CHARACTERIZATION OF POLY(N-ETHYLANILINE) AND POLY(ANILINE-CO-N-ETHYLANILINE) AS SUPERCAPACITOR ACTIVE MATERIALS IN NONAQUEOUS MEDIUM

Poli(N-etilanilin) (PNEA) ve poli(anilin-ko-N-etilanilin) filmleri 0.1 M tetraetilamonyumtetrafloroborat (TEABF4) içeren asetonitril (ACN) çözeltisi kullanılarak dönüşümlü voltametri (CV)yöntemiyle kalem grafit elektrot (PGE) yüzeyinde sentezlenmiştir. Elde edilen filmlerin elektrokimyasalkarakterizasyonu monomersiz çözeltiler içerisinde CV yöntemi kullanılarak gerçekleştirilmiştir.Filmlerin yüzey morfolojileri taramalı elektron mikroskobu (SEM) ile görüntülenmiştir. Polimer filmikaplı PGE’ların (PGE/PNEA ve PGE/co-PNEA) elektrokimyasal enerji depolama özellikleri CV,elektrokimyasal empedans spektroskopisi (EIS), galvanostatik şarj-deşarj ve tekrarlanankronopotansiyometri yöntemleriyle araştırılmıştır. PGE/PNEA ve PGE/co-PNEA için en yüksekspesifik kapasitans değerleri galvanostatik şarj-deşarj yöntemi ile 0.01 mA akımda sırasıyla 1112.72 and1830.00 mF g-1PGE/PNEA’un PGE/co-PNEA’tan daha yüksek şarj-deşarj kararlılığına sahip olduğu gözlenmiştir.olarak elde edilmiştir. Tekrarlanan kronopotansiyometri yöntemine göre

Poly(N-ethylaniline) (PNEA) and poly(aniline-co-N-ethylaniline) (co-PNEA) films have been synthesized on a pencil graphite electrode (PGE) by using cyclic voltammetry (CV) in an acetonitrile (ACN) solution of tetraethylammonium tetrafluoroborate (TEABF4). The electrochemical properties of the electrodeposited coatings have been characterized using CV method in monomer free solution. The surface morphologies of the films have been investigated by Scanning Electron Microscope (SEM). The electrochemical storage properties of polymer coated PGE (PGE/PNEA and PGE/co-PNEA) have been evaluated by CV, electrochemical impedance spectroscopy (EIS), galvanostatic charge-discharge and repeating chronopotentiometry tests. The highest specific capacitance values of PGE/PNEA and PGE/co-PNEA have obtained as 1112.72 mF g-1 and 1830.00 mF g-1 at 0.01 mA by using galvanostatic charge-discharge, respectively. According to repeating chronopotentiometry tests, it is observed that charge-discharge stability of PGE/PNEA is longer than PGE/co-PNEA

Keywords:

Conducting Polymer; Polyaniline; Electropolymerization; Energy Storage; Supercapacitor,

PDF

___

Arbizzani, C., Mastragostino, M., Meneghello, L., Supercapacitors: A Comparative Study”, Electrochimica doi:1016/0013-4686(95)00289-Q. 41, 21

Arslan, A., Hür, E., (2012) “Supercapacitor

Applications of Polyaniline and Poly(N- methylaniline) Coated Pencil Graphite Electrode”, Electrochemical Science, 7, 12558-12572. Journal

Bakhmatyuk, B.P., Venhryn, B.Y., Grygorchak, I.I., Micov, M.M., (2008) “Influence of

Chemical Modification Carbon Surface on Characteristics of Supercapacitors”, Sources, doi:1016/j.jpowsour.2008.02.045. 890-8

Bhadra, S., Chattopadhyay, S., Singha, N.K., Khastgir, D., (2008) “Improvement of Conductivity

Synthesized Polyaniline”, Applied Polymer Science, 108, 57-64. doi:1002/app.26926. Electrochemically Journal of

Bhadra, S., Khastgir, D., Singha, N.K., Lee, J.H., (2009) Processing Polyaniline”, Science, doi:1016/j.progpolymsci.2009.04.003. 783-8

Cebeci, F.C., Geyik, H., Sezer, E., Saraç, A.S., (2007)

Characterization and Impedance Studies on Novel Thiophene-Nonylbithiazole- Thiophene Comonomer”, Electroanalytical Chemistry, 610, 113- doi:10.1016/j.jelechem.2007.07.012.

Devaraj, S., Munichandraiah, M., (2007)

“Electrochemical Supercapacitor Studies of Synthesized by Microemulsion Method and The Effect of Annealing”, Journal of The Electrochemical Society, 154, A80- A doi:10.1149/1.2404775.

