Kinetics‐Controlled Architecture of Binder‐Free Organic Electrodes for Enhanced Ion Transport

ABSTRACT Binder‐free organic electrodes offer a promising route toward efficient energy storage by eliminating inactive components and minimizing interfacial resistance; however, their performance is often limited by insufficient control over growth dynamics that govern morphology and ion transport. Here, a general electrochemical strategy is introduced to engineer binder‐free organic electrodes with controlled ionic accessibility by regulating deposition kinetics. Using pyrene‐derived interfaces formed via intramolecular electrochemical oxidative cyclodehydrogenation as a model system, pulse reverse electrodeposition enables dynamic interfacial reorganization, promoting homogeneous nucleation and the formation of hierarchically porous Py‐derived oligomeric films directly anchored to the current collector. Multiscale characterization combining AFM, SAXS, electron microscopy, and electrochemical transport analysis establishes a direct correlation between nucleation and growth dynamics, mesoscale architecture, and ion‐transport behavior. Pulse reverse synthesis yields architectures with enhanced ionic accessibility, reduced ionic transport resistance, and improved charge‐transfer characteristics, resulting in stable electrochemical performance. Direct Na‐ion half‐cell measurements further confirm reversible sodium‐storage activity in binder‐free electrodes together with mixed capacitive/diffusion‐controlled kinetics and good rate capability, validating the functionality of the kinetically engineered architecture. These findings establish a design principle for architected organic electrodes and provide a scalable route to engineer structure–transport relationships for sodium‐ion energy‐storage applications.