Hierarchically Porous Polyaniline Exhibiting Enhanced Pseudocapacitive Property from Copolymerization of Aniline and Tetrakis(4-aminophenyl)methane

Abstract

Hierarchically porous polyaniline (PANI) was synthesized by oxidative copolymerization of tetrakis(4-aminophenyl)methane (TA) and aniline. Mixing TA with ammonium persulfate (APS) followed by aniline addition generated both tetra-arm star-shaped and linear PANIs; their insolubility in the reaction medium led to aggregation into solid precipitates. During assembly, linear PANI formed nanofibers, while star-shaped PANI created short branches on the nanofiber surfaces. The TA molar fraction in the feed governed morphology and properties: higher TA increased specific surface area and the mesopore fraction but decreased electrical conductivity. Balancing this porosity–conductivity trade-off identified PANI (TA 3%) as optimal, exhibiting the highest CV current response with pseudocapacitive profiles, with a specific capacitance of 556 F g−1 versus 380 F g−1 for pristine PANI. Device-level galvanostatic charge–discharge yielded 239 F g−1 at 0.1 A g−1 (vs. 199 F g−1), while high-rate performance was limited by conductivity. These results show that introducing a small comonomer fraction to promote star-chain growth can produce hierarchical porosity and enhance pseudocapacitive behavior; further conductivity enhancement is expected to improve high-rate capacitance. © 2025 by the authors.