an inner
Teflon tubular column Teflon tubular
attached to a column attached three
speed adjustable to a phase
speed
adjustable three phase motor and an outer cylindrical stainless-steel collector,
motor and an outer cylindrical stainless-steel collector, with a diameter of 40 cm, which was coated with a diameter of on
40
cm, whichwith
the inside was an
coated on thefoil.
aluminum inside
Thewith an aluminum
prepared spinningfoil. The prepared
solution enters thespinning
inner tubesolution enters
at a constant
the
flow rate of about 45 drops/min. Using a slower flow rate causes the droplets to be pre-polarizedthe
inner tube at a constant flow rate of about 45 drops/min. Using a slower flow rate causes in
droplets
the feedingto be pre-polarized
tube and attach to in its
theinner
feeding tubeThe
walls. andbottom
attach toof its
theinner
innerwalls. Theabottom
tube has diameter of the inner
of 15 cm
tube twelve
with has a diameter of 15 cm
metal nozzles, eachwith
withtwelve metalofnozzles,
a diameter 0.5 mm, each
throughwithwhich
a diameter of 0.5 jet
the solution mm,wasthrough
ejected
which
simultaneously. A high voltage power supply was used to apply a voltage of 50 kV to to
the solution jet was ejected simultaneously. A high voltage power supply was used theapply
metal a
voltage
nozzles of 50 kV to
through the metal
a carbon nozzles
brush, withthrough a carbon
resulting electricbrush,
field with resulting
strength of 200electric
kV/m, field strength
and the ejectedof
200 kV/m, and the ejected nanofibers were collected onto the grounded aluminum
nanofibers were collected onto the grounded aluminum foil. The solution jet trajectory initially follows foil. The solution
jet trajectory
a straight pathinitially
and asfollows
it movesa towards
straight path and as
the outer it movescollector,
cylindrical towards athe outer cylindrical
bending instability collector,
develops
aand
bending instability develops and the repulsive charges on the jet cause it to elongate.
the repulsive charges on the jet cause it to elongate. Consequently, ultrafine fibers with nanoscale Consequently,
ultrafine
dimensions fibers
andwith
highnanoscale dimensions
aspect ratios and high aspect ratios were obtained.
were obtained.

Figure 1.
Figure Schematic of
1. Schematic of the
the multinozzle
multinozzle far-field
far-field centrifugal
centrifugal electrospinning
electrospinning setup
setup to
to fabricate
fabricate the
the
polyvinylidene fluoride (PVDF) nanofibers.
polyvinylidene fluoride (PVDF) nanofibers.
2.2. Doping with Multi-Walled Carbon Nanotubes (MWCNT)
2.2. Doping with Multi-Walled Carbon Nanotubes (MWCNT)
The PVDF nanofibers were doped with MWCNT to facilitate the growth of crystalline β-phase and
The PVDF nanofibers were doped with MWCNT to facilitate the growth of crystalline β-phase
enhance the surface charge density on the nanofibers during contact electrification. Before the doped
and enhance the surface charge density on the nanofibers during contact electrification. Before the
spinning solution was prepared, the MWCNT were first acid treated to introduce functional groups
doped spinning solution was prepared, the MWCNT were first acid treated to introduce functional
which can improve their dispersion in the solvent. Briefly, the MWCNT were added to a concentrated
groups which can improve their dispersion in the solvent. Briefly, the MWCNT were added to a
H2 SO4 /HNO3 (1:3 vol %) solution and stirred for 12 h at 60 ◦ C. This was followed by an ultrasonication
concentrated H2SO4/HNO3 (1:3 vol %) solution and stirred for 12 h at 60 °C. This was followed by an
step for 1 hour to remove impurities and increase the concentration of carboxylic groups on the surface
ultrasonication step for 1 hour to remove impurities and increase the concentration of carboxylic
of the MWCNT. Extra acid was removed via filtration and the MWCNT slurry was washed copiously
groups on the surface of the MWCNT. Extra acid was removed via filtration and the MWCNT slurry
with deionized water. The oxidized MWCNT were dried in a vacuum oven at 75 ◦ C overnight followed
was washed copiously with deionized water. The oxidized MWCNT were dried in a vacuum oven
by dispersion in DMF:THF (39:1 vol %) solvent solution. The acid treatment resulted in an extremely
at 75 °C overnight followed by dispersion in DMF: THF (39:1 vol %) solvent solution. The acid
stable and uniform dispersion of MWCNT in the solvent. Finally, the solvent solutions containing
treatment resulted in an extremely stable and uniform dispersion of MWCNT in the solvent. Finally,
MWCNT and PVDF powder were mixed, where the doping concentration of MWCNT was varied up
the solvent solutions containing MWCNT and PVDF powder were mixed, where the doping
to 1 wt. %. The doped PVDF nanofibers were obtained by spinning the prepared solution using the
concentration of MWCNT was varied up to 1 wt. %. The doped PVDF nanofibers were obtained by
same CE protocol as described in the previous section.
spinning the prepared solution using the same CE protocol as described in the previous section.
2.3. Polyvinylidene Fluoride (PVDF) Nanofiber Characterization
2.3. Polyvinylidene Fluoride (PVDF) Nanofiber Characterization
The morphology and diameter of the PVDF nanofibers was characterized by a field emission
scanning morphology
The and diameter
electron microscope of the
(FE-SEM, PVDF nanofibers
JSM-6701F, wasJapan).
JEOL, Tokyo, characterized by astructure
The crystal field emission
of the
scanning electron microscope (FE-SEM, JEOL, Akishima, Japan, JSM-6701F). The crystal structure of
the nanofibers was determined by X-Ray Diffraction (XRD, Bruker, Billerica, CA, USA) where the
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nanofibers was determined by X-Ray Diffraction (XRD, Bruker Taiwan Co. Ltd, Hsinchu, Taiwan)
where the and
incident incident and diffracted
diffracted X-ray beamsX-ray
werebeams were
vertical vertical
to the to themat
nanofiber nanofiber mat and
and analysis was analysis
performedwas
performed using a scan range of a0−30 ◦ and of
a scan rate of 0.5 degrees/min.
using a scan range of 0−30° and scan rate 0.5 degrees/min.

