Journal Pre-proof

Electric-fish-inspired actuator with integrated energy-storage function

Mingcen Weng, Yimin Duan, Peidi Zhou, Feng Huang, Wei Zhang, Luzhuo Chen

PII: S2211-2855(19)31079-1
DOI: https://doi.org/10.1016/j.nanoen.2019.104365
Reference: NANOEN 104365

To appear in: Nano Energy

Received Date: 12 October 2019

Revised Date: 27 November 2019
Accepted Date: 2 December 2019

Please cite this article as: M. Weng, Y. Duan, P. Zhou, F. Huang, W. Zhang, L. Chen, Electric-fish-
inspired actuator with integrated energy-storage function, Nano Energy, https://doi.org/10.1016/
j.nanoen.2019.104365.

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1 Electric-fish-inspired actuator with integrated energy-storage function

3 Mingcen Wenga, b, c, d, 1, Yimin Duana, c, d, 1, Peidi Zhoua, c, d, Feng Huanga, c, d, Wei Zhanga, c, d and

4 Luzhuo Chena, c, d, *

a
6 Fujian Provincial Key Laboratory of Quantum Manipulation and New Energy Materials, College of

7 Physics and Energy, Fujian Normal University, Fuzhou 350117, China.

b
8 School of Materials Science and Engineering, Fujian University of Technology, Fuzhou 350118, China

c
9 Fujian Provincial Collaborative Innovation Center for Optoelectronic Semiconductors and Efficient

10 Devices, Xiamen 361005, China

d
11 Fujian Provincial Engineering Technology Research Center of Solar Energy Conversion and Energy

12 Storage, Fuzhou 350117, China

1
13 These authors contributed equally.

14

15 * Corresponding author: Luzhuo Chen, E-mail: chenluzhuo@163.com

 2

1 Abstract

2 Actuators are energy-conversion devices, which convert different types of energy (e.g. light, electricity

3 and heat) into mechanical energy and exhibit shape-deformations. They have significant applications in

4 artificial muscles, soft robot, etc. However, most of the actuators only possess shape-deformation function,

5 lacking in the integration of multi-functions, which is against the integration of smart devices and

6 miniaturization of soft robots. In nature, electric fishes can produce electricity. Their myogenic electrocytes

7 are formed from skeletal muscles. Here, inspired by the multiple functions of muscle or myogenic cells in

8 the electric fish, we propose a multi-functional actuator with integrated energy-storage function based on

9 graphite/polyaniline (GP) paper-like composites. After in situ polymerization, the surfaces of graphite

10 nanosheets are surrounded by polyaniline nanoparticles. The GP paper-based actuator exhibits advantages

11 of ultralow driving voltage (≤ 2.5 V), large bending curvature (1.03 cm-1) and long cycling life (> 10000

12 cycles). Meanwhile, the GP paper-based supercapacitor shows great electrochemical performances with

13 areal specific capacitance of 402.5 mF cm−2 and capacitance retention of 79.1% after 10000 cycles.

14 According to these characteristics, a multi-functional actuator integrated with supercapacitor units is

15 constructed, which mimics not only the shape-deformation function of muscle cells, but also the

16 discharging property of myogenic electrocytes in electric fish. We believe this study will open a new way to

17 the design and applications of wearable devices, multi-functional artificial muscles and integrated soft

18 robots.

19 Keywords: supercapacitor, multi-functional, actuator, graphite, polyaniline

20 -----------------------------------------------------------------------------------------------------------------------

21 Declarations of interests: none

 3

1 1. Introduction

2 In the past decades, energy storage and conversion devices, such as supercapacitors [1-3], batteries

3 [4-6], photothermic vaporization devices [7-9] and actuators [10-13], have been greatly developed. Among

4 them, actuators are typical energy-conversion devices, which can convert absorbed external stimuli energy

5 into mechanical energy, leading to shape-deformations and motions [14-18]. Dielectric elastomers [10],

6 liquid-crystal elastomers [19], hydrogels [11], carbon-based materials [20] and paper-based materials [16]

7 have been used for fabricating actuators driven by humidity [20], organic vapor [21], light [22], electricity

8 [14, 17, 18] and multi-stimuli [15, 16]. At present, the actuation performance of actuators have been

9 improved remarkably, having potential applications in artificial muscles and soft robots [19, 20, 22-25].

10 Meantime, energy-storage devices, including batteries and supercapacitors, are also essential components

11 of soft robots. However, the actuating components and energy-storage components in most current robots

12 are separated, which makes the robots cumbersome and non-integrated. Hence, the multi-functionality,

13 miniaturization and integration of devices are of great importance for the development of soft robots [26,

14 27]. To the best of our knowledge, multi-functional devices, which integrate the functions of

15 shape-deformation and energy-storage in a single device, have rarely been reported.

16 In nature, electric fishes (i.e. electric eel) can produce electricity by using electric organs (EOs), which

17 are composed of electrocytes. The EOs originate from myogenic precursors and are formed from different

18 skeletal muscles [28, 29]. The output voltages of electric fish can be increased by in-series arrangement of

19 the electrocytes, which are similar to stacked batteries. In this work, inspired by the multiple functions of

20 muscle cells and myogenic electrocytes of the electric fish, we propose that composite materials based on

21 graphite paper (G paper) and polyaniline (PANI) can construct multi-functional actuators with integrated

22 energy-storage function, realizing the functions of actuator and supercapacitor in a single device. On one
 4

1 hand, such devices can be directly used as artificial muscles, mimicking the shape-deformation function of

2 muscle cells in electric fish. On the other hand, they can also be used as power supplies, mimicking the

3 discharging property of myogenic electrocytes in the electric fish. The graphite/PANI (GP) paper, which is

4 fabricated by in situ polymerization PANI on G paper, presents electrical conductivity as high as 875 S cm-1.

