Accepted Manuscript

Enhanced performance of an expanded polytetrafluoroethylene-based triboelectric

nanogenerator for energy harvesting

Zhi Zhang, Yiyang Xu, Dongfang Wang, Huaguang Yang, Jiansheng Guo, Lih-Sheng
Turng
PII: S2211-2855(19)30335-0
DOI: https://doi.org/10.1016/j.nanoen.2019.04.034
Reference: NANOEN 3650

To appear in: Nano Energy

Received Date: 21 February 2019

Revised Date: 24 March 2019
Accepted Date: 8 April 2019

Please cite this article as: Z. Zhang, Y. Xu, D. Wang, H. Yang, J. Guo, L.-S. Turng, Enhanced
performance of an expanded polytetrafluoroethylene-based triboelectric nanogenerator for energy
harvesting, Nano Energy (2019), doi: https://doi.org/10.1016/j.nanoen.2019.04.034.

This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to
our customers we are providing this early version of the manuscript. The manuscript will undergo
copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please
note that during the production process errors may be discovered which could affect the content, and all
legal disclaimers that apply to the journal pertain.
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D
TE
EP
C
AC
 ACCEPTED MANUSCRIPT

Enhanced performance of an expanded polytetrafluoroethylene-

based triboelectric nanogenerator for energy harvesting

Zhi Zhang a, b, c, 1, Yiyang Xu b, c, d, 1, Dongfang Wang b, c, Huaguang Yang b, c,

PT
Jiansheng Guo a, *, Lih-Sheng Turng b, c, *
a
Key Laboratory of Textile Science and Technology, Ministry of Education, College of Textiles, Donghua University,

RI
Shanghai 201620, China
b
Wisconsin Institute for Discovery, University of Wisconsin–Madison, Madison, WI 53715, USA
c
Department of Mechanical Engineering, University of Wisconsin–Madison, Madison, WI 53706, USA

SC
d
School of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450001, China

U
*
Corresponding author. Email address：jsguo@dhu.edu.cn (J. Guo), turng@engr.wisc.edu (L. Turng)
AN
M

Abstract

Triboelectric nanogenerators (TENGs) are a well-known energy supply technology. Their

D

output performance is highly important given their intended use in real-world applications.
TE

Expanded polytetrafluoroethylene (ePTFE) membranes, which are lightweight, fibrillated,

microporous membranes formed by the expansion and stretching of PTFE, possess excellent
EP

flexibility and elasticity, unlike the traditional PTFE films that they are made from. Therefore,
C

ePTFE membranes have tremendous potential to be a triboelectric material for energy harvesting.
AC

As the most important parameter in ePTFE processing, the uniaxial expansion ratio determines

the final morphology of the ePTFE and, thus, the output performance of TENGs. Hence, it

requires systematic study. Here, folded-paper TENGs consisting of ePTFE membranes with

different expansion ratios and nylon fabrics as two paired tribolayers (i.e., ePTFE/Nylon-TENGs)

were fabricated. A systematic study concerning the effect of the expansion ratio on the output

1
 ACCEPTED MANUSCRIPT

performance of the ePTFE/Nylon-TENGs was carried out. The output performance of the

ePTFE/Nylon TENGs with expansion ratios ranging from 0 to 400% were measured and

compared. The results showed that the output electrical signals of the ePTFE/Nylon-TENGs first

increased with the expansion ratio and then decreased steadily, with an optimum performance at

PT
an expansion ratio of 100%. In addition, the output performance of the TENGs with solid PTFE

RI
was approximately the same as that of the ePTFE/Nylon-TENGs with an expansion ratio of

300%. The ePTFE/Nylon-TENGs had excellent and stable performances and yielded a maximum

SC
power density of 1.01 mW/cm², with an effective area of 1 cm² and a load resistance of 1 MΩ.

This work suggests that ePTFE is an effective material for improving the output performance of

ePTFE-based TENGs.
U
AN
Key words: Triboelectric nanogenerator, Expanded PTFE, Expansion ratio, Energy harvesting
M
D

1. Introduction
TE

Triboelectric nanogenerators (TENGs), a well-known energy harvesting technology, are

based on the combination of contact electrification and the electrostatic induction effect [1, 2].
EP

To enable the supply of power for electronic devices, in place of using conventional batteries, the

output performance of TENGs is especially important and has gained extensive attention.
C

Although significant progress has been made in improving their output performance and energy
AC

conversion efficiency [3-5], there is still room for further improvement. One of the key factors

that impact the performance of TENGs is the surface charge density [6, 7], which mainly

depends on the tribomaterials. Therefore, material selection is one of the most effective strategies

for improving the output performance. Typically, it is done by combining two kinds of tribo-

2
 ACCEPTED MANUSCRIPT

materials with distinct differences in capturing electrons. More specifically, a TENG with a high

efficiency requires two tribo-materials: one that is a highly electron-donating material and the

other that is a highly electron-accepting material. According to the triboelectric series [1, 8, 9],

PTFE is positioned on the extremely negative side due to the strong electron-accepting effect of

PT
its carbon–fluorine bonds. Thus, it has been widely used in the fabrication of TENGs [10-19]. In

RI
addition to its electron-donating or electron-receiving property, a material’s flexibility can

provide more deformation under external force, while surface features, such as the surface

SC
microstructure and roughness, can increase the effective contact area [20-23]. All of these

characteristics have significant effects on the output performance.

U
AN
Despite its triboelectric potential, PTFE exhibits inherent high hardness, stiffness, and a

low frictional coefficient [24] compared to other commonly used negative tribomaterials.
M

Furthermore, the extremely good solvent resistance of PTFE, unlike other polymers, presents

many difficulties in processing. To further improve the performance of PTFE, numerous research
D

efforts have been made to increase the surface charge density [25, 26]. These endeavors focus on
TE

surface modification to make an improvement in the effective contact area [16, 27-29], including

incorporating PTFE nanowires [30-34], leaf-shaped PTFE fibers [35, 36], or nanoparticles [16]
EP

onto the surface using an inductively coupled plasma (ICP) etching method. Nevertheless, these
C

techniques are unable to improve the softness and flexibility of PTFE film, especially with the
AC

increasing consumer demands for flexible and soft TENGs with the rapid development of

flexible and wearable electronics in recent years.

