•  
  •  
 

Corresponding Author

Chun-feng XUE(cfxue@fudan.edu.cn);
Xu-li MA;
Xiao-gang HAO(xghao@tyut.edu.cn)

Abstract

Excellent electrode plays vital important role in the performance of supercapacitors. Polyaniline (PANI) with good conductivity is often used to prepare electrode. However, its available surface is limited and results in a poor supercapacitance in many cases. It is desirable to fabricate an electrode containing electroactive PANI with high surface area deriving from its porous structure. Here, the metal-organic framework (MOF) material with high surface area was selected as a hard template for synthesizing porous PANI. Microporous PANI composite electrodes (Micro-PANI/CC) were fabricated by depositing aniline on to carbon cloth (CC) pre-coated with MOF material of HKUST-1 using a unipolar pulse electro-polymerization method. At the same time, the PANI electrodes (PANI/CC) were also synthesized on blank carbon cloth for further comparatively studying their supercapacitor performances. Their microstructure and morphology were characterized by using XRD and SEM. Results indicate that the micro-PANI/CC electrode was composed of aggregated nanosized PANI spheres with pore structure. The cyclic voltammetry, constant current charge and discharge, impedance and stability tests were performed to evaluate the supercapacitor properties in 0.5 mol·L-1 sulfuric acid electrolyte. Specific capacitances of micro-PANI/CC and PANI/CC electrodes were 895.6 F·g-1 and 547.6 F·g-1 at scan rate of 2 mV·s-1 , respectively. At the same given conditions, the specific capacitance of micro-PANI/CC electrode was always 1.64 times higher than that of PANI/CC electrode. Meanwhile, the micro-PANI/CC electrode exhibited better rate capability, lower resistance and better stability of charge and discharge than PANI/CC. all the results imply that the microporous PANI templated from HKUST-1 could be a good candidate for the electrode of supercapacitors.

Graphical Abstract

Keywords

supercapacitor, HKUST-1, porous, polyaniline, unipolar pulse electro-polymerization method

Publication Date

2017-02-28

Online Available Date

2016-03-21

Revised Date

2016-03-12

Received Date

2016-02-01

References

[1] Simon P, Gogotsi Y. Materials for electrochemical capacitors[J]. Nature Materials, 2008, 7 (11):845-854.

[2] Wang Y, Liu Z, Han B, et al. Facile synthesis of polyaniline nanofibers using chloroaurate acid as the oxidant[J]. Langmuir, 2005, 21 (3): 833-836.

[3] Chen L, Song Z, Liu G, et al. Synthesis and electrochemical performance of polyaniline€“MnO2 nanowire composites for supercapacitors[J]. Journal of Physics and Chemistry of Solids, 2013, 74 (2): 360-365.

[4] Lei Z, Chen Z, Zhao X. Growth of polyaniline on hollow carbon spheres for enhancing electrocapacitance[J]. The Journal of Physical Chemistry C, 2010, 114 (46): 19867-19874.

[5] Li Y, Zhao K, Du X, et al. Capacitance behaviors of nanorod polyaniline films controllably synthesized by using a novel unipolar pulse electro-polymerization method[J]. Synthetic Metals, 2012, 162 (1-2): 107-113.

[6] James S L. Metal-organic frameworks[J]. Chemical Society Reviews, 2003, 32 (5): 276-288.

[7] Rowsell J L, Spencer E C, Eckert J, et al. Gas adsorption sites in a large-pore metal-organic framework[J]. Science, 2005, 309 (5739): 1350-1354.

[8] Lu W G, Jiang L, Feng X L, et al. Three-dimensional lanthanide anionic metalˆ’organic frameworks with tunable luminescent properties induced by cation exchange[J]. Inorganic Chemistry, 2009, 48 (15): 6997-6999.

[9] Farrusseng D, Aguado S, Pinel C. Metal€“organic frameworks: opportunities for catalysis[J]. Angewandte Chemie International Edition, 2009, 48 (41): 7502-7513.

[10] Wang L, Feng X, Ren L, et al. Flexible Solid-state supercapacitor based on a metal-organic framework interwoven by electrochemically-deposited PANI[J]. Journal of the American Chemical Society, 2015, 137 (15): 4920-4923.

[11] Zhang Y, Lin B, Sun Y, et al. Carbon nanotubes@metal€“organic frameworks as Mn-based symmetrical supercapacitor electrodes for enhanced charge storage[J]. RSC Advances, 2015, 5 (72): 58100-58106.

[12] Banerjee P C, Lobo D E, Middag R, et al. Electrochemical capacitance of Ni-doped metal organic framework and reduced graphene oxide composites: more than the sum of its parts[J]. ACS Applied Materials & Interfaces, 2015, 7 (6): 3655-3664.

[13] Wen P, Gong P, Sun J, et al. Design and synthesis of Ni-MOF/CNT composites and rGO/carbon nitride composites for an asymmetric supercapacitor with high energy and power density[J]. Journal of Materials Chemistry A, 2015, 3 (26): 13874-13883.

[14] Hu L, Huang Y, Zhang F, et al. CuO/Cu2O composite hollow polyhedrons fabricated from metal€“organic framework templates for lithium-ion battery anodes with a long cycling life[J]. Nanoscale, 2013, 5 (10): 4186-4190.

[15] Liu B, Zhang X, Shioyama H, et al. Converting cobalt oxide subunits in cobalt metal-organic framework into agglomerated Co3O4 nanoparticles as an electrode material for lithium ion battery[J]. Journal of Power Sources, 2010, 195 (3): 857-861.

[16] Li S L, Xu Q. Metal€“organic frameworks as platforms for clean energy[J]. Energy & Environmental Science, 2013, 6 (6): 1656-1683.

[17] Zheng C, Zhou X, Cao H, et al. Synthesis of porous graphene/activated carbon composite with high packing density and large specific surface area for supercapacitor electrode material[J]. Journal of Power Sources, 2014, 258: 290-296.

[18] Yang J, Zheng C, Xiong P, et al. Zn-doped Ni-MOF material with a high supercapacitive performance[J]. Journal of Materials Chemistry A, 2014, 2 (44): 19005-19010.

[19] Lu C, Ben T, Xu S, et al. Electrochemical synthesis of a microporous conductive polymer based on a metal-organic framework thin film[J]. Angewandte Chemie, 2014, 53 (25): 6454-6458.

[20] Chui S S Y, Lo S M F, Charmant J P, et al. A chemically functionalizable nanoporous material [Cu3(TMA)2(H2O)3]n[J]. Science, 1999, 283 (5405): 1148-1150.

[21] Hao X G, Li Y, Pritzker M. Pulsed electrodeposition of nickel hexacyanoferrate films for electrochemically switched ion exchange[J]. Separation and Purification Technology, 2008, 63 (2): 407-414.

[22] Srimuk P, Luanwuthi S, Krittayavathananon A, Sawangphruk M. Solid-type supercapacitor of reduced graphene oxide-metal organic framework composite coated on carbon fiber paper[J]. Electrochimica Acta, 2015, 157: 69-77.

Share

COinS
 
 

To view the content in your browser, please download Adobe Reader or, alternately,
you may Download the file to your hard drive.

NOTE: The latest versions of Adobe Reader do not support viewing PDF files within Firefox on Mac OS and if you are using a modern (Intel) Mac, there is no official plugin for viewing PDF files within the browser window.