Sensors and Actuators B 115 (2006) 488493

Electrochemical actuator based on monolithic polypyrroleTiO2 nanoparticle composite lm

Ximin He, Gaoquan Shi
Department of Chemistry and Key Lab of Organic Optical Electronics and Molecular Engineering of Education Commission, Tsinghua University, Beijing 100084, PR China Received 16 June 2005; received in revised form 8 October 2005; accepted 12 October 2005 Available online 16 November 2005

Abstract A polypyrrole (PPy) composite lm with a pure PPy zone and a PPyTiO2 nanoparticle composite zone in its cross-sectional direction was synthesized by direct oxidation of pyrrole successively in an electrolyte with or without TiO2 nanoparticles. The volume content of TiO2 in the composite lm was tested to be lower than 0.9%. The actuator fabricated from this monolithic PPy lm bends uniformly in two directions with a maximum bending angle larger than 90 and has a high response rate (115 s1 at 1.0 V versus SCE) and a long lifetime (>20,000 cycles) in a 1 M LiClO4 aqueous solution. The high performance of this actuator resulted from the non-delamination and intrinsic asymmetric structure and the high conductivity of PPy lm. 2005 Elsevier B.V. All rights reserved.
Keywords: Polypyrroles; Nanocomposites; Electrochemistry

1. Introduction Electrochemical soft actuators made of conducting polymers (CP) have been studied extensively in the last decades. During the redox processes, electrochemomechanical deformation (ECMD) of CP lms is signicantly affected by the lm morphology [1]. Since a typical CP lm has a symmetric structure, it exhibits uniform volume changes during the redox process and cannot do bending movement as an actuator. Thus, in general, a exible and electrochemically inert layer, which is not subjected to volume changes under electrochemical stimuli is needed to be glued to the free-standing CP lm. Therefore, most of the CP actuators have been constructed based on either bilayer [2,3] or multilayer [46] conguration. However, the inevitable delamination in the multilayer actuators shortens their lifetime, since the physical adhesion between the inert layer and the CP layer(s) cannot sustain repeated volume alteration at their interfaces [7,14]. Moreover, the inert layer contributes additional weight of the actuator and the energy consumed by the deformation at the interfaces decreases the actuator efciency.

Corresponding author. Tel.: +86 10 6277 3743; fax: +86 10 6277 1149. E-mail address: gshi@tsinghua.edu.cn (G. Shi).

In comparison to conventional multilayered actuators, monolithic actuators have advantages of higher efciency and better structural stability. Wang and co-workers prepared monolithic polyaniline (Pani) electrochemical actuators with microvoids distributed across the cross-section [8]. Although the actuators had a very long lifetime (>325,000 cycles), they could only be operated at a high driving potential (2 V) in acidic medium (1 mol l1 HCl) and could not do uniform bending. The main problem is the low conductivity of the Pani lm (0.1 S cm1 ). Then, they fabricated another actuator based on a monolithic asymmetric polyaniline-graphite composite lm, consisting of graphite-rich and -lacking layers [9]. The high conductivity resulted from the incorporated graphite in the Pani lm, and the asymmetric distribution of graphite across the cross-section allows for lower operation potential, larger bending angles and also large life cycles (120,000). However, the lm was prepared through a multi-step procedure, and a high content of graphite powder (70%) in the composite lm reduced the efciency and mechanical strength of the actuator. A PPy lm grown in a slender pipe of polytetrauoroethylene has a considerable vertical anisotropy [10] and can perform bending movements. Recently, we also electrochemically synthesized an anisotropic PPy lm from a mixed solvent of acetoni-

0925-4005/$ see front matter 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.snb.2005.10.011

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Fig. 1. Scheme of the preparation procedure of anisotropic PPyTiO2 composite lms.

