将杯[4]醌(Calix[4]quinone,C4Q)通过灌注法与有序介孔炭CMK-3制备成纳米复合材料,可抑制其在常规有机电解液中的溶解。为了进一步提升其电化学性能,本文在C4Q/CMK-3复合材料中加入单壁碳纳米管(SWCNTs),减少了CMK-3的用量,并代替导电炭...将杯[4]醌(Calix[4]quinone,C4Q)通过灌注法与有序介孔炭CMK-3制备成纳米复合材料,可抑制其在常规有机电解液中的溶解。为了进一步提升其电化学性能,本文在C4Q/CMK-3复合材料中加入单壁碳纳米管(SWCNTs),减少了CMK-3的用量,并代替导电炭黑Super-P作为导电剂,通过脱泡搅拌法制备了C4Q/CMK-3/SWCNTs复合材料。研究表明,当m(C4Q)∶m(CMK-3)∶m(SWCNTs)为1∶1∶1时,电化学性能最佳,0. 1 C电流密度下循环100圈后,电池的容量保持为238. 7 m A·h/g,当电流密度增大到1 C时,放电容量仍有260 m A·h/g,这是由于SWCNTs在复合材料C4Q/CMK-3中构建了三维导电网络,增强了电极的稳定性,降低了电池内阻,从而提升了电池的循环性能与倍率性能。展开更多
Organic quinone compounds have attracted wide attention due to their high theoretical capacities.Here,a novel cyclic macromolecular calix[6]quinone(C6Q),which possesses 6 p-quinone units and can provide 12 electrochem...Organic quinone compounds have attracted wide attention due to their high theoretical capacities.Here,a novel cyclic macromolecular calix[6]quinone(C6Q),which possesses 6 p-quinone units and can provide 12 electrochemical active sites,has been applied as a promising cathode material in lithium ion batteries(LIBs).The as-fabricated LIBs exhibited an initial specific capacity as high as 423 mA h g^-1(Ctheo=447 mA h g^-1)at 0.1 C.After 100 cycles,the capacity of C6Q maintained at 216 mA h g^-1,and even after 300 cycles,C6Q still achieved a high specific capacity of 195 mA h g^-1 with negligible capacity fading(as compared with the 100th cycle).Due to the large capacity and wide electrochemical window,C6Q can deliver a specific energy up to 1201 W h kg^-1.In addition,the method of immobilizing C6Q with ordered mesoporous carbon(OMC)CMK-3 could further enhance the electrochemical performance of C6Q.展开更多
Two crystals of receptor 1, C（42）H（52）N（10）O4S2（anthracene-9,10-dicarbaldehyde bis-（phenyl-semithiocarbazone）） and-1-H2PO4, C（68）H（114）N（10）O（10）P2S2 were obtained at room temperature successfully, a...Two crystals of receptor 1, C（42）H（52）N（10）O4S2（anthracene-9,10-dicarbaldehyde bis-（phenyl-semithiocarbazone）） and-1-H2PO4, C（68）H（114）N（10）O（10）P2S2 were obtained at room temperature successfully, and their structures were characterized by X-ray crystallography diffraction. X-ray diffraction reveals that, receptor 1 crystallizes in monoclinic, space group P21/c, with a = 9.487（3）,b = 20.674（6）, c = 11.821（4）A, β = 113.416（8）o, Mr = 825.06, V = 2127.5（12） A^3, Z = 2, Dc = 1.288g/cm^3, μ = 0.18 mm^-1, F（000） = 876, MoK α radiation（λ = 0.71073 A）, the final R = 0.0472 and wR = 0.0930. A total of 3758 unique reflections were collected, of which 3313 with I 〉 2σ（I） were observed. Compound 1-H2PO4^-crystallizes in triclinic, space group P21/n, with a = 8.767（1）, b =13.6190（15）, c = 16.615（2） ？, α = 98.727（14）, β = 103.061（14）, γ = 91.382（16）°, Mr = 1357.75, V =1906.6（4） A^3, Z = 1, Dc = 1.183 g/cm^3, μ = 0.17 mm-（-1）, F（000） = 734, MoK α radiation（λ = 0.71073？）, the final R = 0.0769 and wR = 0.1884. A total of 6699 unique reflections were collected, of which 2989 with I 〉 2σ（I） were observed. As it was observed in the crystal structure of 1-H2PO4^-, 1bound H2PO4^-at a 1：2 ratio by intermolecular interaction of N-H···O hydrogen bond obviously.Another interesting feature was that H2PO4--groups assembled chains themselves via intramolecular hydrogen bond O-H···O and connected the 1 molecules together through the interaction of H-bonds,which improved the planarity of 1 and increased the stability of the entire structure.展开更多