5 Thus, the GP paper can directly act as a component of electrothermal actuator or as electrodes of

6 supercapacitor. The actuator fabricated by GP paper performs the advantages of ultralow driving voltage (≤

7 2.5 V), large bending curvature (> 1 cm-1), good mechanical property (force density > 8) and long cycling

8 life (> 10000 cycles). Meanwhile, the supercapacitor fabricated by GP paper exhibits areal specific

9 capacitance (CS) up to 402.5 mF cm−2 due to the combination of electric double layer capacitor (EDLC) of

10 graphite and pseudocapacitance of PANI. After bending (angle up to 180°), high temperature (60 °C) and

11 tens of thousands of cycles, the performance of the capacitor can still be maintained, demonstrating high

12 flexibility, long-term stability and high-temperature tolerance. Finally, we demonstrate a multi-functional

13 actuator integrated with supercapacitor units in a single device. A gripper constructed by a pair of such

14 devices can easily grasp and move an object. The devices can serve as power supply units to drive a

15 calculator. Moreover, such devices can also be used in series, mimicking the arrangement of electrocytes in

16 electric fish, so as to increase the output voltage. These results demonstrate the potential applications of GP

17 paper in different kinds of flexible multi-functional devices, which is hopeful to open new application

18 fields in flexible wearable devices, power-supply-integrated soft robots and other multi-functional

19 integrated devices.

20 2. Materials and methods

21 2.1. Materials

22 The chemical reagents of aniline (ANI) monomers (purity of ≥99.5%), ammonium persulfate (APS),
 5

1 polyvinyl alcohol (PVA), hydrochloric acid (HCl) and sulfuric acid (H2SO4) were purchased from

2 Sinopharm Chemical Reagent Co., Ltd. The G paper with thickness of 25 µm was purchased from Beijing

3 Electric Carbon Factory.

4 2.2 Fabrication of GP paper

5 The PANI was coated uniformly on the G paper through the in situ polymerization method. Firstly, the

6 G paper with a typical area of 25 cm2 was immersed in 20 mL aqueous solution containing 0.02 mol HCl

7 and 0.004 mol ANI for a complete infiltration of 1 h. Secondly, 20 mL of precooled aqueous solution

8 containing 0.004 mol APS (an oxidant for polymerization) was dropped slowly in the above solution.

9 Thirdly, the mixed solution was put at 0 °C for completely reaction (12 h). The obtained GP paper was

10 picked out from solution and cleaned with deionized water, ethanol, and acetone. Finally, the GP paper was

11 kept at 60 °C for drying (4 h). The mass ratio of PANI can be precisely controlled by the polymerization

12 time. Corresponding to the polymerization process from one to six times, the GP papers are named as

13 GP1-6 paper, respectively.

14 2.3. Fabrication of actuator and solid-state supercapacitor

15 A commercial biaxially oriented polypropylene (BOPP) film was attached to the U-shape GP paper

16 (30 mm × 6 mm) to form an actuator. PVA-H2SO4 electrolyte was prepared by adding 6 g PVA powder

17 into 60 ml 1 mol L-1 H2SO4 aqueous solution. The whole mixture was heated to 80 °C under vigorous

18 stirring until the solution became clear. After the mixture cooled down, two electrodes (30 mm × 10 mm)

19 were immersed into the PVA-H2SO4 electrolyte for 5 min and dried for a while. After that, they were

20 assembled into a supercapacitor. The active area of the supercapacitor was 2 cm2.

21 2.4. Fabrication of multi-functional actuator

22 One piece of U-shape (45 mm × 25 mm) and two pieces of stripe-shape (25 mm × 10 mm) GP4
 6

1 paper were used for constructing the multi-functional actuator. Firstly, a commercial BOPP film was

2 attached to the U-shape GP4 paper to form the bilayer actuator structure. Secondly, two pieces of

3 stripe-shape GP4 paper, which were served as electrodes of supercapacitors, were immersed into the

4 PVA-H2SO4 electrolyte for 5 min and dried for a while. Finally, they were assembled onto the U-shape GP4

5 paper to form two supercapacitor units and the multi-functional actuator was obtained.

6 2.5. Force measurement

7 An actuator (30 mm × 6 mm) was connected to a polydimethylsiloxane cube (899 mg) as a preload.

8 They were placed on a precision balance with vertical configurations. The generated forces of the actuator

9 were measured as a function of the DC voltage (operating for 5 s).

10 2.6. Characterization

11 The scanning electron microscope (SEM) images were captured by a field-emission SEM (Hitachi

12 SU8010). The Raman spectra were recorded at room temperature by using a HORIBA JobinYvon

13 Evolution Raman spectrometer with the 532 nm He-Ne Laser line. The electrical conductivity and

14 electrothermal actuation were tested by using a digital source meter (Keithley 2410). Cyclic voltammetry

15 (CV) curves were measured on an electrochemical workstation (Zahner Zennium). Galvanostatic

16 charge/discharge (GCD), leakage current and self-discharge experiments were conducted by using a battery

17 testing system (Wuhan LAND Electronics, China). A hot plate was used for testing the supercapacitor at

18 high temperature. Bending angles of the actuators were obtained by reading from optical images and videos,

19 which were captured by using a digital camera (SONY ILCE 6000). The temperature was recorded by

20 using a laser sight infrared thermometer (Optris LS). The Young’s moduli were measured by using a

21 materials testing system (Instron 3343).

22 3. Results and Discussions

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1 3.1. Characterizations of GP paper

2 The GP paper was fabricated by the in situ polymerization method. The fabrication process is

3 schematically shown in Fig. 1a. The detailed fabrication process is described in Materials and Methods

4 Section. The mass of PANI was obtained by calculating the mass difference before and after the

5 polymerization. The PANI mass ratios of GP1-6 papers are presented in Fig. S1a (Supporting Information).

