Coordination Defect‐Induced Lewis Pairs in Metal−Organic Frameworks Boosted Sulfur Kinetics for Bifunctional Photo‐Assisted Li−S Batteries

Abstract The photo‐assisted strategy is regarded as a crucial approach to enhance the conversion kinetics of polysulfides in lithium–sulfur (Li–S) batteries. However, the development of photo‐assisted Li–S batteries still faces important challenges, such as the rapid recombination of photogenerated electron−holes on cathode and more severe shuttle effect. Herein, a breakthrough in overcoming the challenges has been made by constructing a promising photo‐assisted Li−S battery based on semiconducted metal−organic frameworks. During the discharging progress, the photoexcited electrons generated by H₂BPDC ligand based on ligand‐to‐metal charge transfer (LMCT) effect, are injected into the Ti‐oxo clusters in Ti‐MOF, thereby facilitating the sulfur reduction to Li₂S. And photoexcited holes are capable of promoting the decomposition kinetics of Li₂S during charging. More importantly, the stronger chemical interaction between Ti‐BPDC‐d and polysulfides under light inhibits the polysulfides dissolution and shuttling, which fundamentally addresses the issue of light‐accelerated shuttling. As a result, the photo‐assisted Li–S batteries deliver a reversible capability of 1090.21 mAh g⁻¹ at 0.2 C with a capacity retention of 82.91% over 150 cycles, and a superior rate capability of 673.58 mAh g⁻¹ at 5 C. The findings are promising in advancing the design principles for photo‐rechargeable Li−S batteries.