Organic lithium-ion batteries（OLIBs） represent a new generation of power storage approach for their environmental benignity and high theoretical specific capacities.However, it has the disadvantage with regard to th...Organic lithium-ion batteries（OLIBs） represent a new generation of power storage approach for their environmental benignity and high theoretical specific capacities.However, it has the disadvantage with regard to the dissolution of active materials in organic electrolyte. In this study, we encapsulated high capacity material calix[4]quinone（C4Q） in the nanochannels of ordered mesoporous carbon（OMC）CMK-3 with various mass ratios ranging from 1：3 to 3：1, and then systematically investigated their morphology and electrochemical properties. The nanocomposites characterizations confirmed that C4Q is almost entirely capsulated in the nanosized pores of the CMK-3 while the mass ratio is less than2：1. As cathodes in lithium-ion batteries, the C4Q/CMK-3（1：2） nanocomposite exhibits optimal initial discharge capacity of 427 mA h g^（-1） with 58.7% cycling retention after 100 cycles. Meanwhile, the rate performance is also optimized with a capacity of 170.4 mA h g^（-1） at 1 C. This method paves a new way to apply organic cathodes for lithium-ion batteries.展开更多
因具有高安全性和高性价比的优势,水系锌离子电池(AZIBs)成为了当前研究的热点.然而,电极材料溶解、固有电导率低、反应动力学慢等问题严重阻碍了其实际应用.在本文中,我们合成了一种在黑色素瘤治疗中发挥重要作用的含硫有机小分子(seri...因具有高安全性和高性价比的优势,水系锌离子电池(AZIBs)成为了当前研究的热点.然而,电极材料溶解、固有电导率低、反应动力学慢等问题严重阻碍了其实际应用.在本文中,我们合成了一种在黑色素瘤治疗中发挥重要作用的含硫有机小分子(seriniquinone,SQ),将其作为电极材料应用于锌离子电池.通过导电碳修饰的方法制备了SQ/CMK-3复合电极,进一步解决了活性物质SQ的溶解问题并提高了其导电性.在Zn||SQ/CMK-3半电池中,SQ/CMK-3正极在100 mA g^(−1)电流密度下的初始放电比容量达到234.4 mA h g^(−1).在1 A g^(−1)的高电流密度下经过5000次超长循环后,比容量仍保持100.2 mA h g^(−1).此外,通过密度泛函理论计算,我们提出了在两个SQ分子之间嵌入四个Zn^(2+)的储存机理,并通过多种非原位表征测试进行了证实.在采用SQ/CMK-3复合材料作为正负两极的全有机对称电池中,SQ不仅在100 mA g^(−1)的电流密度下获得高达110.9 mA h g^(−1)的可逆比容量,而且在循环2500次后具有82.4%的稳定容量保持率和99.5%的平均库仑效率.展开更多
文摘将杯[4]醌(Calix[4]quinone,C4Q)通过灌注法与有序介孔炭CMK-3制备成纳米复合材料,可抑制其在常规有机电解液中的溶解。为了进一步提升其电化学性能,本文在C4Q/CMK-3复合材料中加入单壁碳纳米管(SWCNTs),减少了CMK-3的用量,并代替导电炭黑Super-P作为导电剂,通过脱泡搅拌法制备了C4Q/CMK-3/SWCNTs复合材料。研究表明,当m(C4Q)∶m(CMK-3)∶m(SWCNTs)为1∶1∶1时,电化学性能最佳,0. 1 C电流密度下循环100圈后,电池的容量保持为238. 7 m A·h/g,当电流密度增大到1 C时,放电容量仍有260 m A·h/g,这是由于SWCNTs在复合材料C4Q/CMK-3中构建了三维导电网络,增强了电极的稳定性,降低了电池内阻,从而提升了电池的循环性能与倍率性能。
基金the financial support of the National Natural Science Foundation of China (21875206 and 21403187)China Postdoctoral Science Foundation (2015T80229)the Natural Science Foundation of Hebei Province (B2019203487)
文摘Organic quinone compounds have attracted wide attention due to their high theoretical capacities.Here,a novel cyclic macromolecular calix[6]quinone(C6Q),which possesses 6 p-quinone units and can provide 12 electrochemical active sites,has been applied as a promising cathode material in lithium ion batteries(LIBs).The as-fabricated LIBs exhibited an initial specific capacity as high as 423 mA h g^-1(Ctheo=447 mA h g^-1)at 0.1 C.After 100 cycles,the capacity of C6Q maintained at 216 mA h g^-1,and even after 300 cycles,C6Q still achieved a high specific capacity of 195 mA h g^-1 with negligible capacity fading(as compared with the 100th cycle).Due to the large capacity and wide electrochemical window,C6Q can deliver a specific energy up to 1201 W h kg^-1.In addition,the method of immobilizing C6Q with ordered mesoporous carbon(OMC)CMK-3 could further enhance the electrochemical performance of C6Q.
