羟基COF的合成及作为锂硫电池正极材料(硫载体)的应用  

Covalent Organic Framework Materials as Cathode Sulfur Carriers for Lithium-sulfur Batteries

作　　者：石元昊 李智琪 付玉林 桂雪峰 许凯[1,2] SHI Yuanhao;LI Zhiqi;FU Yunlin;GUI Xuefeng;XU Kai(Guangzhou Institute of Chemistry,Chinese Academy of Sciences,Guangzhou 510650,China;University of Chinese Academy of Sciences,Beijing 100049,China;CAS Engineering Laboratory for Special Fine Chemicals,Guangzhou 510650,China;CASH GCC Shaoguan Research Institute of Advanced Materials,Shaoguan 512400,China;CASH GCC Fine Chemicals Incubator(Nanxiong)Co.,Ltd,Nanxiong 512400,China)

机构地区：[1]中国科学院广州化学研究所,广东广州510650 [2]中国科学院大学,北京101408 [3]中国科学院新型特种精细化学品工程实验室,广东广州510650 [4]国科广化韶关新材料研究院,广东韶关512400 [5]国科广化(南雄)新材料研究院有限公司,广东南雄512400

出　　处：《广州化学》2025年第1期51-55,I0003,共6页Guangzhou Chemistry

基　　金：中国科学院科技服务网络计划(No.20211600200052)。

摘　　要：用含醛基的三官能度的2,4,6-三甲酰间苯三酚(TP)和含胺基双官能度的4,4'-二氨基-[1,1'-联苯]-3,3'-二醇(DBD)通过席夫碱反应得到羟基化的共价有机框架材料(OH-COF),将含OH-COF材料作为锂硫正极的硫载体,利用熔融法制备了一种具有良好性能的硫正极材料。用傅里叶红外光谱(FTIR)和比表面积测试(BET)表征了OH-COF的结构,用紫外紫外可见分光光度计(UV)测试了OH-COF对多硫化的吸附能力,采用倍率测试和长循环测试评价OH-COF/S正极的电化学性能。结果表明,OH-COF较高的比表面和-OH结构可以吸附多硫化锂、抑制穿梭效应,同时OH-COF结构中的含氧基团也可以为Li^(+)在正极的迁移提高位点,使电池性能有明显提高。这种基于OH-COF的正极材料的锂硫电池在0.5 C倍率下经过100圈的循环后,电池可以保持660.1 mAh/g比容量,其容量保持率可达64.2%。A hydroxylated covalent organic framework material(OH-COF)was obtained from trifunctional 2,4,6-tricarbonylresorcinol(TP)containing aldehyde group and amine-based bifunctional 4,4'-diamino-[1,1'-biphenyl]-3,3'-diol(DBD)containing amine group by Schiff base reaction,and a covalent organic framework material(OH-COF)with hydroxylated OH-COF containing material was used as a sulphur carrier for lithium-sulphur cathodes,which was prepared using the melting method with a sulfur cathode material with good performance.The structure of OH-COF was characterized by BET and FTIR,and the adsorption capacity of OH-COF for polysulfides was tested by UV-Vis spectrophotometer.The electrochemical performance of OH-COF/S cathode was evaluated by rate test and long cycle test.The results showed that the high specific surface area and-OH structure of OH-COF can adsorb lithium polysulfides and suppress the shuttle effect.Meanwhile the oxygen-containing groups in OH-COF structure can also provide sites for the migration of Li^(+)in the cathode,which significantly improved the battery performance.The lithium-sulfur battery based on OHCOF cathode material could maintain a specific capacity of 660.1 mAh/g after 100 cycles at 0.5 C and its capacity retention rate can reach 64.2%.

关 键 词：锂硫电池 硫载体材料 共价有机框架材料 穿梭效应 高比表面积 

分 类 号：TQ314[化学工程—高聚物工业]