6 The electrical conductivities of G paper and GP1-6 papers are presented in Fig. S1b (Supporting

7 Information). The electrical conductivities of the GP papers were found to increase with the polymerization

8 time (1 to 4). Then, the conductivities decreased with the polymerization time (5 to 6). Similar conductivity

9 change phenomenon was reported in graphite-PANI composite previously [30]. A maximum conductivity

10 of 875 S cm-1 can be obtained from the GP4 paper. In this study, we aim to fabricate high-performance

11 multi-functional actuators. Because high conductivity of GP4 paper can reduce the driving voltage of

12 electrothermal actuators, the GP4 paper-based devices are studied in detail, while the GP1-3 paper-based

13 devices are also investigated for comparison.

14

15 Fig. 1. Fabrication and characterizations of GP paper. a) Schematic diagram of the fabrication of GP Paper.

16 b) Optical photos of G paper (I-II) and GP1-4 papers (III-VI). c) SEM image showing the surface
 8

1 morphology of G paper. d) SEM image showing the surface morphology of GP4 paper. e) Cross-sectional

2 SEM image of GP4 paper.

4 The raw G paper has grey metallic luster (Fig. 1b (I)) and excellent flexibility (Fig. 1b (II)). The

5 optical photos of GP1-4 papers with different polymerization time are presented in Fig. 1b (III-VI). With

6 the increase of PANI content, the color of GP paper changed from green to dark green, and finally got close

7 to black. The green color of GP paper indicated that the PANI was electrically conductive. The

8 morphologies of G paper and GP paper were characterized by using a SEM. The SEM image of G paper is

9 shown in Fig. 1c. It can be seen that the G paper consisted of graphite nanosheets, which had smooth

10 surfaces. After polymerization, the morphology of GP paper greatly changed, because the surfaces of

11 graphite nanosheets were surrounded by PANI nanoparticles. Taking the GP4 paper for example, the

12 smooth surfaces changed to rough surfaces, on which the PANI nanoparticles were spherical grains and

13 uniformly distributed (Fig. 1d). The PANI nanoparticles grew firmly on the graphite sheets via strong π-π

14 stacking [31]. The SEM images of surface morphology of GP1-3 papers are also shown in Fig. S2a-c

15 (Supporting Information) for comparison. Fig. 1e demonstrates the cross-sectional SEM image of the GP4

16 paper. The outer layer was PANI nanoparticles and the inner layer was graphite nanosheets, which enables

17 the GP paper to have high electrical conductivity and high ionic conductivity to obtain fast

18 charge/discharge rates as well as good electrothermal property [32]. Therefore, such structure is desirable

19 for further fabrication of actuators or supercapacitors. The SEM images of cross-sectional structures of

20 GP1-3 papers are also shown in Fig. S2d-e (Supporting Information) for comparison.

21 The compositions of G paper and GP papers were probed by using Raman spectra. The Raman spectra

22 in Fig. S3 (Supporting Information) show that the GP papers exhibited several strong characteristics of
 9

1 PANI. The peaks presented at ~1168 cm-1 and ~1254 cm-1 can be attributed to the C-H bending of quinoid

2 ring and C-H bending of the benzenoid ring, while that at ~1337 cm-1 and ~1501 cm-1 are caused by C-N+

3 vibration and C=N stretching of the quinoid rings [33]. The result indicates that PANI can successfully

4 grow on the graphite sheets.

5 3.2. Actuation performance of GP paper-based actuator

6 The GP paper has high electrical conductivity. Meanwhile, its coefficient of thermal expansion (CTE)

7 is very small (natural graphite: -1 ppm K-1) [34]. High electrical conductivity of graphite enables a low

8 driving voltage of the GP papers. When coupled with a polymer film, the polymer/GP structure has the

9 potential to be designed into a low-voltage-driven electrothermal actuator. In this paper, we select the

10 BOPP film (CTE of ~137 ppm K-1) as the polymer film and GP4 paper as the electrothermal heating

11 component to construct an actuator. The bilayer structure is schematically shown in the left panel of Fig. 2a.

12 After a DC voltage is applied, the actuator is Joule-heated and two layers of the actuator expand unequally.

13 The BOPP film expands larger than the GP paper. Therefore, the actuator is expected to bend towards the

14 GP paper side after turning on the voltage (right panel of Fig. 2a). The detailed fabrication process is

15 described in Materials and Methods Section. The fabricated U-shape actuator with dimensions of 30 mm ×

16 6 mm is shown in Fig. 2b. The sliver paste on the actuator was used to reduce the conjunction resistance of

17 top part of the actuator, so as to avoid heat accumulation at the top part. Fig. S4a (Supporting Information)

18 clearly shows the cross-sectional bilayer structure of the BOPP/GP actuator. The layers in the actuator were

19 combined together tightly without delamination.

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2 Fig. 2. GP paper-based actuators. a) Schematic diagram of the bending actuation of actuator. b) Optical

3 photo of the actuator made with GP4 paper. c) Optical photos showing the actuator made with GP4 paper

4 responding to different driving voltages. d) Bending curvature and temperature of the actuator made with

5 GP4 paper as a function of driving voltage. e) Bending curvature and the temperature of the actuators made

6 with G paper and GP1-4 papers (driving voltage: 2.5 V). f) Blocking force of the actuator made with GP4

7 paper as a function of driving voltage. g) Bending curvature of the actuator made with GP4 paper for 10000

8 cycles (driving voltage: 2 V).

9
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1 The actuation performance of BOPP/GP actuator was firstly studied. The bottom part of actuator (10

2 mm) was sandwiched between two pieces of glass slides. A series of optical photos in Fig. 2c clearly

3 illustrates the bending motion of the actuator under different driving voltages for 5 s, respectively. The

4 bending curvatures were calculated from the bending angle and length of the actuator (detailed calculation

5 principle is demonstrated in Note S1 and Fig. S5 of Supporting Information). Fig. S6a (Supporting

6 Information) displays the curvatures of actuator when it was applied with different driving voltages. Every

7 voltage was applied for 5 s and the recovery time was also 5 s. It can be seen that the maximum curvature

8 became larger with higher driving voltage. The temperature of actuator was also measured at the same time

9 (Fig. S6b, Supporting Information), which also increased with higher driving voltage. Obviously, more

10 electrical power is transformed to heat by the GP paper with a higher driving voltage (P = U2/R), resulting

11 in higher temperature. The temperature changing trend is similar to that of the bending curvature, which

12 reveals that the actuation is caused by a Joule-heating effect. The summarized results are shown in Fig. 2d.

