14‐Electron Redox Chemistry Enabled by Salen‐Based π‐Conjugated Framework Polymer Boosting High‐Performance Lithium‐Ion Storage

Abstract A paucity of redox centers, poor charge transport properties, and low structural stability of organic materials obstruct their use in practical applications. Herein, these issues have been addressed through the use of a redox‐active salen‐based framework polymer (RSFP) containing multiple redox‐active centers in π‐conjugated configuration for applications in lithium‐ion batteries (LIBs). Based on its unique architecture, RSFP exhibits a superior reversible capacity of 671.8 mAh g⁻¹ at 0.05 A g⁻¹ after 168 charge‐discharge cycles. Importantly, the lithiation/de‐lithiation performance is enhanced during operation, leading to an unprecedented reversible capacity of 946.2 mAh g⁻¹ after 3500 cycles at 2 A g⁻¹. The structural evolution of RSFP is studied ex situ using X‐ray photoelectron spectroscopy, revealing multiple active C═N, C─O, and C═O sites and aromatic sites such as benzene rings. Remarkably, the emergence of C═O originated from C─O is triggered by an electrochemical process, which is beneficial for improving reversible lithiation/delithiation behavior. Furthermore, the respective strong and weak binding interactions between redox centers and lithium ions, corresponding to theoretical capacities of 670.1 and 938.2 mAh g⁻¹, have been identified by density functional theory calculations manifesting 14‐electron redox reactions. This work sheds new light on routes for the development of redox‐active organic materials for energy storage applications.