Rotational Triboelectric Nanogenerator Based on a PDMS@CS

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C: Energy Conversion and Storage; Energy and Charge Transport

Rotational Triboelectric Nanogenerator Based on PDMS@CSs Composite Material Kai Li, Yesheng Wu, Qi Liu, Guanggui Cheng, Zhongqiang Zhang, Liqiang Guo, Ying Wang, and Jianning Ding J. Phys. Chem. C, Just Accepted Manuscript • DOI: 10.1021/acs.jpcc.8b08361 • Publication Date (Web): 05 Oct 2018 Downloaded from http://pubs.acs.org on October 8, 2018

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The Journal of Physical Chemistry

Rotational Triboelectric Nanogenerator Based on PDMS@CSs Composite Material Li Kaia, Wu Ye-Shenga, Liu Qia, Cheng Guang-Guia,b*ID, Zhang Zhong-Qianga,b, Guo Li-Qianga,b, Wang Ying b , Ding Jian-Ninga,b* a. Research Center of Micro/Nano Science and Technology, Jiangsu University, Zhenjiang, China b. Jiangsu Collaborative Innovation Center of Photovoltaic Science and Engineering, Changzhou University, Changzhou, China

ABSTRACT: Triboelectric nanogenerator (TENG) is a kind of green and clean energy harvesting device based on the principle of triboelectrification and electrostatic induction. In this paper, a rotational triboelectric nanogenerator (RTENG) was designed and fabricated. Three categories of factors as rotating speed, external loads and the air humidity influence on the output performance were studied. Results show that a RTENG having an area of 2.4×6.3 cm2 can produce electric power of 0.52 mW during the compound motion of vertically contact-separating and lateral sliding with the external load of 20 MΩ. The output voltage at the rotation speed of 300 rpm is 200V. The maximum output voltage increases with the external load until the resistance surpasses 300 MΩ, while the current is inversely proportional to the external resistance. The RTENG can instantaneously drive hundreds of light-emitting diodes and can also charging a capacitor. Furthermore, the output performance can be easily adjusted by adding different pairs of rotor blades and be driven by various forms of energy such as wind energy, water energy and even motion energy of body.

*

To whom correspondence should be addressed. E-mail: [email protected], [email protected]

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INTRODUCTION Great attentions have been paid to the energy harvesting methods ，with the growing demand of energy especially in the form of electric. The triboelectric nanogenerator (TENG ） , which is based on the triboelectrification and electrostatic induction1-4 can convert random and irregular mechanical energy like wind energy5,6, flowing water energy 7, body motion energy8,9 and other types of energy10,11 into usable electrical energy. Due to its easily designing and fabricating, high energy conversion efficiency and wide application area, the research of TENG has become a popular frontier. The TENG acting as a self-powered source has been successfully applied in many industrial products12 such as self-powered touch sensor13,14, self-powered photodetection15, self-powered anti-corrosion16,17, self-powered acceleration sensor 18, self-powered wind sensor 19, organics detecting sensor20,21, vibration and position determine sensor22, and also in biomedical engineering23-25. However, the most disadvantage of the TENG is its low output current. In order to enhance the output performance, several methods are carried out, e.g., patterning micro/nano structures on the polymer surface26,27, polymer surface treatment28-30, chemically functionalization of the polymer surface31,32, ionized injection SiO2 Electret33,34, inserting of charge storage layer35 and optimizing the frictional pairs36 etc.. Recently, Wang et al

37

combine TENG with other forms of

generator such as electromagnetic generator, solar cell 38 and so on. All these have greatly enhanced the output performance of the system. Almost all the TENGs are based on contact and separation according to basic theory of


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triboelectrification12(12). There are about three main kinds of contact and motion mode: vertical contact-separation mode14, lateral sliding mode39 and their combination. Great progress has been made ever since 2012, and to date, its maximum output power density can reach to 500 W/m2 85%)

27.

