▎ 摘　　要

The conducting polymer polyaniline (PANI) has been considered to be a promising pseudocapacitive electrode material for supercapacitors due to its high specific capacitance, low cost, and environmental friendliness. However, the poor cycling stability of PANI during the charge-discharge processes limits its widespread practical application. Herein, a facile synthetic method is demonstrated for covalently grafting an aniline tetramer (TANI), the basic building block of PANI, onto 3D graphene networks via perfluorophenylazide coupling chemistry to create a hybrid electrode material for ultralong-life supercapacitors. The design, which substitutes long-chain PANI with short-chain TANI and introduces covalent linkages between TANI and 3D graphene, greatly enhances the charge-discharge cycling stability of PANI-based supercapacitors. The electrode material, as well as the fabricated symmetric all-solid-state supercapacitors, exhibit extraordinary long cycle life (>85% capacitance retention after 30 000 charge-discharge cycles). The capacitance can be further boosted through fast and reversible redox reactions on the electrode surface using a redox-active electrolyte while maintaining outstanding cycling stability (82% capacitance retention after 100 000 cycles for a symmetric all-solid-state device). While conducting polymers are known to be limited by their poor cycling stability, this work provides an effective strategy to achieve enhanced cycle life for conducting polymer-based energy storage devices.