Research Article www.acsami.org
Nanostructured Electrode Materials Derived from Metal−Organic Framework Xerogels for High-Energy-Density Asymmetric Supercapacitor Asif Mahmood, Ruqiang Zou,* Qingfei Wang, Wei Xia, Hassina Tabassum, Bin Qiu, and Ruo Zhao Beijing Key Laboratory for Theory and Technology of Advanced Battery Materials, Department of Material Science and Engineering, College of Engineering, Peking University, Beijing 100871, China
ACS Appl. Mater. Interfaces 2016.8:2148-2157. Downloaded from pubs.acs.org by UNIV OF NEW ENGLAND on 10/20/18. For personal use only.
S Supporting Information *
ABSTRACT: This work successfully demonstrates metal−organic framework (MOF) derived strategy to prepare nanoporous carbon (NPC) with or without Fe3O4/Fe nanoparticles by the optimization of calcination temperature as highly active electrode materials for asymmetric supercapacitors (ASC). The nanostructured Fe3O4/Fe/C hybrid shows high specific capacitance of 600 F/g at a current density of 1 A/g and excellent capacitance retention up to 500 F/g at 8 A/g. Furthermore, hierarchically NPC with high surface area also obtained from MOF gels displays excellent electrochemical performance of 272 F/g at 2 mV/s. Considering practical applications, aqueous ASC (aASC) was also assembled, which shows high energy density of 17.496 Wh/kg at the power density of 388.8 W/kg. The high energy density and excellent capacity retention of the developed materials show great promise for the practical utilization of these energy storage devices. KEYWORDS: metal−organic framework xerogel, iron oxide, nanoporous carbon, aqueous asymmetric supercapacitor, high energy density society.9 Several nanomaterials have been synthesized in conquest toward designing efficient redox-active electrode materials such as RuO2, Co3O4, Fe3O4, Co(OH)2, FeOOH, etc.10−14 Despite the higher performance of those metallic nanostructured electrodes, their cyclic performance is largely limited because of low active surface area and the increased aggregation of the nanomaterials upon cycling.9,15 A widely accepted solution to this problem is to distribute the redoxactive nanomaterials onto highly conductive and elastic substrates with high surface area, like porous carbon materials.16,17 However, the preparation of the ideal composite structure is quite challenging with complex synthesis route at considerably higher costs which hinders their commercial applications.18 Hence, it is quite important to find cost-effective methods to develop high-performance nanostructured electrode materials in bulk quantities under industrially acceptable conditions.3,19 Recently, there is an increasing tendency to use metal− organic frameworks (MOFs) as precursors to synthesize ideal composite structures because of their ordered structure, higher surface areas, controlled porosity, and inherent presence of
1. INTRODUCTION Supercapacitors (SCs) have attracted tremendous attention due to their high power density and long cyclic life. Therefore, a large commercial rise is expected in next decade that might take the current SCs market value to several billion dollars by 2023.1,2 Currently, carbon constitutes the heart of commercial electrode materials which stores charges by electrochemical double layer (EDL) formation with fast charge/discharge kinetics, providing high power densities (>10000 W/kg) but suffer from low energy densities (80%) after 10,000 cycles which is consistent with the other metal/C systems reported as shown in Figure 6f.4−6 The decrease in capacitance upon successive cycling could be due to partial agglomeration of the electrode materials. Figure S11 represent the TEM analysis of electrode materials after testing which clearly suggest that most of the particles retain their original size and shape while few particle undergo agglomeration. We speculate that these aggregated particles are responsible for partial decrease in capacitance. The energy and power densities are very important parameters in optimizing materials for practical applications.3,18 Traditionally, the practical applications of aASCs are enhanced by high power densities but largely limited due to lower energy densities. On the other hand, most of the recently developed SC systems present high energy densities but result in great compromise over the power densities. The asymmetric cells developed here showed high energy density of 17.496 Wh/kg at the power density of 388.8 W/kg (much higher than most of the reported Fe−C systems). The Ragone plot in Figure 7
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ASSOCIATED CONTENT
S Supporting Information *
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsami.5b10725. Insights over BET, XRD, SEM, and XPS analysis of several products presented in this manuscript (PDF)
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AUTHOR INFORMATION
Corresponding Author
*E-mail:
[email protected]. Author Contributions
The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China 51322205 and 21371014, the New Star Program of Beijing Committee of Science and Technology (2012004).
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Figure 7. Ragone plot showing the relationship between energy density and power density.
REFERENCES
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4. CONCLUSIONS In summary, considering advantage of MOF-based structure, we have developed gels which are easily scalable and elaborate their electrochemical applications. Furthermore, problem associated with high temperature carbonization of MOF to derive electrochemically active species has been addressed successfully. We demonstrate that careful selection of the central metal and understanding of the carbonization temper2155
DOI: 10.1021/acsami.5b10725 ACS Appl. Mater. Interfaces 2016, 8, 2148−2157
Research Article
ACS Applied Materials & Interfaces
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