2.4.
2.4.Woven
WovenTriboelectric
TriboelectricNanogenerator
Nanogenerator (WTENG)
(WTENG) Fabrication
Fabrication
The
TheWTENG
WTENG fabrication
fabrication primarily
primarilyconsists
consistsof preparing
of preparing thethe
individual
individualPVDF nanofiber
PVDF nanofiberand and
nylon
based
nylonsingle
basedelectrodes followedfollowed
single electrodes by weaving them together.
by weaving The systematic
them together. fabrication
The systematic protocol is
fabrication
schematically illustrated in illustrated
protocol is schematically Figure 2a. in First, an aluminum
Figure 2a. First, an (5 mm × 60
foilaluminum foilmm) with× a60soldered
(5 mm mm) with copper
a
wire is coated
soldered copperon both
wire issides with
coated onaboth
50 µm thick
sides withdouble-sided
a 50 µm thicktape (Taiwan Nitto
double-sided Co., Ltd.,
tape (Taiwan Taichung,
Nitto Co.,
Ltd., Taichung,
Taiwan). The PVDF Taiwan).
based The PVDF based
electrode electrode
is obtained byisattaching
obtained bytheattaching the PVDFmat
PVDF nanofiber nanofiber
to eachmat
side
oftothe
each side of the
aluminum foilaluminum foil using thermocompression
using thermocompression bonding. The bonding. The nylon-based
nylon-based electrode is electrode
obtained is in
obtained in a similar way by attaching the nylon cloth to both sides of the aluminum
a similar way by attaching the nylon cloth to both sides of the aluminum foil. Lastly, the prepared foil. Lastly, the
prepared
PVDF PVDF based
and nylon and nylonsingle based single electrodes
electrodes are wovenare wovento
together together
form a to10form
× 10 aWTENG,
10 × 10 WTENG,
which has
whicharea
a total hasofa total
aboutarea of about
60 mm 2 , as 60 mm2,in
shown asFigure
shown2b.in Figure 2b.

Figure2.2.(a)
Figure (a)Schematic
Schematic illustration
illustration of
of the
the systematic
systematicprotocol
protocoltotofabricate Woven
thethe
fabricate WovenTriboelectric
Triboelectric
Nanogenerator (WTENG) . (b) An image of the 10
Nanogenerator (WTENG). (b) An image of the 10 × 10 WTENG. × 10 WTENG.