Expanded PTFE (ePTFE) membranes, which are fibrillated, microporous membranes

formed by the expansion and stretching of PTFE, possess excellent flexibility and elasticity,

unlike traditional PTFE film. More importantly, ePTFE membranes offer a significantly large

3
 ACCEPTED MANUSCRIPT

surface contact area for charge transfer and induction, and thus are favorable for triboelectric

electricity output [37]. In recent years, a few studies have reported on the direct use of

commercial ePTFE to fabricate TENGs and proved to be effective. For example, Nahian et al.

fabricated a deionized water and commercial ePTFE-based TENG with contact-separation and

PT
lateral-sliding modes [38]. An ePTFE-based TENG driven by air flow for self-powered, real-

RI
time respiratory monitoring has also been reported [37]. Nevertheless, there have been no

systematic studies on ePTFE-based TENGs to determine the effect of PTFE’s expansion ratio on

SC
the output performance of the TENGs. The expansion ratio, which is an important processing

parameter of ePTFE, not only affects material flexibility, but also determines the effective

U
contact area, both of which exert an influence on the surface charge density. Therefore, through a
AN
detailed and systematic study on how the expansion ratio affects the output performance of

ePTFE membranes, the merits of ePTFE-based TENGs can be adequately explored and
M

examined.
D

In this work, paste-extruded PTFE tubes (8 mm in diameter by 1 mm thick) were

TE

stretched at different expansion ratios via uniaxial expansion. They were then cut open and

trimmed to create 10 mm by 10 mm ePTFE membranes. Folded-paper TENGs using ePTFE

EP

membranes and nylon fabric as paired tribolayers were fabricated to study the effect of the

expansion ratio on the output performance. Specifically, the output performance of

C

ePTFE/Nylon-TENGs with expansion ratios ranging from 0 to 400% were measured and
AC

compared. The results showed that ePTFE/Nylon-TENGs with an expansion ratio of 100%

yielded the maximum electrical signals, while those with 400% generated the minimum output

signals. In addition, the output performance of solid PTFE/Nylon-TENGs without expansion

approximated the performance of a TENG at an expansion ratio of 300%. Interestingly, at any

4
 ACCEPTED MANUSCRIPT

expansion ratio, ePTFE/Nylon-TENGs using the inner surface of the ePTFE tubes had slightly

higher output performances than those using the outer surface of the ePTFE tubes. The

ePTFE/Nylon-TENGs prepared in this study had excellent and stable performances that yielded a

maximum power density of 1.01 mW/cm² at an expansion ratio of 100% and a load resistance of

PT
1 MΩ. This work suggests that the expansion process for ePTFE effectively enhanced the output

RI
performance, thus expanding the application prospects of ePTFE/Nylon TENGs.

SC
2. Experimental section

2.1 Fabrication of ePTFE membranes

U
The ePTFE membranes were fabricated using an Instron 5967 machine (for expansion)
AN
with an environmental chamber (for temperature control), as shown in Fig. 1a. A photo of the

expansion process is shown in Fig. S1 and a clip of it is shown in Video S1 (Supporting

M

Information). First, fine PTFE powders (F301, DAKIN, Japan) were mixed with a lubricant
D

(Isopar G, Exxon Mobile, America) at 18 wt%. Then a custom-made paste extruder was used to
TE

extrude the PTFE powder–lubricant mixture into a cylindrical preform (billet) 50 mm in

diameter. The preform was then pushed through a converging chamber with a center pin (Fig. S2
EP

in the Supporting information) at a reduction ratio of about 100 and formed into PTFE tubes with

internal and external diameters of 8 mm and 10 mm, respectively. Subsequently, the paste-
C

extruded PTFE tubes were stretched at 200 °C at expansion ratios of 0%, 100%, 200%, 300%,
AC

and 400%, with a constant stretching rate of 75%/sec. Figure 1b depicts the tensile stress vs

expansion ratio (strain %) curves during the expansion process corresponding to the ePTFE tubes

with different expansion ratios. We can see that the tensile curves have excellent repeatability,

indicating the stability and repeatability of the ePTFE expansion process. The ePTFE membranes

5
 ACCEPTED MANUSCRIPT

were obtained by cutting the ePTFE tubes open (Fig. S3 in the Supporting Information). For

comparison, the representative tensile properties of ePTFE membranes with different expansion

ratios are shown in Fig.1c. As the expansion ratio increased, the ultimate strength and

elongation-at-break both decreased gradually. The ePTFE membranes with an expansion ratio of

PT
100% demonstrated the best tensile strength and elongation-at-break.

RI
U SC
AN
M
D
TE
EP

Fig. 1. (a) Illustration of the expansion process of ePTFE tubes. (b) Stretching curves and photos of
C

ePTFE tubes with different expansion ratios during the expansion process. (c) Tensile properties of as-
AC

fabricated ePTFE membranes.

2.2 Fabrication of ePTFE/Nylon-TENGs

A schematic structure of the ePTFE/Nylon-TENG is presented in Fig. 2a. The TENG is

comprised of a folded-paper substrate containing ePTFE, nylon, and copper (Cu) foil tape. To

6
 ACCEPTED MANUSCRIPT

fabricate the ePTFE/Nylon-TENG device, ePTFE tubes were first cut open and then trimmed

into a fixed size of 10 mm by 10 mm, as shown in Fig. S3 (Supporting Information). A piece of

ePTFE membrane and a piece of nylon fabric with the same contact area of 1 cm2 were used as

paired tribomaterials, both of which were attached with Cu foil as electrodes. The paper was

PT
selected as the substrate material owing to its flexibility, lightweight nature, and low cost, as well

RI
as being easy to fabricate [39]. Then the two tribolayers were fixed on the folded paper substrate

to form the ePTFE/Nylon-TENG working in a cyclic “contact-separation” (CS) mode. The

SC
photographs of the as-fabricated ePTFE/Nylon-TENG can be seen in Fig. S4. (Supporting

Information).

