Redox-active “Structural Pillar” molecular doping strategy towards High-Performance polyaniline-based flexible supercapacitors

To coordinate flexibility to electrodes without sacrificing their electrochemical properties is critical for the development of wearable supercapacitors (SCs). Polyaniline (PANI) is well-known pseudocapacitive electrode material due to its high conductivity and different oxidation states upon switchable structures. However, its rigid conjugated backbone and structural instability caused by repeated doping/de-doping during cycling severely impede its utilization in flexible SCs. Herein, we deploy a directional freezing and redox-active "structural pillar" molecular doping strategy to boost PANI-based flexible SCs with high performance. The directional freezing strategy constructs an interconnected 3D honeycomb hydrogel structure with PANI nanofibers, which guarantees fast ion diffusion and electron transport and meanwhile exposes abundant active sites. The large-sized dopant 2-amino-4-bromoanthraquinone-2-sulfonic acid sodium (AQNS) is used as the structural pillar to alleviate the structural instability of PANI during cycling and provides additional pseudocapacitance arising from its redox active quinone groups. Moreover, the negatively charged −SO3− on AQNS can further interact with H+ in the electrolyte to act as an internal proton reservoir, assisting the protonation of –NH- and −N = in PANI to facilitate its charge storage process. Consequently, the PANI-AQNS electrode achieves a high specific capacitance of 578F g−1 at 1 A g−1 and its symmetric SCs exhibit a specific capacitance of 199F g−1 at 0.5 A g−1 with an energy density of 13.61 W h kg−1 at a power density of 175 W kg−1. Upon 2000 cycles of dynamic deformations, the SCs can still maintain above 90 % of the initial capacitance, verifying their excellent flexibility-relevant property.