Polymers, electronically conducting organic limitations

Another limiting factor is that it may not be possible to use some of these electronically conducting organic compounds in aqueous solutions. This is true of the polymer most used in new polymer batteries, polyacetylene, for which an appropriate solvent is propylene carbonate (see Fig. 4.115). 

There are some (Heinze, 1996) to whom the polaron explanation of the ionic introduction of electronic conductivity in organic compounds is specious The roughness factor of 400 would limit the degree of penetration of ions into the interstices of the polymer. However, Li+ or even CIOJ is of course much smaller than the test molecules (large dye molecules) which are generally used to probe the real area. Thus, one might conceive of a model of the polymer that is all fibers, the intercalation being all pervasive. It is obvious that an Li+ ion adsorbed on the surface of a fiber will promote an electron that may indeed be free to move under a field, i.e., to conduct. 

Activity in the battery area using electronically conducting polymers has been intense (see Fig. 11.19). The possibilities (MacDiarmid, 1997) point to the provision of cheap (because of the relative cheapness of organic compounds) batteries, e.g., for massive use as a power source for bicycles. The counter-point is the limited stability and hence lifetime of such structures, and the availability of, e.g., rechargeable MnOj-Li cells, in which the (bismuth doped) Mn02 is also a relatively cheap material. 

The major difficulty in the 1990s for the development of electronically conducting polymers lies in the limited understanding we have about the relation between the molecular structure of the organic material and the resulting electronic conductance. 

An electrolyte is a substance with ionic DC conductivity. Intracellular and extracellular liquids contain ions free to migrate. In pure electroljrtes, the charge carriers are ions, and there is no separate flow of electrons—they are all bound to their respective atoms. Therefore, tissue DC currents are ionic currents, in contrast to the electronic current in metals. This is not contradictory to a possible local electronic conductance due to free electrons (e.g., in the intracellular DNA molecules). New solid materials such as organic polymers and glasses may contain an appreciable amount of free ions with considerable mobility therefore, the materials of an electrolytic measuring cell are not limited to liquid media. Some of these solid media show a mixture of ionic and electronic conductivity. 

While an invaluable tool in producing conjugated polymers on conducting substrates, electropolymerization has limitations that include a lack of primary structure verification and characterization along with the inability to synthesize large quantities of processable polymer. To overcome the insolubility of PEDOT, a water-soluble polyelectrolyte, poly(styrenesulfonate) (PSS) was incorporated as the counterion in the doped PEDOT to yield the commercially available PEDOT/PSS (Baytron P) (39), which forms a dispersion in aqueous solutions [140]. While this polymer finds most of its application as a conductor for antistatic films, solid state capacitors, and organic electronic devices, its electrochromism is distinct and should not be ignored. 

In all cases, the films were obtained by oxidative electropolymerization of the cited substituted complexes from organic or aqueous solutions. The mechanism of metalloporphyrin Him formation was suggested to be a radical-cation induced polymerization of the substituents on the periphery of the macrocycle. As it was reported for the case of polypyrrole-based materials ", cyclic voltammetry and UV-visible spectroscopy with optically transparent electrodes were extensively used to provide information on the polymeric films (electroactivity, photometric properties, chemical stability, conductivity, etc.). Based on the available data, it appears that the electrochemical polymerization of the substituted complexes leads to well-structured multilayer films. It also appears that the low conductivity of the formed films, combined with the cross-linking effects due to the steric hindrance induced by the macrocyclic Ugand, confers to these materials a certain number of limitations such as the limited continuous growth of the polymers due to the absence of electronic conductivity of the films. Indeed, the charge transport in many of these films acts only by electron-hopping process between porphyrin sites. 

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