26(26)

with is much higher energy conversion efficiency (up to

Besides, the dual electrodes TENG can be equivalent to a capacitor with

polymer film as dielectric layer, so changing the dielectric constant of the dielectric layer is also an effective method to enhance the output performance. Herein, a RTENG that combining the vertical contact-separation mode and lateral sliding mode was designed and fabricated. Polymer film was prepared by mixing trace of carbon spheres (CSs) with PDMS. Several parameters such as the rotational velocity, the external load resistance and the environmental humidity are considered and their influences on the output performances are analyzed. EXPERIMENTAL FABRICATION OF PDMS@CSS THIN FILMS He et al

36

mixed PDMS with trace graphite particles (3.0%wt), and the output

performance was significantly improved. Inspired by his work, we chose carbon spheres as additives with the same content. In order to strengthen the film, 30 nm of carbon spheres (CSs) rich in chemical groups are prepared in the lab by hydrothermal method of D-glucose

40

and the PDMS solution (Sylgard 184, Dow Corning) is commercially

purchased. Detail structures of the CSs were provided in support information (S1). Figure 1 shows the schematic diagram of the fabricating process of the PDMS@CSs thin



film. Firstly, the CSs dispersion is obtained by weighting 1.2 g of the CSs dispersing in 8.8 g alcohol and ultrasonically vibrating for 30 min. Secondly, to achieve the PDMS@CSs composite film, CSs dispersions were first mixed with PDMS (elastomer was thoroughly mixed with the curing agent in the weight ratio of 10: 1) and then mechanically stirred for 10 min. After the stirring, the mixture was placed in a vacuum chamber for 10 min to remove the bubbles. Finally, the mixture was spin-coated onto a Si wafer at 300 rpm for 30 s, and cured at 80℃ for 1h for subsequent use. Mixing Shaping Spin-coating PDMS CSs Silicon Wafer

Drying

PDMS+CSs Cutting

Figure1. The fabrication of PDMS@CSs film

FABRICATION AND MEASUREMENTS OF THE RTENG The prototype RTENG is shown in Figure 2. It includes a base, a shaft, external frame, flexible rotor blade and rotor blade as can be seen in Figure 2a. The aluminum foils were chosen as electrode. The Al foil is glued to the (Polyvinyl chloride)PVC sheet and fixed on the rotor as rotor blades; the as prepared PDMS@CSs film and Al foil are glued on a (Polyethylene terephthalate) PET film and fixed on the stator as stator blades. Aluminum and PDMS@CSs film act as friction pairs for RTENG. The PVC and PET with thickness


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of 0.1mm, act as supporting layers. Different materials of supporting layers were chosen due to their difference in stiffness (PET film is stiffer than PVC film). The size of the rotor and stator is designed to be 2.4×6.3 cm2. Finally, the conducting copper wires were connected to the two Al electrodes for subsequent electric measurement. The whole structure is driven by a speed regulating motor. By changing the rotation speed, the external loading, the environmental humidity, the output voltages under different parameters are tested by an oscilloscope (Tektronix TBS1102B).

(a)

(b)

Figure 2. The structure of a RTENG. (a) 3D conceptual illustration of RTENG (b) photo of the RTENG RESULTS AND DISCUSSIONS WORKING MECHANISM OF RTENG As we all know, the TENG is based on the compounding effect of contact electrification and electrostatic induction to convert mechanical energy into electrical energy. Once the two materials with different electronegativity namely the PDMS@CSs



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and Al film in this paper are in contact with each other, charge transfer occurs at their interface, with PDMS@CSs surface negatively charged and Al surface positively charged with equivalent of charge. When the two films are separated, the electric balance is broken and the induction potential between the upper and lower electrodes happens. This potential will drive electrons flow between the two electrodes in the short circuit state. The motion of the generator in this study is based on the contact-sliding-separatingcontact processes. The basic form of movement is shown in Figure 3, and the corresponding charge transfer is shown in Figure 4. At the original state where the rotor blade is stationary and the triboelectric layers are separated from each other (Figure 3(a)), there are no tribo-charges generated on the surfaces. When the speed control motor drives the rotor to rotate, the rotor blades will rotate along with the rotating shaft, so that the PDMS@CSs film will contact with the stator Al foil (Figure 3(b) and Figure 4(a)), and in this way electrons would transfer from the Al film to the PDMS@CSs surface according to the difference of triboelectric polarities41,42. The transferred negative charges would be retained on the surfaces of PDMS@CSs for a period of time due to its insulating property. To further demonstrated, the two surfaces are considered to be completely contacted, then the distance between the surfaces is zero, according to the V-Q-X relationship of vertical contact-separation mode42: V 

