Synergistic π‐Conjugation Organic Cathode for Ultra‐Stable Aqueous Aluminum Batteries

Abstract Rechargeable aqueous aluminum batteries (AABs) are promising energy storage technologies owing to their high safety and ultra‐high energy‐to‐price ratio. However, either the strong electrostatic forces between high‐charge‐density Al 3+ and host lattice, or sluggish large carrier‐ion diffusion toward the conventional inorganic cathodes generates inferior cycling stability and low rate‐capacity. To overcome these inherent confinements, a series of promising redox‐active organic materials (ROMs) are investigated and a π ‐conjugated structure ROMs with synergistic C═O and C═N groups is optimized as the new cathode in AABs. Benefiting from the joint utilization of multi‐redox centers and rich π–π intermolecular interactions, the optimized ROMs with unique ion coordination storage mechanism facilely accommodate complex active ions with mitigated coulombic repulsion and robust lattice structure, which is further validated via theoretical simulations. Thus, the cathode achieves enhanced rate performance (153.9 mAh g −1 at 2.0 A g −1 ) and one of the best long‐term stabilities (125.7 mAh g −1 after 4,000 cycles at 1.0 A g −1 ) in AABs. Via molecular exploitation, this work paves the new direction toward high‐performance cathode materials in aqueous multivalent‐ion battery systems.