trile and dichloromethane containing a high concentration of an anion surfactant of sodium 1,4-bis(2-ethylhexyl)sulfosuccinate (AOT) [11]. The lm has compact and porous zones in its vertical direction and the actuator fabricated from this lm can do uniform bending in a neutral medium and has high performance. However, the preparation of this lm needs organic solvents and a large amount of expensive AOT. Moreover, the porous structure may decrease the mechanical strength of the actuator. In this paper, we desire to report that high performance actuators can also be fabricated from an anisotropic PPy-oxide nanoparticle composite lm formed by direct co-deposition of PPy and the nanoparticles from an aqueous medium. Here, choosing TiO2 nanoparticles as the example is nothing special, mainly because it can be commercially obtained. It was found that the introduction of a little amount of TiO2 nanoparticles (<0.9%, by volume) can improve greatly the performance of the single-layer PPy actuator. 2. Experimental 2.1. Materials Pyrrole (99%, Hongyu Chem. Co., Beijing, China) was used after distillation under reduced pressure. Dodecylbenzene sulfonate acid (DBSA, >99%, Acros), anhydrous lilhium perchlorate (>99%, Jinke Inst. Fine Chem., Tianjin, China) and TiO2 nanoparticles with diameters of 2030 nm (Deggusa, USA) were used as received. 2.2. Electrochemical syntheses of anisotropic PPyTiO2 lms Electrochemical syntheses were performed at room temperature in a one-compartment cell by the use of a Model 273 potentiostatgalvanostat (EG&G Princeton Applied Research) under computer control. The working and counter electrodes were both a stainless steel sheet (AISI 304, 6.0 cm 2.0 cm) and placed 2.0 cm apart. All potentials were referred to an Ag/AgCl wire that was immersed directly in the solution.

The procedure of preparation of the anisotropic PPyTiO2 composite lms is schematically illustrated in Fig. 1. First, a pure PPy layer was deposited on the working electrode by direct oxidation of 0.1 mol l1 pyrrole in an aqueous solution of 0.1 mol l1 DBSA galvanostatically at 1.6 mA cm2 (Fig. 1a) for 700 s (112 mC cm2 ). Secondly, 0.2, 0.4 or 0.8 g TiO2 nanoparticle powder was added into the electrolyte and dispersed by ultrasonication for 15 min (the content of TiO2 in the electrolyte was calculated to be 0.0025, 0.005 or 0.01 g ml1 ), then a PPyTiO2 layer was successively deposited on the PPy layer under magnetic stirring for another 700 s (112 mC cm2 ) (Fig. 1b). All solutions were de-aerated by bubbling dry nitrogen, and maintained a light nitrogen overpressure during the experiments. Finally, the composite lm was peeled off from the surface of the working electrode, washed repeatedly with de-ionized water and dried under vacuum at room temperature for characterizations. A pure PPy lm was also synthesized under the same conditions for comparing with the PPyTiO2 composite lm. The thickness of the lms was measured to be approximately 15 m by the use of a thickness monitor (CH-1-ST, Shanghai, China). 2.3. Characterizations The scanning electron micrographs (SEM) were taken out by using a scanning electron microscope (SEM; Sirion-200, FEI, USA). The elemental compositions of the composite lm surface were determined by using an energy dispersive X-ray detector (EDX; Serion-200 132-10, EDAX, USA). The thermal stability and the weight content of TiO2 in the lm were studied by the use of a thermal gravimetric analyzer (TGA 2050, TA Co.). The dc conductivity was measured by conventional fourprobe technique. The electrochemical analyses including cyclic voltammetry and the bending movements of the single-layer PPy lms (size = 15 mm 2 mm 0.015 mm) were carried out in a one-compartment cell by the use of a 1 mol l1 aqueous solution of LiClO4 as the electrolyte. The working electrode was a freestanding PPy lm, the counter electrode was a stainless steel sheet and all the potentials were referred to a saturated calomel electrode (SCE).

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3. Results and discussion 3.1. Morphology and conductivity of PPyTiO2 lm The appearances of the two surfaces of a 15 m thick PPyTiO2 composite lm are different: the TiO2 -rich side is dull black; while the TiO2 -free side is black and shiny. However, the two surfaces of a 15 m thick pure PPy lm have nearly the same appearance. The SEM images of a pure and a PPyTiO2 composite lm are shown in Fig. 2. As can be seen from this Fig. 2a, for a 15 m pure PPy lm, the surface in contact with the electrolyte is compact and smooth. However, for a PPyTiO2 lm, the surface in contact with the electrolyte, e.g. the TiO2 -rich side, is rough and irregular (Fig. 2b), while its TiO2 -free side is at and compact (Fig. 2c). The composite lm does not show an apparent interface between its TiO2 -rich and TiO2 -free layers, and the nanoparticles distribute asymmetrically across its crosssection as shown in Fig. 2d. The SEM micrographs suggest that the incorporation of TiO2 nanoparticles affects the morphology of the lm signicantly and makes the TiO2 -rich side look to be relative loosely piled up with PPy and TiO2 nanoparticles. The chemical composition of the TiO2 -rich surface of the composite lm was examined by EDX analysis (Fig. 3). The result indicates the existence of elements Ti (from TiO2 ), C, N, O (from pyrrole) and S (from DBS). The results of TGA examinations indicated that the lm prepared from the media containing 0.005 or 0.01 g ml1 TiO2 had a TiO2 content of 1.21 or 2.57% (w/w), respectively. Thus, the volume contents of TiO2 nanoparticles in the composite lms were calculated to be 0.40 and 0.87% (v/v), respectively. In contrast, the pure PPy lm showed no weight residue as the sample was heated in air to over 650 C. The conductivity of the PPyTiO2 lm was measured to be approximately 16.0 S cm1 . This value is much higher than that of Pani [12]. Furthermore, these lms are exible enough to be folded or shaped into various structures for the fabrication of actuators.

