Electrochemical Properties of Overoxidized Poly-3,4-Ethylenedioxythiophene

Russian Journal of Electrochemistry - Tập 54 - Trang 893-901 - 2019
M. A. Kamensky1, S. N. Eliseeva1, G. Láng2, M. Ujvári2, V. V. Kondratiev1
1St. Petersburg State University, Institute of Chemistry, St. Petersburg, Russia
2Eötvös Loránd University, Institute of Chemistry, Budapest, Hungary

Tóm tắt

The properties of poly(3,4-ethylenedioxythiophene) (PEDOT) films were studied electrochemically at high positive potentials (from–0.3 to 1.5 V relative to the Ag/AgCl electrode). A cyclic voltammetry (CV) study revealed the range of potentials (up to 1.3–1.5 V) where the cycling leads to significant changes in the electrochemical, structural, and morphological properties of the polymer film due to overoxidation. When the upper cycling potential Eup exceeded 1.4 V, the anodic current significantly increased during the first cycle and then decreased, which suggests a loss of the electroactivity of the polymer and degradation of its properties. In the high-frequency region of the impedance spectra of the PEDOT films, a semicircle appears after overoxidation, which indicates a notable increase of the charge transfer resistance in the system, in contrast to the films subjected to potentiodymanic processing in a limited range of potentials from–0.3 to 1.3 V. The effect of overoxidation on the polymer morphology was studied by scanning electron microscopy. The chemical state of elements in the structure of the polymer film was determined by X-ray photoelectron spectroscopy. The obtained data indicate that–S=O groups formed at the thiophene sulfur in the polymer.