13 When the actuator was applied with a low voltage (0.5 V) for 5 s, it showed a bending curvature of 0.03

14 cm-1 and the temperature was only 28.6 °C. When the actuator was applied with a higher voltage (2.5 V),

15 the curvature increased to 1.03 cm-1 and the temperature was as high as 61.5 °C, The actuation mechanism

16 of the actuator is explained as follows. When the electrical current passes through the GP paper, the

17 electrical power is transformed to heat via Joule-heating effect. Because the two layers of the actuator are

18 combined firmly and the CTE of BOPP is much larger than that of the GP paper, the thermal expansion of

19 the BOPP film will be larger than that of the GP paper. Thus, the BOPP/GP actuator remarkably bends

20 towards the GP paper side. A model is developed to verify the actuation mechanism of the actuator (Note

21 S2 and Fig. S7, Supporting Information). The calculated results are also presented in Fig. 2d, which are

22 almost consistent with the experimental results.

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1 Moreover, the influence of polymerization time on the actuation performance of GP paper-based

2 actuator was also studied. The driving voltage was set as 2.5 V. The bending curvatures and temperature of

3 actuators with different polymerization time are shown in Fig. 2e. With the increasing of polymerization

4 time from 0 to 4, the bending curvature slightly increased from 0.80 cm-1 to 1.03 cm-1. This phenomenon

5 can be attributed to the following two reasons. Firstly, with the increasing of PANI mass ratio, the

6 resistance of the actuator decreases, which leads to more electrical power (P = U2/R) converting to thermal

7 energy and higher temperature of the actuator. When the PANI mass ratio increased from 0% to 12%, the

8 temperature accordingly increased from 50 °C to 61.5 °C. Secondly, the Young’s modulus of GP paper

9 increased from 0.9 GPa to 2.8 GPa with the increasing of polymerization time (Fig. S8 in Supporting

10 Information). Therefore, the mechanical property of the actuator was enhanced. The model developed in

11 Note S2 (Supporting information) was also used to estimate the influence of change in Young's modulus on

12 the bending curvature. The calculation outcome reveals that bending curvature becomes larger with the

13 increase of Young's modulus, as presented in Fig. 2e.

14 The force measurement and repeatability test of the actuator were also conducted. The blocking force

15 of actuator was measured by using a U-shape actuator (30 mm × 6 mm). The maximum blocking force

16 was measured to be 0.94 mN, as shown in Fig. 2f. Force density, which is defined as the blocking force

17 divided by the weight of the actuator, is a key factor for the effective generated force of an actuator. The

18 force density of the actuator was 8.3, which indicated that the force was 8.3 times larger than its own

19 weight (0.113 mN), demonstrating the potential application of the actuator in soft robots. What’s more, the

20 actuator was applied with a voltage of 2 V repeatedly for 10000 cycles. The bending motions were

21 repeatable, as shown in Fig. 2g. The cross-sectional structure of the actuator after the repeatability test is

22 displayed in Fig. S4b (Supporting Information). The two layers of BOPP and GP4 paper were still tightly
 13

1 coupled to each other after the test, revealing good stability of the actuator.

2 3.3. Electrochemical performance of GP paper-based supercapacitors

3 There are abundant PANI nanoparticles on GP paper surface, which can provide large

4 pseudocapacitance. With the properties of high electrical conductivity and high flexibility, the GP paper is

5 also an ideal candidate material for solid-state supercapacitors. As shown in Fig. 3a, a symmetrical

6 solid-state supercapacitor was fabricated by two GP paper electrodes sandwiching solid-state PVA-H2SO4

7 electrolyte. The optical photo in Fig. 3b shows a supercapacitor made with GP4 paper.

8 The electrochemical performances of supercapacitors at room temperature were firstly studied. The

9 CV curves of supercapacitors made with G paper and GP papers at the scan rate of 5 mV s-1 are shown in

10 Fig. 3c. The CV curves of GP paper-based supercapacitors show roughly rectangular images and some

11 redox peaks, which result from the combination of EDLC and pseudocapacitance of GP paper. The

12 supercapacitor made with GP4 paper had the biggest enclosed area on the CV curves, indicating that the

13 supercapacitor had largest capacitance, which was attributed to the high electrical conductivity and large

14 mass loading of PANI. The detailed CV curves for the supercapacitors made with G paper and GP1-4

15 papers are presented in Fig. S9 (Supporting Information) for comparison.

16
 14

1
2 Fig. 3. GP paper-based solid-state supercapacitors. a) Schematic diagram of the fabrication of solid-state

3 supercapacitor made with GP paper electrodes. b) Optical photo of the supercapacitor made with GP4 paper.

4 c) CV curves of the supercapacitors made with G paper and GP1-4 papers (scan rate: 5 mV s-1). d) GCD

5 curves of the supercapacitors made with G paper and GP1-4 papers (current density: 0.5 mA cm-2). e) CS of

6 the supercapacitors made with G paper and GP1-4 papers at different current densities. f) CS of the

7 supercapacitors made with GP1-4 papers with different bending angles (current density: 0.5 mA cm-2). g)
 15

1 Ragone plots of the supercapacitors made with G paper and GP1-4 papers. h) Capacitance retention and

2 Coulombic efficiency of the supercapacitor made with GP4 paper for 10000 cycles (fixed current density: 2

3 mA cm-2). i) Optical photos showing four supercapacitors made with GP4 paper in series connection to

4 light a LED. The inset is the enlarged photo of LED.

