Complementary Weaknesses: A Win‐Win Approach for rGO/CdS to Improve the Energy Conversion Performance of Integrated Photorechargeable Li−S Batteries

Abstract Integrating solar energy into rechargeable battery systems represents a significant advancement towards sustainable energy storage solutions. Herein, we propose a win‐win solution to reduce the shuttle effect of polysulfide and improve the photocorrosion stability of CdS, thereby enhancing the energy conversion efficiency of rGO/CdS‐based photorechargeable integrated lithium‐sulfur batteries (PRLSBs). Experimental results show that CdS can effectively anchor polysulfide under sunlight irradiation for 20 minutes. Under a high current density (1 C), the discharge‐specific capacity of the PRLSBs increased to 971.30 mAh g −1 , which is 113.3 % enhancement compared to that of under dark condition (857.49 mAh g −1 ). Remarkably, without an electrical power supply, the PRLSBs can maintain a 21 hours discharge process following merely 1.5 hours of light irradiation, achieving a breakthrough solar‐to‐electrical energy conversion efficiency of up to 5.04 %. Ex situ X‐ray photoelectron spectroscopy (XPS) and in situ Raman analysis corroborate the effectiveness of this complementary weakness approach in bolstering redox kinetics and curtailing polysulfide dissolution in PRLSBs. This work showcases a feasible strategy to develop PRLSBs with potential dual‐functional metal sulfide photoelectrodes, which will be of great interest in future‐oriented off‐grid photocell systems.