Ganesh, B., Kalpana D., Renganathan, N.G., (2008)

Conducting Polymer Gel Electrolyte for Electric Double Layer Capacitors”, Ionics, 14, 0230- Based Proton 339-3 doi:1007/s11581-008

Genies, E.M., Picart, S., (1995) “Polypyrrole- Latex Electrochemical

Spectroelectrochemical Synthetic doi:1016/0379-6779(94)02507-U. and Studies”, 165-1 69,

Genies, E.M., Syed, A.A., Tsintavis, C., (1985)

“Electrochemical Study of Polyaniline in Aqueous and Organic Medium - Redox and Crystals and Liquid Crystals, 121, 181- 1 doi:10.1080/00268948508074858.

Genies, E.M., Tsintavis, C., (1985) “Redox

Mechanism and Electrochemical-Behavior of Polyaniline Deposits”, Journal of Electroanalytical Chemistry, 195, 109- doi:10.1016/0022-0728(85)80009-7.

Hashmi, S.A., (2004) “Supercapacitor: An Emerging

Academy Science Letters-India, 27, 27-46. National Hashmi, S.A., Latham, R.J., Linford, R.G., Schlindwein, W.S., Electrolyte Based Solid State Redox Supercapacitors with Poly (3-Methyl Thiophene) and Polypyrrole Conducting Polymer Electrodes”, Ionics, 3, 177-183. doi:1007/BF02375614. “Polymer

Heli, H., Yadegari, H., Jabbari, A., (2012) “Graphene aminophenol)

Supercapacitor Applications”, Materials Chemistry and Physic, doi:1016/j.matchemphys.2012.02.065. 134, 21-25.

Hu, C.C., Chu, C.H., (2001) “Electrochemical Impedance

Polyaniline-coated Graphite Electrodes for Electrochemical Capacitors – Effects of Film Coverage/Thickness and Anions”, Journal of Electroanalytical Chemistry, 503, 0728(01)00385-0. of 105- doi:1016/S0022

Hu, C.C., Chu, C.H., (2009) “Electrochemical and Textural Characterization of Iridium- Doped

Electrochemical Capacitors”, Materials Chemistry and Physics, 65, 329-338. doi:1016/S0254-0584(00)00254-6. for

Hu, Y., Zhu, Z., Wang, J., Chen, Z., (2011)

“Synthesis of Layered Birnessite-Type Manganese Oxide Thin Films on Plastic Substrates by Chemical Bath Deposition for Flexible Transparent Supercapacitors”, Journal of Alloys and Compounds, 509, 10234-10240. doi:1016/j.jallcom.2011.08.080. Huggins, R.A., “Supercapacitors”,

Transactions of The Royal Society A- Mathematical Physical and Engineering Sciences, doi:1098/rsta.1996.0064. R., Philosophical 1555-1566.

Khomenko, V., Raymundo-Pinero, E., Beguin, F., Graphite/AC Electrolyte”, Journal of Power Sources, 177,643-651. Density Organic in doi:1016/j.jpowsour.2007.11.101.

Kim, H.S., Popov, B.N., (2003) “Synthesis and Characterization of MnO2-based Mixed

Oxides as Supercapacitors”, Journal of The Electrochemical Society, 150, D56- D doi:10.1149/1.1541675.

Kotz, R., Carlen, M., (2000) “Principles and Applications

Capacitors”, Electrochimica Acta, 45, 2483-2498. doi:1016/S0013-4686(00)00354-6. Laforgue, A., (2011) “All-textile Flexible

Supercapacitors using Electrospun Poly(3,4- ethylenedioxythiophene) Journal of Power Sources, 196, 559-564. doi:1016/j.jpowsour.2010.07.007.

Lota, K., Khomenko, V., Frackowiak, E., (2004) “Capacitance ethylenedioxythiophene)/Carbon Nanotubes

Composites”, Journal of Physics and Chemistry of Solids, doi:1016/j.jpcs.2003.10.051. 65, 295-301.

Ma, R.Z., Liang, J., Wei, B.Q., Zhang, B., Xu, C.L., Wu, C.L., (1999) “Study of Electrochemical

Carbon Nanotube Electrodes”, Journal of Power doi:1016/S0378-7753(99)00252-9. 84, 126

Michael, I., Prabaharan, S.R.S., (2004) “High

Voltage Electrochemical Double Layer Capacitors using Conductive Carbons as Additives”, Journal of Power Sources, 136,250-256. doi:1016/j.jpowsour.2004.03.006.

Mujawar, S.H., Ambade, S.B., Battumur, T., Ambade, R.B., “Electropolymerization of Polyaniline on Titanium Supercapacitor Application”, Electrochimica Nanotubes for 56, 4462-4466.

Naoi, K., Kawase, K.I., Mori, M., Komiyama, M., (1997) “Electrochemistry of Poly(2,2'- dithiodianiline): A New Class of High Energy

Interconnected with S-S bonds”, Journal of the Electrochemical Society, 144, L173- L1 doi:10.1149/1.1837715. Polymer

Nishino, A., (1996) “Capacitors: Operating

Principles, Current Market and Technical Trends”, Journal of Power Sources, 60, 137- doi:1016/S0378-7753(96)80003-6.