6 Fig. 3d presents the GCD curves of supercapacitors made with G paper and GP papers at the current

7 density of 0.5 mA cm-2. The supercapacitor made with GP4 paper had the longest charge-discharge time,

8 which also demonstrated that the supercapacitor had the largest capacitance. The detailed GCD curves of

9 supercapacitors are presented in Fig. S10 (Supporting Information) for comparison. The GCD curves are

10 rough triangular in shape, which shows high Coulombic efficiency. The CS of supercapacitors was

11 calculated from GCD curves according to Note S3 (Supporting Information). In Fig. 3e, the CS was plotted

12 versus discharge current densities. At a discharge current density of 0.25 mA cm-2, the CS for the

13 supercapacitors made with GP1-4 papers were 101, 197.4, 307.4 and 402.5 mF cm-2, respectively. These

14 results are much larger than that of supercapacitors made with G paper (5.6 mF cm-2). The high CS of GP

15 paper-based supercapacitors can be attributed to the abundant PANI nanoparticles. The functions of PANI

16 nanoparticles are that they promote the contact between electrolyte ions and electrodes surfaces, providing

17 high pseudocapacitance and enhancing electrical conductivity of the GP paper electrodes. Moreover, the CS

18 of supercapacitors made with GP4 paper electrodes (402.5 mF cm-2) is larger than that of the

19 supercapacitors fabricated by pencil-drawing graphite/PANI electrodes (~78 mF cm-2) [33], exfoliated

20 graphite/PANI electrodes (80.4 mF cm-2) [31] and PANI/electrochemically surface-treated graphite

21 electrodes (202.7 mF cm-2) [35].

22 Furthermore, for the sake of verifying that the electrochemical performance of supercapacitors can be
 16

1 maintained under electrothermal actuation, the performances of supercapacitor under different bending

2 angles and high temperature were also studied. Due to the large bending obtained by the GP paper-based

3 actuator, we firstly evaluated the performance of supercapacitors under different bending angles. As

4 presented in Fig. 3f, the capacitance of supercapacitors can be almost maintained under different angles.

5 The GCD curves are almost unchanged. The related optical photos and GCD curves are presented in Fig.

6 S11 (Supporting Information). Secondly, because the GP paper-based actuators generated large bending

7 motions under high temperature, we sequentially evaluated high temperature influence on the performance

8 of supercapacitors. At temperature of 60 °C, the capacitance of supercapacitor made with GP4 paper was

9 tested for 100 cycles. As shown in Fig. S12 (Supporting Information), the GCD curves shrink, but the

10 capacitance retention and Coulombic efficiency remain 98% and 95% of the initial values after 100 cycles,

11 respectively. These results indicate that the GP paper-based supercapacitors have potential to be integrated

12 into an actuator to construct a multi-functional device.

13 The energy density and power density of the GP paper-based supercapacitors were studied as well. Fig.

14 3g shows the Ragone plots of the fabricated supercapacitors. Taking the supercapacitor made with GP4

15 paper for example, the highest areal specific energy density (ES) of 16.3 µWh cm-2 was delivered at a

16 corresponding areal specific power density (PS) of 154.5 µW cm-2. The ES still stayed 8.7 µWh cm-2 at PS of

17 1054.5 µW cm-2. The supercapacitor made with GP4 paper was finally tested 10000 GCD cycles to

18 evaluate long-term electrochemical stability. The results of capacitance retention and Coulombic efficiency

19 are presented in Fig. 3h. The capacitance retention gradually decreased and was about 79.1% of the initial

20 value after 10000 cycles, while the Coulombic efficiency remained 95.2% of the initial value after 10000

21 cycles. The supercapacitor made with GP4 paper exhibits good capacitance stability and Coulomb

22 efficiency.
 17

1 In practical applications, leakage current and self-discharge of the supercapacitors are two major

2 concerns. Fig. S13a (Supporting Information) shows that the leakage current of supercapacitors made with

3 GP4 paper dropped significantly in the beginning and gradually became smaller and stable. The value

4 finally reduced to only 26 µA after 3 h. Fig. S13b (Supporting Information) shows that the initial charged

5 potential (0.8 V) of supercapacitor retained 0.26 V (32.5%) after 24 h. These advantages indicate that the

6 fabricated supercapacitors can be used in practical applications. As demonstrated in Fig. 3i, four

7 supercapacitors made with GP4 paper in series connection (charged to potential: 3 V) can be used to light

8 up a light-emitting-diode (LED) (working potential > 2.2 V) for more than 4 min.

9 3.4. Electric-fish-inspired multi-functional actuator with integrated energy-storage function

10 Based on the above-mentioned fascinating characteristics of GP paper-based materials and inspiration

11 from electric fish, a multi-functional actuator made with GP4 paper is elaborately designed, which

12 integrates the functions of actuator and supercapacitor in a single device. The fabrication is summarized as

13 follow. A piece of GP4 paper was cut into U-shape for using as one component layer of the electrothermal

14 actuator. At the same time, it was also used as electrodes for the electrochemical supercapacitors (electrode

15 O1 and O2). A BOPP film was attached to the U-shape GP4 paper to serve as another component layer of

16 the actuator and an insulating substrate of the device. The U-shape GP4 paper together with the BOPP film

17 can realize the function of the eletrothermal actuator. Then, two more strip-shape GP4 paper electrodes

18 (electrodes M and N) together with PVA-H2SO4 electrolyte layers were assembled on the right part of the

19 actuator. In this way, two supercapacitor units were integrated in the multi-functional actuator.
 18

2 Fig. 4. Multi-functional actuator made with GP4 paper. a) Schematic diagram of the multi-functional

3 actuator. b) Optical photo of the fabricated multi-functional actuator. c) Schematic diagram of the bending

4 actuation of multi-functional actuator. d) Optical photos showing the multi-functional actuator without (left

5 panel) and with (right panel) a driving voltage of 3 V. e) Schematic diagrams of the multi-functional

6 actuator used as single supercapacitor units (left panel), two supercapacitor units in series connection

7 (middle panel) and two supercapacitor units in parallel connection (right panel). f) GCD curves of the

8 supercapacitor units used in single, in series connection and in parallel connection (current density: 0.5 mA

9 cm-2).