2.5.
2.5.Measurement
MeasurementSetup
Setup
WeWehave
haveutilized
utilizedaastandard
standarddynamic
dynamic testing platformas
testing platform asshown
shownininthe theschematic
schematic inin Figure
Figure 3 to
3 to
test
testthe
theelectrical
electricaloutput
outputof ofthe
theWTENG
WTENG when mechanically
mechanicallycontacted
contactedwithwitha afreestanding
freestanding dielectric
dielectric
elastomeric
elastomericlayerlayer(PDMS
(PDMS184) 184) under
under different
different applied forces and
applied forces andfrequencies.
frequencies.AAfunction
function generator
generator
(AFG3022,
(AFG3022, Tektronix
Tektronix Inc., Beaverton,
Inc., Beaverton, OR,OR,USA)
USA) linked to to
linked a linear power
a linear power amplifier
amplifier(PA25E, Brüel
(PA25E, & Kjær
Brüel &
Kjær
Co., Co., Nærum,
Nærum, Denmark)Denmark)
was used wastoused to control
control the excitation
the excitation frequency
frequency and normal
and normal forceforce exerted
exerted by the
by therespectively.
shaker, shaker, respectively. A force feedback
A force feedback sensor attached
sensor attached to theoffront
to the front of the shaker
the shaker measures
measures the
the applied
applied
contact contact
force, force,
which which is displayed
is displayed as voltageas voltage waveforms
waveforms on the
on the digital digital phosphor
phosphor oscilloscopeoscilloscope
after signal
after signal conditioning.
conditioning. A 50 mm2 PDMS A 50 mm 2 PDMS layer is attached to the tip of the force sensor as it contacts
layer is attached to the tip of the force sensor as it contacts the surface
ofthe
thesurface
60 mmof the 60 mm thatWTENG
is fixedthat is fixed onblock.
an acrylic
The block. The open circuit voltage and the
2 WTENG 2
on an acrylic open circuit voltage and the transferred
transferred charge were measured using an electrometer (Keithley 6514
charge were measured using an electrometer (Keithley 6514 System Electrometer, Beaverton, OR, USA) System Electrometer,
Cleveland,
with OH, USA)
a high input with a high
resistance. input resistance.
For simulating human Formotion
simulating
suchhuman motion
as walking andsuch
armasmovement,
walking
and arm movement, the WTENG was contacted under different forces
the WTENG was contacted under different forces and frequencies and the resulting electrical and frequencies andoutput
the
resulting electrical output was measured by the electrometer.
was measured by the electrometer.
Micromachines 2019, 10, 438 5 of 13
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Figure 3. Schematic of the standard dynamic testing platform used to measure the electrical output of
Figure 3. Schematic of the standard dynamic testing platform used to measure the electrical output
the WTENG under different applied forces and frequencies.
of the WTENG under different applied forces and frequencies.
3. Results and Discussion
3. Results and Discussion
3.1. Polyvinylidene Fluoride (PVDF) Nanofibers
3.1. Polyvinylidene Fluoride (PVDF) Nanofibers
The morphology of the pure and MWCNT doped PVDF nanofiber mat obtained via centrifugal
The morphology
electrospinning of the pure
was observed usingand MWCNT
FE-SEM, asdoped
shownPVDF in thenanofiber
images in mat obtained
Figure 4a,b.viaItcentrifugal
can be seen
electrospinning was observed using FE-SEM, as shown in the
that PVDF nanofibers with diameters ranging from 100 nm to 300 nm were obtained with images in Figure 4a,b. It can be seen
fully
that PVDF nanofibers with diameters ranging from 100 nm to 300 nm were obtained with fully
interconnected pores and a high degree of porosity of about 70% to 80%. Furthermore, the fiber surface
interconnected pores and a high degree of porosity of about 70% to 80%. Furthermore, the fiber
was smooth without any observable bead formation or presence of wrinkles. The smooth surface
surface was smooth without any observable bead formation or presence of wrinkles. The smooth
and porous structure of the nanofibers can be attributed to the DMF: THF solvent ratio used during
surface and porous structure of the nanofibers can be attributed to the DMF: THF solvent ratio used
electrospinning. The use of a cosolvent with high DMF content results in a smooth fiber surface while
during electrospinning. The use of a cosolvent with high DMF content results in a smooth fiber
the use of THF that has a low boiling point and high vapor pressure increases the porosity of the fibers.
surface while the use of THF that has a low boiling point and high vapor pressure increases the
Among the crystalline phases present in PVDF, the non-polar α-phase consisting of TGTG
porosity of the fibers.
(alternating
Among trans
thegauche confirmation)
crystalline is the most
phases present abundant
in PVDF, the form while the
non-polar β-phase
α-phase consisting
consisting of of TTTT
TGTG
(all(alternating
trans confirmations)
trans gauche is polar and demonstrates
confirmation) is the mostthe largest spontaneous
abundant form while the polarization per unit of
β-phase consisting cell.
Herein, we have tried to use a combination of electrospinning and MWCNT
TTTT (all trans confirmations) is polar and demonstrates the largest spontaneous polarization per doping to synergistically
increase theHerein,
unit cell. β-phasewe content
have in thetoobtained
tried PVDF nanofibers.
use a combination The electrospinning
of electrospinning and MWCNT process resultstoin
doping
uniaxial mechanical drawing and electrical poling of the PVDF nanofibers.
synergistically increase the β-phase content in the obtained PVDF nanofibers. The electrospinning The mechanical drawing
process forces the molecules into an extended conformation with all dipoles
process results in uniaxial mechanical drawing and electrical poling of the PVDF nanofibers. The aligned in the same
direction
mechanical (β-phase).
drawingSimultaneously,
process forces the themolecules
poling processinto ancauses the polar
extended axis of the
conformation withcrystallites
all dipolesto
bealigned
oriented in along
the samethedirection
electric field direction,
(β-phase). resulting inthe
Simultaneously, spontaneous polarization
poling process causes theofpolar
the β-phase.
axis of
In the
addition, doping
crystallites to bewith MWCNT
oriented alongfurther promotes
the electric the conversion
field direction, of the
resulting α-phase intopolarization
in spontaneous the β-phase
byofincreasing
the β-phase.
the In addition, doping
crystallization rate with MWCNT interfacial
and inducing further promotes
chargethe conversion ofThis
accumulation. the increased
α-phase
into the β-phase
polarization by increasing
and charge the crystallization
storage ability of the PVDF rate and inducing
nanofibers due tointerfacial
MWCNTcharge doping accumulation.
should result
in This increasedtriboelectric
an increased polarization and charge
output storageofability
performance of the PVDF nanofibers due to MWCNT
the WTENG.
doping
PVDF nanofibers with high β-phase content can be obtainedofby
should result in an increased triboelectric output performance thecooperative
WTENG. effect of the
PVDF nanofibers
electrospinning process and with high β-phase
addition of smallcontent
amounts can of be obtained
MWCNT by cooperative
as confirmed by theeffect
XRDof the
spectra
electrospinning process and addition of small amounts of MWCNT
shown in Figure 4c. The as obtained PVDF powder showed strong absorption peaks at 18.6 , 20.1◦ as confirmed by the ◦ XRD
andspectra
26.8◦ shown in Figure 4c. to
which corresponds Thetheas(020),
obtained
(110)PVDF powder
and (021) showed
planes of thestrong absorption
α-phase. peaks
In the case of at
the
18.6°, 20.1° and 26.8° which corresponds to the (020), (110) and (021) planes
bare PVDF nanofiber mat obtained after centrifugal electrospinning, the peaks related to the α-phase of the α-phase. In the
case of the bare PVDF nanofiber mat obtained◦ after centrifugal electrospinning, the peaks related to
decreased significantly and a new peak at 20.9 emerged which corresponds to the (110) plane of the
the α-phase decreased significantly and a new peak at 20.9° emerged which corresponds to the
Micromachines 2019, 10, 438 6 of 13