基金supported by the China Postdoctoral Science Foundation(No.2014M551053)Natural Science Foundation of Hebei Province(No.B2015203124)Key Laboratory of Advanced Energy Materials Chemistry(Ministry of Education),Nankai University
文摘Two crystals of receptor 1, C（42）H（52）N（10）O4S2（anthracene-9,10-dicarbaldehyde bis-（phenyl-semithiocarbazone）） and-1-H2PO4, C（68）H（114）N（10）O（10）P2S2 were obtained at room temperature successfully, and their structures were characterized by X-ray crystallography diffraction. X-ray diffraction reveals that, receptor 1 crystallizes in monoclinic, space group P21/c, with a = 9.487（3）,b = 20.674（6）, c = 11.821（4）A, β = 113.416（8）o, Mr = 825.06, V = 2127.5（12） A^3, Z = 2, Dc = 1.288g/cm^3, μ = 0.18 mm^-1, F（000） = 876, MoK α radiation（λ = 0.71073 A）, the final R = 0.0472 and wR = 0.0930. A total of 3758 unique reflections were collected, of which 3313 with I 〉 2σ（I） were observed. Compound 1-H2PO4^-crystallizes in triclinic, space group P21/n, with a = 8.767（1）, b =13.6190（15）, c = 16.615（2） ？, α = 98.727（14）, β = 103.061（14）, γ = 91.382（16）°, Mr = 1357.75, V =1906.6（4） A^3, Z = 1, Dc = 1.183 g/cm^3, μ = 0.17 mm-（-1）, F（000） = 734, MoK α radiation（λ = 0.71073？）, the final R = 0.0769 and wR = 0.1884. A total of 6699 unique reflections were collected, of which 2989 with I 〉 2σ（I） were observed. As it was observed in the crystal structure of 1-H2PO4^-, 1bound H2PO4^-at a 1：2 ratio by intermolecular interaction of N-H···O hydrogen bond obviously.Another interesting feature was that H2PO4--groups assembled chains themselves via intramolecular hydrogen bond O-H···O and connected the 1 molecules together through the interaction of H-bonds,which improved the planarity of 1 and increased the stability of the entire structure.
基金supported by the National Natural Science Foundation of China (21403187)the Natural Science Foundation of Hebei Province of China (B2015203124)the Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Nankai University
文摘Organic lithium-ion batteries（OLIBs） represent a new generation of power storage approach for their environmental benignity and high theoretical specific capacities.However, it has the disadvantage with regard to the dissolution of active materials in organic electrolyte. In this study, we encapsulated high capacity material calix[4]quinone（C4Q） in the nanochannels of ordered mesoporous carbon（OMC）CMK-3 with various mass ratios ranging from 1：3 to 3：1, and then systematically investigated their morphology and electrochemical properties. The nanocomposites characterizations confirmed that C4Q is almost entirely capsulated in the nanosized pores of the CMK-3 while the mass ratio is less than2：1. As cathodes in lithium-ion batteries, the C4Q/CMK-3（1：2） nanocomposite exhibits optimal initial discharge capacity of 427 mA h g^（-1） with 58.7% cycling retention after 100 cycles. Meanwhile, the rate performance is also optimized with a capacity of 170.4 mA h g^（-1） at 1 C. This method paves a new way to apply organic cathodes for lithium-ion batteries.
基金financially supported by the National Natural Science Foundation of China (21875206 and 21403187)the Subsidy for Hebei Key Laboratory of Applied Chemistry after Operation Performance (22567616H)+1 种基金the Open Project in the Key Laboratory of Advanced Energy Materials Chemistry (Nankai University)the Postgraduate Innovation Funding Project of Hebei Province (CXZZBS2022144)
文摘因具有高安全性和高性价比的优势,水系锌离子电池(AZIBs)成为了当前研究的热点.然而,电极材料溶解、固有电导率低、反应动力学慢等问题严重阻碍了其实际应用.在本文中,我们合成了一种在黑色素瘤治疗中发挥重要作用的含硫有机小分子(seriniquinone,SQ),将其作为电极材料应用于锌离子电池.通过导电碳修饰的方法制备了SQ/CMK-3复合电极,进一步解决了活性物质SQ的溶解问题并提高了其导电性.在Zn||SQ/CMK-3半电池中,SQ/CMK-3正极在100 mA g^(−1)电流密度下的初始放电比容量达到234.4 mA h g^(−1).在1 A g^(−1)的高电流密度下经过5000次超长循环后,比容量仍保持100.2 mA h g^(−1).此外,通过密度泛函理论计算,我们提出了在两个SQ分子之间嵌入四个Zn^(2+)的储存机理,并通过多种非原位表征测试进行了证实.在采用SQ/CMK-3复合材料作为正负两极的全有机对称电池中,SQ不仅在100 mA g^(−1)的电流密度下获得高达110.9 mA h g^(−1)的可逆比容量,而且在循环2500次后具有82.4%的稳定容量保持率和99.5%的平均库仑效率.