10

11 As shown in the right panel of Fig. 4a, the entire device is an actuator, while the right part of it

12 integrates two supercapacitor units. The fabricated multi-functional device is shown in Fig. 4b. First of all,

13 this device can be directly used as an electrothermal actuator, when the electrodes O1 and O2 are connected
 19

1 to a DC power source. The actuation mechanism is shown in Fig. 4c. The actuator showed a large bending

2 deformation when it was applied with a DC voltage of 3 V for 5 s (Fig. 4d). Secondly, in this

3 multi-functional device, the supercapacitor units can be used in single, in series (increase operating voltage)

4 or in parallel (increase operating current), which is suitable for practical situations (Fig. 4e). Each

5 integrated supercapacitor unit has an active area of 2 cm-2. As shown in Fig. 4e, Device A has electrodes O1

6 and M. Similarly, Device B has electrodes O2 and N. In the left panel of Fig. 4e, when electrodes O1 and M

7 are used for discharging, Devices A is used in single. Similarly, when electrodes O2 and N are used for

8 discharging, Device B is used independently. The related GCD curves of Device A and Device B used in

9 single are presented in Fig. 4f. The capacitance for Device A and Device B were 351 and 370.9 mF,

10 respectively. The middle panel of Fig. 4e schematically shows the device used in series, while the right

11 panel of Fig. 4e shows it used in parallel. The GCD curves of the device used in series and in parallel are

12 also shown in Fig. 4f. The capacitances of the supercapacitor units used in series and in parallel were

13 calculated to be 191.1 and 750.7 mF respectively, which were close to the predicted values (180.6 and 721

14 mF) according to basic laws of series and parallel connections.

 20

2 Fig. 5. Applications of the multi-functional actuators. a) Schematic diagram of two multi-functional

3 actuators used as a gripper. b) Optical photos showing the gripper based on multi-functional actuators to

4 grasp and move an object. c) Schematic diagram of two multi-functional actuators used as power supply

5 units. d) Optical photos showing two multi-functional actuators used as power supply units to drive a

6 calculator.

8 In the end, a pair of such multi-functional actuators was fabricated to demonstrate two practical

9 applications. Firstly, the two multi-functional actuators together can be used as a gripper to carry an object
 21

1 (schematically shown in Fig. 5a). Optical photos in Fig. 5b shows that the gripper can grasp an object that

2 was 2.8 times heavier than itself and move the object (driving voltage: 3 V). Secondly, four supercapacitor

3 units integrated in two multi-functional actuators were connected in series, mimicking the arrangement of

4 electrocytes in electric fish. Then, they can be used as power supply units (schematically shown in Fig. 5c).

5 As presented in Fig. 5d, four supercapacitor units in series (charged to potential: 3 V) can successfully

6 drive a calculator (working potential > 1.5 V). These results indicate that the multi-functional integrated

7 device can accomplish the functions of actuator and supercapacitor in a single device, which is more

8 integrated than a reported graphene oxide-based system consisted of independent supercapacitor and

9 actuator [36].

10 4. Conclusions

11 In summary, we fabricate graphite and PANI composite materials by the in situ polymerization method.

12 The fabricated GP paper can be used for the component layer of actuator and supercapacitor electrodes. On

13 one hand, the GP papers have high electrical conductivity (up to 875 S cm-1) and small CTE (-1 ppm K-1).

14 Thus, it can be used as a component layer of the electrothermal actuator. The GP paper-based actuators

15 perform large bending curvatures (up to 1.03 cm-1) and long cycling stability (> 10000 cycles). On the other

16 hand, there are large amount of PANI nanoparticles on the surface of GP paper, which can provide large

17 pseudocapacitance. Therefore, high-performance supercapacitors made with GP papers can be obtained. We

18 study the influence of polymerization time on the properties of supercapacitors and find that the CS of the

19 supercapacitors increases with the increase of polymerization time. The value of CS is up to 402.5 mF cm-2

20 by using GP4 paper. The supercapacitor also exhibits high flexibility, high PS (1054.5 µWh cm-2) and great

21 cycling stability (capacitance retention 79.1% after 10000 cycles). Especially, inspired by the electric fish,

22 we propose a multi-functional actuator based on GP paper, which integrates the function actuator and
 22

1 supercapacitor in a single device. Therefore, such novel multi-functional devices can not only serve as

2 artificial muscles, but also as power supply units in soft robots. With further arrangement design of these

3 devices, the output voltage or current can be greatly increased, which is also inspired from the electric fish

4 and makes the multi-functional devices more practical in daily applications. Based on this multi-functional

5 actuator, future robots may not require specific and separated power supply units, because they can be

6 discretely integrated into the artificial muscles that make up the robot, which contributes to the versatility

7 and miniaturization of soft robots. We believe that this study will open a new path to the design of

8 multi-functional devices and have applications in wearable devices, artificial muscles and integrated soft

9 robots.

10 Acknowledgements

11 This work was supported by National Natural Science Foundation of China [grant number 51773039];

12 Natural Science Foundation of Fujian Province for Distinguished Young Scientists [grant numbers

13 2017J06014, 2018J06001]; Education Department of Fujian Province [grant number JZ160428] and Open

14 Research Fund Program of the State Key Laboratory of Low-Dimensional Quantum Physics [grant number

15 KF201810].

16

17 References

18 [1] Y. Zhang, Y. Wang, T. Cheng, L. Yao, X. Li, W. Lai, W. Huang, Printed supercapacitors: materials,

19 printing and applications, Chem. Soc. Rev. 48 (2019) 3229-3264.

20 [2] L. Liu, Y. Feng, W. Wu, Recent progress in printed flexible solid-state supercapacitors for portable and

21 wearable energy storage, J. Power Sources 410 (2019) 69-77.

22 [3] J. Wang, F. Li, F. Zhu, O.G. Schmidt, Recent progress in micro‐supercapacitor design, integration, and

23 functionalization, Small Methods 2 (2018) 1800367.