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β phase. Furthermore, this peak became more dominant as the PVDF nanofibers were doped with
increasing concentrations of MWCNT from 0.5 to 1 wt. %. We have utilized a 1 wt. % MWCNT loading
increasing concentrations of MWCNT from 0.5 to 1 wt. %. We have utilized a 1 wt. % MWCNT
toloading
fabricate the W-TENG
to fabricate as the as
the W-TENG relative peakpeak
the relative intensity corresponding
intensity corresponding to to
the
theββphase
phase decreases
decreases for
higher doping concentrations.
for higher doping concentrations.
To
Toanalyze
analyze the
the triboelectric response,aasingle
triboelectric response, singleelectrode
electrode system
system comprising
comprising of electrospun
of electrospun PVDF PVDF
nanofiber 2
nanofibermatmat (with
(with and withoutMWCNT)
and without MWCNT)attached
attachedtotoanan aluminum
aluminum foilfoil
withwith dimensions
dimensions ofmm
of 25 25 mm
2

was
wasfabricated and periodically
fabricated and periodicallycontacted
contactedwithwith a PDMS
a PDMS sheetsheet
underunder
a normal a normal
appliedapplied
force of force
3 N of
3and
N and a frequency
a frequency of The
of 1 Hz. 1 Hz. The resulting
resulting electricalelectrical
output as output
measured as by
measured by the electrometer
the electrometer is shown in is
shown
Figure in
4d.Figure 4d. PVDF
The pure The pure PVDF nanofibers
nanofibers produced an produced an average peak-to-peak
average peak-to-peak current of about current
4 nAof about
that
4increased to about 8to
nA that increased nA and 16
about 8 nAnAandas the
16 MWCNT
nA as theloading
MWCNT increased
loading from 0.5 wt. from
increased % to 10.5wt.wt.%,% to
1respectively. These results
wt. %, respectively. highlight
These results the feasibility
highlight of theofMWCNT
the feasibility the MWCNT loading in enhancing
loading in enhancing the the
triboelectric response.
triboelectric response.

