The advantage of highly structural designability endows high voltage p‐type organic cathode materials (OCMs) with great potential for high energy density via rational molecular design. In this study, we design an active‐site‐rich OCM (denoted as DPZ) featuring a high active‐to‐inactive group (A/I) ratio (twice as much as TPA) and weak intermolecular interactions. The two characteristics enable a remarkable theoretical capacity of 209.1 mAh g −1 and a high active site utilization rate of 96.2%. Benefiting from the high A/I ratio, DPZ delivers a high reversible capacity of 201.1 mAh g −1 at 0.1 A g −1 and maintains excellent rate capability with a capacity retention of 95.1% at 2 A g −1 relative to 0.1 A g −1 . This high capacity translates into a superior energy density of 652.3 Wh kg −1 based on the cathode mass. Furthermore, DPZ demonstrates exceptional cycling stability, with no capacity decay over 250 cycles at 0.1 A g −1 . Finally, comprehensive characterization analyses demonstrate that DPZ undergoes structural rearrangement during the charging process, where C–N + · partially rearranges to C═N + . This work presents a targeted molecular design strategy for high‐energy‐density OCMs in sodium metal batteries and contributes to a better understanding of the energy‐storage process in p‐type OCMs.
Liu et al. (Mon,) studied this question.