Pandolfo, A.G., Hollenkamp, A.F., (2006)

“Carbon Properties And Their Role In Supercapacitors”, Sources, doi:1016/j.jpowsour.2006.02.065. 11

Patil, U.M., Kulkarni, S.B., Jamadede, V.S., Lokhande, C.D., (2011) “Chemically

Synthesized Hydrous Ruo2Thin Films for Supercapacitor Application”, Journal of Alloys and Compounds, 509, 1677-1682. doi:1016/j.jallcom.2010.09.133.

Portet, C., Chmiola, J., Gogotsi, Y., Park, S., Lian, K., Characterizations of Carbon Nanomaterials by The Cavity Microelectrode Technique”, Electrochimica Acta, doi:1016/j.electacta.2008.05.019. 53, 7675-7680.

Prasad, K.R., Munichandraiah, N., (2002)

“Fabrication and Evaluation of 450 F Electrochemical Redox Supercapacitors using Inexpensive and High-Performance, Polyaniline Electrodes”, Journal of Power Sources, 112, 443-451. doi:1016/S0378-7753(02)00419-6.

Şahin, Y., Perçin, S., Özkan, G., (2003a)

“Electrochemical Synthesis of Poly(2- iodoaniline) iodoaniline) in Acetonitrile”, Journal of Applied Polymer Science, 89, 1652-1658. doi:1002/app.12395. Poly(aniline-co-2

Şahin, Y., Perçin, S., Şahin, M., Özkan, G., (2003b) “Electrochemical Preparation of

Poly(2-bromoaniline) and Poly(aniline-co- 2-bromoaniline) in Acetonitrile” Journal of Applied Polymer Science, 90, 2460- 24 doi:10.1002/app.12994.

Şahin, Y., Perçin, S., Şahin, M., Özkan, G., (2004) “Electrochemical Polymerization of

Anilines and Copolymers with Aniline”, Journal of Applied Polymer Science, 9, 2302-2312. doi:10.1002/app.13367.

Saraç, A.S., Doğru, E., Ateş, M., Parlak, E.A., (2006) “Electrochemical Synthesis of N- Methylpyrrole Copolymer Microelectrodes, Characterization”, Chemistry, 30, 401-408. Carbon and Their Turkish Journal of

Sarangapani, S., Tilak, B.V., Chen, C.P., (1996)

“Materials For Electrochemical Capacitors -Theoretical and Experimental Constraints”, Journal of Electrochemical Society, 143, 3791-3799. doi:10.1149/1.1837291.

Sen, P., De, A., (2010) “Electrochemical Performances ethylenedioxythiophene)-NiFe2O4 Nanocomposite

Supercapacitor”, Electrochimica Acta, 55, 4677-4684. doi:1016/j.electacta.2010.03.077. for

Sharma, R.K., Oh, H.S., Shul, Y.G., Kim, H.S., (2007)

Structured, Manganese Oxide Composite Electrode Supercapacitor”, Sources, doi:1016/j.jpowsour.2007.08.076. 1024-1028. 173,

Sharma, R.K., Oh, H.S., Shul, Y.G., Kim, H.S., (2008) “Growth and Characterization of

Carbon-Supported Mno2 Nanorods for Supercapacitor Electrode”, Physica B, 403,1763-1769. doi:1016/j.physb.2007.10.007.

Sharma, R.K., Zhai, L., (2009) “Multiwall

Carbon Nanotube Supported Poly(3,4- ethylenedioxythiophene)/Manganese Oxide Nano-Composite Electrode Super-Capacitors”, Electrochimica Acta, 54,7148-7155. doi:1016/j.electacta.2009.07.048. for

Wang, J., Xu, Y., Chen, X., Du, X., (2007)

“Electrochemical supercapacitor Electrode Material ethylenedioxythiophene)/Polypyrrole Composites, Journal of Power Sources, 163,1120-1125. doi:1016/j.jpowsour.2006.10.004.

Wang, Q., Li, J.L., Gao, F., Li, W.S., Wu, K.S., Wang, X.D., (2008) “Activated Carbon

Coated with Polyaniline as An Electrode Material Carbon doi:1016/S1872-5805(08)60030-X. 23, 275-2

White, A.M., Slade, R.C.T., (2003) “Polymer Electrodes

Heteropolymetallates and Their use within Solid-State Supercapacitors”, Metals, 139, 123-131. doi:10.1016/S0379- 6779(03)00039-0. with Synthetic

Yang, C.M., Kim, Y.J., Endo, M., Kanoh, H., Yudasaka, M., Iijima, S., Kaneko, K., (2007) “Nanowindow-Regulated Specific

Capacitance of Supercapacitor Electrodes of Single-Wall Carbon Nanohorns”, Journal of The American Chemical Society, doi:1021/ja065501k. 20