Figure4.
Figure 4. (a)
(a) FE-SEM
FE-SEM images
imagesofof(i)(i)pure
purePVDF
PVDF nanofibers and
nanofibers (ii)(ii)
and after doping
after with
doping 1 wt.1 %
with wt.MWCNT.
% MWCNT.
(b) XRD spectra of PVDF powder and pure and MWCNT doped PVDF nanofiber
(b) XRD spectra of PVDF powder and pure and MWCNT doped PVDF nanofiber mats obtained mats obtained afterafter
centrifugal electrospinning.
centrifugal electrospinning. (c)
(c)Triboelectric
Triboelectriccurrent generation
current generation forfor
pure andand
pure MWCNT
MWCNT doped PVDF
doped PVDF
nanofiber mats when contacted with a freestanding PDMS layer under an applied force
nanofiber mats when contacted with a freestanding PDMS layer under an applied force and frequencyand frequency
of 3 N and 1 Hz, respectively.
of 3 N and 1 Hz, respectively.

AA few
few recent
recentstudies have
studies alsoalso
have beenbeen
reported in literature
reported utilizingutilizing
in literature an increase
aninincrease
β-phase in
content
β-phase
of PVDF to enhance the triboelectric response. Kim et al. [33], who fabricated a TENG with
content of PVDF to enhance the triboelectric response. Kim et al. [33], who fabricated a TENG with a PVDF-
aMWCNT nanocomposite
PVDF-MWCNT film and film
nanocomposite aluminum tape as thetape
and aluminum twoastriboelectric layers, reported
the two triboelectric layers,similar
reported
observations. The nanocomposite film was formed by dropping and drying the composite solution
similar observations. The nanocomposite film was formed by dropping and drying the composite
and they observed a maximum output voltage that was about eight times higher than that for the
solution and they observed a maximum output voltage that was about eight times higher than that for
pure PVDF based TENG. These findings lead them to conclude that the increased β-phase content
Micromachines 2019, 10, 438 7 of 13

the pure PVDF based TENG. These findings lead them to conclude that the increased β-phase content
with a highly polarized crystal structure resulted in the enhanced triboelectric response. Recently,
Lee et al. synthesized poly (tert-butyl acrylate) (PtBA)-grafted PVDF copolymers and demonstrated
that the copolymers were very effective in increasing TENG output performance as compared to
pristine PVDF [34]. The grafting process produced high β-phase content that doubled the measured
dielectric constant while the output performance of the TENG also showed a two-fold enhancement.
They concluded that the high net dipole moment of the β-phase and resulting increase in dielectric
constant enhanced the surface charge density during contact electrification, which was responsible for
the improved TENG response. This was one of the first studies to experimentally prove the direct
correlation between the phase and dielectric constant with the output power of TENG. In addition,
Soin et al. [35] reported a triboelectric generator with vertical contact-separation mode that consisted
of zinc stannate nanocubes-PVDF nanocomposites and a polyamide-6 membrane. As compared to
the pristine PVDF, the nanocomposites showed a higher β-phase content and dielectric constant with
an increased piezoelectric coefficient. Furthermore, the resulting triboelectric output voltage and
current also showed an enhancement of 70% and 200% respectively. This improved performance was
related to the enhanced polarization of PVDF leading to an increase in the β-phase content and higher
surface charge density by stress induced polarization of zinc stannate.

3.2. Freestanding TENG—Working Mechanism

To understand the working mechanism of the WTENG, we have first analyzed a freestanding
TENG (FTENG) using PVDF nanofiber mat (25 mm × 25 mm) and nylon fabric (25 mm × 25 mm) as the
two triboelectric surfaces and two aluminum foils as the electrodes. The structure of the FTENG under
vertical contact mode is schematically illustrated in Figure 5a, where a PDMS sheet (25 mm × 50 mm)
is utilized as the freestanding triboelectric layer. During the first stage (Figure 5a-i), the freestanding
PDMS sheet is brought into complete contact with the FTENG. Considering that the FTENG is initially
uncharged, the triboelectric effect during contact will cause the PVDF fabric to be negatively charged
while the nylon fabric to be positively charged. Simultaneously, this will render the part of the PDMS
sheet that contacts the PVDF fabric to become positively charged, while the part that contacts the nylon
fabric to become negative charged. When the PDMS sheet starts to move away from the FTENG as
shown in the second stage (Figure 5a-ii), an electrical potential difference begins to develop that drives
electrons from the PVDF electrode to the nylon electrode through an external circuit to counteract
the generated triboelectric potential. As the separation between the PDMS sheet and the FTENG
increases, an electrostatic equilibrium state is reached and the electron flow stops as shown in stage
three (Figure 5a-iii). As the freestanding PDMS sheet is again driven towards the FTENG in stage
four (Figure 5a-iv), the electrostatic equilibrium is broken and the electrons flow back from the nylon
electrode to the PVDF electrode, thus reducing the number of induced charges. Finally, all the induced
charges are neutralized when the PDMS sheet contacts the FTENG again. The FTENG performance
was analysed by periodically contacting it with the freestanding PDMS sheet at an applied normal force
of 3 N and frequency of 1 Hz, thus generating an alternating electrical output as shown in Figure 5b-i,ii.
Under these conditions, the FTENG could generate an open circuit voltage (Voc ) of about 14 V and
short circuit current (Isc ) up to about 28 nA.
Micromachines 2019, 10, 438 8 of 13
Micromachines 2019, 10, x 8 of 13

