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Synthetic Metals 194 (2014) 176–181

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Synthetic Metals
journal homepage: www.elsevier.com/locate/synmet

Study on horn-shaped polypyrrole prepared by pulse potential

a r t i c l e i n f o a b s t r a c t

Keywords: Polypyrrole (PPy) films were prepared by direct current (DC), pulse current (PC) and pulse potential (PP)
Polypyrrole in aqueous solutions. The scanning electron microscope (SEM) images of PPy films indicated that a lot
Pulse current of horn-shaped PPy was formed during PP-PPy polymerization process. The top-end of horn-shaped PPy
Pulse potential
exhibits both open and closed structures. The body of horn-shaped PPy has a hollow structure with a thin
Electrochemical supercapacitors
wall. The micelles composed by PPy monomer and p-toluenesulfonate anions (PTS− ) was formed when
Horn-shaped
pyrrole monomer was dispersed in aqueous solution containing PTS− anions by mechanical stirring. In
PP polymerization, the micelles with negative charge were repelled and hence left the surface of PPy
films at switch off time. As a result, the PTS− anions on the surface of micelles were effectively supplied,
and thus stabilized the micelles. This process results in the continuous growth of horn-shaped PPy.
The hollow horn-shaped PPy films showed big specific capacitance, high charging/discharging rate and
better stability.
© 2014 Elsevier B.V. All rights reserved.

1. Introduction (Py) and the active amino-functionalized Py. Gao et al. [15] reported
a critical evaluation of template-prepared polymer-metal tubular
Conducting polymers have attracted considerable attentions microbots based on different materials and synthesis conditions.
due to their wide applications including batteries, supercapacitors, However, the electrochemical properties of PPy nanomaterial
electrochemical sensors, artificial muscles, electromagnetic inter- were not shown in these references. Wang et al. [16] synthesized
ference shielding, anti-static coatings and drug delivery systems the micro/nano structure PPy in p-toluenesulfonate alkaline
[1–3]. Polypyrrole (PPy) is one of the most extensively studied solution. However, it was difficult to maintain the pH value of p-
conducting polymers since it possesses high electronic conductiv- toluenesulfonate alkaline solution at 9.0 during PPy polymerization
ity, long-term environmental stability, environmental friendliness process, which resulted in an unstable preparation process. To con-
and relatively easy synthesis process [4–6]. In recent years, a clude, a simple and more stable synthesis process is required for the
lot of researches have been carried out on the study of PPy future utilization of PPy electrode with micro/nanometer structure.
based supercapacitors electrode [6–9]. The preparation of PPy with In this paper, a new synthesis process of PPy films with
micro/nano structure and PPy composites was considered being micro/nano structure is proposed and conducted, with detailed
able to improve PPy electrochemical properties including specific mechanism presented and explained. PPy films with micro/nano
capacitance, charge/discharge rate and stability. structure showed large specific area, high specific capacitance, fast
Carbon nanomaterials, i.e. carbon fiber, carbon nanotubes and charge/discharge process and good stability.
graphene, are one type of most effective reinforcement material for
PPy composites [9–11]. In general, carbon nanomaterials lead to 2. Experimental
the porous structure in PPy matrix, which will enhance the specific
capacitance of PPy electrode. Furthermore, carbon nanomaterials 2.1. Materials
used as the reinforcement material can improve the stability of
PPy electrode. However, the complicated preparation process of Pyrrole (Fluka, 99%) was distilled prior to use and stored at
PPy/carbon nanomaterials limited the industrial applications. In −10 ◦ C in a nitrogen atmosphere. All other chemical reagents were
addition, the porous structure of PPy/carbon nanomaterials often used as received.
decreased cell charging/discharging rate. Therefore, much recent
attention has been paid to the design and fabrication of PPy with 2.2. Electrode preparation
micro/nano structure [12–16].
McCarthy et al. [12] prepared PPy nanowire in LiClO4 and The polymerization of PPy was carried out in an aqueous solu-
(NH4 )H2 PO4 aqueous solution. Mangeney et al. [14] prepared tion containing 0.1 M pyrrole, 0.1 M p-toluenesulfonate acid (PTSA),
polypyrrole-coated polystyrene latex particles bearing reactive N- and 0.3 M sodium p-toluenesulfonate (PTSS). A three-electrode
amino functional groups by the in-situ copolymerization of pyrrole electrochemical cell was used for all the polymerizations. The

http://dx.doi.org/10.1016/j.synthmet.2014.04.026
0379-6779/© 2014 Elsevier B.V. All rights reserved.
Study on horn-shaped polypyrrole prepared by pulse potential / Synthetic Metals 194 (2014) 176–181 177

