A Photoelectronic‐Triggered Defect‐Induced Local Charge Separation Strategy for Promoting Bidirectional Sulfur Redox Kinetics in Lithium‐Sulfur Batteries

Abstract Photo‐assisted strategies have demonstrated compelling prospects for addressing critical challenges of polysulfides shuttle and sluggish reaction kinetics in lithium‐sulfur batteries (LSBs), but a spatial shielding effect is inevitable to impede bidirectional redox kinetics of polysulfides with conventional heterojunction photoelectrodes. Herein, a local charge separation strategy enhanced by photoelectronic effect is developed with titanium‐vacancy defective TiO ₂ (Tiv‐TiO ₂ ) photoelectrodes for enhancing surface potentials, promoting photogenerated electron/hole separation, and optimizing bidirectional sulfur redox kinetics in photo‐assisted LSBs (PA‐LSBs). Therefore, the chemical interactions of Tiv‐TiO ₂ with polysulfides are intensified, significantly lowering lithiation/delithiation energy barriers and mitigating the shuttle effect. The resulting PA‐LSBs achieve an exceptional cyclability of a minimal capacity decay rate of 0.056% per cycle over 400 cycles at 2C under light irradiation. This work not only provides rational designs of high‐adsorption and fast‐kinetic catalysts in PA‐LSBs, but also highlights the transformative potential of light‐energy coupling in advancing next‐generation energy storage technologies.