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用于超级电容器的双金属金属有机框架纳米片及其衍生的多孔镍钴硫化物的制备

Formation of bimetallic metal-organic framework nanosheets and their derived porous nickel-cobalt sulfides for supercapacitors.

作者信息

Chen Chen, Wu Meng-Ke, Tao Kai, Zhou Jiao-Jiao, Li Yan-Li, Han Xue, Han Lei

机构信息

School of Materials Science & Chemical Engineering, Ningbo University, Ningbo, Zhejiang 315211, China.

出版信息

Dalton Trans. 2018 Apr 24;47(16):5639-5645. doi: 10.1039/c8dt00464a.

Abstract

Metal-organic frameworks (MOFs) show great advantages as new kinds of active materials for energy storage. In this study, bimetallic metal-organic frameworks (Ni/Co-MOFs) with nanosheet-assembled flower-like structures were synthesized by etching Ni-MOF microspheres in a cobalt nitrate solution. It can be clearly observed that the amount of Co(NO3)2 and etching time play crucial roles in the formation of Ni/Co-MOF nanosheets. The Ni/Co-MOFs were used as electrode materials for supercapacitors and the optimized Ni/Co-MOF-5 exhibited the highest capacitances of 1220.2 F g-1 and 986.7 F g-1 at current densities of 1 A g-1 and 10 A g-1, respectively. Ni/Co-MOF-5 was further sulfurized, and the derived Ni-Co-S electrode showed a higher specific capacitance of 1377.5 F g-1 at a current density of 1 A g-1 and a retention of 89.4% when the current density was increased to 10 A g-1, indicating superior rate capability. Furthermore, Ni/Co-MOF-5 and Ni-Co-S showed excellent cycling stability, i.e. about 87.8% and 93.7% of initial capacitance can be still maintained after 3000 cycles of charge-discharge. More interestingly, the Ni/Co-MOF-5//AC ASC shows an energy density of 30.9 W h kg-1 at a power density of 1132.8 W kg-1, and the Ni-Co-S//AC ASC displays a high energy density of 36.9 W h kg-1 at a power density of 1066.42 W kg-1. These results demonstrate that the as-synthesized bimetallic Ni/Co-MOF nanosheets and their derived nickel-cobalt sulfides have promising applications in electrochemical supercapacitors.

摘要

金属有机框架材料(MOFs)作为新型储能活性材料展现出巨大优势。在本研究中,通过在硝酸钴溶液中蚀刻镍基金属有机框架(Ni-MOF)微球,合成了具有纳米片组装花状结构的双金属金属有机框架(Ni/Co-MOFs)。可以清楚地观察到,硝酸钴的用量和蚀刻时间在Ni/Co-MOF纳米片的形成中起着关键作用。将Ni/Co-MOFs用作超级电容器的电极材料,优化后的Ni/Co-MOF-5在电流密度为1 A g⁻¹和10 A g⁻¹时分别表现出最高电容1220.2 F g⁻¹和986.7 F g⁻¹。对Ni/Co-MOF-5进一步硫化,得到的Ni-Co-S电极在电流密度为1 A g⁻¹时表现出更高的比电容1377.5 F g⁻¹,当电流密度增加到10 A g⁻¹时电容保持率为89.4%,表明其具有优异的倍率性能。此外,Ni/Co-MOF-5和Ni-Co-S表现出出色的循环稳定性,即在3000次充放电循环后仍可分别保持约87.8%和93.7%的初始电容。更有趣的是,Ni/Co-MOF-5//AC不对称超级电容器在功率密度为1132.8 W kg⁻¹时能量密度为30.9 W h kg⁻¹,而Ni-Co-S//AC不对称超级电容器在功率密度为1066.42 W kg⁻¹时表现出36.9 W h kg⁻¹的高能量密度。这些结果表明,所合成的双金属Ni/Co-MOF纳米片及其衍生的镍钴硫化物在电化学超级电容器中具有广阔的应用前景。

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