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Fabrication of MOF-derived mixed metal oxides with carbon residues for pseudocapacitors with long cycle life

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High electroactivity and good mechanical robustness of electrode materials are essential to deliver excellent electrochemical energy storage performance. Herein, metal–organic frameworks (MOF) derived mixed metal oxides (MMO, ZnO@NiO and Co3O4@NiO) are prepared by a two-step annealing process in air. Zinc-based MOF (ZIF-8) and cobalt-based MOF (ZIF-67) were employed, respectively, as hard templates for the chemical encapsulation of Ni(OH)2 nanostructures by hydrothermal synthesis. The as-prepared ZIF-8@Ni(OH)2 and ZIF-67@Ni(OH)2 were then converted to corresponding MMO through annealing in air. Meanwhile, MOF-derived carbon was preserved in the as-fabricated MMO structure, thus improving the electronic conductivity as well as the mechanical stability of the materials. In virtue of these features, high specific capacitance of 1017 and 744 F·g−1 can be delivered at a current density of 1 A·g−1 for the Co3O4@NiO and ZnO@NiO samples, respectively. In addition, both of the samples have shown excellent cycling performance, which exhibited excellent capacitance retentions of 90.1% and 93.0% after 10,000 cycles for the Co3O4@NiO and ZnO@NiO samples, respectively, demonstrating their very promising use in next-generation pseudocapacitors.

Graphic abstract

摘要

高电化学活性和良好的机械性能是电极材料拥有优秀的电化学储能性能的关键。由此, 我们通过在空气中分级热处理制备了金属有机框架(MOF)衍生的混合金属氧化物(MMO, ZnO@NiO和Co3O4@NiO)。首先, 锌基MOF (ZIF-8)和钴基MOF (ZIF-67)分别作为硬模板, 通过水热法进行Ni(OH)2纳米片包覆得到前驱体。之后将制备的ZIF-8@Ni(OH)2和ZIF-67@Ni(OH)2在空气中退火后转化为相应的混合金属氧化物。同时, MOF衍生碳保留在制备的MMO结构中, 从而提高了材料的电导率和力学稳定性。基于这些特性, 在1 A·g−1的电流密度下, Co3O4@NiO和ZnO@NiO分别能够取得1017和744 F·g−1的高比容量。此外, 两种样品均表现出良好的循环性能, 在10000次循环后, Co3O4@NiO和ZnO@NiO的容量分别为90.1%和93.0%, 表明它们在下一代赝电容器中具有很好的应用前景。

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Acknowledgements

This work was financially supported by the Start-Up Grant of Central South University (No. 202045001), the Innovation-Driven Project of Central South University (No. 2019CX028) and Huxiang Assembly Program for High-level Talents (No. 2018RS3018).

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Authors and Affiliations

  1. School of Materials Science and Engineering, Central South University, Changsha, 410083, China

    Yuan-Fu Ren, Zhi-Liang He, Hao-Zhen Zhao & Ting Zhu

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Correspondence to Ting Zhu.

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Ren, YF., He, ZL., Zhao, HZ. et al. Fabrication of MOF-derived mixed metal oxides with carbon residues for pseudocapacitors with long cycle life. Rare Met. 41, 830–835 (2022). https://doi.org/10.1007/s12598-021-01836-8

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