U
AN
2.3 Characterization and measurement

The mechanical properties of ePTFE during and after processing were tested using a
M

mechanical testing machine (Instron 5967). Surface morphological observations of ePTFE

D

membranes and nylon fabric were performed with a scanning electron microscope (SEM, LEO
TE

GEMINI 1530, Zeiss) at an acceleration voltage of 3 kV. The surface water contact angles

(WCA) of the ePTFE membranes with different expansion ratios were measured by the sessile
EP

droplet method with a 5 µL water droplet using an optical contact angle measuring and contour

analysis system (OCA 15, DataPhysics). To evaluate the output performance, the ePTFE/Nylon-
C

TENGs were attached to a mechanical shaker (LDS V201, Brüel & Kjær) that provided cyclical
AC

contact-separation motions with a controlled force of 6 N and a frequency of 10 Hz. The output

voltages of the ePTFE/Nylon-TENG were acquired using an oscilloscope (DS1102E, Rigol).

Output currents, charges and charge/discharge curves were recorded using a potentiostat

(VersaSTAT-3, Princeton Applied Research).

7
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D

Fig. 2. (a) Construct of an ePTFE/Nylon-TENG with ePTFE membrane and nylon fabric. (b) Electricity
TE

generation mechanism of an ePTFE/Nylon-TENG for one cycle, which including four stages: (I) pressed,

(II) releasing, (III) released, and (IV) pressing.

C EP

3. Results and discussion

AC

3.1 Working mechanism of ePTFE/Nylon-TENGs

Expanded PTFE (ePTFE) was chosen as one of the tribomaterials because of its strong

ability to capture electrons, as well as its extraordinary softness and flexibility compared to

conventional PTFE. A comparison of the flexibility and elasticity of an ePTFE membrane versus

a PTFE film can be seen in Fig. S5 and Fig. S6, respectively (Supporting Information). After

8
 ACCEPTED MANUSCRIPT

expansion, the tensile strength of the ePTFE membrane decreased, but its flexibility, softness,

and elasticity increased. A detailed discussion can be found in Discussion S1 (Supporting

Information). More importantly, ePTFE membranes offer a significantly increased contact

surface area for charge transfer and induction, and thus are favorable for triboelectric electricity

PT
output [37]. The nylon fabric acts as the other tribomaterial owing to the large polarity difference

RI
between it and ePTFE, thereby enabling large charge transfer upon contact [40, 41].

Generally, the fundamental theory of TENGs starts from Maxwell’s displacement current

SC
[42], which is attributed to the coupling effect of contact electrification and electrostatic

induction. The electricity generation process of the TENG within one cycle is illustrated in Fig.

U
2b. To start, at the original state, the initial contact of the ePTFE membrane with the nylon fabric
AN
brings about the charge transfer at the interface due to the electron affinity difference, resulting

in positive charges on the nylon fabric surface and negative charges on the ePTFE membrane
M

surface (Fig. 2b I). Because there is no separation distance and no potential drop between the two
D

surfaces, the TENG stays in an electrostatic equilibrium state. The ePTFE membrane is
TE

composed of a large number of nanofibers intertwined together, as shown in the enlarged part of

Fig. 2a, and yields very high porosity and extremely large surface areas within and on the surface
EP

of the ePTFE membrane [37], thus resulting in high surface charges. Then, when the external

force is releasing, some additional charges inside the pores are generated due to the recovery of
C

the original shape and associated electrostatic effects upon the force release [43]. As a result,
AC

both high surface charges and additional inner charges result in an increase of the total

accumulated charges. At the same time during releasing, an electric potential drop occurs

between the two tribomaterials, driving the electrons to flow from the ePTFE membrane to the

nylon fabric through the connecting electrodes. Thus, a current is generated in the external circuit

9
 ACCEPTED MANUSCRIPT

(Fig. 2b II). Once the external force is fully released, a maximum gap distance between the

ePTFE membrane and the nylon fabric is formed, where all of the triboelectric charges are

screened and electrons stop flowing (Fig. 2b III). At this point, another electrostatic equilibrium

state is formed (Fig. 2b III). As the two tribomaterials are approaching each other once again

PT
under the external force, electrons are driven back from the nylon fabric to the ePTFE membrane

RI
through the connecting electrodes to balance the change of potential difference (Fig. 2b IV) and

reach a new electrostatic equilibrium state again (Fig. 2b I).

SC
3.2 Surface properties of the tribomaterials in ePTFE/Nylon-TENGs

U
The surface morphologies of the tribomaterials can be found in Fig. 3, which shows SEM
AN
images of the nylon fabric and ePTFE membranes under different expansion ratios on the inner

and outer surfaces. From Fig. 3a it can be seen that the interwoven structure of the nylon fabric
M

provides a large contact area and deforms when an external force is applied [40, 44]. The surface
D

features of a PTFE membrane without expansion are shown in Fig. 3b, where it can be seen that
TE

the PTFE membrane consisted of sub-micron PTFE particles despite having a fairly smooth

surface at a lower magnification. Due to the stiffness of the unexpanded PTFE, the effective
EP

contact surface area was limited under the same external force [45]. In comparison, the expanded

ePTFE membrane (ePTFE) exhibited a completely different morphology, as depicted in Fig. 3d.
C

The ePTFE membrane can be described as a porous structure with ePTFE fibrils oriented parallel
AC

to the direction of expansion and interconnected with strip-shaped “islands” or “nodes” [46].