Q S 0

 d   x(t ) (  x(t )   0  r 

(1)

equation (1) is the potential difference between the upper and lower electrodes at any


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time. Considering the open circuit state, the transferred charge Q between the upper and lower electrodes is zero and the open circuit voltage ( Voc ) can be obtained by substituting the equation (1):

Voc 

 x(t ) 0

(2)

where d is the thickness of the PDMS@CSs film, V is the induction voltage, x(t ) is the distance between the PDMS@CSs surface and the Al electrode,  r is the relative permittivity of the PDMS@CSs,  0 is the vacuum dielectric constant. From equation (2), it can be seen that when x (t) is zero, Voc is zero. When the flexible rotor continues to rotate (Figure 3(c) and Figure 4(b)), the Al surface will be guided to slide outward across the PDMS@CSs film, leading to a continuous decrease in the overlapping area of the two tribo-charged surfaces and thus the in-plane charge separation. The lateral moment in parallel to the sliding surface will generate a higher potential on the Al surface, thus drives a current flow in the external load from the Al electrode to the electrode of PDMS@CSs to offset the tribo-charge-induced potential. This process will last until the Al surface fully slides out of the PDMS@CSs film (Figure 3(d) and Figure 4(c)), and the total transferred charges will equal the amount of the triboelectric charges on each surface. Figure 3(e) and Figure 4(d) is the process that the rotor is far away from the stator. At this point, negative charges stay on the PDMS@CSs surface due to its insulating property and it is balance with the bottom Al electrode. When the flexible rotor continues to rotate (Figure 4 (e)), the rotor will again approach to the stator, and the



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charge will flow from upper Al electrode to bottom Al electrode to maintain the balance of charge until the two surfaces approach each other again and form an inverted current. Due to the electrostatic induction effect, Figure 4(f) is the output voltages of one cycle. It is found that the curves of output voltage can be divided into three segments, which is corresponding to the above approaching, contacting and lateral sliding stage, respectively. The voltage produced by vertical contact dominates the other several output voltages. This is the working mechanism of the RTENG in the compound motion mode. Therefore, with the rotor continuously rotating, current will be obtained.

approaching detached

(a)

(e)

contact (b)

detaching (d)

sliding (c)

Figure 3. The relative position of stator and rotor (a) the rotor is approaching the stator (b) the rotor contact with the stator (c) the rotor slides on the stator (d) rotor separating (e) the rotor recover to the original state


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Pressing

Sliding (b)

（a） + + + + + + + + + + - - - - -- - - - -

++ ++ ++ - - - - -- - - - ++ ++

e

(c)

PVC substrate Al foil electrode

- - - - -- - - - ++ ++++ ++ ++

PDMS@CSs film PET substrate

Pressing

(e)

++ ++

(d)

e

- - - - -- - - - ++ ++++ ++ ++

- - - - -- - - - ++ ++++ 200 contact

Output voltage V

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100

approaching

lateral sliding

0

-100 0.10

0.15

Time s

0.20

(f) Figure 4. The process of charge generates and transfer.(a) contact under press (b)(c) sliding and detaching (d)fully recover to its original state (e) beginning of the new cycling (f) the output voltage of the whole contact-slid cycle.

Figure 5 shows the output voltage of the RTENG for one pair of blade at the speed of 300 rpm tested by oscilloscope, and the maximum peak voltage is 196 V.



200

Output voltage V

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100

0

-100

0

2

4

6

Time s Figure 5. Electric measurement results of the RTENG with the time at the speed of 300 rpm.

INFLUENCE OF THE ROTATION SPEED Increasing the contact area of two surfaces is an effective method to improve the output performance of TENG. The contact pressure results from the stator rotation and higher rotation speed will result in higher contact pressure and accelerating the contact-separating frequency, thereby affecting the output performance. Figure 6 is the variation curve of output voltage at different rotational speed with a pair of rotor stator with external loading of 100 M. It can be seen that at low speed, the output voltage increases significantly with the increase of rotating speed, which is mainly due to the following three reasons: firstly, with the increase of the speed, the centrifugal force of the rotor increases at the same diameter, which results in larger contact area and hence higher charge density during contacting with the stator; secondly, the variety of the capacitance. As we all know, a dual electrodes TENG can be equivalent as a parallel plate capacitor, change either the distance or face-to-face area will result in the change of capacitance value. The speed of


