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Sensors and Actuators B 115 (2006) 488–493

Electrochemical actuator based on monolithic polypyrrole–TiO2 nanoparticle composite film
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 film with a pure PPy zone and a PPy–TiO2 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 film was tested to be lower than 0.9%. The actuator fabricated from this monolithic PPy film bends uniformly in two directions with a maximum bending angle larger than 90◦ and has a high response rate (∼115◦ s−1 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 film. © 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 films is significantly affected by the film morphology [1]. Since a typical CP film 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 flexible and electrochemically inert layer, which is not subjected to volume changes under electrochemical stimuli is needed to be glued to the free-standing CP film. Therefore, most of the CP actuators have been constructed based on either bilayer [2,3] or multilayer [4–6] configuration. 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 efficiency.

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 efficiency 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 l−1 HCl) and could not do uniform bending. The main problem is the low conductivity of the Pani film (∼0.1 S cm−1 ). Then, they fabricated another actuator based on a monolithic asymmetric polyaniline-graphite composite film, consisting of graphite-rich and -lacking layers [9]. The high conductivity resulted from the incorporated graphite in the Pani film, 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 film was prepared through a multi-step procedure, and a high content of graphite powder (∼70%) in the composite film reduced the efficiency and mechanical strength of the actuator. A PPy film grown in a slender pipe of polytetrafluoroethylene has a considerable vertical anisotropy [10] and can perform bending movements. Recently, we also electrochemically synthesized an anisotropic PPy film from a mixed solvent of acetoni-

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Secondly. Experimental 2. FEI.. China). Dodecylbenzene sulfonate acid (DBSA. Tianjin. The thermal stability and the weight content of TiO2 in the film were studied by the use of a thermal gravimetric analyzer (TGA 2050. anhydrous lilhium perchlorate (>99%. The working electrode was a freestanding PPy film. 1b). The procedure of preparation of the anisotropic PPy–TiO2 composite films is schematically illustrated in Fig. USA) were used as received. the counter electrode was a stainless steel sheet and all the potentials were referred to a saturated calomel electrode (SCE). trile and dichloromethane containing a high concentration of an anion surfactant of sodium 1. Serion-200 132-10. It was found that the introduction of a little amount of TiO2 nanoparticles (<0. Here. Hongyu Chem. 1a) for 700 s (112 mC cm−2 ). we desire to report that high performance actuators can also be fabricated from an anisotropic PPy-oxide nanoparticle composite film formed by direct co-deposition of PPy and the nanoparticles from an aqueous medium.2.2. 2. Moreover. a pure PPy layer was deposited on the working electrode by direct oxidation of 0. 1. In this paper. by volume) can improve greatly the performance of the single-layer PPy actuator.1 mol l−1 pyrrole in an aqueous solution of 0. then a PPy–TiO2 layer was successively deposited on the PPy layer under magnetic stirring for another 700 s (112 mC cm−2 ) (Fig. Electrochemical syntheses of anisotropic PPy–TiO2 films Electrochemical syntheses were performed at room temperature in a one-compartment cell by the use of a Model 273 potentiostat–galvanostat (EG&G Princeton Applied Research) under computer control.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. choosing TiO2 nanoparticles as the example is nothing special.0 cm × 2.0025.1. the preparation of this film needs organic solvents and a large amount of expensive AOT. The electrochemical analyses including cyclic voltammetry and the bending movements of the single-layer PPy films (size = 15 mm × 2 mm × 0.4 or 0. G.01 g ml−1 ).X. China) and TiO2 nanoparticles with diameters of 20–30 nm (Deggusa. All potentials were referred to an Ag/AgCl wire that was immersed directly in the solution. 0. Sirion-200. Acros). Co. EDAX. The thickness of the films was measured to be approximately 15 ␮m by the use of a thickness monitor (CH-1-ST. Finally. 6.. The working and counter electrodes were both a stainless steel sheet (AISI 304.005 or 0.6 mA cm−2 (Fig. A pure PPy film was also synthesized under the same conditions for comparing with the PPy–TiO2 composite film. 2.9%. the composite film was peeled off from the surface of the working electrode. >99%. He. Jinke Inst. 1. 0. the porous structure may decrease the mechanical strength of the actuator. and maintained a light nitrogen overpressure during the experiments. Beijing.0 cm apart. Shi / Sensors and Actuators B 115 (2006) 488–493 489 Fig. The dc conductivity was measured by conventional fourprobe technique. However. . TA Co. First. USA).3. Shanghai. Scheme of the preparation procedure of anisotropic PPy–TiO2 composite films. mainly because it can be commercially obtained. 0. China) was used after distillation under reduced pressure. 2. Materials Pyrrole (99%. Characterizations The scanning electron micrographs (SEM) were taken out by using a scanning electron microscope (SEM.015 mm) were carried out in a one-compartment cell by the use of a 1 mol l−1 aqueous solution of LiClO4 as the electrolyte.1 mol l−1 DBSA galvanostatically at 1.0 cm) and placed 2. washed repeatedly with de-ionized water and dried under vacuum at room temperature for characterizations. The elemental compositions of the composite film surface were determined by using an energy dispersive X-ray detector (EDX. The film has compact and porous zones in its vertical direction and the actuator fabricated from this film can do uniform bending in a neutral medium and has high performance.).4-bis(2-ethylhexyl)sulfosuccinate (AOT) [11]. USA). All solutions were de-aerated by bubbling dry nitrogen. Fine Chem.