Clearly, these increased fibrils yielded very high porosities and extremely large surfaces within

and on the surface of the ePTFE membranes [37], thereby effectively increasing the contact

surface area. With an increase of the expansion ratio, the ePTFE fibril length increased gradually,

resulting in a synchronous increase of porosity, as shown in Fig. 3c. The statistics of measured

10
 ACCEPTED MANUSCRIPT

fibril lengths and the distribution of ePTFE membranes under different expansion ratios can be

found in Fig. S7 (Supporting Information). It should be noted that the length of the ePTFE fibril

increased from about 5 µm to over 30 µm as the expansion ratio grew from 100 to 400%.

Furthermore, the outside surfaces had longer ePTFE fibrils than the inner surfaces at the same

PT
expansion ratio, which was attributed to greater material deformation along the converging

RI
outside surface. This special structure affected the output performance of the ePTFE/Nylon-

TENGs. On the one hand, with the

U SC
AN
M
D
TE
C EP
AC

Fig. 3. (a) SEM image showing the surface morphologies of the nylon fabric. (b) SEM images of the

PTFE membrane without expansion (0%) under low magnification and high magnification (inset). (c)

Measured fibril length of ePTFE membranes with an expansion ratio ranging from 100% to 400%. (d)

SEM images of ePTFE membranes with expansion ratios from 100% to 400% on the (I) inner surfaces

and (O) outer surfaces.

11
 ACCEPTED MANUSCRIPT

porous structure, some additional charges were generated within the pores due to the restoration

of the pores to their original shapes, as well as the associated electrostatic effects after release,

resulting in an increased total electrical output [43, 47, 48]. On the other hand, a certain amount

PT
of pores effectively increased the contact surface area upon compressing, which yielded more

RI
charges and a higher output power. Nonetheless, ePTFE membranes with overly long fibrils

brought about a significant attenuation of the effective contact area. As a result, there exists an

SC
optimal expansion ratio in terms of the maximum output performance of the ePTFE/Nylon-

TENGs. For comparison, the surface morphologies after TENG measurements are shown in Fig.

U
S8, and the corresponding ePTFE fibril length distribution can be seen in Fig. S9. The ePTFE
AN
membranes retained a fibrous and porous structure, even though the ePTFE fibril length

distribution became wider. (Fig. S10 in the Supporting Information and Discussion S2).
M

To further characterize the surface properties of the as-fabricated ePTFE membranes,

D

water contact angle (WCA) [49, 50] measurements were performed and the obtained results are
TE

show in Fig. 4a. As shown, the contact angle of PTFE without expansion (122.3°) increased

slightly when a 100% expansion ratio was applied due to increased surface roughness.
EP

Furthermore, an upward force was generated by the air inside the pores, thereby lifting the water

droplets [51]. Subsequently, the contact angle then decreased linearly with the expansion ratio,
C

due to the increase in the number of pores that pemitted water permeation into the interior of the
AC

ePTFE membranes through pores, thus enhancing the hydrophilicity. Moreover, a slight

difference was observed between the inner and outer surfaces, where the contact angle on the

inner surface was slightly larger than that on the outer surface. The results of the water contact

angle also confirmed the changes of the fiber length and porosity of the ePTFE membranes,

12
 ACCEPTED MANUSCRIPT

which were consistent with the SEM images shown in Fig. 3d. Figure 4b shows the final

thickness of the ePTFE membranes, which decreased steadily with increasing expansion ratio.

The reason why the membrane thickness increased slightly when the expansion ratio increased

from 0 to 100% was due to the formation of a porous structure after expansion. Beyond the 100%

PT
expansion ratio, ePTFE tube thickness started to decrease as it expanded primarily in the

RI
stretching direction.

U SC
AN
M
D
TE
C EP
AC

Fig. 4. (a) Water contact angle of ePTFE membranes under different expansion ratios. (b) The measured

thickness of an ePTFE membrane versus the expansion ratio. Insets are of the corresponding SEM images

at different expansion ratios.

13
 ACCEPTED MANUSCRIPT

3.3 The impact of the expansion ratio on the output performance of ePTFE/Nylon-TENGs

ePTFE membranes with expansion ratios from 0 to 400% were prepared and

ePTFE/Nylon-TENG devices were fabricated accordingly. In view of the different surface

morphologies due to the paste extrusion method, both the inner and outer surfaces of the ePTFE

PT
tubes were tested to evaluate the performance of ePTFE/Nylon-TENGs. To systematically

RI
investigate the effect of the expansion ratio and surface morphology, the output signals of

ePTFE/Nylon-TENGs were measured and compared, as depicted in Fig. 5. Although

SC
considerable electrical outputs have been obtained using PTFE membrane without expansion,

with a peak open-circuit voltage, short-circuit current, and charge density of 38.51 V, 3.65

U
µA/cm², and 4.94 nC/cm², respectively, the effect of expansion on the electrical signals is still
AN
evident.

Taking the output performance of the ePTFE/Nylon-TENG using the inner surface (I-
M

ePTFE/Nylon-TENG) as an example, at an expansion ratio of 100%, the electrical signals

D

exhibited a remarkable improvement of about 55%, with the output signals leaping to 61.23 V,
TE

5.63 µA/cm², and 7.42 nC/cm² for the peak open-circuit voltage, short-circuit current, and charge

density, respectively. The porous structure of the surface was caused by expansion, which
EP

enlarged the contact surface area and provided additional charges inside the pores [43, 47, 48].