Tài liệu tham khảo

Tourillon, G., in Handbook of Conducting Polymers, Skotheim, T.A., Ed., New York: Marcel Dekker, 1986. Heinze, J. Electronically Conducting Polymers, in Top. Curr. Chem., vol. 152, Springer, 1990, p. 1. Roncali, J., Conjugated Poly(Thiophenes): Synthesis, Functionalization, and Applications, Chem. Rev. (Washington, DC, U.S.), 1992. doi 10.1021/Cr00012a009 Inzelt, G., Pineri, M., Schultze, J.W., and Vorotyntsev, M.A., Electron and proton conducting polymers: recent developments and prospects, Electrochim. Acta, 2000, vol. 45, p. 1016. doi 10.1016/S0013-4686(00)00329-7 Novak, P., Muller, K., Santhanam, K.S.V., and Haas, O., Electrochemically active polymers for rechargeable batteries, Chem. Rev. (Washington, DC, U. S.), 1997. doi 10.1021/Cr941181o Inzelt, G., Conducting Polymers: A New Era in Electrochemistry, Berlin: Springer, 2008. Inzelt, G., Rise and rise of conducting polymers, J. Solid State Electrochem., 2011, vol. 15, p. 1007. doi 10.1007/s10008-011-1338-3 Holze, R. and Wu, Y.P., Intrinsically conducting polymers in electrochemical energy technology: Trends and progress, Electrochim. Acta, 2014, vol. 122, p. 1016. doi 10.1016/j.electacta.2013.08.100 Groenendaal, L., Jonas, F., Freitag, D., Pielartzik, H., and Reynolds, J.R., Poly(3,4-ethylenedioxythiophene) and Its Derivatives: Past, Present, and Future, Adv. Mater., 2000, vol. 12, p. 481. doi 10.1002/(sici)1521-4095(200004)12:7<481::aid-adma481>3.0.co;2-c Murugan, A.V., Kwon, C.W., Campet, G., Kale, B.B., Maddanimath, T., and Vijayamohanan, K., Electrochemical lithium insertion into a poly(3,4-ethylenedioxythiophene) PEDOT/V2O5 nanocomposite, J. Power Sources, 2002, vol. 105, p. 1. doi 10.1016/s0378-7753(01)00992-2 Arbizzani, C., Balducci, A., Mastragostino, M., Rossi, M., and Soavi, F., Characterization and electrochemical performance of Li-rich manganese oxide spinel/poly(3,4-ethylenedioxythiophene) as the positive electrode for lithium-ion batteries, J. Electroanal. Chem., 2003, vol. 553, p. 125. doi 10.1016/S0022-0728(03)00305-X Murugan, A.V., Viswanath, A.K., Campet, G., Gopinath, C.S., and Vijayamohanan, K., Enhancement of double-layer capacitance behavior and its electrical conductivity in layered poly(3,4-ethylenedioxythiophene)-based nanocomposites, Appl. Phys. Lett., 2005, vol. 87. doi 10.1063/1.2140468 Murugan, A.V., Novel organic-inorganic poly(3,4-ethylenedioxythiophene) based nanohybrid materials for rechargeable lithium batteries and supercapacitors, J. Power Sources, 2006, vol. 159, p. 312. doi 10.1016/j.jpowsour.2006.04.033 Zhan, L.Z., Song, Z.P., Zhang, J.Y., Tang, J., Zhan, H., Zhou, Y.H., and Zhan, C.M., PEDOT: Cathode active material with high specific capacity in novel electrolyte system, Electrochim. Acta, 2008, vol. 53, p. 1016. doi 10.1016/j.electacta.2008.06.053 Lei, C.H., Wilson, P., and Lekakou, C., Effect of poly(3,4-ethylenedioxythiophene) (PEDOT) in carbon-based composite electrodes for electrochemical supercapacitors, J. Power Sources, 2011, vol. 196, p. 7823. doi 10.1016/j.jpowsour.2011.03.070 Fabre-Francke, I., Aubert, P.H., Alfonsi, S., Vidal, F., Sauques, L., and Chevrot, C., Electropolymerization of 3,4-ethylenedioxythiophene within an insulating nitrile butadiene rubber network: Application to electroreflective surfaces and devices, Sol. Energy Mater. Sol. Cells, 2012, vol. 99, p. 109. doi 10.1016/j.solmat. 2011.07.004 Hong, S.F. and Chen, L.C., Nano-Prussian blue analogue/PEDOT:PSS composites for electrochromic windows, Sol. Energy Mater. Sol. Cells, 2012, vol. 104, p. 1016. doi 10.1016/j.solmat.2012.04.032 Romyen, N., Thongyai, S., Praserthdam, P., and Sotzing, G.A., Enhancement of poly(3,4-ethylenedioxy thiophene)/poly(styrene sulfonate) properties by poly(vinyl alcohol) and doping agent as conductive nano-thin film for electronic application, J. Mater. Sci.: Mater. Electron., 2013, vol. 24, p. 2897. doi 10.1007/s10854-013-1188-0 Trinh, N.D., Saulnier, M., Lepage, D., and Schougaard, S.B., Conductive polymer film supporting LiFePO4 as composite cathode for lithium ion batteries, J. Power Sources, 2013, vol. 221, p. 284. doi 10.1016/j.jpowsour.2012.08.006 Kim, J., Park, H.S., Kim, T.H., Kim, S.Y., and Song, H.K., An inter-tangled network of redox-active and conducting polymers as a cathode for ultrafast rechargeable batteries, Phys. Chem. Chem. Phys., 2014, vol. 16, p. 1039. doi 10.1039/C3cp54624a Wang, X., Shen, L., Li, H., Wang, J., Dou, H., and Zhang, X., PEDOT coated Li4 Ti5O12 nanorods: Soft chemistry approach synthesis and their lithium storage properties, Electrochim. Acta, 2014, vol. 129, p. 283. doi 10.1016/j.electacta.2014.02.112 Cintora-Juarez, D., Perez-Vicente, C., Kazim, S., Ahmad, S., and Tirado, J.L., Judicious design of lithium iron phosphate electrodes using poly(3,4-ethylenedioxythiophene) for high performance batteries, J. Mater. Chem. A, 2015, vol. 3, p. 14254. doi 10.1039/c5ta03542b