Alveoli‐Inspired Carbon Cathodes with Interconnected Porous Structure and Asymmetric Coordinated Vanadium Sites for Superior Li‐S Batteries

Abstract Accelerating sulfur conversion catalysis to alleviate the shuttle effect has become a novel paradigm for effective Li−S batteries. Although nitrogen‐coordinated metal single‐atom (M−N 4 ) catalysts have been investigated, further optimizing its utilization rate and catalytic activities is urgently needed for practical applications. Inspired by the natural alveoli tissue with interconnected structure and well‐distributed enzyme catalytic sites on the wall for the simultaneously fast diffusion and in situ catalytic conversion of substrates, here, we proposed the controllable synthesis of bioinspired carbon cathode with interconnected porous structure and asymmetric coordinated V−S 1 N 3 sites for efficient and stable Li−S batteries. The enzyme‐mimetic V−S 1 N 3 shows asymmetric electronic distribution and high tunability, therefore enhancing in situ polysulfide conversion activities. Experimental and theoretical results reveal that the high charge asymmetry degree and large atom radius of S in V−S 1 N 3 result in sloping adsorption for polysulfide, thereby exhibiting low thermodynamic energy barriers and long‐range stability (0.076 % decay over 600 cycles).