Further increasing the expansion ratio led to a gradual decrease in the output performance of the
C

I-ePTFE/Nylon-TENG. This was because, as the expansion ratio grew, the length of the PTFE
AC

fibrils extended progressively, which also meant that the porosity of the ePTFE increased. When

the length of the PTFE fibrils in the ePTFE membranes reached a certain length, the expansion

process no longer increased the contact surface area. Namely, when the expansion ratio was too

large, the length of the PTFE fibrils was so long that the porosity of the membrane actually led to

14
 ACCEPTED MANUSCRIPT

a decrease in the contact area. Nevertheless, the output electrical signals of I-ePTFE/Nylon-

TENGs with an expansion ratio of 200% were still much higher than those without expansion

(Fig. 5a to c) owing to the additional charges induced inside of the ePTFE membranes. Until the

expansion ratio reached 300%, the output electric signals came close to those measured without

PT
expansion. The electrical signals of the I-ePTFE/Nylon-TENGs with an expansion ratio of 400%

RI
were lower than those without expansion, which indicated the weakening effect of the effective

contact area and thus the reduced output signal.

U SC
AN
M
D
TE
C EP
AC

Fig. 5. The (a) open-circuit voltages, (b) short-circuit currents, and (c) transferred charge densities of

ePTFE/Nylon-TENGs under different expansion ratios on both surfaces (where “I” stands for the inner

15
 ACCEPTED MANUSCRIPT

surface and “O” is the outer surface). Dependence of (d) voltages, (e) currents, and (f) instantaneous

power density of ePTFE/Nylon-TENGs on load resistances.

The output performance of ePTFE/Nylon-TENGs using the outer surfaces (O-

PT
ePTFE/Nylon-TENGs) showed the same trend as those of the I-ePTFE/Nylon-TENGs. It is

notable that all of the I-ePTFE/Nylon-TENGs yielded somewhat higher electrical outputs than

RI
the O-ePTFE/Nylon-TENGs. More precisely, the output electrical signals of unexpanded

SC
PTFE/Nylon-TENGs fell between the signals of the I-ePTFE/Nylon-TENGs and the O-

ePTFE/Nylon-TENGs under an expansion ratio of 300%. The results clearly showed that the

U
expansion had a significant effect on the output performance, and the inner surfaces performed
AN
better than the outer surfaces.

The dependence of output voltages and currents on the load resistances was also systema-
M

tically investigated. It was found that all of the output voltages exhibited an increasing trend with
D

increased load resistance, while the currents exhibited a reverse-proportional relationship, as

TE

plotted in Fig. 5d and e. More specifically, the output curves were divided into four groups

according to the expansion ratios from 100% to 400%, which was consistent with the variation of
EP

surface microstructures observed by SEM in Fig. 3. In other words, the effect of the expansion

ratio of the ePTFE membranes on the output performance was relatively greater than the
C

different surfaces; namely, the inner surface and the outer surface. It is worth mentioning that at
AC

each load resistance, both of the output voltages and currents showed the same trends as the

results shown in Fig. 5a and b, respectively. In addition, it can be seen more clearly that the

electrical outputs of the PTFE/Nylon-TENG without expansion fell between the signals of the I-

ePTFE/Nylon-TENG and the O-ePTFE/Nylon-TENG under an expansion ratio of 300%,

consistent with the results in Fig. 5a to c. Figure 5f shows the curves of the instantaneous power

16
 ACCEPTED MANUSCRIPT

densities versus the external resistance of the I-ePTFE/Nylon-TENGs and O-ePTFE/Nylon-

TENGs under different expansion ratios. The I-ePTFE/Nylon-TENG yielded a maximum power

density of 1.01 mW/cm² at an expansion ratio of 100% and a load resistance of 1 MΩ, compared

to only 0.37 mW/cm² for the PTFE/Nylon-TENG without expansion.

PT
In addition, Fig. 6 displays the direct relationship between the output electrical signals

RI
and the expansion ratio. As the expansion ratio increased, all of the electrical signals presented a

similar trend for the output voltage (Fig. 6a), current (Fig. 6b), and power density (Fig. 6c).

SC
Specifically, as the expansion ratio increased, the output signals first increased and then

decreased, with the best performance at an expansion ratio of 100%. It can be seen that all of the

U
ePTFE/Nylon-TENGs with an expansion ratio of 100% and 200% involving inner and outer
AN
surfaces possessed clearly superior output performances compared to that of 0% expansion,

signifying that the expansion process tremendously enhanced the output performance of
M

ePTFE/Nylon-TENGs. Furthermore, the influence of the ePTFE membrane thickness on the

D

output performance of ePTFE/Nylon-TENG was investigated and the results are shown in Fig.
TE

S11 and Discussion S3 in the Supporting Information.

C EP
AC

Fig. 6. Curves showing the relationship between the (a) open-circuit voltage, (b) short-circuit current, and

(c) power density and expansion ratio of the inner and outer surfaces.

17
 ACCEPTED MANUSCRIPT

As discussed above, the ePTFE/Nylon-TENGs using inner ePTFE membranes with an

expansion ratio of 100% exhibited the best output performance among all of the ePTFE/Nylon-

TENGs. To better characterize the output performance of the as-fabricated ePTFE/Nylon-

TENGs and their potential for practical applications, a series of measurements were carried out,

PT
as demonstrated in Fig. 7. The output voltage and current before and after rectifying at the

RI
optimum power (1 MΩ) are shown in Figs. 7a and b, respectively. After rectification, a

waveform of one polarity was obtained operating at a frequency twice that of the ePTFE/Nylon-

SC
TENG supply. When applying an alternative mechanical force by the shaker on the

ePTFE/Nylon-TENG, the mechanical energy was simultaneously converted into electric energy

U
and then stored in capacitors [52]. To test the performance of the ePTFE/Nylon-TENG for
AN
capacitive load, different capacitors were charged with the ePTFE/Nylon-TENG, as shown in Fig.

7c, with the equivalent circuit diagram in the inset. The results showed that the charging time for
M

the same charging potential grew longer as the capacitance increased. Typically, the
D

ePTFE/Nylon-TENG can charge a capacitor of 4.7 µF to about 5 V within 100 s; thus, the stored
TE

energy could be used to power small electronics. As shown in Fig. 7d, the voltage of the 4.7 µF

capacitor initially increased linearly to ~5 V in 100 s, making it capable of powering one

EP

commercial light emitting diode (LED) while the voltage of the capacitor dropped 2 V rapidly.