Fig. 3. EDX spectrum of the TiO2 -rich side of the PPyTiO2 lm.

3.2. Electrochemistry and actuations of the PPyTiO2 lm The cyclic voltammograms (CVs) of an as-grown PPyTiO2 lm (size = 15 mm 2 mm 0.015 mm) containing 0.40% (v/v) TiO2 and coated on the working electrode surface or the same lm in freestanding state were carried out in an aqueous solution of 1.0 mol l1 LiClO4 at 30 mV s1 , and the results are shown in Fig. 4. As can be seen from the gure, each CV cycle has a couple of broad redox waves. Furthermore, the lms can be cycled repeatedly between the conducting (oxidized) and insulating (neutral) states without signicant decomposition. The CV of a composite lm coated on a metallic electrode shows a reduction wave at approximately 0.58 V and an oxidation wave at approximately 0.10 V (Fig. 4). Thus, the potential difference between the oxidation and reduction current peaks ( Ep ) is calculated to be 0.48 V. On the other hand, the CV of a freestanding PPyTiO2 lm shows a broad reduction wave centered at approximately 0.80 V and an oxidation wave

Fig. 2. SEM images of (a) a PPy lm without TiO2 and (bd) a PPyTiO2 lm electrochemically prepared at 1.6 mA cm2 with a thickness of 15 m: (a) and (b) the surface in contact with the electrolyte (TiO2 rich side), (c) the surface in contact with the electrode (TiO2 free side) and (d) the cross-section.

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Fig. 4. Cyclic voltammograms of (a) a PPyTiO2 lm grown at 1.6 mA cm2 on a stainless steel electrode and (b) a free-standing PPyTiO2 lm (solid line) and a pure PPy lm (dashed line). All lms are in size of 15 mm 2 mm 0.015 mm and are studied in a 1.0 mol l1 aqueous solution of LiClO4 at a scan rate of 30 mV s1 .

Fig. 5. Photographs of bending motion of a PPyTiO2 composite lm actuator, which is held as TiO2 -rich side in left, at various redox potential of (a) 1.0 V, (b) 0.8 V, (c) 0.6 V, (d) 0.2 V and (e) 0.5 V (vs. SCE).

at approximately 0.30 V (Fig. 4b, solid line). The Ep (1.1 V) is larger than that of the lm coated on a metallic electrode (0.48 V). In contrast, the CV of a free-standing pure PPy lm has a broad oxidation wave at 0.08 V and a broad reduction wave at 0.62 V, and has a Ep of only 0.7 V (Fig. 4b, dashed line). This is mainly because the conductivity of the composite lm is lower than that of the pure PPy lm and also much lower than that of the metallic electrode. Similar phenomena were observed by carrying out the cyclic voltammetry at different scan rates. The results demonstrated that the reversibility of the electrochemical processes increased, while the electrochemical behavior difference between the pure PPy and the PPyTiO2 composite lms decreased with the decreasing the potential scan rate. The bending movements of the pure PPy and composite lms with different TiO2 contents were studied electrochemically in a

1.0 mol l1 LiClO4 aqueous solution. It was found that the pure PPy lm could bend only to one side, while the asymmetric PPyTiO2 lm could bend to both sides. This is mainly because the PPyTiO2 lm has a much better anisotropic structure than that of a pure PPy lm. As demonstrated in Fig. 5, a composite lm containing 0.4% (v/v) TiO2 of 10 mm 2 mm 0.015 mm can uniformly bend from the position of 0 (vertical) to +60 (Fig. 5d) and +90 (Fig. 5e) as it was oxidized at 0.2 and 0.5 V (versus SCE), respectively, or to 60 (c) and 90 (Fig. 5b) when reduced at 0.6 and 0.8 V (versus SCE), respectively. Furthermore, this lm was curled at 1.0 V, indicating its maximum bending angle is much larger than 90 . Fig. 6 plots the bending movement rates of a pure PPy and a PPyTiO2 lm at different driving potentials. The PPyTiO2

Fig. 6. Plots of movement rates of a free-standing (a) pure PPy lm and (b) PPyTiO2 lm at different driving potentials in a 1.0 mol l1 aqueous solution of LiClO4 .

