Influence of Acidity and Oxidant Concentration on the Nanostructures and Electrochemical Performance of Polyaniline during Fast Microwave-Assisted Chemical Polymerization.

Polyaniline (PANI), a typical conducting polymer, has attracted great interest as an electrode material. A series of PANIs were prepared through fast microwave-assisted chemical oxidative polymerization with varying HCl and APS concentrations here. It was found that the microwave synthesized PANIs had ~4 times higher for the yields and 7~10 times higher for the electrical conductivity in comparison to PANI samples prepared using conventional method. PANI nanosheets could easily be fabricated in weakly acidic solution due to their oligomeric structure, which contained flat phenazine rings. By contrast, linear PANI chains produced in highly acidic solutions formed nanofibers. The APS concentration did not significantly affect the molecular structures of PANIs under the conditions here. However, increasing the concentration of APS produced nanofibers with shorter branches, which may be due to secondary nucleation during chain growth resulting from increases in active initiation centers. The electrical conductivity and electrochemical performance of PANIs were both improved with increasing HCl and APS concentrations. Improvements due to increases in HCl concentration may be attributed to additions in conjugation length and enrichment of doping levels, while improvements due to increases in APS concentration could be attributed to the increased crystallinity of PANI, which facilitates ion transport.