Figure 5. (a) Schematic of structure and working mechanism of freestanding TENG (FTENG) under
Figure 5. (a) Schematic of structure and working mechanism of freestanding triboelectric-layer TENG
vertical contact mode as the freestanding PDMS layer approaches contacts and separates from the
(FTENG) under the vertical contact mode. (b) Electrical performance of the FTENG: (i) Voltage output
FTENG. (b) Electrical performance of the FTENG: (i) Voltage output and (ii) current output.
and (ii) current output.
3.3. WTENG Electrical Performance
3.3. WTENG Electrical Performance
The proposed WTENG is based on the previously discussed FTENG to enable implementation
The proposed
in wearable devices WTENG is basedmechanical
for harvesting on the previouslyenergydiscussed
from human FTENG to enable
motion implementation
and converting it into
in
useful electrical energy. The structure and fabrication of the WTENG has been described ininto
wearable devices for harvesting mechanical energy from human motion and converting it the
useful
previouselectrical
section.energy.
Herein,The structure
we have and fabrication
investigated of the WTENG
the non-deformation has been
working mode described
of the WTENGin the
previous
as shownsection.
in FigureHerein,
6a. The weWTENG
have investigated
is fixed on the top non-deformation
of an acrylic blockworking mode of the
and periodically WTENG
contacted by
as shown in Figure 6a. The WTENG is fixed on top of an acrylic block
a freestanding PDMS sheet under normal applied force with varying magnitudes and frequencies. and periodically contacted by
aThe
freestanding PDMS of
electrical output sheet under normal
the WTENG whenapplied
contacted force
withwiththevarying magnitudes
same normal force ofand
5 Nfrequencies.
at different
The electrical output of the WTENG when contacted with the same normal force
applied frequencies ranging from 1 to 5 Hz is shown in Figure 6b. It can be seen that the peak-to-peak of 5 N at different
applied frequencies ranging from 1 to 5 Hz is shown in Figure 6b. It can
voltage, current and power density increased from 3 V, 160 nA and 0.1 mW/m to 7 V, 700 nA and be seen that
2 the peak-to-peak
voltage,
0.85 mW/m current andapplied
2 as the power frequency
density increased
increasedfrom from3 V, 160tonA
1 Hz andrespectively.
5 Hz, 0.1 mW/m2 to The7 V,
Isc 700 nA and
increases as
0.85 mW/m 2 as the applied frequency increased from 1 Hz to 5 Hz, respectively.
more charges are transferred in a shorter time at higher frequencies. Since the internal resistance of The Isc increases as

more charges areistransferred

the electrometer not infinitelyin alarge,
shorter time
there willatbe higher
chargefrequencies.
leakage andSince the internal
the obtained valuesresistance
of the Vofoc
the electrometer is not infinitely large, there will be charge leakage and the
may be lower than those actually generated by the WTENG under different frequencies. Experimental obtained values of the Voc
may be lower than those actually generated by the WTENG under different frequencies.
Experimental analysis using calibrated resistances and capacitances could be utilized to figure out
Micromachines 2019, 10, 438 9 of 13

Micromachines
analysis using2019, 10, x
calibrated resistances and capacitances could be utilized to figure out the exact 9 of 13
value
of the Voc and internal capacitance of the WTENG based on input frequency [36]. We have also
the exact value of the Voc and internal capacitance of the WTENG based on input frequency [36]. We
investigated the WTENG output under different normal applied forces ranging from 1 N to 5 N at
have also investigated the WTENG output under different normal applied forces ranging from 1 N
atoconstant frequency of 1 Hz as shown in Figure 6c. It was observed that the peak-to-peak voltage,
5 N at a constant frequency of 1 Hz as shown in Figure 6c. It was observed that the peak-to-peak
current and power density 2 2
voltage, current and powerincreased from 6 V, from
density increased 80 nA6 and
V, 800.12
nA mW/m
and 0.12to 14 V, 2180
mW/m nAV,and
to 14 1800.42
nA mW/m
and
as0.42
themW/m
applied normal
2 as forcenormal
the applied increased from
force 1 to 5 N,
increased respectively.
from 1 to 5 N, respectively.

