Intercalation electronically conducting polymer

The concept of electrochemical intercalation/insertion of guest ions into the host material is further used in connection with redox processes in electronically conductive polymers (polyacetylene, polypyrrole, etc., see below). The product of the electrochemical insertion reaction should also be an electrical conductor. The latter condition is sometimes by-passed, in systems where the non-conducting host material (e.g. fluorographite) is finely mixed with a conductive binder. All the mentioned host materials (graphite, oxides, sulphides, polymers, fluorographite) are studied as prospective cathodic materials for Li batteries. 

It is perhaps useful to mention that the use of electronically conducting polymers, such as poly(acetylene), (CH) poly(pyrrole), (C4H5N)X, and poly(aniline), (CeHgNf ), has been proposed for positives for lithium batteries. The electrochemical process of these lithium-polymer positives is somewhat similar to an intercalation reaction. On charging, the polymer (P) is oxidized by acquiring a positive charge to form a polaron, and this is... 

The materials sciences continue to bring forth new electronically conducting solids (2-4). Virtually all of these have possible applications in electrochemical systems. Among the more interesting candidates in recent times have been semiconductors, electronically conducting polymers, intercalation materials, new forms of carbon, and oxide and sulfide compounds, especially the perovskites. A wide variety of applications could arise from these materials, including new or... 

UVERS study of the formation of electron conducting polymer films at a gold electrode, and of their modification by intercalation of metal aggregates or of iron phthalocyanine ... 

Intensive research on the electrocatalytic properties of polymer-modified electrodes has been going on for many years Until recently, most known coatings were redox polymers. Combining redox polymers with conducting polymers should, in principle, further improve the electrocatalytic activity of such systems, as the conducting polymers are, in addition, electron carriers and reservoirs. One possibility of intercalating electroactive redox centres in the conducting polymer is to incorporate redoxactive anions — which act as dopants — into the polymer. Most research has been done on PPy, doped with inter alia Co 96) RyQ- 297) (--q. and Fe-phthalocyanines 298,299) Co-porphyrines Evidently, in these... 

As our quantum-chemical calculations show, similar transformation and delocalization of bonds takes place in the conductive forms of some other types of CPs (polyaniline, polypyrolle, etc.). Delocalization of chemical bonds after activation leads to appearance of an electronic conductivity in such types of conducting polymers and creates prerequisites for their application as electrode materials of electrochemical power sources. Such activation can be stimulated by intercalation of ions, applying the potential, and by use of some other low energetic factors. 

The benefit of a hybrid phase for the intercalation-deintercalation of mobile species such as Li+ cations is well illustrated by the study of conductive polymers such as polyaniline or polypyrrole intercalated into a V2O5 framework as potential electrode materials in lithium batteries [34]. For PANI/V2O5, an oxidative post-treatment performed under an oxygen atmosphere allowed the authors to compare the conductivity attributed to the polymer, as in absence of reduced cations, there was no electronic hopping between ions, and the conductive state was due only to the... 

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. 

Electrically conducting polymers are quite different systems to the above elec-troinitiated chain polymerizations since they are formed by an unusual step-growth mechanism involving stoichiometric transfer of electrons. The polymers are obtained directly in a conductive polycationic form in which charge-compensating counter anions from the electrolyte system are intercalated into the polymer matrix [173], Exact mechanistic details remain the subject of discussion, but Scheme 4, which shows polypyrrole formation is plausible. Polythiophene is similar where S replaces NH in the ring. 

Polypyrrole, polythiophene, polyaniline, polyfuran, polyacetylene, and poly-methylthiophene may exhibit a mixed electronic and ionic conductivity, similar to inorganic intercalation, or insertion compounds [43]. In the conductive form these polymers are partly oxidized and these positive charges are equilibrated by inorganic anions, which can diffuse through the polymer net. Alternatively, the conductive polymers can be partly reduced, with cations as counter ions. The eleetronic conductivity originates Irom partial oxidation of conjugated jt-bonds. The positive charge... 

In the past three decades, several types of r-electron systems have shown very interesting features in electrical transport properties [1-4]. Charge-transfer complexes, intercalated graphite, conjugated polymers, carbon-60, carbon nanotubes, etc., are some of the well-known r-electron systems. Polymeric materials were considered as insulators before the discovery of metallic poly(sulfur nitride), [SN],, and the enhancement of conductivity in doped poly acetylene, (CH),, by several orders of magnitude [4, 5]. 

An alternative to in situ polymerization involves direct intercalation of macromolecules into layered structures. Silicates are most often used. The insertion of polymer molecules into layered host lattices is of interest from different points of view. First, this insertion process leads to the construction of organic-inorganic polylayered composites. Second, the intercalation physical chemistry by itself and the role intercalation plays in the gain of electronic conductivity are of interest. This becomes important in the construction of reversible electrodes " or when improving the physicomechanical properties of nylon-layered silicate nanocomposites, hybrid epoxide clay composites," and nanomaterials based on hectorite and polyaniline, polythiophene or polypyrrole. ... 

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