Electrochemical cells polymer films

When one tries to determine the structure of the materials, the undoping should be done as thoroughly as possible in order not to involve any impurities which may smear the spectral features characteristic of each polymer species. The structural and specfroscopic features of the doped form are then referred to the undoped (pristine) form. For this, the electrochemically synthesized polymer films are reduced either electrochemically [30] (cathode reduction) or chemically. The former method is carried out by reversing the polarity of the electrochemical cell after electrochemical synthesis of the polymer, the latter method being imdertaken by exposing the as-synthesized films to a reductant such as ammonia [31]. Hotta et al. [32,33], however, have pointed out that for the purpose of rigorous undoping,... 

The changes in the optical absorption spectra of conducting polymers can be monitored using optoelectrochemical techniques. The optical spectmm of a thin polymer film, mounted on a transparent electrode, such as indium tin oxide (ITO) coated glass, is recorded. The cell is fitted with a counter and reference electrode so that the potential at the polymer-coated electrode can be controlled electrochemically. The absorption spectmm is recorded as a function of electrode potential, and the evolution of the polymer s band stmcture can be observed as it changes from insulating to conducting (11). 

A second major event in the saga of polymer conductors was the discovery that the doping processes of polyacetylene could be promoted and driven electrochemically in a reversible fashion by polarising the polymer film electrode in a suitable electrochemical cell (MacDiarmid and Maxfield, 1987). Typically, a three-electrode cell, containing the (CH) film as the working electrode, a suitable electrolyte (e.g. a non-aqueous solution of lithium perchlorate in propylene carbonate, here abbreviated to LiC104-PC) and suitable counter (e.g. lithium metal) and reference (e.g. again Li) electrodes, can be used. 

Once deposited as conductive films, the heterocyclic polymers can be repeatedly cycled from the undoped to the doped forms (and vice versa) in electrochemical cells substantially similar to those used for the electropolymerisation reactions. 

In addition to the criticisms from Anderman, a further challenge to the application of SPEs comes from their interfacial contact with the electrode materials, which presents a far more severe problem to the ion transport than the bulk ion conduction does. In liquid electrolytes, the electrodes are well wetted and soaked, so that the electrode/electrolyte interface is well extended into the porosity structure of the electrode hence, the ion path is little affected by the tortuosity of the electrode materials. However, the solid nature of the polymer would make it impossible to fill these voids with SPEs that would have been accessible to the liquid electrolytes, even if the polymer film is cast on the electrode surface from a solution. Hence, the actual area of the interface could be close to the geometric area of the electrode, that is, only a fraction of the actual surface area. The high interfacial impedance frequently encountered in the electrochemical characterization of SPEs should originate at least partially from this reduced surface contact between electrode and electrolyte. Since the porous structure is present in both electrodes in a lithium ion cell, the effect of interfacial impedances associated with SPEs would become more pronounced as compared with the case of lithium cells in which only the cathode material is porous. 

It usually takes place close to the melting temperature of the polymer when the pores collapse turning the porous ionically conductive polymer film into a nonporous insulating layer between the electrodes. At this temperature there is a significant increase in cell impedance and passage of current through the cell is restricted. This prevents further electrochemical activity in the cell, thereby shutting the cell down before an explosion can occur. 

Assume that a disk-shaped electrode (gold, platinum, carbon, etc.) has been coated with a Film of poly (vinyl ferrocene) (Table 13.2). This can be accomplished by dissolving the polymer in chloroform, applying a drop of the solution to the electrode surface, and allowing the solvent to evaporate. The electrochemistry of the resulting polymer film-coated electrode can be investigated using the same electrochemical cell and equipment as described in the previous example. 

Experiments have been done where the polymer film is grown on an electrode surface, doped, and then removed from the electrochemical cell and placed... 

Electric double layer forces between polyelectrolyte and non-polymer surfaces in aqueous media have also been studied very intensively [371,394,400-402]. The adhesion between polyelectrolyte surfaces could be reduced considerably by increasing the ionic strength of the medium [400]. Using an electrochemical cell and a gold coated tip, the adhesion between electroactive layer of p oly( vinyl-ferrocene) was controlled through the selective oxidation or reduction of the polymer films [401]. 

Figure 1 Schema of an electrochemical cell. The polymer is a film deposited on the metal working electrode.

---