Lv Sen, Ma Xingkai, Ke Siwen, Wang Yaoda, Ma Tianrui, Yuan Shuai, Jin Zhong, Zuo Jing-Lin
State Key Laboratory of Coordination Chemistry, MOE Key Laboratory of Mesoscopic Chemistry, MOE Key Laboratory of High Performance Polymer Materials and Technology, Jiangsu Key Laboratory of Advanced Organic Materials, Tianchang New Materials and Energy Technology Research Center, Institute of Green Chemistry and Engineering, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China.
J Am Chem Soc. 2024 Apr 3;146(13):9385-9394. doi: 10.1021/jacs.4c01620. Epub 2024 Mar 21.
The shuttling of polysulfides on the cathode and the uncontrollable growth of lithium dendrites on the anode have restricted the practical application of lithium-sulfur (Li-S) batteries. In this study, a metal-coordinated 3D covalent organic framework (COF) with a homogeneous distribution of nickel-bis(dithiolene) and N-rich triazine centers (namely, NiS-TAPT) was designed and synthesized, which can serve as bifunctional hosts for both sulfur cathodes and lithium anodes in Li-S batteries. The abundant Ni centers and N-sites in NiS-TAPT can greatly enhance the adsorption and conversion of the polysulfides. Meanwhile, the presence of Ni-bis(dithiolene) centers enables uniform Li nucleation at the Li anode, thereby suppressing the growth of Li dendrites. This work demonstrated the effectiveness of integrating catalytic and adsorption sites to optimize the chemical interactions between host materials and redox-active intermediates, potentially facilitating the rational design of metal-coordinated COF materials for high-performance secondary batteries.
多硫化物在阴极上的穿梭以及锂枝晶在阳极上的不可控生长限制了锂硫（Li-S）电池的实际应用。在本研究中，设计并合成了一种具有均匀分布的镍双（二硫烯）和富氮三嗪中心的金属配位三维共价有机框架（COF）（即NiS-TAPT），它可以作为Li-S电池中硫阴极和锂阳极的双功能主体。NiS-TAPT中丰富的镍中心和氮位点可以极大地增强多硫化物的吸附和转化。同时，镍双（二硫烯）中心的存在使锂阳极处锂均匀成核，从而抑制锂枝晶的生长。这项工作证明了整合催化和吸附位点以优化主体材料与氧化还原活性中间体之间化学相互作用的有效性，这可能有助于合理设计用于高性能二次电池的金属配位COF材料。
