Phenoxazine Polymer‐based p‐type Positive Electrode for Aluminum‐ion Batteries with Ultra‐long Cycle Life

Abstract Aluminum‐ion batteries (AIBs) are a promising candidate for large‐scale energy storage due to the abundant reserves, low cost, good safety, and high theoretical capacity of Al. However, AIBs with inorganic positive electrodes still suffer from sluggish kinetics and structural collapse upon cycling. Herein, we propose a novel p‐type poly(vinylbenzyl‐N‐phenoxazine) (PVBPX) positive electrode for AIBs. The dual active sites enable PVBPX to deliver a high capacity of 133 mAh g −1 at 0.2 A g −1 . More impressively, the expanded π‐conjugated construction, insolubility, and anionic redox chemistry without bond rearrangement of PVBPX for AIBs contribute to an amazing ultra‐long lifetime of 50000 cycles. The charge storage mechanism is that the AlCl 4 − ions can reversibly coordinate/dissociate with the N and O sites in PVBPX sequentially, which is evidenced by both experimental and theoretical results. These findings establish a foundation to advance organic AIBs for large‐scale energy storage.