Lithium-sulfur (Li-S) batteries show great potential to achieve high-density energy storage, but their commercial application is severely hindered by the notorious shuttling effect of lithium polysulfides (LiPS) and their sluggish conversion kinetics. Herein, we develop a Quasi Zr-based metal–organic frameworks with the tritopic carboxylate ligand 1,3,5-tris(4-carboxyphenyl)benzene (BTB) microflowers with cross-linked CNTs (Q-Zr-BTB@CNTs). The deficiency of Zr-O coordination at the Zr₆ node is realized via a control of the deligandation behavior, which subtly modulates the local environment and electronic structure towards enhanced chemical affinity to polysulfides. Meanwhile, the interweave of the ultrathin Q-Zr-BTB nanosheets and CNTs establishes a porous and conductive network for fast charge transfer as well as a vast exposure of active interfaces. As a result, such a combination of defect engineering and architecture construction imposes strong sulfur adsorption and catalyzation, endowing the S/Q-Zr-BTB@CNTs cathode with a high initial capacity (1130 mAh g⁻¹ at 0.2 C) and an excellent cycling stability (500 cycles at 1 C with 0.05% decay per cycle), as well as a decent electrochemical performance even under a high sulfur loading up to 12.7 mg cm⁻². This study provides a novel strategy of designing unsaturated coordination centers to boost sulfur catalysis for high-performance lithium sulfur batteries.

锂硫（Li-S）电池显示出实现高密度储能的巨大潜力，但其商业应用受到多硫化锂（LiPS）臭名昭著的穿梭效应及其缓慢的转换动力学的严重阻碍。在此，我们开发了一种具有三位羧酸配体1,3,5-三（4-羧基苯基）苯（BTB）微花和交联碳纳米管（Q-Zr-BTB@CNTs）的准锆基金属有机框架。_{Zr 6}位点Zr-O配位缺陷节点是通过控制脱配位行为来实现的，该行为巧妙地调节局部环境和电子结构，以增强对多硫化物的化学亲和力。同时，超薄 Q-Zr-BTB 纳米片和 CNT 的交织建立了多孔导电网络，可实现快速电荷传输以及大量活性界面的暴露。因此，这种缺陷工程和结构构造的结合产生了强硫吸附和催化作用，赋予S/Q-Zr-BTB@CNTs正极高初始容量（0.2 C下1130 mAh g -1 ）和优异的^性能。循环稳定性（1 C 下 500 次循环，每次循环衰减 0.05%），即使在高达 12.7 mg cm -2 的高硫负载下也具有良好的电化学^性能。这项研究提供了一种设计不饱和配位中心以增强高性能锂硫电池的硫催化作用的新策略。