As the ePTFE/Nylon-TENG continuously charged, the capacitor was charged back up to ~5 V,

C

suggesting that the harvested energy was not only sufficient to charge the capacitor but also to
AC

drive small electronics. The enlarged inset in Fig. 7d shows the charging curve in 1 s, from

which it can be seen that the capacitor was charged by 6.37 mV within one operating cycle of the

ePTFE/Nylon-TENG. Meanwhile, to explore the charging and discharging characteristics of the

4.7 µF capacitor using an ePTFE/Nylon-TENG, resistors with diverse resistances were used to

18
 ACCEPTED MANUSCRIPT

characterize the discharging speed (Fig. 7e). As shown in Fig. 7e, the charging curve before 100

s had excellent repeatability, thus verifying the working stability of the ePTFE/Nylon-TENG.

Furthermore, as expected, the discharging time of the capacitor increased with the increment of

discharge resistance.

PT
To demonstrate the capability of the ePTFE/Nylon-TENG as a sustainable power source,

RI
it was directly connected to LEDs without a storage unit. As shown in Fig. 7f and Video S2

(Supporting Information), LEDs forming the letters “WID” (the abbreviation of the “Wisconsin

SC
Institute for Discovery”) were simultaneously lit up to full brightness.

Finally, the durability and stability of the ePTFE/Nylon-TENGs were investigated, as

U
there are important concerns for TENGs in real-world applications [53]. The output performance
AN
of 50 cycles, including open-circuit voltage and short-circuit current, were recorded after 100,

1000, and 10,000 continuous cycles under the same operating conditions. As confirmed in Fig.
M

7g, the short-circuit current density and open-circuit voltage exhibited no measurable
D

degradation, indicating the excellent durability of the fabricated ePTFE/Nylon-TENG devices.

TE
C EP
AC

19
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D
TE

Fig. 7. (a) Output voltage at a load resistance of 1 MΩ. (b) Output current at a load resistance of 1 MΩ. (c)

Charging curves of commercial capacitors with different capacitances using the ePTFE/Nylon-TENG
EP

through a bridge rectifier. The inset shows the equivalent circuit diagram for charging and discharging. (d)
C

Potential of a 4.7 µF capacitor connected to an ePTFE/Nylon-TENG via a rectifier bridge that powered an

LED three times for 1 s each time. The inset shows the enlarged curve between 17 and 18 s. (e)
AC

Continuous charging and discharging curves for different resistors. (f) Equivalent circuit diagram for

lighting the LEDs and a digital photograph of the powered LEDs spelling out the letters “WID.” (g)

Electrical output stability test of the ePTFE/Nylon-TENG.

20
 ACCEPTED MANUSCRIPT

4. Conclusions

In summary, lightweight ePTFE membranes at different expansion ratios ranging from 0%

to 400% via uniaxial expansion were prepared. As the expansion ratio increased, the ePTFE

PT
fibril length increased gradually, which affected the effective contact surface area and induced

charges within the ePTFE membrane. Flexible folded-paper TENGs using ePTFE membranes

RI
and nylon fabric as the two tribomaterials were fabricated to systematically study the effect of

the expansion ratio on the output performance. The results showed that the expansion ratio had a

SC
significant influence on the output performance of the ePTFE/Nylon-TENGs. As the expansion

U
ratio increased, the output electrical signals of the ePTFE/Nylon-TENGs first increased
AN
significantly, and then decreased gradually, with an optimum performance at an expansion ratio

of 100%. In addition, the output performance of the PTFE/Nylon-TENG without expansion had
M

an approximate performance to that of the ePTFE/Nylon-TENGs at an expansion ratio of 300%.

The ePTFE/Nylon-TENGs fabricated here demonstrated excellent and stable performances,

D

yielding a maximum power density of 1.01 mW/cm² with an effective area of 1 cm², at an
TE

expansion ratio of 100% and a load resistance of 1 MΩ. This work shows that the expansion

process for ePTFE materials used here effectively enhanced the output performance of
EP

ePTFE/Nylon-TENGs, thus expanding the application prospects of ePTFE for energy harvesting
C

applications.
AC

Conflicts of Interest

The authors declare no competing financial interest.

Acknowledgments

21
 ACCEPTED MANUSCRIPT

Z. Zhang and Y. Xu contributed equally to this work. The research was supported by the

Wisconsin Institute for Discovery at University of Wisconsin–Madison and the grants from

Donghua University (No. 101-02-000120). Zhi Zhang also would like to acknowledge the

fellowship from the China Scholarship Council (CSC) under the Grant CSC No. 201806630079.

PT
RI
Appendix A. Supporting information

Supplementary data associated with this article is provided.

U SC
AN
M
D
TE
C EP
AC

22
 ACCEPTED MANUSCRIPT

References

[1] Z.L. Wang, ACS Nano 7 (2013) 9533.

[2] Z.L. Wang, Faraday Discuss. 176 (2014) 447.
[3] R. Wen, J. Guo, A. Yu, K. Zhang, J. Kou, Y. Zhu, Y. Zhang, B.-W. Li, J. Zhai, Nano Energy 50

PT
(2018) 140.
[4] X.-W. Zhang, G.-Z. Li, G.-G. Wang, J.-L. Tian, Y.-L. Liu, D.-M. Ye, Z. Liu, H.-Y. Zhang, J.-C.
Han, ACS Sustain. Chem. Eng. 6 (2018) 2283.

RI
[5] Z.L. Wang, J. Chen, L. Lin, Energ. Environ. Sci. 8 (2015) 2250.
[6] Z. Fang, K.H. Chan, X. Lu, C.F. Tan, G.W. Ho, J. Mater. Chem. A 6 (2018) 52.

