摘要: Aniline-based polymers represent promising anion-hosting cathode materials for multivalent-ion batteries that hold great promise for next generation renewable electrochemical energy storage. However, aniline-based polymer cathodes face a fundamental challenge in simultaneously achieving high power and long cycle life due to their densely packed polymer chains and pH-sensitive -NH- groups. Herein, we employ a tertiary arylamine as the building block to construct a highly crosslinked poly(triphenylamine) (HCTPA) cathode for both rechargeable Zn batteries (RZDIBs) and Al batteries (RADIBs). The tertiary arylamine structure confers enhanced stability to the p-type doping reaction of HCTPA. Furthermore, the highly crosslinked framework ensures intrinsic insolubility in electrolytes, while the porous architecture provides ample space for anion storage. As a result of these synergistic advantages, HCTPA displays excellent cycle stability, sustaining over 20,000 cycles in RZDIBs. Moreover, the crosslinked skeleton endows HCTPA with an ultrahigh specific surface area of 1752 m² g^-1, which not only exposes abundant electrochemically active sites but also shortens the diffusion pathways of charge carriers. Consequently, HCTPA cathode in RZDIBs can deliver a high specific capacity of 110.2 mAh g^-1 at 0.5 C and an exceptional rate capability of 68.0 mAh g^-1 at an ultrahigh current rate of 300 C, significantly outperforming its linear polymer counterpart. Notably, this superior electrochemical performance can be also extended to RADIBs, underscoring the general efficacy of the crosslinked porous architecture in designing high-performance aniline-based cathodes for multivalent batteries.