Intermolecular Hydrogen Bonding Networks Stabilized Organic Supramolecular Cathode for Ultra‐High Capacity and Ultra‐Long Cycle Life Rechargeable Aluminum Batteries

Abstract Rechargeable aluminum batteries (RABs) are a promising candidate for large‐scale energy storage, attributing to the abundant reserves, low cost, intrinsic safety, and high theoretical capacity of Al. However, the cathode materials reported thus far still face challenges such as limited capacity, sluggish kinetics, and undesirable cycle life. Herein, we propose an organic cathode benzo[i] benzo[6,7] quinoxalino [2,3‐a] benzo [6,7] quinoxalino [2,3‐c] phenazine‐5,8,13,16,21,24‐hexaone (BQQPH) for RABs. The six C=O and six C=N redox active sites in each molecule enable BQQPH to deliver a record ultra‐high capacity of 413 mAh g −1 at 0.2 A g −1 . Encouragingly, the intermolecular hydrogen bonding network and π–π stacking interactions endow BQQPH with robust structural stability and minimal solubility, enabling an ultra‐long lifetime of 100,000 cycles. Moreover, the electron‐withdrawing carbonyl group induces a reduction in the energy level of the lowest unoccupied molecular orbital and expands the π‐conjugated system, which considerably enhances both the discharge voltage and redox kinetics of BQQPH. In situ and ex situ characterizations combined with theoretical calculations unveil that the charge storage mechanism is reversible coordination/dissociation of AlCl 2 + with the N and O sites in BQQPH accompanied by 12‐electron transfer. This work provides valuable insights into the design of high‐performance organic cathode materials for RABs.