Conducting polymers electronic conductivity

This article addresses the synthesis, properties, and appHcations of redox dopable electronically conducting polymers and presents an overview of the field, drawing on specific examples to illustrate general concepts. There have been a number of excellent review articles (1—13). Metal particle-filled polymers, where electrical conductivity is the result of percolation of conducting filler particles in an insulating matrix (14) and ionically conducting polymers, where charge-transport is the result of the motion of ions and is thus a problem of mass transport (15), are not discussed. 

The active layer consists of a polymer having electronic conductive, ionic conductive, and luminescent properties, is blended with an ionic salt [48]. The polymer with the required properties can be realized by a blend of a conjugated and an ionic conductive polymer [481 or by specially designed polymers [71-73],... 

Another model assumes that gel zones are formed by hydrated lead dioxide (PbO(OH)2) and act as bridging elements between the crystallite particles. Electrons can move along the polymer chains of this gel and so cause electronic conductivity between the crystalline zones 137],... 

Composite structures that consist of carbon particles and a polymer or plastic material are useful for bipolar separators or electrode substrates in aqueous batteries. These structures must be impermeable to the electrolyte and electrochemical reactants or products. Furthermore, they must have acceptable electronic conductivity and mechanical properties. The physicochemical properties of carbon blacks, which are commonly used, have a major effect on the desirable properties of the conductive composite structures. Physicochemical properties such as the surface... 

Rotations around torsional barriers induce changes in chain conformation. For conjugated systems like polydiacetylenes, flow-induced changes in chain conformation can have a profound influence on the photon absorption and electronic conductivity properties of the material [73]. Flow-induced changes in molecular conformation form the basis for several technically important processes, the best known examples are the production of oriented fibers by gel spinning [74], the compatibility enhancement [75] and the shear-induced modification of polymer morphology [76]. 

Conducting Polymers Electronically conducting polymers (such as polypyrrole, polythiophene, and polyaniline) have attracted considerable attention due to their ability to switch reversibly between the positively charged conductive state and a neutral, essentially insulating, form and to incorporate and expel anionic species (from and to the surrounding solution), upon oxidation or reduction ... 

Figure 3. Cyclic voltammograms of 3-methylpyrrole-4-carboxylic acid in acetonitrile + 0.1 MEt4NC104.58 (Reprinted from P. G. Pickup, Poly-(3-methylpyrrole-4-carbox-ylic acid) An electronically conducting ion-exchange polymer, J. Electroanal. Chem. 225, 273-280, 1987, with kind permission from Elsevier Sciences S.A.)...

The huge literature on the electronic conductivity of dry conducting polymer samples will not be considered here because it has limited relevance to their electrochemistry. On the other hand, in situ methods, in which the polymer is immersed in an electrolyte solution under potential control, provide valuable insights into electron transport during electrochemical processes. It should be noted that in situ and dry conductivities of conducting polymers are not directly comparable, since concentration polarization can reduce the conductivity of electrolyte-wetted films considerably.139 Thus in situ conductivities reported for polypyrrole,140,141 poly thiophene,37 and poly aniline37 are orders of magnitude lower than dry conductivities.15... 

Impedance spectroscopy is best suited for the measurement of electronic conductivities in the range 10 -7to 10 2S cm 1.145 In principle, it is perhaps the best method for this range, but it is often difficult to interpret impedance data for conducting polymer films. The charge-transfer resistance can make measurements of bulk film resistances inaccurate,145 and it is often difficult to distinguish between the film s ionic and electronic resistances.144 This is even more of a problem with chronoamperometry146 and chronopotentiometry,147 so that these methods are best avoided. 

The electronic conductivity of a conducting polymer can vary by more than 10 orders of magnitude with changing potential. For lightly p-doped materials, the conductivity generally increases exponentially with increasing potential (see Fig. 11). Slopes of 60-130 mV decade-1 are... 

Because of their high electronic conductivities, the rates of electrochemical processes in conducting polymers are generally controlled by ion transport. The ionic content of a film also has a strong influence on its... 

---