Natural Materials Assembled, Biodegradable, and Transparent Paper

Dec 1, 2016 - ... ChandrasekharSophia SelvarajanSang-Jae Kim. ACS Applied Materials & Interfaces 2018 Article ASAP. Abstract | Full Text HTML | PDF ...
2 downloads 0 Views 1MB Size
Subscriber access provided by Washington University | Libraries

Article

Natural Materials Assembled Biodegradable and Transparent Paper-Based Electret Generator Xiang Gao, Liang Huang, Bo Wang, Dingfeng Xu, Junwen Zhong, Zhimi Hu, Lina Zhang, and Jun Zhou ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.6b12913 • Publication Date (Web): 01 Dec 2016 Downloaded from http://pubs.acs.org on December 5, 2016

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

ACS Applied Materials & Interfaces is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 20

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

ACS Applied Materials & Interfaces

1

Natural Materials Assembled Biodegradable and Transparent Paper-

2

Based Electret Nanogenerator

3

Xiang Gaoa‡, Liang Huanga‡, Bo Wanga‡, Dingfeng Xub, Junwen Zhonga, Zhimi Hua, Lina Zhangb* and

4

Jun Zhoua*

5

a

6

Wuhan 430074, China. Email: [email protected];

7

b

8

Email:[email protected].

9

‡These authors contributed equally for this work.

Wuhan National Laboratory for Optoelectronics, Huazhong University of Science and Technology,

College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, China.

10 11

KEYWORDS: : biodegradable, transparent, electret nanogenerators, paper-based, self-powered

12

ABSTRACT Developing eco-friendly and low-cost electronics is an effective strategy to address the

13

electronic waste issue. In this study, transparent cellulose nanopaper (T-paper) and polylactic acid (PLA)

14

electret were used to construct a biodegradable and transparent paper-based electret nanogenerator. The

15

nanogenerator could be assembled with paper products to form a self-powered smart packaging system

16

without impairing the appearance, due to the high transparency and desirable output performance.

17

Furthermore, the self-degradation property in the natural soil of the nanogenerator is demonstrated,

18

indicating that the nanogenerator is recycled and will not pollute the environment. We anticipate that this

19

study will provide new insights to develop eco-friendly power source and paper-based electronics.

ACS Paragon Plus Environment

ACS Applied Materials & Interfaces

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 2 of 20

1

Introduction

2

The rapid development of flexible and portable electronics revolutionizes people’s life.1-5 For instance,

3

wearable electronics and smart sensors attract growing interest for their specific attempt in health

4

monitoring,6-8 wireless communication9 and smart packaging10. However, the fast upgrading of

5

electronics has brought a serious problem, that is, the electronic waste, which will result in a waste of

6

money and cause pollution to environment.11 Hence, flexible devices entirely built with biodegradable

7

and non-toxic materials receive growing attention.12-15 Paper-based electronics with low cost, eco-friendly

8

property, high flexibility and light weight may be an appropriate solution to address above issue.16-20

9

Specifically, transparent nanopaper (T-paper) consisting of nano cellulose is a promising substrate for

10

flexible electronics, by virtue of its high transparence, smooth surface and excellent mechanical

11

strength.10,

12

(OLED), thin film transistors (TFTs) and antennas, have been successfully assembled on the T-paper.1, 13,

13

17, 25

14

invented, establishing self-powered paper-based electronic systems.5,

15

piezoelectric,28-29 triboelectric5, 27,30 and electret nanogenerators7, 10, 30 can convert irregular mechanical

16

energy from ambient environment and human motions into electricity. However, these paper-based

17

nanogenerators are not completely recycled or harmless to the environment, as the piezoelectric or

18

dielectric materials in the nanogenerators are not biodegradable.5, 10

21-24

A series of flexible electronics, such as touch screens, organic light-emitting diodes

In order to sustainably supply power for above-mentioned devices, paper-based nanogenerators are 20, 26-30

Normally, paper-based

19

In this work, a biodegradable and transparent paper-based electret nanogenerator with a basic working

20

mechanism electrostatic induction is presented. We successfully demonstrate the design, fabrication,

21

output and applications of the nanogenerator. Our designs possesses the following features and

22

advantages: (1) the building elements, T-paper and polylactic acid (PLA) electret, are derived from

23

natural materials (Figure 1a); (2) T-paper and PLA are flexible and transparent (Figure 1b); (3) the

24

whole nanogenerator is invisible and can generate electricity for powering electronics, with potential 2

ACS Paragon Plus Environment

Page 3 of 20

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

ACS Applied Materials & Interfaces

1

applications in self-powered smart packaging (Figure 1c); (4) the nanogenerator is biodegradable and

2

harmless to the environment (Figure 1d). This study opens up a new strategy for developing eco-friendly

3

power sources, and promotes the progress of paper-based electronics.

