Spatiotemporal Coordination-Engineered Core–Shell Zeolitic Imidazolate Frameworks Enable Self-Adaptive Electrocatalyst Reconstruction and Self-Tandem Sulfur Conversion

Upon electrocatalysts being intertwined with lithium polysulfides (LiPSs) in lithium-sulfur (Li-S) batteries, the intricate relationship between the spatial landscape of electrocatalysts and the corresponding electrocatalytic performance necessitates elaborate elucidation. Consequently, leveraging specialized functions of different components and organizing their spatial arrangement culminate in the holistic integration of spatial-temporal specificity, facilitating both self-adaptive electrocatalyst reconstruction and self-tandem LiPSs conversion. Inspired by the responsiveness and molecular recognition in cell membranes, a pertinent morphological design paradigm is proposed, which features a universal core-shell structure with spatially heterogeneous components. Specifically, ionic Zn conducive to Li⁺ mobility and covalent Co conducive to LiPSs immobilization are conscripted to ameliorate LiPSs redox kinetics. By configuring their specific spatial organization within core-shell zeolite imidazolate frameworks, we elucidate the distinguished role of the spatial landscape of covalency-ionicity couplings in steering the pathway of temporal-specific active site reconstruction and manipulating the self-regulation of LiPSs distribution. Ascribed to the in situ reconstructed spatial landscape for self-tandem LiPSs conversion, wherein the Zn-N shell facilitates Li⁺ transport and the Co-(S)-Zn-(N) core contributes to bidirectional electrocatalysis of LiPSs, thus-derived Ah-level pouch cell maintains a stable cycling for 100 cycles at 1C. Additionally, with an electrolyte-to-sulfur ratio of 3.3 μL mg^-1 and a negative-to-positive capacity ratio of approximately 1.5, a high energy density of up to 374 W h kg_total^-1 is achieved. These findings highlight the spatial architectures of components in the design of heterogeneous electrocatalysts for advanced Li-S batteries.