Tandem Catalysis inside Double‐Shelled Nanocages with Separated and Tunable Atomic Catalyst Sites for High Performance Lithium‐Sulfur Batteries

Abstract Single‐atomic catalysts are effective in mitigating the shuttling effect and slow redox kinetics of lithium polysulfides (LiPSs) in lithium‐sulfur (Li‐S) batteries, but their ideal performance has yet to be achieved due to the multi‐step conversion of LiPSs requiring multifunctional active sites for tandem catalysis. Here double‐shelled nano‐cages (DSNCs) have been developed to address this challenge, featuring separated and tunable single‐atom sites as nano reactors that trigger tandem catalysis and promote the efficient electrochemical conversion of LiPSs. This enables high capacity and durable Li‐S batteries. The DSNCs, with inner Co‐N 4 and outer Zn‐N 4 sites (S/CoNC@ZnNC DSNCs), exhibit a high specific capacity of 1186 mAh g −1 at 1 C, along with a low capacity fading rate of 0.063% per cycle over 500 cycles. Even with a high sulfur loading (4.2 mg cm −2 ) and a low E/S ratio (6 µL mg −1 ), the cell displays excellent cycling stability. Moreover, the Li‐S pouch cells are capable of stable cycling for more than 160 cycles. These results demonstrate the feasibility of driving successive sulfur conversion reactions with separated active sites, and are expected to inspire further catalyst design for high performance Li−S batteries.