Figure6.6. (a)
Figure (a) Schematic
Schematic ofof WTENG
WTENG working
working mechanism
mechanismunder
undernon-deformation
non-deformationmode modewhere
wherePDMS
PDMS is
is chosen as the freestanding triboelectric layer. The measured (i) voltage (ii) current and (iii)
chosen as the freestanding triboelectric layer. (b) The measured (i) voltage (ii) current and (iii) power power
densitywhen
density when the the WTENG
WTENG is iscontacted
contactedbybythe
thefreestanding PDMS
freestanding PDMS layer under
layer undervarying (b) frequencies
varying (b) frequencies
(1–5 Hz) and (c) applied forces (1–5
(1–5 Hz) and (c) applied forces (1–5 N). N).

ToTocharacterize
characterizethe
the practical
practical applicability
applicability of the
of the proposed
proposed WTENGWTENG as a power
as a power source,source, we
we measured
measured the power density under different load resistances as shown in Figure 7a.
the power density under different load resistances as shown in Figure 7a. A maximum instantaneous A maximum
instantaneous
output output power
power density density
of 0.065 mW/m of2 0.065 mW/m2 was
was observed at aobserved at a loadofresistance
load resistance 400 MΩ.ofFurthermore,
400 MΩ.
Furthermore, we have also tested the current output of the WTENG when contacted with free
we have also tested the current output of the WTENG when contacted with free standing triboelectric
standing triboelectric layers made of different materials as shown in Figure 7b. The peak-to-peak
layers made of different materials as shown in Figure 7b. The peak-to-peak current of the WTENG
current of the WTENG when contacted with copper foil, latex, textile and PET (Polyethylene
when contacted with copper foil, latex, textile and PET (Polyethylene Terephthalate) under a normal
Terephthalate) under a normal applied force of 5 N (3 Hz) was 90, 95, 105 and 130 nA, respectively.
applied force of 5 N (3 Hz) was 90, 95, 105 and 130 nA, respectively. This implies that PET is a relatively
This implies that PET is a relatively better triboelectric material for the WTENG. Furthermore, an
better triboelectric material for the WTENG. Furthermore, an output current of 105 nA for textile shows
output current of 105 nA for textile shows promise for applicability in wearable devices.
promise for applicability in wearable devices.
Micromachines 2019, 10, 438 10 of 13
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Micromachines 2019,
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FigureFigure 7. (a)
7. (a) TheThe dependence of
dependence of the
theWTENG
WTENG power
powerdensity on the
density onresistance of the external
the resistance load. (b) load.
of the external
Current output of WTENG on contact with different freestanding triboelectric layers.
(b)Figure 7. (a)
Current The dependence
output of WTENGof onthe WTENG
contact power
with density
different on the resistance
freestanding of the layers.
triboelectric external load. (b)
Current output of WTENG on contact with different freestanding triboelectric layers.
3.4. Applications
3.4. Applications of WTENG
of WTENG
3.4. Applications
Owing toof
itsWTENG
wearability, flexibilityand and ability
ability to
Owing to its wearability, flexibility tobe betriggered
triggered byby anyanyfreestanding
freestanding triboelectric
triboelectric
layer, the proposed WTENG could be easily integrated into clothes, gloves, shoes and carpets. Besides
layer, theOwing to its wearability,
proposed WTENG could flexibility
be easily andintegrated
ability to beinto triggered
clothes, by any freestanding
gloves, shoes and carpets.triboelectric
Besides
the above tested materials like PDMS, latex, and PET; the freestanding triboelectric layer could also
thelayer,
above thetested
proposed WTENG
materials likecould
PDMS, be easily
latex, and integrated
PET; the intofreestanding
clothes, gloves,
be wool, cotton, polymer, paper, the hand and so on. For example, a 5 cm2 WTENG placed on a table
shoes andlayer
triboelectric carpets. Besides
could also be
the above
wool, tested materials like PDMS, latex, and PET; the freestanding 2 triboelectric layeron could also
and tapped using the hand could generate a maximum peak-to-peak current of about 4 µA as shown and
cotton, polymer, paper, the hand and so on. For example, a 5 cm WTENG placed a table
be
tapped wool, cotton,
using 8a. polymer,
theThe
hand paper,
could generatethe hand and
a maximum so on. For example,
peak-to-peak a 5 cm 2 WTENG placed on a table
current of aboutof 4 µA as shown in
in Figure movement of hands, legs and arms represents important sources mechanical
and
Figure tapped
8a. The
energy using
provided the
movementby hand
theof could
hands,
human generate
legsWe
body. and ahave
maximum
armsalso peak-to-peak
represents
integrated important
the same current
sources
WTENG of about 4 µA as shown
of mechanical
into clothing and energy
in can
Figure
provided by8a.theThe
harvest energy
humanmovement
bybody. of have
the motion
We hands,ofalsolegs
the arm andas arms
integrated shown represents
the in
sameFigure important
WTENG8b. Here, sources
intothe clothing
clothing ofand
mechanical
material
can harvest
energy
energy byprovided
represents
the motion by the human
the freestanding
of the body.
triboelectric
arm as shownWelayer.
have also integrated
The movement
in Figure 8b. Here,of the same
the
the armWTENG
clothing causes ainto
change
material clothing
in the
represents andthe
cancontact
harvestareaenergy
betweenby the
the WTENG
motion of andthe thearm as shown
clothing, in Figure
resulting in a 8b. Here,peak-to-peak
maximum the clothingoutputmaterial
freestanding triboelectric layer. The movement of the arm causes a change in the contact area between
represents
current ofthe freestanding
about µA. Wetriboelectric layer. The movement of oftheintegrating
arm causes theaWTENG
change intoin the
the WTENG and the0.6
clothing, have also demonstrated
resulting in a maximum the feasibility
peak-to-peak output current of about 0.6 µA.
contact area between
floor mats. The WTENG the was
WTENG attachedandtothe theclothing,
floor and resulting in a maximum
the triboelectric peak-to-peak
effect resulting from stepping output
We have also demonstrated the feasibility of integrating the WTENG into floor mats. The WTENG was
current of about
on it while 0.6 µA.
walking We have
generated also demonstrated
a maximum peak-to-peak theoutput
feasibility of integrating
current of about 2 µA theasWTENG
shown in into
attached
Figure
to 8c.
theBased
floor on
anda similar
the triboelectric
concept,
effect
the WTENG
resulting
may
from
also
stepping
be attached
onto
itthe
while walking
bottom of
generated
shoes to
floor mats. The WTENG was attached to the floor and the triboelectric effect resulting from stepping
a maximum
onharvest peak-to-peak
it whilemechanical energy
walking generated output
from currentor
walking
a maximum ofpeak-to-peak
about 2 µA output
running. as shown in Figure
current of about 8c.2Based
µA as on a similar
shown in
concept,
Figure 8c. Based on a similar concept, the WTENG may also be attached to the bottom of shoes from
the WTENG may also be attached to the bottom of shoes to harvest mechanical energy to
walking
harvestormechanical
running. energy from walking or running.