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lateral sliding will increases after contact of the stator and the rotor simultaneously with the rotation speed increases, and this result in the increasing change rate of the capacitor and hence the output voltage. However, when the rotating speed surpass 420 rpm, the increasing rate of output voltage begins to moderate and no obvious increase of the output voltage can be seen when furthering increase the rotating speed to 500 rpm with the output voltage keeps stable at about 185 V. Thirdly, deforming and springback of the rotor and the stator. Since the blades will deform during the contact, the contact area and corresponding output voltage will also change with the deformation. It can be seen from the error bar in Figure 6 that at low speed, both the stator and the rotor will endure deformation and springback during each period of contact, and the output voltage error bars is about 5 V. The error bars slightly go up with the increasing speed. However, when the speed is more than 350 rpm, the error bars decrease due to the increasing frequency of contact and separation. This decreases the influence of mechanical deformation gradually and the output voltage peaks become stable at high rotation speed. 200

Output voltage (V)

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160

120

80

40

100

200

300

400

500

600

Rotational Speed (rpm)

Figure 6. Variation of the output voltage with rotation speed



INFLUENCE OF EXTERNAL LOADING The load matching of the external circuit has a great influence on its output power because TENG relies on the electrostatic induction to generate electricity, and its inherent capacitance impedance is larger. Figure 7 (a) is the change of output voltage with the external loading when the rotational speed is 300 rpm. At first, the output voltage goes up with the increase of the external resistance. When the external resistance increases from 100 k to 300 M, the output voltage measured is 196 V, and no obvious increase of output voltage if further increasing the external resistance value. Therefore, the voltage that no longer increases with external resistance can be considered as Voc which is an important parameter for power source. Figure 7 (b) shows the calculated current and the output power with the external loading. It is found that the current decreases with the increase of the load resistance, while the power increases first and then decreases with the increase of load resistance. The maximum output power of about 0.52 mW is obtained when the external load is 20 MΩ, while the maximum current of 8.4 μA is obtained when the load is 5 MΩ. 0.6

10 200

8 0.4

100 50 0

6

Power mW

150

Current A

Voltage (V)

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4

0.2

2

0.0

0 0

500

1000

1500

Resistance (M)

2000

0

100

200

300

Resistance ()

(a)

(b)


400

500

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Figure 7. The output voltage, output current and output power vary with the external resistance (a) the output voltage varies with the external resistance (b) the output current (blue) and output power (red) change with the external resistance.

THE INFLUENCE OF ENVIROMENTAL HUMIDITY In our daily life, the triboelectrification is easier to happen especially in dry autumn and winter seasons than that in wetting summer. This indicates that the environmental humidity may also dominantly influence the output performance of the TENG. In order to investigate the humidity interactive mechanism on the surface charge, we put the whole equipment in a humidity controllable chamber. The output voltage was measured and shown in Figure 8 with carefully changing the relative humidity (RH) from 30% to 60%. The output voltage of RTENG decreases rapidly with the increase of humidity. When the humidity increases to 57%, the output voltage is only 50V. Literatures show that in dry environment, electrostatic charge can stably stay on the surface of an insulated material for several months43. Study of Grzybowski44showed that trace of water on the surface is beneficial to improve the stability of electron on the polymer surface. This maybe the reason why the RTENG keeps excellent output performance even when the RH increases to 40%.While further increasing the RH, the droplet aggregate on the surface of polymer which leads to increasing discharge rate and result in the deterioration of output performance45-47. The maximum error is about 4 V when RH is below 40%, and the output voltage becomes unstable with larger error bar for high RH.



