Selenium-Anchored Chlorine Redox Chemistry in Aqueous Zinc Dual-Ion Batteries

Chlorine-based batteries with Cl⁰ to Cl⁻ redox reaction (ClRR) are promising for high-performance energy storage due to their high redox potential and large theoretical capacity. However, the inherent gas–liquid conversion feature of ClRR together with poor Cl fixation can cause Cl₂ leakage, reducing battery reversibility. Herein, we utilize a Se-based organic molecule, diphenyl diselenide (di-Ph-Se), as the Cl anchoring agent and realize an atomic level-Cl fixation through chalcogen-halogen coordinating chemistry. The promoted Cl fixation, with two oxidized Cl⁰ anchoring on a single Ph-Se, and the multivalence conversion of Se contribute to a six-electron conversion process with up to 507 mAh g⁻¹ and an average voltage of 1.51 V, as well as a high energy density of 665 Wh Kg⁻¹. Based on the superior reversibility of the developed di-Ph-Se electrode with ClRR, a remarkable rate performance (205 mAh g⁻¹ at 5 A g⁻¹) and cycling performance (capacity retention of 77.3 % after 500 cycles) are achieved. Significantly, the pouch cell delivers a record arealcapacity of up to 6.87 mAh cm⁻² and extraordinary self-discharge performance. This chalcogen-halogen coordination chemistry between the Se electrode and Cl provides a new insight for developing reversible and efficient batteries with halogen redox reactions. © 2023 Wiley-VCH GmbH.