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Influence of the electrolyte cation and anion sizes on the redox process of PPy/PVS films in acetonitrile solution

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Abstract

Polypyrrole/poly(vinyl sulfonate) (PPy/PVS) films have been synthesized by a potentiodynamic method in aqueous solution. The voltammetric study of this polymer in acetonitrile (MeCN) reveals an anomalous behavior of its redox process in the three electrolytes used: LiClO4, LiF3CSO3, and (Bu)4NClO4. The anion and cation sizes of the electrolyte clearly affect the reduction/oxidation process of a PPy/PVS film in MeCN medium. This result is explained by both anions and cations participating during the redox reaction of this polymer in MeCN medium: initially, the cations penetrate the polymer forming ion pairs with sulfonate groups, and the anions behave as the main mobile species during the potential sweeps. However, a large cation or anion will penetrate with difficulty inside the polymer, providing a lower amount of electroactive polymeric chains and a lower value of peak charges.

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Acknowledgements

The authors would like to thank Dr. I. Ibarra and Mr. L.A. Alcolea from the Technological Instrumentation Service of the UPCT for their technical assistance in the EDX measurements. We also thank the financial support from the Spanish government and from the Seneca Foundation.

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Authors and Affiliations

  1. Área de Química Física, Universidad Politécnica de Cartagena, Campus de Alfonso XIII, 30203, Cartagena, Spain

    Pilar Pérez Mañogil & Antonio J. Fernández Romero

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  1. Pilar Pérez Mañogil
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  2. Antonio J. Fernández Romero
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Correspondence to Antonio J. Fernández Romero.

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Pérez Mañogil, P., Fernández Romero, A.J. Influence of the electrolyte cation and anion sizes on the redox process of PPy/PVS films in acetonitrile solution. J Solid State Electrochem 14, 841–849 (2010). https://doi.org/10.1007/s10008-009-0863-9

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  • DOI: https://doi.org/10.1007/s10008-009-0863-9

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