Exchange of counter anions in electropolymerized polyaniline films

Mobile counter anion exchange of electropolymerized polyaniline (PANI) films with the anions in acid solutions has been investigated by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), scanning electron microscopy, Raman, UV-vis, and fluorescence spectra. The studied acids include camphorsulfonic acid, p-toluene sulfonic acid, HCl, HClO₄, H₂SO₄ and H₃PO₄. In two cases of small and large counter ions of PANI films, CV tests have been performed alternately three times in each of two electrolytes containing organic or inorganic acid. The investigation of electrochemical and spectrophotometric measurements reveals that large counter anions can be easily replaced by the small anions; and the reverse exchange also occurs, but shows very low efficiency. This indicates that the achieved anion exchange in both cases leads to the remarkable alteration in electrochemical behavior and electrical conductance of PANI films. This implies counter anions, whatever the original or redoping ones, play an important role in the electrical, electrochemical, even optical properties of PANI. However, the polymer morphology does not be changed after exchange tests. This allows us to point out a ‘morphology-memory’ effect which is very significant for the development and application of PANI films with the same morphology and different properties.