4

Results and discussion

5

The device structure of the biodegradable and transparent paper-based electret nanogenerator is given

6

in Figure 2a. Specifically, a PLA/conductive T-paper component and a conductive T-paper component

7

were assembled together to form an arch-structured nanogenerator, in which the PLA electret was faced

8

to the PEDOT:PSS conductive electrode. PEDOT:PSS was covered on the T-paper surface via a simple

9

spin coating method with spin rate of 1000 rpm (Figure S1-I and Figure S2), as the smooth surface and

10

hydrophilic features of the T-paper endow itself the ability to be modified by the PEDOT:PSS aqueous

11

ink.21, 31 Scanning electron microscope (SEM) images and corresponding element mapping images of the

12

conductive T-paper surface reveal the uniformly coating of PEDOT:PSS (Figure 2b). Atomic force

13

microscopy (AFM) images indicate that the roughness of the conductive T-paper surface was ~83 nm

14

(Figure 2c), which has little effect on the transmittance. The transmittance of the T-paper, conductive T-

15

paper and the nanogenerator were ~90%, ~ 87% and ~ 81%, respectively (Figure 2d). A digital

16

photograph of the nanogenerator (inset in Figure 2d) also reveals its excellent transparency. Moreover,

17

deformation tests under different bending angles (from 30o to 90o, Figure S3a) indicate that the sheet

18

resistance of the conductive T-paper almost remained at ~ 0.9 MΩ sq-1 (suitable conductivity for electret

19

nanogenerators) for the first bending, first recovery and second bending process (Figure 2e). Meanwhile,

20

the conductive T-paper was continuously bent under a 60o bending angle for 1000 cycles. The I-V curves

21

remained almost the same, revealing a good stability and flexibility (Figure S3b). A tape test also proves

22

the outstanding adhesion between PEDOT:PSS and T-paper (Figure S3c).

23

The spin rates during the spin coating process will affect the surface morphology, sheet resistance,

24

transmittance and mechanical behavior of the conductive T-paper. When the spin rate increased, the 3

ACS Paragon Plus Environment

ACS Applied Materials & Interfaces

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 4 of 20

1

surface roughness reduced, as indicated in Figure S2. With increase of the spin rate from 500 to 1500

2

r/min, the sheet resistance increased from ~ 0.24 MΩ sq-1 to ~ 4.7 MΩ sq-1, respectively (Figure S3d).

3

Simultaneously, the transmittance reached the maximum value of ~ 90% when the spin rate was 1000

4

rpm (Figure S3d). The trend of transmittance is coincident with the fact that the surface of the nanopaper

5

is more compact while the PEDOT:PSS coating thickness on the paper surface decreased with increasing

6

spin rate. Moreover, the strength was enhanced with the spin rate increasing (Figure S4).

7

A PLA electret film with thickness of 55 µm was adhered to a conductive T-paper to form the

8

PLA/conductive T-paper component (Figure S1-II and Figure S5a). Fourier transform infrared (FTIR)

9

spectroscopy was employed to identify the molecular structure of PLA. As depicted in Figure S5b, the

10

spectrum of the electret used in our device is coincident with the standard spectrum of PLA, confirming

11

the normal PLA material in the device.32 Compared with traditional electret materials like

12

polytetrafluoroethylene (PTFE), polypropylene (PP) and polyethylene (PE), PLA is a biodegradable

13

polyester derived from renewable resources, such as trees, corn starch, tapioca roots or sugarcane.32-34 By

14

virtue of the rich oxygen functional groups, PLA can be strongly polarized and charged, making it a well-

15

suited natural material to construct eco-friendly electret nanogenerators.35-38

16

As our nanogenerator is arch-structured, it can be regarded as a parallel capacitor in ideal analysis,

17

ignoring the edge effect. In the original state (Figure 3a-I), the PLA electret in the PLA/conductive T-

18

paper component was pre-charged via a corona charging process, which was investigated by measuring

19

the surface potential. Specifically, the surface potential dropped rapidly for the first two days and

20

remained at ~ 0.97 kV for 32 days (Figure 3b). Because of the existence of the surplus charges (σ0) in the

21

PLA electret surface, corresponding induced charges will be generated on the top (σ1) and bottom (σ2)

22

PEDOT:PSS electrode. Assuming that the charges are uniformly distributed on the materials surface,

23

thus:39

24

 = −( +  )

(1)

4

ACS Paragon Plus Environment

Page 5 of 20

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 2

ACS Applied Materials & Interfaces

Meanwhile, at any equilibrium state of the nanogenerator, the induced charge in the bottom electrode σ2 is given by:20  = −  ⁄(  +  )

3

(2)

4

where d1 and εrp are thickness and relative permittivity of the PLA, which are constants. d2 is the

5

thickness of air gap between the PLA/conductive T-paper component and the conductive T-paper

6

component.