Figure 8. Applications of WTENG to harvest mechanical energy from human motion: (a) Tapping by
hand. (b) Integrated into clothing to harvest energy from arm movement. (c) Stepping during
walking.
Figure
Figure 8. 8.Applications
Applicationsof
ofWTENG
WTENG to to harvest
harvest mechanical
mechanicalenergy
energyfrom
fromhuman
humanmotion: (a)(a)
motion: Tapping by by
Tapping
hand. (b) Integrated into clothing to harvest energy from arm movement. (c) Stepping during
hand. (b) Integrated into clothing to harvest energy from arm movement. (c) Stepping during walking.
walking.
Micromachines 2019, 10, 438 11 of 13

4. Conclusions
In summary, we have demonstrated a woven structured TENG or WTENG comprising of PVDF
nanofibers and commercial nylon cloth for biomechanical energy harvesting from human motion.
The electricity is generated by a free-standing triboelectric layer that moves relative to the WTENG
surface. A multinozzle centrifugal electrospinning process was employed for scalable manufacturing
of PVDF nanofibers, which were also doped with MWCNT to increase the β-phase content and
triboelectric charge generation. The proposed WTENG demonstrates feasibility for operating under
contact with several freestanding triboelectric layers and can effectively harvest mechanical energy
from a range of human motions including tapping, arm movement and footsteps with peak-to-peak
current output reaching as high as 2 µA when the WTENG with dimensions of 5 cm2 is stepped
on during walking. Consequently, the proposed WTENG shows promise as a power generator for
wearable devices and can be extended to a range of other applications.

Author Contributions: M.O.S. and C-H.C. conceptualized the study, performed data analysis and wrote the
manuscript. M.O.S. and Y-B.H. collected and validated the data. C-C.W. provided resources and supervised the
fabrication of the PVDF nanofibers. C-H.C. guided and supervised the study.
Funding: This research was funded by the Ministry of Science and Technology of Taiwan under project number
MOST 106-2632-E-218-003.
Acknowledgments: The authors would like to thank the materials characterization facility at the Southern Taiwan
University of Science and Technology for assisting in X-ray Diffraction and Electron Microscopy analysis of the
PVDF nanofibers.
Conflicts of Interest: The authors declare no conflict of interest.

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