Fig. 1. Plots of PPy polymerization at (a) direct current, (b) pulse current and (c) pulse potential (vs. SCE).

working electrode was a polished tantalum sheet with a sur- constant value at switch on time. However, the potential decreased
face area of 1 × 2 cm2 . The tantalum sheet of 2 × 2 cm2 was used slowly and reached a minimum value of 0.48 V at the end of switch
as counter electrode and the electrochemical potentials were off time, which is much higher than open circuit potential (0.226 V
measured against a saturated calomel electrode (SCE). All polyme- vs. SCE). The polarization of working electrode, including concen-
rizations were performed in an ice-water bath. tration polarization and electrochemical polarization, should occur
PPy films were prepared by direct current (DC), pulse current during PC-PPy polymerization process. The elimination of electrode
(PC) and pulse potential (PP). The total polymerization charge of dif- polarization was a gradual process after the polymerization current
ferent methods was 2 coulombs. DC-PPy films were polymerized at switched off, which was main reason for slow decrease of potential
a current density of 3 mA cm−2 . PC-PPy polymerization was carried at switch off time in PC-PPy polymerization. However, in PP-PPy
out with switch on/off time of 50 ms/150 ms and current density polymerization process, negative current appeared in Fig. 1c when
of 3 mA cm−2 . PP-PPy polymerization was carried out with pulse the potential decreased to 0.1 V. The value of negative current
high/low potential of 0.7 V/0.1 V versus SCE. The duration time of approaches 0 at the end of low potential time during PP-PPy poly-
pulse high/low potential was 50 ms and 150 ms, respectively. merization. As the open circuit potential was 0.226 V, the potential
decreased to 0.1 V, the negative current must occur in a reversible
2.3. Characterization and measurements electrochemical system. PPy discharging can contribute to negative
current during PP-PPy polymerization. Moreover, the decrease of
The morphology of PPy films was examined by field emis- current at high potential time during PP-PPy polymerization can
sion scanning electron microscope (FESEM, Hitachi, S-4800) and be attributed to lack of reactants due to insufficient diffusion.
transmission electronic microscope (TEM, JEOL, JEM-2100). XRD
patterns of PPy films were collected using an x-ray diffractometer
(PANalytical, X’Pert PRO X) with Cu Ka radiation. The diffraction 3.2. Surface morphology
data were collected with a 0.03◦ step-width over a 2 range from
10◦ to 35◦ . The PPy films for FESEM, TEM and XRD measurements Fig. 2 shows the surface morphology of PPy prepared by differ-
were washed with alcohol before they were dried. The surface area ent methods. DC-PPy films show the typical ‘cauliflower’ structures
of PC-PPy and PP-PPy was determined using a Beckman Coulteraut with large variations in surface morphology, which has been
SA3100. The samples were dried at 100 ◦ C for 10 h before measure- reported in many references [6,17,18]. PC-PPy films exhibit a homo-
ment and degassed at 130 ◦ C for 6 h until the vacuum was less geneous and smooth appearance in comparison to that prepared
than 10−3 Torr. All electrochemical tests were performed on the by the other two methods. However, PP-PPy films show many
Versatile Multichannel Potentiostat 2/Z (VMP2, Princeton applied horn-shaped structures on the surface of PPy films. The top-end
research). The cells were let standing for 20 min before every elec- of horn-shaped PPy includes both open and closed structures. The
trochemical test for a steady electrochemical state. root and top-end diameters of the horn-shaped PPy are 1–2 ␮m and
0.1–0.6 ␮m, respectively. The diameter of open structure is about
3. Results and discussion 0.2–0.3 ␮m. A lot of horns on the surface of PPy films must result
in the increase of its surface area and charge capacitance. Fig. 3
3.1. Electrochemical synthesis shows the TEM image of the horn-shaped PPy. The horn-shaped
PPy has a hollow structure and the wall thickness of the horn is
Fig. 1 shows plots of PPy polymerization at direct current, about 100–200 nm. This hollow structure should improve the ions
pulse current and pulse potential. The potential was maintained at diffusion in PPy matrix. The cyclic stability can be improved by the
0.72 ± 0.1 V when the current density was 3 mA cm−2 during DC- hollow structure of PPy because thin wall of horn-shaped PPy is
PPy polymerization. The current of PC-PPy polymerization had a more flexible during ions doping/dedoping process.
178 Study on horn-shaped polypyrrole prepared by pulse potential / Synthetic Metals 194 (2014) 176–181

Fig. 2. Surface morphology of (a)DC-PPy, (b)PC-PPy and (c)–(f)PP-PPy.

