Synthesis and Characterization of PANI/Ferric Chloride Composite for Fabrication of Electrodes in Supercapacitor

Deebankarthikeyan Sivalingam1, Hemalatha Elangovan1, Manikandan Subramanian1,a, Senthil Kumar Kandasamy2,b

and Murugesan Govindasamy3 1Student, Department of ECE, Kongu Engineering College, Erode, Tamilnadu, India

2Assistant Professor, Department of ECE, Kongu Engineering College, Erode, Tamilnadu, India 3Professor, Department of ECE, Kongu Engineering College, Erode, Tamilnadu, India

amaniece2013@gmail.com, bsenthilkumar6k@gmail.com

Keywords: aniline; electrode; ferric chloride; PANI; supercapacitor

Abstract. The main objective of this work is to synthesize polyaniline/ferric chloride composite and

to measure the conductivity of the as prepared composite. And also, to analyze the ability of using

Ferric Chloride doped polyaniline as an electrode material for the fabrication of supercapacitor

application. By in-situ polymerization method, polyaniline in pure form and doped form with the

ferric chloride were synthesized using ammonium persulfate as initiator in HCl medium.

Polyaniline nanoparticles and its composite are characterized by UV-Vis spectroscopy, FTIR, XRD

and Conductivity meter.

Introduction

A capacitor is a component that is used to store electrical charge. Among the different family of

capacitors, electrostatic and electrolytic capacitor has the major limitations in storage of energy.

The capacitance value of supercapacitor is high because of large surface area and separation

between the electrodes is very small. Advantages include shorter charging time, high power density,

longer cycle and shelf life. Conducting polymer has high capacitance, high conductivity and low

ESR [1].

Supercapacitor is similar to capacitor but has energy density higher than that of various

capacitors and has power density higher than that of batteries. In this type of capacitor, the charge is

stored at the metal/electrolyte interface. For the construction of electrode, the main component is

activated carbon. Supercapacitor has larger value of capacitance which is due to larger surface area

and smaller separation distance between the electrodes. It can also be used instead of batteries.

The specific capacitance value is 174 F/g when ZnCl2 is used as active reagent [2] with PANI.

By varying anodic pulse duration various proportions of carbon nanotube [3] were acquired with

polymeric material [4]. When tungsten trioxide material used as electro active material for pseudo

capacitor the specific capacitance value is in the range of 0.014 to 0.039 F/cm2 [5]. When the

temperature increases the specific capacitance also increases. For the electrode material Ni-Co-O

nanorods / Co3O4 microsheet / Ni foam electrode the estimated specific capacitance 24.95 F/cm2

[6].

PVA combined with the KOH as active reagent [7], the activated carbon [8] is used as electrode

material which shows excellent electrochemical performance because the specific capacitance

depends on the surface area, pore structure [9] and electrolyte were used. There are several

materials are used as electrode material in supercapacitor. They are including carbon xerogels [10],

PANI doped with copper chloride [11], PANI/MnOx , Oxide and Phosphor silicate nanocomposite

[12], Mn3O4 [13], KCl assisted graphene oxide [14], Co3O4 nanoplates/graphene nanosheets [15],

NiO/Co3O4 [16], PANI doped with lithium salt [17]. When the thickness of electrode is less, then

the performance will be increases [18] than that of thicker electrode. Compared to the two

dimensional electrode [19], 3D electrode has high specific capacitance [20].

Synthesis

Materials Used. Aniline and Ferric Chloride were used as the precursors to obtain the Polyaniline

and Polyaniline/Ferric chloride composite. Ammonium persulfate was used as oxidizing agent.

Advanced Materials Research Vol. 768 (2013) pp 334-337Online available since 2013/Sep/04 at www.scientific.net© (2013) Trans Tech Publications, Switzerlanddoi:10.4028/www.scientific.net/AMR.768.334

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Synthesis of Polyaniline. Aniline of 10 ml was dissolved in 150 ml HCl solution in a beaker. This

solution is kept on the magnetic stirrer. 10 gm of ammonium persulfate was dissolved in 50 ml

Double distilled water and this solution is added to aniline solution drop wise. For the proper

mixing of chemicals in the solution, ammonium persulfate is added in drop wise. After 5 hours of

stirring process, diamond green solution was formed. The whole reaction system was kept still at

temperature of 25ºC. Then the stirred solution was filtered, and the obtained product was washed by

double distilled water. The polyaniline solution was dried in vacuum oven at temperature of 40º C.

Finally, Polyaniline powder was obtained.