SC
[7] X. Cheng, L. Miao, Y. Song, Z. Su, H. Chen, X. Chen, J. Zhang, H. Zhang, Nano Energy 38
(2017) 448.
[8] M. Seol, S. Kim, Y. Cho, K.E. Byun, H. Kim, J. Kim, S.K. Kim, S.W. Kim, H.J. Shin, S. Park,
Adv. Mater. 30 (2018) 1801210.
U
AN
[9] S. Pan, Z. Zhang, Friction 7 (2019) 2.
[10] Y. Bian, T. Jiang, T. Xiao, W. Gong, X. Cao, Z. Wang, Z.L. Wang, Adv. Mater. Technol. 3 (2018)
1700317.
M

[11] B.D. Chen, W. Tang, C. He, C.R. Deng, L.J. Yang, L.P. Zhu, J. Chen, J.J. Shao, L. Liu, Z.L.
Wang, Mater. Today 21 (2018) 88.
D

[12] H. Guo, X. Jia, L. Liu, X. Cao, N. Wang, Z.L. Wang, ACS Nano 12 (2018) 3461.
TE

[13] M. Ma, Z. Kang, Q. Liao, Q. Zhang, F. Gao, X. Zhao, Z. Zhang, Y. Zhang, Nano Res. 11 (2018)
2951.
[14] Z. Li, Z. Saadatnia, Z. Yang, H. Naguib, Energy Convers. Manage. 174 (2018) 188.
EP

[15] G. Zhu, J. Chen, T. Zhang, Q. Jing, Z.L. Wang, Nat. Commun. 5 (2014) 3426.
[16] G. Zhu, Y.S. Zhou, P. Bai, X.S. Meng, Q. Jing, J. Chen, Z.L. Wang, Adv. Mater. 26 (2014) 3788.
[17] J. Chen, Y. Huang, N. Zhang, H. Zou, R. Liu, C. Tao, X. Fan, Z.L. Wang, Nature Energy 1 (2016)
C

16138.
AC

[18] Z. Li, J. Chen, J. Zhou, L. Zheng, K.C. Pradel, X. Fan, H. Guo, Z. Wen, M.-H. Yeh, C. Yu, Z.L.
Wang, Nano Energy 22 (2016) 548.
[19] Y. Xi, H. Guo, Y. Zi, X. Li, J. Wang, J. Deng, S. Li, C. Hu, X. Cao, Z.L. Wang, Adv. Energy
Mater. 7 (2017) 1602397.
[20] B. Dudem, D.H. Kim, A.R. Mule, J.S. Yu, ACS Appl. Mater. Inter. 10 (2018) 24181.
[21] X.-S. Zhang, M.-D. Han, R.-X. Wang, F.-Y. Zhu, Z.-H. Li, W. Wang, H.-X. Zhang, Nano Lett.
13 (2013) 1168.

23
 ACCEPTED MANUSCRIPT

[22] J.-W. Lee, W. Hwang, Nano Energy 52 (2018) 315.

[23] I.-W. Tcho, W.-G. Kim, S.-B. Jeon, S.-J. Park, B.J. Lee, H.-K. Bae, D. Kim, Y.-K. Choi, Nano
Energy 42 (2017) 34.
[24] W.X. Chen, F. Li, G. Han, J.B. Xia, L.Y. Wang, J.P. Tu, Z.D. Xu, Tribol. Lett. 15 (2003) 275.
[25] J. Chen, Z.L. Wang, Joule 1 (2017) 480.

PT
[26] M. Lai, B. Du, H. Guo, Y. Xi, H. Yang, C. Hu, J. Wang, Z.L. Wang, ACS Appl. Mater. Inter. 10
(2018) 2158.
[27] S.H. Wang, L. Lin, Y.N. Xie, Q.S. Jing, S.M. Niu, Z.L. Wang, Nano Lett. 13 (2013) 2226.

RI
[28] R. Cao, T. Zhou, B. Wang, Y. Yin, Z. Yuan, C. Li, Z.L. Wang, ACS Nano 11 (2017) 8370.
[29] S.W. Chen, X. Cao, N. Wang, L. Ma, H.R. Zhu, M. Willander, Y. Jie, Z.L. Wang, Adv. Energy

SC
Mater. 7 (2017) 1601255.
[30] W. Yang, J. Chen, Q. Jing, J. Yang, X. Wen, Y. Su, G. Zhu, P. Bai, Z.L. Wang, Adv. Funct.

U
Mater. 24 (2014) 4090.
[31] W.Q. Yang, J. Chen, G. Zhu, J. Yang, P. Bai, Y.J. Su, Q.S. Jing, X. Cao, Z.L. Wang, ACS Nano
AN
7 (2013) 11317.
[32] J.C. Jin Yang, Ying Liu, Weiqing Yang, Yuanjie Su, and Zhong LinWang, ACS Nano 8 (2014)
2649.
M

[33] J. Chen, J. Yang, H.Y. Guo, Z.L. Li, L. Zheng, Y.J. Su, Z. Wen, X. Fan, Z.L. Wang, ACS Nano 9
(2015) 12334.
D

[34] J. Chen, G. Zhu, W. Yang, Q. Jing, P. Bai, Y. Yang, T.C. Hou, Z.L. Wang, Adv. Mater. 25 (2013)
TE

6094.
[35] J. Zhu, Y. Zhu, X. Wang, Adv. Mater. Interfaces 5 (2018) 1700750.
[36] B.D. Chen, W. Tang, C. He, T. Jiang, L. Xu, L.P. Zhu, G.Q. Gu, J. Chen, J.J. Shao, J.J. Luo, Z.L.
EP

Wang, Adv. Mater. Technol. 3 (2018) 1700229.