The result indicates the existence of elements Ti (from TiO2 ). and the results are shown in Fig. The SEM micrographs suggest that the incorporation of TiO2 nanoparticles affects the morphology of the film significantly and makes the TiO2 -rich side look to be relative loosely piled up with PPy and TiO2 nanoparticles. and the nanoparticles distribute asymmetrically across its crosssection as shown in Fig. 2a. 2d. 2c). Furthermore. As can be seen from the figure. 3). As can be seen from this Fig. This value is much higher than that of Pani [12].2. Shi / Sensors and Actuators B 115 (2006) 488–493 3. 3.57% (w/w).21 or 2. Electrochemistry and actuations of the PPy–TiO2 film The cyclic voltammograms (CVs) of an as-grown PPy–TiO2 film (size = 15 mm × 2 mm × 0. the CV of a freestanding PPy–TiO2 film shows a broad reduction wave centered at approximately −0. C. the TiO2 -rich side. 4. In contrast. respectively. 2. The SEM images of a pure and a PPy–TiO2 composite film are shown in Fig. G. 3.40 and 0.01 g ml−1 TiO2 had a TiO2 content of 1. e. The conductivity of the PPy–TiO2 film was measured to be approximately 16.48 V. However. these films are flexible enough to be folded or shaped into various structures for the fabrication of actuators. Results and discussion 3. On the other hand. Furthermore. He. Fig. Thus.0 S cm−1 . while the TiO2 -free side is black and shiny. while its TiO2 -free side is flat and compact (Fig. the potential difference between the oxidation and reduction current peaks ( Ep ) is calculated to be 0. The chemical composition of the TiO2 -rich surface of the composite film was examined by EDX analysis (Fig. 2b). for a PPy–TiO2 film.58 V and an oxidation wave at approximately −0. the volume contents of TiO2 nanoparticles in the composite films were calculated to be 0. SEM images of (a) a PPy film without TiO2 and (b–d) a PPy–TiO2 film electrochemically prepared at 1. Thus.005 or 0.40% (v/v) TiO2 and coated on the working electrode surface or the same film in freestanding state were carried out in an aqueous solution of 1. the films can be cycled repeatedly between the conducting (oxidized) and insulating (neutral) states without significant decomposition. each CV cycle has a couple of broad redox waves. the surface in contact with the electrolyte is compact and smooth. 4).87% (v/v). the pure PPy film showed no weight residue as the sample was heated in air to over 650 ◦ C.80 V and an oxidation wave Fig. for a 15 ␮m pure PPy film. (c) the surface in contact with the electrode (TiO2 free side) and (d) the cross-section. respectively. However. The CV of a composite film coated on a metallic electrode shows a reduction wave at approximately −0.10 V (Fig.1. O (from pyrrole) and S (from DBS). EDX spectrum of the TiO2 -rich side of the PPy–TiO2 film.490 X. 2. the two surfaces of a 15 ␮m thick pure PPy film have nearly the same appearance.g. the surface in contact with the electrolyte.6 mA cm−2 with a thickness of 15 ␮m: (a) and (b) the surface in contact with the electrolyte (TiO2 rich side). Morphology and conductivity of PPy–TiO2 film The appearances of the two surfaces of a 15 ␮m thick PPy–TiO2 composite film are different: the TiO2 -rich side is dull black. The composite film does not show an apparent interface between its TiO2 -rich and TiO2 -free layers.015 mm) containing 0. is rough and irregular (Fig. The results of TGA examinations indicated that the film prepared from the media containing 0. N. .0 mol l−1 LiClO4 at 30 mV s−1 .

