Establishing a Unified Light‐Driven Dual‐Electrode Strategy to Synchronize Interfacial Kinetics for Quasi‐Solid‐State Silicon‐Air Batteries

Abstract Silicon‐air batteries (SABs) suffer from severe kinetic mismatch between the sluggish Si oxidation and complex cathodic ORR, limiting practical output. Herein, a unified light‐driven dual‐electrode strategy is developed, enabling carrier‐specific interfacial enhancement: photogenerated holes in n‐type Si enable deep excitation‐shallow oxidation by lowering energy barriers and accelerating reaction, while photoelectrons in pTTh restructure surface electronic states to accelerate O 2 activation and intermediate conversion. Density functional theory (DFT) and multi‐dimensional characterizations confirm dynamic rate matching under illumination, improving the matching coefficient from 0.69 to 0.90. The cable‐type quasi‐solid‐state SAB shows a 50.6% increase in discharge voltage and over 225% boost in power density, maintaining stable output under wide‐temperature and flexible conditions. This work establishes a general paradigm of light‐driven dynamic kinetic matching for resolving interfacial asymmetry in dual‐electrode energy systems.