共轭微孔聚合物由于其高的比表面积、优良的物理化学稳定性以及沿分子链延伸的共轭结构等特点,使其在锂离子电池电极材料方面具有巨大的应用前景.本工作以四溴芘和对苯二硼酸为构建单元,通过Suzuki偶联反应合成了具有高比表面积的芘基...共轭微孔聚合物由于其高的比表面积、优良的物理化学稳定性以及沿分子链延伸的共轭结构等特点,使其在锂离子电池电极材料方面具有巨大的应用前景.本工作以四溴芘和对苯二硼酸为构建单元,通过Suzuki偶联反应合成了具有高比表面积的芘基共轭微孔聚合物Py DB,并研究了其作为锂离子电池电极材料的电化学性能.当Py DB用作锂离子电池正极材料时,在50 m A·g^(-1)的电流密度下,放电容量达到163 m Ah·g^(-1),即使在3000 m A·g^(-1)的电流密度下仍具有62 m Ah·g^(-1)的可逆容量,在100 m A·g^(-1)的电流密度下循环300次仍具有167 m Ah·g^(-1)的容量.当该聚合物用作负极材料时,在50 m A·g^(-1)电流密度下的放电容量达到495 m Ah·g^(-1),在200 m A·g^(-1)的电流密度下循环300次,仍具有245m Ah·g^(-1)的容量.PyDB优异的电化学性能主要归因于其延伸的共轭结构和高比表面积的多孔结构,大的共轭结构有利于分子链的掺杂反应和电子传导,高比表面积的多孔结构有利于提供大量的活性位点并促进离子的迁移.展开更多
Na-ion batteries(NIBs)have attracted considerable attention in recent years owing to the high abundance and low cost of Na.It is well known that S doping can improve the electrochemical performance of carbon materials...Na-ion batteries(NIBs)have attracted considerable attention in recent years owing to the high abundance and low cost of Na.It is well known that S doping can improve the electrochemical performance of carbon materials for NIBs.However,the current methods for S doping in carbons normally involve toxic precursors or rigorous conditions.In this work,we report a creative and facile strategy for preparing S-doped porous carbons(SCs)via the pyrolysis of conjugated microporous polymers(CMPs).Briefly,thiophene-based CMPs served as the precursors and doping sources simultaneously.Simple direct carbonization of CMPs produced S-doped carbon materials with highly porous structures.When used as an anode for NIBs,the SCs exhibited a high reversible capacity of 440 mAh g?1 at 50 mA g?1 after 100 cycles,superior rate capability,and excellent cycling stability(297 mAh g?1 after 1000 cycles at 500 mA g?1),outperforming most S-doped carbon materials reported thus far.The excellent performance of the SCs is attributed to the expanded lattice distance after S doping.Furthermore,we employed ex situ X-ray photoelectron spectroscopy to investigate the electrochemical reaction mechanism of the SCs during sodiation-desodiation,which can highlight the role of doped S for Na-ion storage.展开更多
以2,2',7,7'-四频哪醇硼酸酯-9,9'-螺二芴、1,4-苯二硼酸和4,4'-二溴偶氮苯为聚合物中间体,采用钯催化的Suzuki-Miyaura偶联反应制备了2种含偶氮苯结构的共轭微孔聚合物Azo-SBF和Azo-PH,对聚合物的结构进行了表征,并研...以2,2',7,7'-四频哪醇硼酸酯-9,9'-螺二芴、1,4-苯二硼酸和4,4'-二溴偶氮苯为聚合物中间体,采用钯催化的Suzuki-Miyaura偶联反应制备了2种含偶氮苯结构的共轭微孔聚合物Azo-SBF和Azo-PH,对聚合物的结构进行了表征,并研究了调节构筑单元后共轭微孔聚合物作为正极材料的聚合物的锂离子电池性能。结果表明,2种聚合物Azo-PH和Azo-SBF的BET比表面积分别为113 m2·g-1和446 m2·g-1,热力学分解温度均超过了400℃;100 m A·g-1的电流密度下对聚合物锂离子电池充放电特性测试表明,相比Azo-PH,Azo-SBF电极展现出10.226 m A·h·g-1的初始充电比容量和稳健的循环稳定性,800次充放电循环后,Azo-SBF仍然展现出9.333 m A·h·g-1的放电比容量。展开更多