Voltage (V)

200

150

100

50 30

40

50

60

Relative humidity (%)

Figure 8. The output voltage varies with the humidity in the air APPLICATIONS OF RTENG In order to expand the practical application of RTENG, a circuit was designed which was shown in the insert of Figure 9(a). Figure 9 is the charging curve of a 1 μF capacitor. It can be seen that the capacitor can be charged to 1.5 V within 8 s, and this means the amount of charge transferred in 8 s is 1.5 μC. Finally, we connect the RTENG to the LED array directly and it can turn on 60 blue LED lights directly at the rotational speed of 300 rpm (Figure 9(b)). 2.0 1.5 Voltage (V)

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1.0 0.5 0.0

0

4

8

Time (s )

12

16

(a)


(b)

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Figure 9. Applications of the RTENG. (a) Charging curve of a capacitor, (b) lighting up LED arrays CONCLUSIONS In summary, a RTENG based on the contact modes of vertical contact-separating mode and lateral sliding mode was developed and its working principle was analyzed. It generated electricity through triboelectric effect when harvesting rotational motion in ambient. The influence of rotational speed, external load and ambient humidity on the electrical output is studied. For one pair of frictional pair, the maximum output power is 0.52 mW, it has successfully charged the capacitor and lit up the LED array. The RTENG shows great output performance when the RH is below 40%, and the output voltage can reach 196V. It can substantially boost the electric output by increasing the number of rotor and stator. Due to its rotational structure design, further integration into different size and friction pairs can improve its output performance. ■AUTHOR INFORMATION Corresponding Author *E-mail: [email protected], [email protected]. ORCID Guanggui Cheng: 0000-0001-7327-4836 Notes The authors declare no competing ﬁnancial interest ACKNOWLEDGMENTS This work is supported by the National Natural Science Foundation of China (Grand No. 51675236, 91648109), the Research Innovation Program for College Graduates of Jiangsu Province (Grant No. SJCX18_0737).



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TOC graphic


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Graphic of the Manuscript Figure.1

The fabrication of PDMS@CSs film

Figure. 2

The structure of a RTENG (a) 3D conceptual illustration of RTENG (b)

photo of the RTENG Figure.3

The relative position of stator and rotor (a) the rotor is approaching the

stator (b) the rotor contact with the stator (c) the rotor slides on the stator (d) Rotor separating (e) The rotor recover to original state Figure.4

The process of charge generates and transfer.(a) contact under press (b)(c)

sliding and detaching (d)fully recover to its original state (e) beginning of the new cycling (f) the output voltage of the whole contact-slid cycle. Figure. 5

Electric measurement results of the RTENG with the time at the speed of

300rpm. Figure.6 Variation of the output voltage with rotation speed Figure.7

The output voltage, output current and output power vary with the external

resistance (a) the output voltage varies with the external resistance (b)the output current (blue)and output power(red) change with the external resistance. Figure.8

The output voltage varies with the humidity in the air

Figure.9

Applications of the RTENG (a) Charging curve of a capacitor, (b).lighting

up LED arrays



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Mixing Shaping Spin-coating PDMS CSs Silicon Wafer

Drying

PDMS+CSs Cutting

Figure.1

(a)

(b) Figure. 2

approaching detached

(a)

(e)

contact (b)

detaching (d)

sliding (c)

Figure.3


Page 23 of 25

Pressing

Sliding

(b)

（a） + + + + + + + + + + - - - - -- - - - -

++ ++ ++ - - - - -- - - - ++ ++

(c)

PVC substrate Al foil electrode

- - - - -- - - - ++ ++++ ++ ++

PDMS@CSs film PET substrate

++ ++

(d)

e

- - - - -- - - - ++ ++++ ++ ++

- - - - -- - - - ++ ++++ 200 contact

Output voltage V

(e)

Pressing

100

lateral sliding

approaching

0

-100 0.10

0.15

0.20

Time s (f)

Figure.4 200

Output voltage V

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


100

0

-100

0

2

4

Time s Figure 5


6

e


Output voltage (V)

200

160

120

80

40 100

200

300

400

500

600

Rotational Speed (rpm)

Figure.6 0.6

10 200 8

0.4

100 50 0

6

Power (mW)

Current (mA)

150

4

0.2

2

0.0

0 0

500

1000

1500

2000

0

Resistance (MΩ)

100

200

300

Resistance (ΜW)

（a）

400

(b) Figure.7

200

Voltage (V)

Voltage (V)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 24 of 25

150

100

50 30

40

50

Relative humidity (%) Figure.8


60

500

Page 25 of 25

2.0 1.5 Voltage (V)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


1.0 0.5 0.0 0

4

8

Time (s)

12

16

(a)

(b) Figure. 9


Rotational Triboelectric Nanogenerator Based on a PDMS@CS

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