or to −60◦ (c) and −90◦ (Fig. It was found that the pure PPy film could bend only to one side. 4b. 5b) when reduced at −0. indicating its maximum bending angle is much larger than −90◦ .8 V (versus SCE).0 mol l−1 aqueous solution of LiClO4 at a scan rate of 30 mV s−1 . 5. Cyclic voltammograms of (a) a PPy–TiO2 film grown at 1. The PPy–TiO2 Fig. while the asymmetric PPy–TiO2 film could bend to both sides. Photographs of bending motion of a PPy–TiO2 composite film actuator. SCE). Fig.0 mol l−1 aqueous solution of LiClO4 . Similar phenomena were observed by carrying out the cyclic voltammetry at different scan rates. He. . 6. This is mainly because the conductivity of the composite film is lower than that of the pure PPy film and also much lower than that of the metallic electrode.1 V) is larger than that of the film coated on a metallic electrode (∼0.X. As demonstrated in Fig.0 mol l−1 LiClO4 aqueous solution.0 V. The Ep (∼1. (c) −0.8 V. (d) 0. Furthermore.6 and −0.30 V (Fig. Shi / Sensors and Actuators B 115 (2006) 488–493 491 Fig.7 V (Fig. The results demonstrated that the reversibility of the electrochemical processes increased.6 mA cm−2 on a stainless steel electrode and (b) a free-standing PPy–TiO2 film (solid line) and a pure PPy film (dashed line).62 V.2 and 0.015 mm can uniformly bend from the position of 0◦ (vertical) to +60◦ (Fig. G. this film was curled at −1. In contrast.08 V and a broad reduction wave at −0. 5e) as it was oxidized at 0. dashed line). which is held as TiO2 -rich side in left.2 V and (e) 0. a composite film containing 0. at various redox potential of (a) −1. 5. respectively. 6 plots the bending movement rates of a pure PPy and a PPy–TiO2 film at different driving potentials.6 V.5 V (versus SCE). 4b. This is mainly because the PPy–TiO2 film has a much better anisotropic structure than that of a pure PPy film. 4. The bending movements of the pure PPy and composite films with different TiO2 contents were studied electrochemically in a 1.5 V (vs. respectively. and has a Ep of only ∼0. 5d) and +90◦ (Fig. All films are in size of 15 mm × 2 mm × 0.0 V.015 mm and are studied in a 1.48 V). solid line). the CV of a free-standing pure PPy film has a broad oxidation wave at 0. Plots of movement rates of a free-standing (a) pure PPy film and (b) PPy–TiO2 film at different driving potentials in a 1. while the electrochemical behavior difference between the pure PPy and the PPy–TiO2 composite films decreased with the decreasing the potential scan rate.4% (v/v) TiO2 of 10 mm × 2 mm × 0. Fig. (b) −0. at approximately 0.

