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IONIC EXCHANGE OF A CONDUCTING-POLYMER FILM WITH THE SOLUTION DURING THE CYCLIC-VOLTAMMETRY PROCESSстатья
Информация о цитировании статьи получена из
Web of Science
Статья опубликована в журнале из списка Web of Science и/или Scopus
Дата последнего поиска статьи во внешних источниках: 29 мая 2015 г.
- Авторы: VOROTYNTSEV MA, VIEIL E., HEINZE J.
- Журнал: Russian Journal of Electrochemistry
- Том: 31
- Номер: 10
- Год издания: 1995
- Издательство: Maik Nauka/Interperiodica Publishing
- Местоположение издательства: Russian Federation
- Первая страница: 1027
- Последняя страница: 1035
- Аннотация: Two theoretical approaches to the interpretation of the EQCM data for the charging-discharging process in electron-conducting polymer film coated electrodes have been proposed, with their application to systems without attached charged groups or fixed charges. The first model treats cations and anions inside the polymer phase as ''free'' mobile species, whose exchange with the solution may be retarded due to low values of the interfacial exchange constants. Depending on its value for the anion transfer, three limiting regimes of the charging process have been found: (I)complete ionic equilibrium with the solution, (2) ''irreversible anion transfer'', and (3) ''cation compensation'', the electronic charge in the two former regimes being dominantly balanced by the counterion as opposed to the colon process taking place in the latter. Theoretical EQCM curves upon cyclic variation of the potential may possess a complicated shape, with a pronounced ''first cycle'' and ''relaxation'' effects as well as considerable hysteresis, the mass at the anodic scan being greater than that at the cathodic branch for the anion exchange constants between regimes 2 and 3. Another model proposes the existence of two different forms of ions inside the film - ''free'' and ''bound'' - with possible kinetic limitations for their mutual transformation but a complete equilibrium between the ''free'' ions and the solution. The corresponding theoretical EQCM plots demonstrate the great variety of shapes depending on the maximum amount and thermodynamical stability of ''bound'' species as well as on the kinetic exchange parameters. This model has made it possible to reproduce most of the features of experimental stabilized EQCM curves for PPy: nonmonotonic variation of the film mass (''coion'' type at low charges and ''counterion'' type at higher charges), with a drastic change in the mass versus charge slope at the cathodic scan and a flat extremum in the anodic branch as well as a lower mass at the cathodic scan at very low charges and a crossing point of the branches.
- Добавил в систему: Воротынцев Михаил Алексеевич