7

When pressing the nanogenerator (Figure 3a-II), d2 reduces. According to Equation 2, more σ2 will

8

be induced in the bottom electrode. Current flows from the top to the bottom electrode, generating a

9

positive current peak (left in Figure 3c). In the releasing process (Figure 3a-III), the d2 variation

10

tendency is opposite to the pressing process, thus, a negative current peak can be observed (left in Figure

11

3c, black curve). In general, the variation of d2 breaks the electrical potential equilibrium between the

12

two electrodes, driving electrons to flow alternately. As a result, alternating electricity is generated by the

13

nanogenerator. Switching polarity tests were also carried out to confirm that the measured output signals

14

were generated from the nanogenerator rather than from the measurement system (right in Figure 3c,

15

blue curve).

16

Significantly, the PLA electret determines the output property of the nanogenerator. Under the same

17

stimulating conditions, the peak current of the device with PLA reached ~ 1.33 µA, while the device

18

without PLA was only ~ 4 nA (Figure 3d).

19

The output performances of a biodegradable and transparent paper-based electret nanogenerator with

20

effective area of 2×2 cm2 was carefully studied by periodically pressing and releasing with controlled

21

amplitude and frequency. Under stimulating amplitude and frequency of 2 mm and 5 Hz, the

22

nanogenerator obtained a maximal power of ~ 84.4 µW, with a corresponding load peak current and load 5

ACS Paragon Plus Environment

ACS Applied Materials & Interfaces

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 6 of 20

1

resistance of ~ 0.92 µA and 100 MΩ, respectively (Figure 4a). For a given frequency of 5 Hz, both of the

2

load peak current and corresponding transferred charges (△Q) increased step by step with increasing the

3

amplitude, from ~ 0.17 µA and ~ 7.11 nC at 0.5 mm to ~ 1.47 µA and ~ 19.29 nC at 2.5 mm, respectively

4

(Figure S6a and S6b). On the other hand, for a given amplitude of 2.5 mm, only the load peak current

5

increased gradually with increasing the frequency, while the corresponding △Q remained at ~ 19.4 nC

6

(Figure S6c and S6d). Moreover, by connecting two nanogenerators in parallel, the output performance

7

would be enhanced (Figure S7).

8

The excellent stability performance of the nanogenerator is an important factor to ensure its

9

applications. In this work, the nanogenerator was continuously stimulated for 54000 cycles, with an

10

amplitude and frequency of 2.5 mm and 5 Hz, respectively (Figure S8). For different stimulated cycles,

11

the peak current and corresponding △Q remained almost consistent at ~ 1.47 µA and ~ 19.3 nC,

12

respectively (Figure 4b). This outstanding stability performance may be attributed to the good charge

13

maintaining ability of PLA electret and the robust mechanical property of the nanogenerator.

14

Benefited from the high transparency and desirable output performance, our biodegradable and

15

transparent paper-based electret nanogenerator can be assembled with paper products, demonstrating its

16

typical application in smart packaging. Herein, a nanogenerator was used to power one red light emitting

17

diode (LED) in the mouth and two blue LEDs in the eyes of the paper toy, and the specific equivalent

18

circuit is given in Figure 4c. As the nanogenerator was invisible, it could be stacked on the surface

19

without impairing its appearance (left in Figure 4d). If people pressed the paper toy, the nanogenerator

20

was stimulated, generating electricity for lighting up the three LEDs (right in Figure 4d). When the

21

nanogenerator was pressed, the voltage across the LEDs was ~ 7.5 V (Figure 4e), which matched the

22

threshold voltage of the LEDs (Figure S9). Meanwhile, the peak current through the LEDs reached ~ 18

23

µA (Figure 4f). When the nanogenerator was released, the open-circuit voltage generated by the

24

nanogenerator was recorded as high as ~ 75 V (Figure S10). Besides, the nanogenerator has the ability to 6

ACS Paragon Plus Environment

Page 7 of 20

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

ACS Applied Materials & Interfaces

1

power other low-power consumption electronics, such as liquid crystal displays (LCD) (Figure 1c). The

2

above-mentioned smart packaging system is battery-free, low-cost and simple-structured, and will endow

3

paper products with newfangled and unique functions, such as attractive decoration, advertisement, anti-

4

theft or anti-fake.