Fig. 4 shows the schematic for the growth processes of Py in water, the hydrophilic heads of p-toluenesulfonate anions
different preparation methods. Both sodium p-toluenesulfonate were directed to the aqueous phase and the hydrophobic tails to
and p-toluenesulfonate acids are anionic emulsifier containing the oil phase of Py when Py were dispersed in water by mechanical
hydrophilic head and a hydrophobic tail. Due to poor solubility of stirring, which resulted in the formation of many micelles. In gen-
eral, the micelles with negative charge of p-toluenesulfonate anions
(PTS− ) move in supporting electrolyte and reach anode surface dur-
ing PPy polymerization. As DC-PPy or PC-PPy polymerization was
performed, the micelles on anode surface should split soon due to
sustained loss of PTS− which entered PPy matrix as doped anion.
Even in PC-PPy polymerization, most micelles cannot leave from
anode surface at switch off time because the anodic potential at the
end of switch off time was high and reached 0.48 V (vs. SCE). If PTS−
on the surface of micelles was not supplied in time, the micelles
are easy to split during PPy polymerization. As shown in Fig. 4a, the
split of micelles must result in Py monomer covering on the elec-
trode surface. The area covered by Py monomer grew more quickly
due to enough reactants and protruded on electrode surface. The
protruded area was easier to receive the Py monomer and doping
ions from supporting electrolyte. This unbalance growth on elec-
trode surface induced the typical ‘cauliflower’ structures of DC-PPy
Fig. 3. TEM image of horn-shaped PPy. and PC-PPy films. In addition, the insufficient diffusion of reactants
Study on horn-shaped polypyrrole prepared by pulse potential / Synthetic Metals 194 (2014) 176–181 179

Fig. 4. Schematic for PPy polymerization by (a) direct current and pulse current, (b) pulse potential.

and unbalanced growth of PPy films can be improved at switch van der Waals distance for aromatic groups [20,21]. The diffrac-
off time during PC-PPy polymerization, so PC-PPy films exhibited a tion peak of PC-PPy at 26◦ is obviously sharper than that of DC-PPy
smoother appearance than that of DC-PPy films. and PP-PPy. The diffraction peak of DC-PPy is similar to that of
The low potential of 0.1 V (vs. SCE) during PP-PPy polymeriza- PP-PPy. It is apparent that the alignment and orientation of PC-
tion can repel a lot of micelles with negative charge leaving the PPy molecules are more regular than that of DC-PPy and PP-PPy
surface of PPy films. As shown in Fig. 4b, the PTS− anions on A-side molecules, which is in accordance with our previous results [6]. PC-
of micelles were supplied in time when micelles left the surface PPy films with more regular alignment and orientation of molecules
of PPy films. Therefore, most micelles became stable and did not have higher electronic conductivity and density, since electrons
split at low potential time during PP-PPy polymerization, which transfer more easily between different molecules in a more ordered
ensured the continuous growth of horn-shaped PPy. However, the PPy matrix. The low potential time during PP-PPy polymerization
Py monomer in the micelles became shorter and shorter with the process repelled the ions and micelles with negative charge leav-
growth of horn-shaped PPy. At last, the top-end of horn-shaped ing the surface of PPy films, which were absorbed again on the
PPy closed when the Py monomer was used up, or the top-end anionic surface at next high potential time. The re-absorption pro-
of horn-shaped PPy was open when Py had a surplus before the cess would result in the change of molecular alignment on the
polymerization was terminated. Moreover, the decrease of current surface of PP-PPy films. In addition, the spherical diffusion of doped
value at high potential time during PP-PPy polymerization (Fig. 1c) anions on the surface of micelles during PP-PPy polymerization can
indicated the lack of reactants on the surface of working electrode, affect the alignment and orientation of PPy molecular chains.
which resulted in a slow growth of PPy in the area without micelles.
This should contribute to the formation of horn-shaped PPy with
thin-wall structure. 3.4. BET specific surface area

Fig. 6 shows BET specific surface area of PC-PPy (2.1 m2 g−1 )


3.3. X-ray diffraction
and PP-PPy (13.2 m2 g−1 ). The specific surface area of DC-PPy
(2.6 m2 g−1 ) was presented in our previous work [11]. Therefore,
Fig. 5 shows the XRD patterns of DC-PPy, PC-PPy and PP-PPy.
more active material on horn-shaped PPy electrode can contacts
There is not a sharp peak in Fig. 5, indicating that PPy films pre-
with the electrolyte, which should improve the specific capacitance
pared by different methods are mainly amorphous structure [19].
of horn-shaped PPy. In addition, the counterions should possess
The peak at 26◦ results from PPy chains close to the interplanar

Fig. 5. X-ray diffraction patterns of DC-PPy, PC-PPy and PP-PPy films. Fig. 6. Nitrogen adsorption and desorption isotherms.
180 Study on horn-shaped polypyrrole prepared by pulse potential / Synthetic Metals 194 (2014) 176–181

Fig. 7. Cyclic voltammograms of DC-PPy, PC-PPy and PP-PPy films in 3 M KCl aque-
ous solution.

more channels of entering the PPy matrix, which can improve the
charge/discharge rate of horn-shaped PPy electrode.
Fig. 8. Constant current charging/discharging of DC-PPy, PC-PPy and PP-PPy films
3.5. Electrochemical properties of PPy films in 3 M KCl aqueous solution.