 23

1 [4] D. Chen, Z. Lou, K. Jiang, G. Shen, Device configurations and future prospects of flexible/stretchable

2 lithium-ion batteries, Adv. Funct. Mater. 28 (2018) 1805596.

3 [5] J.H. Kim, D. Lee, Y.H. Lee, W. Chen, S.Y. Lee, Nanocellulose for energy storage systems: beyond the

4 limits of synthetic materials, Adv. Mater. 31 (2018) 1804826.

5 [6] Z. Wu, Y. Wang, X. Liu, C. Lv, Y. Li, D. Wei, Z. Liu, Carbon-nanomaterial-based flexible batteries for

6 wearable electronics, Adv. Mater. 31 (2019) 1800716.

7 [7] X. Li, B. Zhu, J. Zhu, Graphene oxide based materials for desalination, Carbon 146 (2019) 320-328.

8 [8] P. Tao, G. Ni, C. Song, W. Shang, J. Wu, J. Zhu, G. Chen, T. Deng, Solar-driven interfacial evaporation,

9 Nat. Energy 3 (2018) 1031-1041.

10 [9] Z. Li, C. Wang, J. Su, S. Ling, W. Wang, M. An, Fast-growing field of interfacial solar steam generation:

11 evolutional materials, engineered architectures, and synergistic applications, Solar RRL 2 (2019) 1800206.

12 [10] Y. Qiu, E. Zhang, R. Plamthottam, Q. Pei, Dielectric elastomer artificial muscle: Materials innovations and

13 device explorations, Accounts Chem. Res. 52 (2019) 316-325.

14 [11] L. Hu, Y. Wan, Q. Zhang, M.J. Serpe, Harnessing the power of stimuli-responsive polymers for actuation,

15 Adv. Funct. Mater. 29 (2019) 1903471.

16 [12] D. Melling, J.G. Martinez, E.W.H. Jager, Conjugated polymer actuators and devices: progress and

17 opportunities, Adv. Mater. 31 (2019) 1808210.

18 [13] H. Gao, J. Li, F. Zhang, Y. Liu, J. Leng, The research status and challenges of shape memory

19 polymer-based flexible electronics, Mater. Horiz. 6 (2019) 931-944.

20 [14] L.Z. Chen, C.H. Liu, C.H. Hu, S.S. Fan, Electrothermal actuation based on carbon nanotube network in

21 silicone elastomer, Appl. Phys. Lett. 75 (2008) 263104.

22 [15] Y. Hu, J. Liu, L. Chang, L. Yang, A. Xu, K. Qi, P. Lu, G. Wu, W. Chen, Y. Wu, Electrically and
 24

1 sunlight-driven actuator with versatile biomimetic motions based on rolled carbon nanotube bilayer composite,

2 Adv. Funct. Mater. 27 (2017) 1704388.

3 [16] M. Weng, P. Zhou, L. Chen, L. Zhang, W. Zhang, Z. Huang, C. Liu, S. Fan, Multiresponsive bidirectional

4 bending actuators fabricated by a pencil on paper method, Adv. Funct. Mater. 26 (2016) 7244-7253.

5 [17] G. Wu, Y. Hu, Y. Liu, J. Zhao, X. Chen, V. Whoehling, C. Plesse, G.T.M. Nguyen, F. Vidal, W. Chen,

6 Graphitic carbon nitride nanosheet electrode-based high-performance ionic actuator, Nat. Commun. 6 (2015)

7 7258.

8 [18] G. Wu, X. Wu, Y. Xu, H. Cheng, J. Meng, Q. Yu, X. Shi, K. Zhang, W. Chen, S. Chen, High‐performance

9 hierarchical black‐phosphorous‐based soft electrochemical actuators in bioinspired applications, Adv. Mater.

10 32 (2019) 1806492.

11 [19] Y.Y. Xiao, Z.C. Jiang, X. Tong, Y. Zhao, Biomimetic locomotion of electrically powered “Janus” soft

12 robots using a liquid crystal polymer, Adv. Mater. 32 (2019) 1903452.

13 [20] Y.L. Zhang, Y.Q. Liu, D.D. Han, J.N. Ma, D. Wang, X.B. Li, H.B. Sun, Quantum‐confined‐

14 superfluidics‐enabled moisture actuation based on unilaterally structured graphene oxide papers, Adv. Mater. 32

15 (2019) 1901585.

16 [21] Z. Wang, Q. Yu, Y. Huang, H. An, Y. Zhao, Y. Feng, X. Li, X. Shi, J. Liang, F. Pan, P. Cheng, Y. Chen, S.

17 Ma, Z. Zhang, PolyCOFs: A new class of freestanding responsive covalent organic framework membranes with

18 high mechanical performance, ACS Central Sci. 5 (2019) 1352-1359.

19 [22] G. Cai, J. Ciou, Y. Liu, Y. Jiang, P.S. Lee, Leaf-inspired multiresponsive MXene-based actuator for

20 programmable smart devices, Sci. Adv. 5 (2019) eaaw7956.

21 [23] I. Must, E. Sinibaldi, B. Mazzolai, A variable-stiffness tendril-like soft robot based on reversible osmotic

22 actuation, Nat. Commun. 10 (2019) 344.

 25

1 [24] J. Mu, M.O.N. Jung De Andrade, S. Fang, X. Wang, E. Gao, N. Li, S.H. Kim, H. Wang, C. Hou, Q. Zhang,

2 M. Zhu, D. Qian, H. Lu, D. Kongahage, S. Talebian, J. Foroughi, G. Spinks, H. Kim, T.H. Ware, H.J. Sim, D.Y.

3 Lee, Y. Jang, S.J. Kim, R.H. Baughman. Sheath-run artificial muscles.: Science 365 (2019) 150-155.

4 [25] T. Jia, Y. Wang, Y. Dou, Y. Li, M. Jung De Andrade, R. Wang, S. Fang, J. Li, Z. Yu, R. Qiao, Z. Liu, Y.

