Hierarchically structured layered-double-hydroxide@zeolitic-imidazolate-framework derivatives for high-performance electrochemical energy storage

Abstract

CoAl-based layered-double-hydroxide@zeolitic-imidazolate-framework-67 (LDH@ZIF-67) was fabricated via a hydrothermal synthesis of LDH film on Ni substrate followed by the in situ growth of ZIF-67. Its derivatives, MMO@Co₃O₄, spinelle@C and LDH@CoS with hierarchical structures were obtained by the subsequent oxidation, carbonization and sulfurization of LDH@ZIF-67, respectively, which exhibit distinct specific capacitances of 692, 781 and 1205 F g⁻¹ at a discharge current density of 1 A g⁻¹. Interestingly, these derivatives retained hierarchical structures with large surface area, which ensures that the majority of exposed active species can participate in the charge–discharge process and thus effectively contribute to total capacitances. The synergistic effect from fast electronic transfer reduces reversible ion accumulation at the interface, which imparts LDH@ZIF-67 derivatives improved electrochemical activities, in contrast to conventional bulk MOF derivatives. In addition, it was found that the combination of the remarkable electrical conductivity of sulfides (compared with their oxide counterparts) and the strong electronic coupling between LDH and CoS can facilitate fast electron transfer. As a result, LDH@CoS exhibits an excellent specific energy of 44.5 W h kg⁻¹ at a current density of 20 A g⁻¹, as well as good capacitance retention of 88.5% after 2000 cycles. This work thus demonstrates a feasible strategy for the design and fabrication of LDH@MOF derived composites as SCs components, which is applicable in constructing other novel electrode materials with hierarchical structures for applications in energy storage systems.