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Fabrication of hierarchical porous metal–organic framework electrode for aqueous asymmetric supercapacitor Gao Weimin, Dezhi Chen, Hongying Quan, Ren Zou, Wenxiu Wang, Xubiao Luo, and Lin Guo ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.7b00112 • Publication Date (Web): 07 Apr 2017 Downloaded from http://pubs.acs.org on April 8, 2017
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Fabrication of hierarchical porous metal-organic framework electrode for aqueous asymmetric supercapacitor Weimin Gaoa, Dezhi Chena*, Hongying Quanb, Ren Zoua, Wenxiu Wanga, b, Xubiao Luoa, Lin Guoa, c* a
Key Laboratory of Jiangxi Province for Persistent Pollutants Control and Resources Recycle,
School of Environmental and Chemical Engineering, Nanchang Hangkong University, No. 696, Fenghe South Avenue, Nanchang, 330063, China. b
School of Materials Science and Engineering, Nanchang Hangkong University, No. 696,
Fenghe South Avenue, Nanchang 330063, China. c
Key Laboratory of Bio-Inspired Smart Interfacial Science and Technology of Ministry of
Education, School of Chemistry and Environment, Beihang University, No.37 Xueyuan Road, Haidian District, Beijing 100191, China. *Email:
[email protected] (Dr. D. Chen);
[email protected] (Prof. L. Guo) Fax: +86 791 83953373
KEYWORDS supercapacitor; MOF; electrode materials; hierarchical porous; defect;
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ABSTRACT.
As promising electrode materials in supercapacitor, metal-organic frameworks (MOFs) have attracted significant attention recently. However, the poor electrical conductivity and the almost exclusively microporous largely limited the possibility for MOFs to fabricate high-performance electrodes of supercapacitor. To overcome these obstacles, hierarchical porous Zr-MOFs (HPUiO-66) have successfully fabricated using bimetallic Zn/Zr MOFs as precursor, subsequent wiping off Zr-MOFs. When used as electrode materials for supercapacitors, under a current density of 0.2 A g-1, the specific capacitance of the prepared HP-UiO-66 is 849 F g-1, which is 8.36 times higher than the 101.5 F g-1 of bare UiO-66. The clearly enhanced electrochemical performance of HP-UiO-66 was benefited from the advantages of the hierarchical porous structure, the higher specific surface area and pore volume, as well as the sufficient surface defects. Furthermore, an aqueous asymmetric supercapacitor (ASC) based on the HP-UiO-66 and porous carbon could show an energy density of 32 W h kg-1 at a power density of 240 W kg1
. This strategy may offer a versatile idea of tailoring new type of MOFs and opens the
possibility of MOFs using in the future high energy storage device.
INTRODUCTION Supercapacitor is a type of energy-storage device between double capacitance capacitor and battery, and drawn great attentions owing to their high power density.1-2 To meet the requirement for higher energy and electricity supply, it is necessary to choose an appropriate and remarkable electrode material, such as carbon materials3-7, metal oxides/sulfides8-13, polymer14-16. Recently, porous electrode materials have been aroused intense scientific and industry attention because of
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their elite performance in supercapacitor.2, 4, 17 Whereas, traditional tailoring porous electrode materials with single-pore structures vastly limits ions and electrons diffusion. Therefore, the construction and development of porous electrode materials with favorable pore sizes are requisite, and still a challenge up to now.
Metal-organic frameworks (MOFs), consisted of inorganic nodes and organic linkers, have emerged as newly developed and burgeoning kind of porous solid-state materials18. Owing to their high specific surface area and large internal pore volumes with explicit pore sizes and pore structure, MOFs have exhibited great potential applications in electrochemical supercapacitor2, 1923
. However, most of MOFs have typically poor electrical conductivity, which far prevents the
use of these materials as active electrodes in supercapacitor. Therefore, most MOFs have been limited as precursors/templates for preparing porous carbons24-29, which usually require the use of harsh pre-treatment reagents, such as alkali bases, and high carbonization temperatures more than 800 ◦C. To improve the bulk electrical conductivity of MOFs, hybrid composites with conductive additives such as ZIF-67/PANI30, Ni-MOF/CNT31, Ni-MOFs@rGO32, Ni-doped MOFs/rGO33, Mn-MOFs/CNT34, HKUST-1/GO/PEDOT35, were prepared and exhibited an enhanced electrochemical performance than pure MOFs as supercapacitor electrodes. Apart from poor conductivity, the almost exclusively microporous (
