Electrode polymer

The discovery that certain classes of polymers may acquire high electronic conductivity following chemical or electrochemical treatment has opened a new and exciting area of research and development. 

The concept of electric transport in polymers due to the availability of polymeric materials with characteristics similar to those of metals is certainly fascinating and, indeed, many studies have been directed towards the preparation and the characterisation of these new electroactive conductors. The final goal is their use as new components for the realisation of electronic and electrochemical devices with exotic designs and diverse applications. 

The idea of exploiting these new conducting polymers for the development of flexible diodes and junction transistors, as well as for selective field effect transistor sensors, has been proposed and experimentally confirmed, and thus we may, perhaps optimistically, look forward to a time when popular electronic devices can be based on low cost, flexible and modular polymer components. 

Furthermore, since the electrochemical processes modify the optical 

In this chapter we will attempt to provide a brief but illustrative description of the various aspects of the research and technology of conducting polymers. To appreciate fully the diverse range of operations that these materials may fulfil, it is crucial to understand their basic properties. Therefore, particular attention will be devoted here to the description of the mechanism of charge transport and to the characteristics of the electrodic processes in electrochemical cells. 

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Table 3. Battery Characteristics for Conductive Polymer Electrodes...

The first tme commercialization of a conductive polymer electrode in a battery ceU has been carried out by Bridgestone/Sienko who market a... 

Pseudocapacitance is used to describe electrical storage devices that have capacitor-like characteristics but that are based on redox (reduction and oxidation) reactions. Examples of pseudocapacitance are the overlapping redox reactions observed with metal oxides (e.g., RuO,) and the p- and n-dopings of polymer electrodes that occur at different voltages (e.g. polythiophene). Devices based on these charge storage mechanisms are included in electrochemical capacitors because of their energy and power profiles. 

A conductive polymer electrode has been designed specifically for the cathodic protection of steel reinforcing bars in concrete and is marketed under the trade name Ferex . The anode consists of a 16 AWG stranded copper conductor surrounded by a carbon-loaded polymeric coating similar to that used on the Anodeflex system ) to provide a nominal anode diameter of 8 mm The manufacturer claims that at the maximum recommended current density of 0 08 Am the anode life in concrete will be 32 years with a proportionately longer life at lower current densities. 

By comparing impedance results for polypyrrole in electrolyte-polymer-electrolyte and electrode-polymer-electrolyte systems, Des-louis et alm have shown that the charge-transfer resistance in the latter case can contain contributions from both interfaces. Charge-transfer resistances at the polymer/electrode interface were about five times higher than those at the polymer/solution interface. Thus the assignments made by Albery and Mount,203 and by Ren and Pickup145 are supported, with the caveat that only the primary source of the high-frequency semicircle was identified. Contributions from the polymer/solution interface, and possibly from the bulk, are probably responsible for the deviations from the theoretical expressions/45... 

Theoretical aspects of mediation and electrocatalysis by polymer-coated electrodes have most recently been reviewed by Lyons.12 In order for electrochemistry of the solution species (substrate) to occur, it must either diffuse through the polymer film to the underlying electrode, or there must be some mechanism for electron transport across the film (Fig. 20). Depending on the relative rates of these processes, the mediated reaction can occur at the polymer/electrode interface (a), at the poly-mer/solution interface (b), or in a zone within the polymer film (c). The equations governing the reaction depend on its location,12 which is therefore an important issue. Studies of mediation also provide information on the rate and mechanism of electron transport in the film, and on its permeability. 

The development of a rechargeable polymer battery is being pursued worldwide. Its attraction lies in the specific weight of polymers, which is considerably lower than that of ordinary inorganic materials, as well as potential environmental benefits. In principle there are three different types of battery. The active polymer electrode can be used either as cathode (cell types 1, 2), or as anode (cell type 3), or as both cathode and anode (cell type 4) (Fig. 14). As the most common polymer materials are usually only oxidizable, recent research has concentrated on developing cells with a polymer cathode and a metal anode. 

An important problem encountered with polymer electrodes is that of overoxidation. It occurs after reversible charging of the electrode at high oxidation potentials and leads to polymer degeneration. The results of thorough studies show that such degenerative mechanisms are promoted by the nucleophilicity of the solvent. Especially the activity of water leads to the formation of quinone-type compounds, to the cleavage of C—C bonds, the liberation of CO2, and the formation of carboxylic acids Hence, there is a clear tendency to avoid both nucleophile solvents... 

In the case of Ni(OH)2 and conductive polymer electrodes, solvent and anions intercalate into the electrode at anodic potentials. Electrochemical quartz crystal microbalance (EQCM) is a useful technique for monitoring the ingress and egress of solvent and anions in these materials. 

Coutanceau C, El Hourch A, Crouigneau P, Leger JM, Lamy C. 1995. Conducting polymer electrodes modified by metal tetrasulfonated phthalocyanines Preparation and electro-catalytic behaviour towards dioxygen reduction in acid medium. Electrochim Acta 40 2739-2748. 

Anson FC, Ni CL, Saveant JM. 1985. Electrocatalysis at redox polymer electrodes with separation of the catalytic and charge propagation roles. Reduction of dioxygen to hydrogen peroxide as catalyzed by cobalt(II) tetrakis(4-A-methylpyridyl)porphyrin. J Am Chem Soc 107 3442. 

Organic salt and conducting polymer electrodes The surface of an organic electrode may provide enzymes with smooth electron transfer. 

Kato T, Liu JK, Yamamoto K, Osborne PG, Niwa O. 1996. Detection of basal acetylcholine release in the microdialysis of rat frontal cortex by high- performance liquid chromatography using a horseradish peroxidase-osmium redox polymer electrode with pre-enzyme reactor. J Chromatogr B 682 162-166. 

For example, the p-doping process of a typical heterocyclic polymer, say polypyrrole, can be reversibly driven in an electrochemical cell by polarising the polymer electrode vs a counterelectrode (say Li) in a suitable electrolyte (say LiC104-PC). Under these circumstances the p-doping redox reaction (9.15) can be described by the scheme ... 

As is well known in the field of electrochemistry in general, electrode kinetics may be conveniently examined by cyclic voltammetry (CV) and by frequency response analysis (ac impedance). The kinetics of the various polymer electrodes considered so far in this chapter will be discussed in terms of results obtained by these two experimental techniques. 

Further information on this subject can be obtained by frequency response analysis and this technique has proved to be very valuable for studying the kinetics of polymer electrodes. Initially, it has been shown that the overall impedance response of polymer electrodes generally resembles that of intercalation electrodes, such as TiS2 and WO3 (Ho, Raistrick and Huggins, 1980 Naoi, Ueyama, Osaka and Smyrl, 1990). On the other hand this was to be expected since polymer and intercalation electrodes both undergo somewhat similar electrochemical redox reactions, which include the diffusion of ions in the bulk of the host structures. One aspect of this conclusion is that the impedance response of polymer electrodes may be interpreted on the basis of electrical circuits which are representative of the intercalation electrodes, such as the Randles circuit illustrated in Fig. 9.13. The figure also illustrates the idealised response of this circuit in the complex impedance jZ"-Z ) plane. 

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