文摘共轭微孔聚合物由于其高的比表面积、优良的物理化学稳定性以及沿分子链延伸的共轭结构等特点,使其在锂离子电池电极材料方面具有巨大的应用前景.本工作以四溴芘和对苯二硼酸为构建单元,通过Suzuki偶联反应合成了具有高比表面积的芘基共轭微孔聚合物Py DB,并研究了其作为锂离子电池电极材料的电化学性能.当Py DB用作锂离子电池正极材料时,在50 m A·g^(-1)的电流密度下,放电容量达到163 m Ah·g^(-1),即使在3000 m A·g^(-1)的电流密度下仍具有62 m Ah·g^(-1)的可逆容量,在100 m A·g^(-1)的电流密度下循环300次仍具有167 m Ah·g^(-1)的容量.当该聚合物用作负极材料时,在50 m A·g^(-1)电流密度下的放电容量达到495 m Ah·g^(-1),在200 m A·g^(-1)的电流密度下循环300次,仍具有245m Ah·g^(-1)的容量.PyDB优异的电化学性能主要归因于其延伸的共轭结构和高比表面积的多孔结构,大的共轭结构有利于分子链的掺杂反应和电子传导,高比表面积的多孔结构有利于提供大量的活性位点并促进离子的迁移.
基金Financial support from National Natural Science Foundation of China(Nos.51702056 and 51772135)the Ministry of Education of China(6141A02022516)China Postdoctoral Science Foundation(2017M622902 and 2019T120790).
文摘Na-ion batteries(NIBs)have attracted considerable attention in recent years owing to the high abundance and low cost of Na.It is well known that S doping can improve the electrochemical performance of carbon materials for NIBs.However,the current methods for S doping in carbons normally involve toxic precursors or rigorous conditions.In this work,we report a creative and facile strategy for preparing S-doped porous carbons(SCs)via the pyrolysis of conjugated microporous polymers(CMPs).Briefly,thiophene-based CMPs served as the precursors and doping sources simultaneously.Simple direct carbonization of CMPs produced S-doped carbon materials with highly porous structures.When used as an anode for NIBs,the SCs exhibited a high reversible capacity of 440 mAh g?1 at 50 mA g?1 after 100 cycles,superior rate capability,and excellent cycling stability(297 mAh g?1 after 1000 cycles at 500 mA g?1),outperforming most S-doped carbon materials reported thus far.The excellent performance of the SCs is attributed to the expanded lattice distance after S doping.Furthermore,we employed ex situ X-ray photoelectron spectroscopy to investigate the electrochemical reaction mechanism of the SCs during sodiation-desodiation,which can highlight the role of doped S for Na-ion storage.
基金国家自然科学基金项目(21922814,22138012,21961160745,21921005,22178349,22078333,22108281,31961133019)中国科学院青年创新促进会优秀会员(Y202014)山东能源研究所(Grant Number SEI I202133)资助
文摘以2,2',7,7'-四频哪醇硼酸酯-9,9'-螺二芴、1,4-苯二硼酸和4,4'-二溴偶氮苯为聚合物中间体,采用钯催化的Suzuki-Miyaura偶联反应制备了2种含偶氮苯结构的共轭微孔聚合物Azo-SBF和Azo-PH,对聚合物的结构进行了表征,并研究了调节构筑单元后共轭微孔聚合物作为正极材料的聚合物的锂离子电池性能。结果表明,2种聚合物Azo-PH和Azo-SBF的BET比表面积分别为113 m2·g-1和446 m2·g-1,热力学分解温度均超过了400℃;100 m A·g-1的电流密度下对聚合物锂离子电池充放电特性测试表明,相比Azo-PH,Azo-SBF电极展现出10.226 m A·h·g-1的初始充电比容量和稳健的循环稳定性,800次充放电循环后,Azo-SBF仍然展现出9.333 m A·h·g-1的放电比容量。
