4.7 Article

Composition engineering of ZIF-derived cobalt phosphide/cobalt monoxide heterostructures for high-performance asymmetric supercapacitors

Journal

JOURNAL OF COLLOID AND INTERFACE SCIENCE
Volume 588, Issue -, Pages 557-570

Publisher

ACADEMIC PRESS INC ELSEVIER SCIENCE
DOI: 10.1016/j.jcis.2020.11.129

Keywords

Supercapacitor; Cobalt phosphide; Cobalt monoxide; Heterostructure; Zeolitic-imidazolate framework

Funding

  1. Priority Research Centers Program through the National Research Foundation of Korea (NRF) - Ministry of Education, Science, and Technology [2018R1A6A1A03024334]
  2. Nano-Material Technology Development Program through the National Research Foundation of Korea (NRF) - Ministry of Science, ICT, and Future Planning [2017M3A7B4014045]

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The synthesis of leaf-shaped cobalt phosphide/cobalt oxide heterostructure from a ZIF-Co-L precursor via gas-phase phosphorization enhances the supercapacitor performance through the variation of surface/bulk composition. The study also demonstrates that using graphene can further improve the cycling stability of the supercapacitor.
The fabrication of interpenetrated heterostructures from desirable energy materials for the development of efficient supercapacitors is promising yet challenging. Herein, a leaf-shaped cobalt phosphide/cobalt oxide heterostructure, (CoPx)(1-y)/CoOy (0.44 > y > 0.06), was synthesized from 2D-zeolitic-imidazolate-fra mework (ZIF-Co-L) molecular precursor via phosphidation of the Co3O4 intermediate. The efficient construction of heterostructure through the variation of surface/bulk composition significantly alters the interfacial properties and electronic structure, yielding enhanced supercapacitor performance. Further, gas-phase phosphidation entails a core-shell formation mechanism via gas diffusion, regulated by the Kirkendall effect. The optimized heterostructure (y = 0.10) exhibits remarkable interfacial properties derived from the CoO/Co-0/CoP interface, thus facilitating a high specific capacitance (467 F g(-1) at 5 A g(-1)) and excellent cycling stability (similar to 91% after 10000 cycles) at 30 A g(-1). A further increase in the cyclability (similar to 107%) was achieved by employing a graphene hybrid. Further, an asymmetric supercapacitor device was fabricated, that delivers reasonably high energy density of 12.7 Wh kg(-1) at a power density of 370 W kg(-1) and cycling stability of similar to 93% after 10000 cycles. This study reports on the modulation of interfacial properties of CoPx/CoO heterostructure to enhance energy storage performance via bulk/surface compositional variation, thereby providing a strategy to develop heterostructure electrodes for high-performance supercapacitor. (C) 2020 Elsevier Inc. All rights reserved.

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