5 Cheng, Y. Su, M. Minary Jolandan, R.H. Baughman, D. Qian, Z. Liu, Moisture sensitive smart yarns and textiles

6 from self‐balanced silk fiber muscles, Adv. Funct. Mater. 29 (2019) 1808241.

7 [26] K. Hoon Park, B. Soo Yoon, N. Trung Nguyen, N. Seo Goo, T. Sam Kang, K. Joon Yoon, Piezo-composite

8 actuated control surface system for flying vehicle, Aircr. Eng. Aerosp. Tec. 82 (2010) 372-375.

9 [27] U. Simu, S. Johansson, Fabrication of monolithic piezoelectric drive units for a miniature robot, J.

10 Micromech. Microeng. 12 (2002) 582-589.

11 [28] J.R. Gallant, L.L. Traeger, J.D. Volkening, H. Moffett, P.H. Chen, C.D. Novina, G.N. Phillips, R. Anand,

12 G.B. Wells, M. Pinch, R. Guth, G.A. Unguez, J.S. Albert, H.H. Zakon, M.P. Samanta, M.R. Sussman, Genomic

13 basis for the convergent evolution of electric organs, Science 344 (2014) 1522-1525.

14 [29] G.A. Unguez, H.H. Zakon, Reexpression of myogenic proteins in mature electric organ after removal of

15 neural input, J. Neurosci. 18 (1998) 9924-9935.

16 [30] S. Bourdo, Z. Li, A.S. Biris, F. Watanabe, T. Viswanathan, I. Pavel, Structural, electrical, and thermal

17 behavior of graphite-polyaniline composites with increased crystallinity, Adv. Funct. Mater. 18 (2008) 432-440.

18 [31] O. Sadak, M.U.A. Prathap, S. Gunasekaran, Facile fabrication of highly ordered polyaniline–exfoliated

19 graphite composite for enhanced charge storage, Carbon 144 (2019) 756-763.

20 [32] L. Nikzad, S. Alibeigi, M.R. Vaezi, B. Yazdani, M.R. Rahimipour, Synthesis of a Graphite-Polyaniline

21 nanocomposite and evaluation of its electrochemical properties, Chem. Eng. Technol. 32 (2009) 861-866.

22 [33] B. Yao, L. Yuan, X. Xiao, J. Zhang, Y. Qi, J. Zhou, J. Zhou, B. Hu, W. Chen, Paper-based solid-state
 26

1 supercapacitors with pencil-drawing graphite/polyaniline networks hybrid electrodes, Nano Energy 2 (2013)

2 1071-1078.

3 [34] Y. Wang, K. Li, X. Li, H. Cui, G. Liu, H. Xu, X. Wu, W. Yao, B. Zhong, X. Huang, H. Wang, T. Wu,

4 Electro-thermally driven flexible robot arms based on stacking-controlled graphite nanocomposites, Carbon 152

5 (2019) 873-881.

6 [35] H. Zhou, W. Zhang, X. Zhi, H. Zhai, Remarkably enhanced performances of polyaniline/electrochemically

7 surface-treated graphite electrodes with optimal charge transfer pathways for flexible supercapacitor application,

8 J. Power Sources 402 (2018) 311-319.

9 [36] J. Yang, J. Zhang, X. Li, J. Zhou, Y. Li, Z. Wang, J. Cheng, Q. Guan, B. Wang, Single Janus iodine-doped

10 rGO/rGO film with multi-responsive actuation and high capacitance for smart integrated electronics, Nano

11 Energy 53 (2018) 916-925.

12
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1 Mingcen Weng received his bachelor’s degree in 2014 from Fujian Normal University,

2 China. Then, he was recommended to join Dr. Luzhuo Chen’s group as a Ph.D.

3 candidate at Fujian Normal University and received his Ph.D. degree in 2019. He is

4 currently an associate professor in Fujian University of Technology. His research

5 interests include smart actuators and energy conversion & storage devices.

6 Yimin Duan received her bachelor’s degree in 2019 from Fujian Normal University,

7 China. She is currently a postgraduate student in Dr. Luzhuo Chen’s group in Fujian

8 Normal University. Her research interests focus on carbon-based energy conversion &

9 storage devices.

10 Peidi Zhou received his master’s degree in 2018 from Fujian Normal University, China.

11 He is currently a Ph.D. candidate in Dr. Luzhuo Chen’s group in Fujian Normal

12 University. His research interests focus on carbon-based actuators and sensors.

13

14 Feng Huang has obtained his Ph.D. in University of Science and Technology of China

15 in 2009. He is currently a professor in Fujian Normal University. His current research

16 includes energy-conversion materials and localized surface plasmon resonance in

17 nanocrystals and nano-heterostructures.

18 Wei Zhang received her bachelor’s degree from Northeast Normal University, China

19 (2006). She received her Ph.D. from Institute of Physics, Chinese Academic of Sciences,

20 China (2011). She worked on the new technology of polymer at Global Innovation

21 Center (Beijing) of Proctor and Gamble (P&G) Company (2011–2014). Now she is an

22 associate professor in Fujian Normal University, China. Her research interests involve actuator material
 28

1 design and unique properties of 2D materials.

2 Luzhuo Chen received his bachelor’s degree from Xiamen University, China (2006).

3 Then, he was recommended to join Prof. Shoushan Fan’s group as a Ph.D. candidate

4 at Tsinghua University, China and received his Ph.D. in 2011. He is currently a

5 doctoral supervisor and an associate professor in Fujian Normal University, China.

6 His research interests include smart actuators, sensors, intelligent robots, chromic materials and energy

7 conversion & storage devices.

Highlights

1. Inspired by electric fishes, an actuator with energy-storage function is proposed.

2. Actuator shows a large bending actuation when driven by an ultralow driving

voltage.

3. Supercapacitor unit shows great electrochemical performances.

4. Multi-functional actuators can be used as artificial muscles and power supply units.