Das, P.R., Komsiyska, L., Osters, O., and Wittstock, G., PEDOT: PSS as a Functional Binder for Cathodes in Lithium Ion Batteries, J. Electrochem. Soc., 2015, vol. 162, p. 1149. doi 10.1149/2.0581504jes Eliseeva, S.N., Levin, O.V., Tolstopjatova, E.G., Alekseeva, E.V., Apraksin, R.V., and Kondratiev, V.V., New functional conducting poly-3,4-ethylenedioxythiophene: polystyrene sulfonate/carboxymethycellulose binder for improvement of capacity of LiFePO4-based cathode materials, Mater. Lett., 2015, vol. 161, p. 117. doi 10.1016/j.matlet.2015.08.078 Eliseeva, S.N., Levin, O.V., Tolstopyatova, E.G., Alekseeva, E.V., and Kondratiev, V.V., Effect of addition of a conducting polymer on the properties of the LiFePO4-based cathode material for lithium-ion batteries, Russ. J. Appl. Chem., 2015, vol. 88, p. 1146. doi 10.1134/S1070427215070071 Lee, J. and Choi, W., Surface Modification of Over-Lithiated Layered Oxides with PEDOT:PSS Conducting Polymer in Lithium-Ion Batteries, J. Electrochem. Soc., 2015, vol. 162, p. 1149. doi 10.1149/2.0801504jes Smolin, A.M., Novoselov, N.P., Babkova, T.A., Eliseeva, S.N., and Kondrat’ev, V.V., Use of composite films based on poly(3,4-ethylenedioxythiophene) with inclusions of palladium nanoparticles in voltammetric sensors for hydrogen peroxide, J. Anal. Chem., 2015, vol. 70, p. 967. doi 10.1134/S1061934815080171 Tolstopjatova, E.G., Eliseeva, S.N., Nizhegorodova, A.O., and Kondratiev, V.V., Electrochemical Properties of Composite Electrodes, Prepared by Spontaneous Deposition of Manganese Oxide into Poly-3,4-ethylenedioxythiophene, Electrochim. Acta, 2015, vol. 173, p. 40. doi 10.1016/j.electacta/2015.05.033 Zykwinska, A., Domagala, W., Pilawa, B., and Lapkowski, M., Electrochemical overoxidation of poly(3,4-ethylenedioxythiophene)—PEDOT studied by means of in situ ESR spectroelectrochemistry, Electrochim. Acta, 2005, vol. 50, p. 1625. doi 10.1016/j.electacta. 2004.10.026 Ujvári, M., Takacs, M., Vesztergom, S., Bazso, F., Ujhelyi, F., and Láng, G.G., Monitoring of the electrochemical degradation of PEDOT films on gold using the bending beam method, J. Solid State Electrochem., 2011, vol. 15, p. 1007. doi 10.1007/s10008-011-1472-y Láng, G.G., Ujvári, M., Bazso, F., Vesztergom, S., and Ujhelyi, F., In situ monitoring of the electrochemical degradation of polymer films on metals using the bending beam method and impedance spectroscopy, Electrochim. Acta, 2012, vol. 73, p. 1016. doi 10.1016/j.electacta. 2012.01.068 Ujvári, M., Zalka, D., Vesztergom, S., Eliseeva, S., Kondratiev, V., and Láng, G.G., Electrochemical impedance measurements in non-stationary systems: application of the 4-dimensional analysis method for the impedance analysis of overoxidized poly(3,4-ethylenedioxythiophene)-modified electrodes, Bulg. Chem. Commun., 2017, vol. 49, p. 106. Ujvári, M., Gubicza, J., Kondratiev, V., Szekeres, K.J., and Láng, G.G., Morphological changes in electrochemically deposited poly(3,4-ethylenedioxythiophene) films during overoxidation, J. Solid State Electrochem., 2015, vol. 19, p. 1247. doi 10.1007/s10008-015-2746-6 Láng, G.G., Ujvári, M., Vesztergom, S., Kondratiev, V., Gubicza, J., and Szekeres, K.J., The Electrochemical Degradation of Poly(3,4-ethylenedioxythiophene) Films Electrodeposited from Aqueous Solutions, Z. Phys. Chem., 2016, vol. 230, p. 1281. doi 10.1515/zpch-2016-0752 Zhuzhel’skii, D.V., Yalda, K.D., Spiridonov, V.N., Eliseeva, S.N., and Kondratiev, V.V., Electrochemical deposition of molybdenum oxide into films of poly(3,4-ethylenedioxythiophene) conducting polymer on glassy carbon substrates, Russ. J. Appl. Chem., 2016, vol. 89, p. 1252. doi 10.1134/s1070427216080061 Kondratiev, V.V., Malev, V.V., and Eliseeva, S.N., Composite electrode materials based on conducting polymers loaded with metal nanostructures, Russ. Chem. Rev., 2016, vol. 85, p. 1070. doi 10.1070/rcr4509 Fall, M., Diagne, A.A., Dieng, M.M., Deflorian, F., Rossi, S., Bonora, P.L., Volpe, C.D., and Aaron, J.J., Electrochemical impedance spectroscopy of poly(3-methoxythiophene) thin films in aqueous LiClO4 solutions, Synth. Met., 2005, vol. 155, p. 569. doi 10.1016/j.synthmet.2005.09.043 Refaey, S.A.M., Electrochemical impedance studies on the electrochemical properties of poly(3-methylthiophene) in aqueous solutions, Synth. Met., 2004, vol. 140, p. 87. doi 10.1016/s0379-6779(03)00357-6 Greczynski, G., Kugler, T., Keil, M., Osikowicz, W., and Fahlman, M., and Salaneck, W.R., Photoelectron spectroscopy of thin films of PEDOT-PSS conjugated polymer blend: a mini-review and some new results, J. Electron Spectrosc. Relat. Phenom., 2001, vol. 121, p. 1016. doi 10.1016/s0368-2048(01)00323-1 King, Z.A., Shaw, C.M., Spanninga, S.A., and Martin, D.C., Structural, chemical and electrochemical characterization of poly(3,4-ethylenedioxythiophene) (PEDOT) prepared with various counter-ions and heat treatments, Polymer, 2011, vol. 52, p. 1302. doi 10.1016/j.polymer.2011.01.042