Conjugated Microporous Polymer‐Based Hierarchical Porous Cathode, Separator, and Anode for Next‐Generation All‐Organic Batteries

ABSTRACT Emerging technologies increasingly demand lithium‐ion batteries with high energy density, ultrafast charging, and long life. All‐organic batteries (AOBs), built from lightweight, tunable, and sustainable materials, are attracting growing interest as promising alternatives. Herein, we present a novel all‐hierarchical conjugated microporous polymer (CMP) battery (AHCB) featuring polytriphenylamine (PTPA)‐based hierarchical porous cathode, anode, and separator. The cathode (PTPAG) constructed from PTPA/reduced graphene oxide composites offers enhanced electronic conductivity and ion diffusion. The anode (PTAA) provides azobenzene‐based Li + ‐binding sites and accelerates charge transport and redox kinetics. The PTPA‐based nanofiber separator delivers high ionic conductivity and efficient mass transport through its hierarchical porous structure. Benefiting from their synergy, the AHCB delivers a high energy density of 220 Wh kg −1 and a remarkable power density of 26.5 kW kg −1 , requiring only 20 s to achieve ultrafast charging. At a high current density of 20 A g −1 (180 C), it still delivers 120 mAh g −1 and maintains 74% of initial capacity after 20,000 cycles. Notably, the assembled pouch cell shows excellent electrochemical properties and operates stably under mechanical stresses. This work highlights CMPs as a versatile platform for next‐generation fast‐charging and high‐energy‐density AOBs.