Non-Substituted Imidazolium-Based Electrolytes as Potential Alternatives to the Conventional Acidic Electrolytes of Polyaniline-Based Electrode Materials for Supercapacitors.

Although disubstituted imidazolium cation is sterically crowded, hundreds of ionic liquids based on this cation have been reported as electrolytes for energy storage devices. In contrast to disubstituted imidazolium, non-substituted imidazolium is uncrowded sterically and has not yet been investigated as an electrolyte, to the best of our knowledge. Hence, imidazolium hydrogen sulfate [Imi][HSO4], in mixture with water, was studied as an electrolyte for PANI-based electrode materials. For comparison, pyrrolidinium with hydrogen sulfate or p-toluene sulfonate ([Pyrr][HSO4] or [Pyrr][PTS]), in mixture with water, were also investigated as alternatives to the conventional electrolyte (i.e., aqueous H2SO4) for PANI electrodes. Walden plots of binary mixture ionic liquid-water weight ratios with the optimal ionic conductivity (i.e., [Imi][HSO4]/water 48/52 wt% (195.1 mS/cm), [Pyrr][HSO4]/water 41/59 wt% (186.6 mS/cm), and [Pyrr][PTS]/water 48/52 wt% (43.4 mS/cm) along with the electrochemical performances of PANI in these binary mixtures showed that [Pyrr][HSO4]aq or [Imi][HSO4]aq are convenient electrolytes for PANI/PIL, as opposed to [Pyrr][PTS]aq. Furthermore, replacing the conventional aqueous electrolyte H2SO4 with [Imi][HSO4] aq increased the specific capacitance of PANI/PIL from 249.8 to 268.5 F/g at 15 mV/s. Moreover, PANI/PIL electrodes displayed a quasi-ideal capacitive behavior in [Imi][HSO4]aq (the correction factor of CPE4 was 0.99). This primary study has shown that non-substituted imidazolium as an electrolyte could enhance the electrochemical performances of PANI electrodes and could be a good alternative to the conventional electrolyte.

Enhanced Storage Performance of PANI and PANI/Graphene Composites Synthesized in Protic Ionic Liquids.

Polyaniline (PANI) was synthesized using oxidative polymerization in a mixture of water with pyrrolidinium hydrogen sulfate [Pyrr][HSO4], which is a protic ionic liquid PIL. The obtained PANI (PANI/PIL) was compared with conventional PANI (PANI/HCl and PANI/HSO4) in terms of their morphological, structural, and storage properties. The results demonstrate that the addition of this PIL to a polymerization medium leads to a fiber-like morphology, instead of a spherical-like morphology, of PANI/HSO4 or an agglomerated morphology of PANI/HCl. In addition, PAN/PIL exhibits an improvement of the charge transfer kinetic and storage capability in H2SO4 1 mol·L-1, compared to PANI/HCl. The combination of PANI/PIL and graphene oxide (GO), on the other hand, was investigated by optimizing the PANI/GO weight ratio to achieve the nanocomposite material with the best performance. Our results indicate that the PANI/PIL/GO containing 16 wt% of GO material exhibits a high performance and stability (223 F·g-1 at 10 A·g-1 in H2SO4 1 mol·L-1, 4.9 Wh·Kg-1, and 3700 W·Kg-1 @ 10 A·g-1). The obtained results highlight the beneficial role of PIL in building PANI and PANI/GO nanocomposites with excellent performances for supercapacitor applications.