5

Note that since our nanogenerator is mainly composed of natural materials, the nanogenerator should

6

have the ability to be degraded. In the degradation test, nanogenerators were buried in the natural soil

7

without any other treatment. From the digital pictures it can be seen that the degradation process of the T-

8

paper was more easy than for the PLA electret (Figure 5a). A porous structure with fungal mycelia on the

9

T-paper surface indicates that the microorganisms in the soil directly decompose the T-paper via

10

penetrating into the cellulose to obtain nutrients (Figure 5b).40 Digital pictures and weight loss of the

11

nanogenerators during the degradation process indicate that T-paper was almost completely degraded

12

after 40 days (Figure 5c). After 210 days, a porous structure was observed on the surface of PLA electret

13

(Figure 5d). Moreover, tensile strength measurement was employed to investigate the degradation

14

property of the PLA electret. The mechanical strength of the PLA electret decreased after 90 days,

15

demonstrating the start of structural damage (Figure 5e).41 The above results indicate that the

16

biodegradable and transparent paper-based electret nanogenerator can be recycled and will not cause

17

pollution in the environment.

18 19 20

Conclusions

21

In summary, we report a biodegradable and transparent paper-based electret nanogenerator based on

22

natural materials of T-paper and PLA electret. By virtue of the high transparency and desirable output

23

performance, the nanogenerators were assembled with paper products to power low-power consumption 7

ACS Paragon Plus Environment

ACS Applied Materials & Interfaces

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 8 of 20

1

electronics without impairing their appearance, obtaining a self-powered smart packaging system.

2

Moreover, the nanogenerator was biodegradable when buried in the natural soil, revealing that it recycled

3

and can be harmless to the environment. This study provides a significant approach for developing eco-

4

friendly power sources to solve the electronic waste problem, simultaneously expanding the applications

5

of paper-based electronics.

6

Experimental Section

7

Fabrication of T-paper. Cellulose was dissolved in 7 wt% NaOH / 12 wt% urea solution and pre-cooled

8

to -12 °C through using a previously reported method to form a 4 wt% transparent cellulose solutions

9

within 3 min.42 The solution was then subjected to centrifuging to degas at 7200 rpm for 10 min at 5 oC.

10

The transparent solution was immediately cast on a glass plate to give a solution layer with 0.5 mm

11

thickness, and then immersed into a coagulation bath of ethanol to give a regenerated cellulose hydrogel.

12

The cellulose gels were thoroughly rinsed with deionized water, and then dried in air to give the cellulose

13

film. Cellulose T-paper was made by cutting the film into a suitable size.

14

Fabrication of conductive T-paper. The transparent conductive nanopaper was prepared via spin

15

coating of poly(3,4-ethylenedioxythiophene) polystryrene sulfonate (PEDOT:PSS) on the surface of T-

16

paper. The conductive inks was diluted to 10 % with DI water and then spin coatted onto the prepared

17

cellulose film with different spinning rates for 2 min. Subsequently, the prepared modified cellulose films

18

were dried in air.

19

Fabrication of biodegradable and transparent paper-based electret nanogenerator. Firstly, a

20

commercial PLA electret film (Changzhou Rong Sunny Advaced Materials Technology company, China)

21

was adhered to a conductive T-paper to form a PLA/conductive T-paper component. Then, the PLA film

22

was polarized in the direction perpendicular to the film via the corona method under a high voltage of -15

23

kV for 5 min. A PLA/conductive T-paper component and a conductive T-paper component were 8

ACS Paragon Plus Environment

Page 9 of 20

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

ACS Applied Materials & Interfaces

1

assembled to fabricate the nanogenerator. Specifically, the PLA side of the PLA/conductive T-paper

2

component was faced to the PEDOT:PSS side of the conductive T-paper component, and then two edges

3

of the two components were adhered together to obtain an arch-structured nanogenerator with effective

4

area of 2×2 cm2.

5

Biodegradation tests. Nanogenerators with similar size of which the initial weight was recorded were

6

buried about 20 cm in the natural soil. The average values of the temperature and moisture of the soil

7

were about 25 oC and 25%, respectively. The tests were observed gradually during 210 days. At different

8

time intervals, triplicate specimens for each sample condition were removed from the soil. The samples

9

were first rinsed several times with distilled water and dried at room temperature for 2 days under

10

vacuum. The degree of degradation could directly be detected follow the change of the weight,

11

morphology and mechanical strength.