K. Moreover. large bending angle and fast response rate. its movement rate decreased with increasing the cycling number. in order to maintain the overall charge neutrality. Han. Fabrication and characterization of polyaniline monolithic actuators based on a novel configuration: integrally skinned asymmetric membrane. The effects of varying deposition current density on bending behaviour in PPy(DBS)-actuated bending beams. Stein. The cyclic voltammograms of the film after 30.0 V (versus SCE).12] and PPy bi-ionic actuators (∼30◦ s−1 at 1.L. K. Smela.B. and therefore. the large DBS anions (immobile counter ions) could not be ejected from the film. mainly due to the high conductivity and good mechanical properties of the film. Wang. [7] S. M. Thus.L. [12] H. [9] W. respectively. R. [10] K.8 V at 0. [5] T. Met.90 V and a reduction wave at −0. particularly the maximum bending angle was 90◦ after the multiple potential steps.H.492 X. This overcomes the strong friction generated between the stretching and supporting layer of the multilayer actuators and extends the lifetime.M. Q. Mater. Cortes. Onoda. Smela. Bioenerg. M. I. This result indicated that the monolithic PPy–TiO2 film maintained the ability of bending. 6b) is much higher than those of a singlelayer AOT (sodium 1. Adv. Li. Artificial muscles based on conducting polymers. H. which is about four times that of the pure PPy film (∼31◦ s−1 ) at the same potential. Their current densities are much lower than those of the original film.B. 10 (1998) 491–494. as observed in the actuation test. The high performance of this actuator is mainly because the PPy film has a high conductivity and can do uniform bending at a low driving potential and without delamination problems. After that. while the bending motion of the PPy film increases linearly. 4. Kaneto. Pei. Otero. [8] J. B: Condensed Matter 1 (1992) 10515–10539.L.T. Adv. [4] R. 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Mechanism of actuation The as-grown PPy film doped with DBS anions is in an oxidized state. 50225311). 50533030. Electrochemical muscles: micromachining fingers and corkscrews. the bending movement rate of the film decreased from 100 to about 45◦ s−1 or 5◦ s−1 . which causes the PPy-free zone to contract more than the TiO2 -rich zone. 135–136 (2003) 59–60. Sommer-Larsen. Sens.8 V and oxidation at 0. Effect of film morphology on the actuation behavior in polypyrrole films. G. Maw.5 Hz (bending angle >45◦ ) showed a weak and broad oxidation wave at 0. Sansi˜ nena.80 V. and the film swelled [15. Pandey.B. Accordingly. J. Mater. Synth. the electrochemical process was dominated by cation driving. Acknowledgement This work was supported by National Science Foundation of China (Nos. Wang. For the first several cycles. it is a cation-driven (or cation swelling) film.G. Soft and wet conducting polymers for artificial muscles. Sansi˜ nena. in press. Adv. the film still can bend to 90◦ at a potential of 0.000 cycles. Charge oscillations and structure for alkali-metal-doped polyacetylene. Eckhardt. the single-layer polyaniline film (∼20◦ s−1 at 1. Fuchiwake. Synth. Mater. Gao. Actuators B.F. 5 (1993) 630– 632. Conclusion An actuator based on a monolithic PPy–TiO2 nanoparticle composite film with a pure PPy layer and a PPy–TiO2 composite layer has been successfully prepared by using an electrochemical co-deposition technique. Polymer 45 (2004) 4769–4775. On the other hand.Q.B. Mater. J. the electrolyte cations (Li+ ions) and water molecules from the electrolyte were incorporated into the film. Wang. Furthermore. Nishiyama.M.0 V) [13]. J. Preparation and characterization of monolithic polyaniline–graphite composite actuators. He. G.0 to +1. the ClO4 − anions in the electrolyte may also participate in the ionic motion. . C.M. Inganas. 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X. Davey.F. M. [16] J.B.O. He joined Nanjing University as an assistant professor in 1992. Takashima. Murray. Too. Chem.R. Wallace. 15 (2003) 916–922. Spinks. Tsinghua University as a professor (2000 to date). Synthesis. Met. S. She then entered the graduate school of Tsinghua University as a master candidate (2004–2007). C. Pyo. Appl. [15] M. [14] M. 99 (1999) 191–199. Fuchiwaki. Mechanism of electrochemical actuation in polypyrrole.G. Kaneto. Gaoquan Shi received his BS (1985) and PhD (1992) degrees from Nanjing University.R. and then was promoted to an associate professor in 1993 and a professor in 1995. 73 (1995) 247–256. Panidey. He.C. 493 Biographies Ximin He received her bachelor from Shanghai Jiaotong University in 2003. 41 (2002) 7532–7536.G. Met. A. Gandhi. G. J. G. G. Smela. G. K. Mater. He moved to Department of Chemistry. E. Ralph. C. His interests focus on syntheses and applications of conducting polymers. Brennan. Cyclic stepvoltammetric analysis of cation-driven and anion-driven actuation in polypyrrole films.S.M. characterisation and ion transport studies on polypyrrole/polyvinylphosphate conducting polymer materials. J. Direct strain measurement of polypyrrole actuators controlled by the polymer/cold interface. Reynolds. Bohn. Jpn.M. . P. S. Wallace. Shi / Sensors and Actuators B 115 (2006) 488–493 [13] W. Synth. Phys. Synth.