Zhang Panpan, Wang Mingchao, Liu Yannan, Yang Sheng, Wang Faxing, Li Yang, Chen Guangbo, Li Zichao, Wang Gang, Zhu Minshen, Dong Renhao, Yu Minghao, Schmidt Oliver G, Feng Xinliang
Center for Advancing Electronics Dresden (cfaed) and Faculty of Chemistry and Food Chemistry, Technische Universität Dresden, Mommsenstraße 4, 01062 Dresden, Germany.
Material Systems for Nanoelectronics, Chemnitz University of Technology, Reichenhainer Straße 70, 09107 Chemnitz, Germany.
J Am Chem Soc. 2021 Jul 14;143(27):10168-10176. doi: 10.1021/jacs.1c03039. Epub 2021 Jun 29.
Advanced supercapacitor electrodes require the development of materials with dense redox sites embedded into conductive and porous skeletons. Two-dimensional (2D) conjugated metal-organic frameworks (-MOFs) are attractive supercapacitor electrode materials due to their high intrinsic electrical conductivities, large specific surface areas, and quasi-one-dimensional aligned pore arrays. However, the reported 2D -MOFs still suffer from unsatisfying specific capacitances and narrow potential windows because large and redox-inactive building blocks lead to low redox-site densities of 2D -MOFs. Herein, we demonstrate the dual-redox-site 2D -MOFs with copper phthalocyanine building blocks linked by metal-bis(iminobenzosemiquinoid) (M[CuPc(NH)], M = Ni or Cu), which depict both large specific capacitances and wide potential windows. Experimental results accompanied by theoretical calculations verify that phthalocyanine monomers and metal-bis(iminobenzosemiquinoid) linkages serve as respective redox sites for pseudocapacitive cation (Na) and anion (SO) storage, enabling the continuous Faradaic reactions of M[CuPc(NH)] occurring in a large potential window of -0.8 to 0.8 V vs Ag/AgCl (3 M KCl). The decent conductivity (0.8 S m) and high active-site density further endow the Ni[CuPc(NH)] with a remarkable specific capacitance (400 F g at 0.5 A g) and excellent rate capability (183 F g at 20 A g). Quasi-solid-state symmetric supercapacitors are further assembled to demonstrate the practical application of Ni[CuPc(NH)] electrode, which deliver a state-of-the-art energy density of 51.6 Wh kg and a peak power density of 32.1 kW kg.
先进的超级电容器电极需要开发出具有嵌入导电和多孔骨架中的密集氧化还原位点的材料。二维（2D）共轭金属有机框架（-MOF）由于其高本征电导率、大比表面积和准一维排列的孔阵列，是有吸引力的超级电容器电极材料。然而，报道的2D -MOF仍然存在比电容不令人满意和电位窗口窄的问题，因为大的且无氧化还原活性的构建块导致2D -MOF的氧化还原位点密度低。在此，我们展示了具有通过金属 - 双（亚氨基苯半醌）（M[CuPc(NH)]，M = Ni或Cu）连接的铜酞菁构建块的双氧化还原位点2D -MOF，其具有大的比电容和宽的电位窗口。实验结果与理论计算相结合，证实酞菁单体和金属 - 双（亚氨基苯半醌）键分别作为赝电容阳离子（Na）和阴离子（SO）存储的氧化还原位点，使得M[CuPc(NH)]在相对于Ag/AgCl（3 M KCl）为 -0.8至0.8 V的大电位窗口中发生连续的法拉第反应。良好的电导率（0.8 S m）和高活性位点密度进一步赋予Ni[CuPc(NH)]显著的比电容（在0.5 A g时为400 F g）和优异的倍率性能（在20 A g时为183 F g）。进一步组装了准固态对称超级电容器以展示Ni[CuPc(NH)]电极的实际应用，其提供了51.6 Wh kg的先进能量密度和32.1 kW kg的峰值功率密度。