12

Characterization. The morphology of the sample was probed by a field emission scanning electron

13

microscope (SEM. FEI Nova Nano450) and an atomic force microscope (AFM, Dimension 3100 Veeco).

14

Fourier transform infrared spectra was recorded by a Bruker, Equinox 55 spectrometer. The tensile

15

strength measurements were carried out by an electronic universal testing machine (M-4005T, Shenzhen).

16

The conductance of the samples was studied by Keithley 2400 sourcemeter. The transmittance of the

17

samples were measured by a UV 2550 spectrophotometer (Shimadzu). The corona charging method was

18

carried out with high voltage source (DW-N503-4ACDE, Tianjin). The surface potential of the sample

19

was detected by an electrometer (EST102, Huajing Beijing, China). In the electrical measurements, the

20

periodically pressing-releasing process of the samples was provided by a resonator (JZK, Sinocera,

21

China) which was controlled by a swept signal nanogenerator (YE 1311-D, Sinocera, China). The output

22

current of the samples were measured by a Stanford low-noise current preamplifier (Model SR570) and

23

NI PCI-6259. The output voltage of the samples were measured by a Keithley 6514 electrometer. It

9

ACS Paragon Plus Environment

ACS Applied Materials & Interfaces

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 10 of 20

1

should be noted that all the electrical measurements were carried out after the surface potential of the

2

PLA electret had reached stable states.

3

Supporting Information. More detailed information about detailed device fabrication process and

4

supporting figures. This material is available free of charge via the Internet at http://pubs.acs.org.

5 6

ACKNOWLEDGMENT

7

This work was financially supported by the National Natural Science Foundation of China (51322210,

8

51602115, 61501215, 61434001, 20874079, and 81171480), the Major Program of National Natural

9

Science Foundation of China (21334005) and the Director Fund of WNLO. The authors thank to the

10

National Program for Support of Top-Notch Young Professionals, the facility support of the Center for

11

Nanoscale Characterization & Devices, WNLO-HUST and the Analysis and Testing Center of Huazhong

12

University of Science and Technology.

13

REFERENCES

14 15 16

(1) Tok, J. B. H.; Bao, Z., Recent Advances in Flexible and Stretchable Electronics, Sensors and Power Sources. Sci. China Chem. 2012, 55, 718-725. (2)

Xiao, X.; Yuan, L.; Zhong, J.; Ding, T.; Liu, Y.; Cai, Z.; Rong, Y.; Han, H.; Zhou, J.; Wang, Z.

17

L., High-strain Sensors Based on ZnO Nanowire/Polystyrene Hybridized Flexible Films. Adv. Mater.

18

2011, 23, 5440-5444.

19

(3)

Bauer, S., Flexible Electronics: Sophisticated Skin. Nat. Mater. 2013, 12, 871-872.

20

(4)

Boland, J. J., Flexible Electronics: Within Touch of Artificial Skin. Nat. Mater. 2010, 9, 790-792.

21

(5)

Fan, F. R.; Tang, W.; Wang, Z. L., Flexible Nanogenerators for Energy Harvesting and Self-

22

Powered Electronics. Adv. Mater. 2016, 28, 4283-4305. 10

ACS Paragon Plus Environment

Page 11 of 20

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

ACS Applied Materials & Interfaces

(6)

Wu, N.; Cheng, X.; Zhong, Q.; Zhong, J.; Li, W.; Wang, B.; Hu, B.; Zhou, J., Cellular

2

Polypropylene Piezoelectret for Human Body Energy Harvesting and Health Monitoring. Adv. Funct.

3

Mater. 2015, 25, 4788-4794.

4 5

6

(7)

Zhong, J.; Zhong, Q.; Hu, Q.; Wu, N.; Li, W.; Wang, B.; Hu, B.; Zhou, J., Stretchable Self‐

Powered Fiber‐Based Strain Sensor. Adv. Funct. Mater. 2015, 25, 1798-1803.

(8)

Persano, L.; Dagdeviren, C.; Su, Y.; Zhang, Y.; Girardo, S.; Pisignano, D.; Huang, Y.; Rogers, J.

7

A., High Performance Piezoelectric Devices Based on Aligned Arrays of Nanofibers of

8

Poly(vinylidenefluoride-co-trifluoroethylene). Nat. Commun. 2013, 4, 1633.