Synthesis of PANI/Ferric Chloride composite. Polyaniline of 1.3 gm and Ferric chloride of 1gm

was dissolved in 40mL double distilled water in a beaker. This solution is kept on the magnetic

stirrer. After 2 hours of stirring process, the composite material is formed. The whole reaction

system was kept still at temperature of 25ºC. Then the stirred solution was filtered and the obtained

product was washed by doubled distilled water. The filtered solution is dried for few minutes in

vacuum oven at the temperature of 40ºC.Finally, the PANI with ferric chloride composite powder

was obtained.

Results and Discussion

UV-Vis Spectroscopy. In general, the UV-VIS characterization concerns the absorption spectra in

Ultra Violet – Visible spectral and Near Infrared region. This measurement gives the absorption

spectra for the as prepared nanoparticles. The absorption spectra obtained for PANI is shown in the

fig.1.

Optical absorbance spectra in the regions (400 – 700 nm) were recorded at room temperature using

perkin - elmer- spectrophotometer (Lambda 35). The absorption peak was occurred at 430 and 560

nm for PANI dispersed in methanol. From the fig 1, it is clearly shown that beyond 500 nm, the

absorbance value continually decreases for the as prepared polyaniline nanoparticles. The

absorption spectra for the PANI doped with Ferric chloride are depicted in the fig 2. The absorption

peak occurred at 460 and 570 nm for PANI doped with Ferric chloride dispersed in methanol. In

this case, the absorbance value is increased when compared to that of the polyaniline nanoparticle.

FTIR spectroscopy.In general, it is used to identify certain functional groups in a molecule and

also to confirm the presence of pure compound and to detect the presence of impurities. The FTIR

spectrum for PANI is given in the Fig. 3 & 4 shows the FTIR spectra in the wave number region of

4500 to 400 cm-1

of both polyaniline and its nanocomposite. The nanocomposite shows peaks at

420, 423, 852, 1246, 1303, 1482, 1496.7, 2974 and 3280 cm-1

. FTIR spectra show the strongest

absorbance band at 1246 cm-1

. The FTIR spectra showed the broad absorbance at 3324 cm-1

was

assigned to O-H stretching mode. N-H stretching at 3280 cm-1. C-H stretching at 2974 cm-1.

Benzene ring stress deformation and quinine ring stress deformation at 1482 and 1496.7 cm-1

,

respectively. The bands at 852.29, 1246 and 1303 cm-1

are the vibration modes of N-H . The band

appears at 420 and 423 cm-1

represent the Fe-O bond.

XRD characterization. In general, XRD characterization depicts the crystalline material structure

including its atomic arrangement, crystallite size and imperfections. It is used to analyze whether

the prepared composite is crystalline or amorphous. Based on the XRD result, polyaniline and the

composite has amorphous form in nature.

4 0 0 4 5 0 5 0 0 5 5 0 6 0 0 6 5 0 7 0 0

0 .2

0 .3

0 .4

0 .5

0 .6

0 .7

0 .8

0 .9

A

W a v e le n g th , n m

Fig.1.Absorbance spectra for PANI

4 0 0 4 5 0 5 0 0 5 5 0 6 0 0 6 5 0 7 0 0

2 .0

2 .1

2 .2

2 .3

2 .4

2 .5

A

W a v e le n g t h , n m

F e C l3/P A N I

Fig.2. Absorbance spectra for PANI/FeCl3

Advanced Materials Research Vol. 768 335

Conductivity measurement. The conductivity of the polyaniline and PANI/ Ferric chloride

composite was measured using CM-180 (with the measurement range 20-200 µS and 2-200 mS) at

specific

Fig.3.FTIR spectra for PANI Fig.4.FTIR spectra for PANI/FeCl3 composite

temperature of 0 to 50oC. The as prepared nanocomposite is dispersed in methanol and the

corresponding conductivity values are measured. Conductivity of Methanol (0.002mS),

Conductivity of PANI (0.025mS), Conductivity of PANI doped FeCl3 (0.067mS). From the

conductivity values, it is concluded that the conductivity of the composite is tremendously increased

than the polyaniline nanoparticles. This is performed only for a single doping level of ferric chloride

with polyaniline. When the doping value increases, then automatically the increase in conductivity

has to be expected.

Conclusion

In summary, polyaniline nanoparticles and polyaniline / ferric chloride composite have been

synthesized. From the UV Vis spectroscopy two absorbance bands located at 430 nm and 560 nm

are found for the polyaniline nanoparticles. And two absorbance bands located at 460 nm and 570

nm are found for the polyaniline / ferric chloride composite. From this concluded that there is a red

shift occurred in the composite. FTIR studies confirm that the presence of bonding. XRD results

confirm that the as prepared nanoparticles and the composite are amorphous in nature. Finally, the

conductivity of the composite is checked. This composite can effectively work as an electrode in

supercapacitors.

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