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lm has a bending rate of 115 s1 at a driving potential of 1.0 V (versus SCE), which is about four times that of the pure PPy lm (31 s1 ) at the same potential. The movement rate of the PPyTiO2 lm increases quadratically with an increase of the applied driving potential in the range of 1.0 to +1.0 V (versus SCE), while the bending motion of the PPy lm increases linearly. Moreover, the movement rate of the PPyTiO2 lm (Fig. 6b) is much higher than those of a singlelayer AOT (sodium 1,4-bis(2-ethylhexyl)sulfosuccinate) doped PPy lm (60 s1 at 1.0 V)[11], the single-layer polyaniline lm (20 s1 at 1.0 V) [8,12] and PPy bi-ionic actuators (30 s1 at 1.0 V) [13]. In lifetime test, the PPy lm was subjected to multiple potential steps of reduction at 0.8 V and oxidation at 0.8 V at 0.5 Hz (bending angle >45 ). After 30,000 cycles, the lm still can bend to 90 at a potential of 0.8 V. However, its movement rate decreased with increasing the cycling number. After 22,000 or 30,000 cycles, the bending movement rate of the lm decreased from 100 to about 45 s1 or 5 s1 , respectively. This result indicated that the monolithic PPyTiO2 lm maintained the ability of bending, particularly the maximum bending angle was 90 after the multiple potential steps. Accordingly, the lifetime of the actuator based on this monolithic PPyTiO2 lm is much higher than those of the PPy/Au actuators (2000 cycles) [14]. The high performance of this actuator is mainly because the PPy lm has a high conductivity and can do uniform bending at a low driving potential and without delamination problems. The cyclic voltammograms of the lm after 30,000 cycles bending movements under multiple potential steps of reduction at 0.8 V and oxidation at 0.8 V at 0.5 Hz (bending angle >45 ) showed a weak and broad oxidation wave at 0.90 V and a reduction wave at 0.80 V. Their current densities are much lower than those of the original lm. This is mainly because the lm experienced an enormous number of repeated redox processes caused the decomposition or over-oxidation of the PPy chains [8]. 3.3. Mechanism of actuation The as-grown PPy lm doped with DBS anions is in an oxidized state, and therefore, it is a cation-driven (or cation swelling) lm. When the lm was reduced, the large DBS anions (immobile counter ions) could not be ejected from the lm. For the rst several cycles, in order to maintain the overall charge neutrality, the electrolyte cations (Li+ ions) and water molecules from the electrolyte were incorporated into the lm, and the lm swelled [15,16]. After that, the ClO4 anions in the electrolyte may also participate in the ionic motion. Thus, the electrochemical process was dominated by cation driving, while being slightly affected by the incorporation of ClO4 . As the monolithic asymmetric PPyTiO2 lm has a PPy density gradient along the lm cross-section, it bends to the TiO2 -rich side, as observed in the actuation test. On the other hand, when the lm is oxidized, smaller cations were released from the TiO2 -free zone than those from the TiO2 -rich zone, which causes the PPy-free zone to contract more than the TiO2 -rich zone, so the lm bends to the TiO2 -free side direction.

4. Conclusion An actuator based on a monolithic PPyTiO2 nanoparticle composite lm with a pure PPy layer and a PPyTiO2 composite layer has been successfully prepared by using an electrochemical co-deposition technique. The incorporation of a little amount of TiO2 nanoparticles changed the morphology and properties of the PPy lm greatly and constructed a vertical anisotropic conguration. The actuator fabricated from this monolithic PPyTiO2 composite lm has a low driving potential, large bending angle and fast response rate, mainly due to the high conductivity and good mechanical properties of the lm. Furthermore, there is no physical interface between the pure and composite layers of the lm. This overcomes the strong friction generated between the stretching and supporting layer of the multilayer actuators and extends the lifetime. The simple and cheap method developed here can be used to synthesize various anisotropic conducting polymer-nanoparticle composite lms and corresponding actuators. Acknowledgement This work was supported by National Science Foundation of China (Nos. 50533030, 50225311). References
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Biographies
Ximin He received her bachelor from Shanghai Jiaotong University in 2003. She then entered the graduate school of Tsinghua University as a master candidate (20042007). Gaoquan Shi received his BS (1985) and PhD (1992) degrees from Nanjing University. He joined Nanjing University as an assistant professor in 1992, and then was promoted to an associate professor in 1993 and a professor in 1995. He moved to Department of Chemistry, Tsinghua University as a professor (2000 to date). His interests focus on syntheses and applications of conducting polymers.