9

(9)

Hussain, A. M.; Ghaffar, F. A.; Park, S. I.; Rogers, J. A.; Shamim, A.; Hussain, M. M.,

10

Metal/Polymer Based Stretchable Antenna for Constant Frequency Far-Field Communication in

11

Wearable Electronics. Adv. Funct. Mater. 2015, 25, 6565-6575.

12

(10) Zhong, J.; Zhu, H.; Zhong, Q.; Dai, J.; Li, W.; Jang, S. H.; Yao, Y.; Henderson, D.; Hu, Q.; Hu,

13

L.; Zhou, J., Self-Powered Human-Interactive Transparent Nanopaper Systems. ACS Nano 2015, 9, 7399-

14

7406.

15 16

(11) Irimia-Vladu, M.; Głowacki, E. D.; Voss, G.; Bauer, S.; Sariciftci, N. S., Green and Biodegradable Electronics. Mater. Today 2012, 15, 340-346.

17

(12) Hwang, S. W.; Huang, X.; Seo, J. H.; Song, J. K.; Kim, S.; Hage-Ali, S.; Chung, H. J.; Tao, H.;

18

Omenetto, F. G.; Ma, Z.; Rogers, J. A., Materials for Bioresorbable Radio Frequency Electronics. Adv.

19

Mater. 2013, 25, 3526-3531.

20

(13) Hwang, S. W.; Kim, D. H.; Tao, H.; Kim, T.; Kim, S.; Yu, K. J.; Panilaitis, B.; Jeong, J. W.;

21

Song, J. K.; Omenetto, F. G.; Rogers, J. A., Materials and Fabrication Processes for Transient and

22

Bioresorbable High-Performance Electronics. Adv. Funct. Mater. 2013, 23, 4087-4093. 11

ACS Paragon Plus Environment

ACS Applied Materials & Interfaces

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 12 of 20

1

(14) Kang, S. K.; Park, G.; Kim, K.; Hwang, S. W.; Cheng, H.; Shin, J.; Chung, S.; Kim, M.; Yin, L.;

2

Lee, J. C.; Lee, K. M.; Rogers, J. A., Dissolution Chemistry and Biocompatibility of Silicon- and

3

Germanium-based Semiconductors for Transient Electronics. ACS Appl. Mater. Interfaces. 2015, 7, 9297-

4

9305.

5

(15) Hwang, S. W.; Lee, C. H.; Cheng, H.; Jeong, J. W.; Kang, S. K.; Kim, J. H.; Shin, J.; Yang, J.;

6

Liu, Z.; Ameer, G. A.; Huang, Y.; Rogers, J. A., Biodegradable Elastomers and Silicon

7

Nanomembranes/Nanoribbons for Stretchable, Transient Electronics, and Biosensors. Nano Lett. 2015,

8

15, 2801-2808.

9

(16) Liu, J.; Yang, C.; Wu, H.; Lin, Z.; Zhang, Z.; Wang, R.; Li, B.; Kang, F.; Shi, L.; Wong, C. P.,

10

Future Paper Based Printed Circuit Boards for Green Electronics: Fabrication and Life Cycle Assessment.

11

Energy Environ. Sci. 2014, 7, 3674-3682.

12 13

(17) Bettinger, C. J.; Bao, Z., Organic Thin-film Transistors Fabricated on Resorbable Biomaterial Substrates. Adv. Mater. 2010, 22, 651-655.

14

(18) Tobjork, D.; Osterbacka, R., Paper Electronics. Adv. Mater. 2011, 23, 1935-1961.

15

(19) Yuan, L.; Yao, B.; Hu, B.; Huo, K.; Chen, W.; Zhou, J., Polypyrrole-Coated Paper for Flexible

16 17 18

Solid-State Energy Storage. Energy Environ. Sci. 2013, 6, 470-476. (20) Zhong, Q.; Zhong, J.; Hu, B.; Hu, Q.; Zhou, J.; Wang, Z. L., A Paper-based Nanogenerator as A Power Source and Active Sensor. Energy Environ. Sci. 2013, 6, 1779-1784.

19

(21) Hu, L.; Zheng, G.; Yao, J.; Liu, N.; Weil, B.; Eskilsson, M.; Karabulut, E.; Ruan, Z.; Fan, S.;

20

Bloking, J. T.; McGehee, M. D.; Wågberg, L.; Cui, Y., Transparent and Conductive Paper from

21

Nanocellulose Fibers. Energy Environ. Sci. 2013, 6, 513-518.