Fig. 7 shows CV curves of DC-PPy, PC-PPy and PP-PPy films in the demonstrated an evident advantage in cycle stability. The capac-
three-electrode system. The capacitance of PP-PPy films is dramat- itance of PP-PPy films decreased by only 2% after 10,000 cycles,
ically bigger than that of DC-PPy and PC-PPy films especially at the while that of DC-PPy films decreased by 88% after 10,000 cycles.
high scan rate. The results of constant current charging/discharging The horns on the surface of PPy films had a thin wall, which should
in Fig. 8 confirmed further high capacitance of PP-PPy films. The be more flexible than PC-PPy and DC-PPy films. The less stress con-
capacitance of DC-PPy films only reached 10% of that of PP-PPy centration can occur in thin-wall structure during redox process. In
films when the charging/discharging current reached 120 mA. The PPy matrix, the cracks, which result from the stress concentration
bigger surface area of horn-shaped PPy provided more channels during the redox process, were considered as one of main reasons
for the inserting/extracting of ions, which was the main reason for for the capacitance decay of PP-PPy films [9]. Therefore, there must
the higher specific capacitance of PP-PPy films. PC-PPy films had a be shorter cracks growing in the horn-shaped PPy matrix during
bigger diffusion coefficient of ions and electrons than that of DC- the redox process, which lead to an outstanding stability of PP-PPy
PPy films, which resulted in a higher specific capacitance of PC-PPy films. Moreover, the stability of PP-PPy films can decrease when
films [6]. The difference of PPy specific capacitance should reduce the wall thickness of horn-shaped PPy increases further because
when the charging/discharging rate decrease or PPy films become
thin.
Fig. 9 shows the specific capacitance of DC-PPy, PC-PPy and PP-
PPy films at various scanning rates. The specific capacitance of PPy
films in this work was calculated as Ref. [22]. In general, the spe-
cific capacitance of PPy films decreased when the CV scanning rate
increased because the diffusion coefficient of ion is lower than that
of electron. PP-PPy films showed not only big specific capacitance
but also slow decline compared with that of DC-PPy and PC-PPy
films. This should be closely related to the big specific area and
thin-wall structure horn-shaped PPy films.

3.6. Cyclic stability

Fig. 10 shows the discharge capacitance retention of PPy films


at a charge/discharge current of 60 A g-1 in 3 M KCl aqueous solu- Fig. 9. Specific capacitance of DC-PPy, PC-PPy and PP-PPy films at various scanning
tion. Compared with PC-PPy films and DC-PPy films, PP-PPy films rates in 3 M KCl aqueous solution.
Study on horn-shaped polypyrrole prepared by pulse potential / Synthetic Metals 194 (2014) 176–181 181

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The stable micelles maintained the continuous growth of horn-
shaped PPy, which should be the main reason of the formation Jingping Wang a,b
horn-shaped PPy during PP polymerization process. Xiaoming Tao a
The hollow structure and big specific surface area of horn- Li Li a,∗
shaped PPy films resulted in the big specific capacitance and high a Institute of Textiles and Clothing, the Hong Kong
charging/discharging rate. The thin wall of horn-shaped PPy had Polytechnic University, Hung Hom, Kowloon,
better flexibility and less stress concentration. Therefore, the horn- Hong Kong
shaped PPy films demonstrated enhanced electrochemical stability b College of chemistry and chemical engineering,
during prolonged cycling. The horn-shaped PPy film will be a Shaanxi University of Science and Technology,
promising potential material for electrochemical sensors and solar Xi’an 710021, China
cells in the near future.
Corresponding author. Tel.: +85227664106.
Acknowledgements E-mail address: li.lilly@inet.polyu.edu.hk (L. Li)
The authors wish to thank for the financial supports by The Hong
18 September 2013
Kong Polytechnic University Internal Competitive Research Grant
(DA) (Grant No. A-PM29), Natural Science Basic Research Plan in 21 April 2014
Shaanxi Province of China (Grant No. 2011JM6003), Doctor Startup
Fund of Shaanxi University of Science and Technology (Grant No. 23 April 2014
BJ12-05). Available online 25 May 2014

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