[37] M. Wang, J. Zhang, Y. Tang, J. Li, B. Zhang, E. Liang, Y. Mao, X. Wang, ACS Nano 12 (2018)
6156.
C

[38] S. Abu Nahian, R.K. Cheedarala, K.K. Ahn, Nano Energy 38 (2017) 458.
AC

[39] X. Fan, J. Chen, J. Yang, P. Bai, Z.L. Li, Z.L. Wang, ACS Nano 9 (2015) 4236.
[40] Z. Zhang, Y. Chen, D.K. Debeli, J.S. Guo, ACS Appl. Mater. Inter. 10 (2018) 13082.
[41] S. Liu, W. Zheng, B. Yang, X. Tao, Nano Energy 53 (2018) 383.
[42] Z.L. Wang, Mater. Today 20 (2017) 74.
[43] K.Y. Lee, J. Chun, J.-H. Lee, K.N. Kim, N.-R. Kang, J.-Y. Kim, M.H. Kim, K.-S. Shin, M.K.
Gupta, J.M. Baik, S.-W. Kim, Adv. Mater. 26 (2014) 5037.
[44] S.S. Kwak, H. Kim, W. Seung, J. Kim, R. Hinchet, S.-W. Kim, ACS Nano 11 (2017) 10733.

24
 ACCEPTED MANUSCRIPT

[45] Z. Zhang, X. Sun, Y. Chen, D.K. Debeli, J. Guo, J. Appl. Phys. 124 (2018) 045106.
[46] S. Ebnesajjad, Expanded PTFE Applications Handbook, Elsevier, (2017) pp. 163-169.
[47] Q. Zheng, L. Fang, H. Guo, K. Yang, Z. Cai, M.A.B. Meador, S. Gong, Adv. Funct. Mater. 28
(2018) 1706365.
[48] H.-Y. Mi, X. Jing, Q. Zheng, L. Fang, H.-X. Huang, L.-S. Turng, S. Gong, Nano Energy 48

PT
(2018) 327.
[49] J. Chen, G. Zhu, J. Yang, Q.S. Jing, P. Bai, W.Q. Yang, X.W. Qi, Y.J. Su, Z.L. Wang, ACS Nano
9 (2015) 105.

RI
[50] X. Yang, S. Chan, L. Wang, W.A. Daoud, Nano Energy 44 (2018) 388.
[51] C. Cui, X. Wang, Z. Yi, B. Yang, X. Wang, X. Chen, J. Liu, C. Yang, ACS Appl. Mater. Inter. 10

SC
(2018) 3652.
[52] H. Guo, M.-H. Yeh, Y. Zi, Z. Wen, J. Chen, G. Liu, C. Hu, Z.L. Wang, ACS Nano (2017) 11

U
(2017) 4475.
[53] Z.L. Li, J.L. Shen, I. Abdalla, J.Y. Yu, B. Ding, Nano Energy 36 (2017) 341.
AN
M

Vitae
D
TE
EP

Zhi Zhang received her B.S. degree in Textile Engineering from Qingdao University, China in
C

2014. She is now a Ph.D. candidate in the College of Textiles in Donghua University, China and
AC

a visiting scholar in Wisconsin Institute for Discovery and Department of Mechanical

Engineering at University of Wisconsin-Madison, US. Her research interests mainly focus on

flexible triboelectric nanogenerator and wearable electronics.

25
 ACCEPTED MANUSCRIPT

PT
Yiyang Xu graduated from the Zhengzhou University of China in 2016. He has been working in

RI
the University of Wisconsin Madison as a postdoc since 2017. His research interests mainly

include nanomaterial, polymer processing and tissue engineering.

U SC
AN
M

Dongfang Wang received his Master degree in Materials Engineering from Zhengzhou

University, China in 2016. He is now a Ph.D. candidate in the School of Mechanics and
D

Engineering Sciences in Zhengzhou University, China and a visiting scholar in Wisconsin

TE

Institute for Discovery and Department of Mechanical Engineering at University of Wisconsin-

Madison, US. His research interests mainly focus on polymer engineering and artificial small
EP

diameter blood vessel.

C
AC

26
 ACCEPTED MANUSCRIPT

Huaguang Yang received his B.S. degree in Mechanical Engineering from Beijing University of

Chemical Technology, China in 2014. He is now a Ph.D. candidate in the College of Mechanical

and Electrical Engineering in Beijing University of Chemical Technology, China and a visiting

scholar in Wisconsin Institute for Discovery and Department of Mechanical Engineering at

PT
University of Wisconsin-Madison, US. His research interests mainly focus on polymer

RI
processing and thin-film graphene heater.

U SC
AN
M

Jiansheng Guo received his Ph.D. degree in University of Stuttgart, Germany in 2000. Now he

is a Full Professor in College of Textiles in Donghua University, China. His research mainly
D

focuses on bionic and functional textile materials, textile based nanogenerator, textile surface
TE

treatment technology, textile composites et al.

C EP
AC

Lih-Sheng Turng received his Ph.D. from Cornell University, US. He now is the Kuo K. and

Cindy F. Wang professor, Vilas Distinguished Achievement Professor in Wisconsin Institute for

27
 ACCEPTED MANUSCRIPT

Discovery and Department of Mechanical Engineering at University of Wisconsin-Madison, US.

His research interests focus on nanotechnology, precision medicine and tissue engineering.

PT
RI
U SC
AN
M
D
TE
C EP
AC

28
 ACCEPTED MANUSCRIPT
Highlights

• Expanded PTFE (ePTFE) membranes, which possess excellent flexibility and

elasticity, as well as a unique fibrillated, porous structure different from
traditional PTFE films, were prepared and used to fabricate triboelectric
nanogenerators (TENGs) with enhanced output performances.

PT
• Flexible triboelectric generators using ePTFE membranes (with different
uniaxial expansion ratios) and nylon fabrics acting as two tribolayers

RI
(ePTFE/Nylon TENGs) were fabricated to systematically study the effect of the

SC
PTFE expansion ratio on the output performance.

• Based on the fibrillated morphologies of the ePTFE membranes and the

U
corresponding electrical output of the ePTFE/Nylon TENGs, the underlying
AN
mechanism of the expansion ratio on the output performance was explored and
elaborated upon.
M
D
TE
C EP
AC