12

ACS Paragon Plus Environment

Page 13 of 20

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 2 3 4 5 6 7 8 9 10

ACS Applied Materials & Interfaces

(22) Fang, Z.; Zhu, H.; Bao, W.; Preston, C.; Liu, Z.; Dai, J.; Li, Y.; Hu, L., Highly Transparent Paper with Tunable Haze for Green Electronics. Energy Environ. Sci. 2014, 7, 3313-3319. (23) Zhu, H.; Fang, Z.; Preston, C.; Li, Y.; Hu, L., Transparent Paper: Fabrications, Properties, and Device Applications. Energy Environ. Sci. 2014, 7, 269-287. (24) Jin, J.; Lee, D.; Im, H. G.; Han, Y. C.; Jeong, E. G.; Rolandi, M.; Choi, K. C.; Bae, B. S., Chitin Nanofiber Transparent Paper for Flexible Green Electronics. Adv. Mater. 2016, 28, 5169-5175. (25) Zhu, H.; Xiao, Z.; Liu, D.; Li, Y.; Weadock, N. J.; Fang, Z.; Huang, J.; Hu, L., Biodegradable Transparent Substrates for Flexible Organic-light-emitting Diodes. Energy Environ. Sci. 2013, 6, 2105. (26) Hu, Q.; Wang, B.; Zhong, Q.; Zhong, J.; Hu, B.; Zhang, X.; Zhou, J., Metal-free and Non-fluorine Paper-based Generator. Nano Energy 2015, 14, 236-244.

11

(27) Li, J.; Zhang, C.; Duan, L.; Zhang, L. M.; Wang, L. D.; Dong, G. F.; Wang, Z. L., Flexible

12

Organic Tribotronic Transistor Memory for a Visible and Wearable Touch Monitoring System. Adv.

13

Mater. 2016, 28, 106-110.

14

(28) Fan, X.; Chen, J.; Yang, J.; Bai, P.; Li, Z.; Wang, Z. L., Ultrathin, Rollable, Paper-Based

15

Triboelectric Nanogenerator for Acoustic Energy Harvesting and Self-Powered Sound Recording. ACS

16

Nano 2015, 9, 4236-4243.

17 18

(29) Kim, K. H.; Lee, K. Y.; Seo, J. S.; Kumar, B.; Kim, S. W., Paper-Based Piezoelectric Nanogenerators with High Thermal Stability. Small 2011, 7, 2577-2580.

19

(30) Zheng, Q.; Zou, Y.; Zhang, Y.; Liu, Z.; Shi, B.; Wang, X.; Jin, Y.; Ouyang, H.; Li, Z.; Wang, Z.

20

L., Biodegradable Triboelectric Nanogenerator as A Life-time Designed Implantable Power Source. Sci.

21

Adv. 2016, 2, e1501478.

13

ACS Paragon Plus Environment

ACS Applied Materials & Interfaces

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 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16

Page 14 of 20

(31) Hu, L.; Pasta, M.; Mantia, F. L.; Cui, L.; Jeong, S.; Deshazer, H. D.; Choi, J. W.; Han, S. M.; Cui, Y., Stretchable, Porous, and Conductive Energy Textiles. Nano Lett. 2010, 10, 708-714. (32) Jun, C. L., Reactive Blending of Biodegradable Polymers: PLA and Starch. J. Polym. Environ. 2000, 8, 33-37. (33) Irimia-Vladu, M., "Green" Electronics: Biodegradable and Biocompatible Materials and Devices for Sustainable Future. Chem. Soc. Rev. 2014, 43, 588-610. (34) Gross, R. A.; Kalra, B., Biodegradable Polymers for the Environment. Science 2002, 297, 803807. (35) Sessler, G. M.; Hillenbrand, J., Electromechanical Response of Cellular Electret Films. Appl. Phys. Lett. 1999, 75, 3405-3407. (36) Raquez, J. M.; Habibi, Y.; Murariu, M.; Dubois, P., Polylactide (PLA)-based Nanocomposites. Prog. Polym. Sci. 2013, 38, 1504-1542. (37) Sessler, G. M., Physical Principles of Electrets. In Electrets, Sessler, G. M., Ed. Springer Berlin Heidelberg, Berlin, Heidelberg, 1987; pp 13-80. (38) Mitcheson, P.; Yeatman, E.; Rao, G.; Holmes, A.; Green, T., Energy Harvesting from Human and Machine Motion for Wireless Electronic Devices. Proc. IEEE 2008, 96, 1457-1486.

17

(39) Zhong, J.; Zhong, Q.; Chen, G.; Hu, B.; Zhao, S.; Li, X.; Wu, N.; Li, W.; Yu, H.; Zhou, J.,

18

Surface Charge Self-recovering Electret Flm for Wearable Energy Conversion in A Harsh Environment.

19

Energy Environ. Sci. 2016. DOI: 10.1039/C6EE02135B.

14

ACS Paragon Plus Environment

Page 15 of 20

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

ACS Applied Materials & Interfaces

1

(40) Jung, Y. H.; Chang, T. H.; Zhang, H.; Yao, C.; Zheng, Q.; Yang, V. W.; Mi, H.; Kim, M.; Cho, S.

2

J.; Park, D. W.; Jiang, H.; Lee, J.; Qiu, Y.; Zhou, W.; Cai, Z.; Gong, S.; Ma, Z., High-performance Green

3

Flexible Electronics Based on Biodegradable Cellulose Nanofibril Paper. Nat. commun. 2015, 6, 7170.

4

(41) Vieira, A. C.; Vieira, J. C.; Ferra, J. M.; Magalhães, F. D.; Guedes, R. M.; Marques, A. T.,

5

Mechanical Study of PLA–PCL Fibers During in Vitro Degradation. J. Mech. Behav. Biomed. Mater.

6

2011, 4, 451-460.

7

(42) Cai, J.; Zhang, L.; Zhou, J.; Qi, H.; Chen, H.; Kondo, T.; Chen, X.; Chu, B., Multifilament Fibers

8

Based on Dissolution of Cellulose in NaOH/Urea Aqueous Solution: Structure and Properties. Adv.

9

Mater. 2007, 19, 821-825.

10 11 12

13

15

ACS Paragon Plus Environment

ACS Applied Materials & Interfaces

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 16 of 20

1

Figure 1. Features and advantages of the biodegradable and transparent electret nanogenerator. (a) PLA

2

and cellulose transparent paper (T-paper) were derived from the nature; (b) These transparent "green

3

materials" can be assembled to an invisible electret nanogenerator; (c) The nanogenerator can generate

4

electricity for powering electronics and be degraded in the soil; (d) The degraded nanogenerator is finally

5

cycled back to the nature without detrimental environmental effects.

6 7

Figure 2. Fabrication of the biodegradable and transparent electret nanogenerator. (a) Device structure of

8

the nanogenerator; (b) SEM image and corresponding elements mapping image of the conductive T-paper

9

surface; (c) AFM image of the conductive T-paper surface; (d) The transmittance of T-paper, conductive

10

T-paper and nanogenerator, respectively. Insert shows the digital picture of the nanogenerator; (e) the

11

sheet resistance of the conductive T-paper for the first bending, first recovery and second bending process,

12

respectively. Inset shows the digital picture for T-paper.

16

ACS Paragon Plus Environment

Page 17 of 20

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

ACS Applied Materials & Interfaces

1 2

3 4

Figure 3. Working mechanism of the biodegradable and transparent electret nanogenerator. (a) Schematic

5

diagram indicating the working process of a nanogenerator, when it is at (I) original state, (II) pressing

6

state and (III) releasing state; (b) Surface potential decay of the PLA electret of the PLA/conductive T-

7

paper component; (c) Corresponding current-time curves for a nanogenerator when it is forward-

8

connected and reverse-connected to the measurement system; (d) Output currents for the devices with and

9

without PLA electret.

17

ACS Paragon Plus Environment

ACS Applied Materials & Interfaces

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 18 of 20

1 2

Figure 4. Output performances and the biodegradable and transparent electret nanogenerator and

3

its application in smart packaging. (a) Load peak currents and corresponding peak power curves

4

as a function of the load resistance, under stimulating amplitude and frequency of 2 mm and 5

5

Hz; (b) Output stability measurement for the nanogenerator, under stimulating amplitude and

6

frequency of 2 mm and 5 Hz; (c) Equivalent circuit for the smart packaging system; (d) Digital

7

pictures of smart packaging system; (e) Voltage across and (f) current went through the LEDs,

8

when they were lit up.

9 10

18 Environment ACS Paragon Plus

Page 19 of 20

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

ACS Applied Materials & Interfaces

1

2 3

Figure 5. Degradation test. (a) Digital pictures indicating the degradation process; (b) SEM

4

image of the T-paper surface after degrading for 21 days; (c) Weight loss of the nanogenerator

5

depended on degradation time in soil; (d) SEM image of the PLA electret surface after degrading

6

for 210 days; (e) Tensile strength measurement of the PLA depended on degradation time in soil.

7 8 9 10 11 12

19 Environment ACS Paragon Plus

ACS Applied Materials & Interfaces

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

TOC

2 3

20 Environment ACS Paragon Plus

Page 20 of 20