Abstract
We report the first example of a practical and efficient template-free strategy for synthesizing ordered mesoporous NiO/poly(sodium-4-styrene sulfonate) (PSS) functionalized carbon nanotubes (FCNTs) composites by calcining a Ni(OH)2/FCNTs precursor prepared by refluxing an alkaline solution of Ni(NH3) x 2+ and FCNTs at 97 °C for 1 h. The morphology and structure were characterized by X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. Thermal decomposition of the precursor results in the formation of ordered mesoporous NiO/FCNTs composite (ca. 48 wt% NiO) with large specific surface area. Due to its enhanced electronic conductivity and hierarchical (meso- and macro-) porosity, composite simultaneously meets the three requirements for energy storage in electrochemical capacitors at high rate, namely, good electron conductivity, highly accessibleelectrochemical surface areas owing to the existence of mesopores, and efficient mass transport from the macropores. Electrochemical data demonstrated that the ordered mesoporous NiO/FCNTs composite is capable of delivering a specific capacitance (SC) of 526 F/g at 1 A/g and a SC of 439 F/g even at 6 A/g, and show a degradation of only ca. 6% in SC after 2000 continuous charge/discharge cycles.
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Hu, C. C.; Chang, K. H.; Lin, M. C.; Wu, Y. T. Design and tailoring of the nanotubular arrayed architecture of hydrous RuO2 for next generation supercapacitors. Nano Lett. 2006, 6, 2690–2695.
Yuan, C. Z.; Chen, L.; Gao, B.; Su, L. H.; Zhang, X. G. Synthesis and utilization of RuO2·xH2O nanodots well dispersed on poly(sodium 4-styrene sulfonate) functionalized multiwalled carbon nanotubes for supercapacitors. J. Mater. Chem. 2009, 19, 246–252.
Zheng, M. B.; Cao, J.; Liao, S. T.; Liu, J. S.; Chen, H. Q.; Zhao, Y.; Dai, W. J.; Ji, G. B.; Cao, J. M.; Tao, J. Preparation of mesoporous Co3O4 nanoparticles via solid-liquid route and effects of calcination temperature and textural parameters on their electrochemical capacitive behaviors. J. Phys. Chem. C 2009, 113, 3887–3894.
Xiong, S. L.; Yuan, C. Z.; Zhang, X. G.; Xi, B. J.; Qian, Y. T. Controllable synthesis of mesoporous Co3O4 nanostrucutres with tunable morphology for application in supercapacitors. Chem. Eur. J. 2009, 15, 5320–5326.
Yuan, C. Z.; Gao, B.; Zhang, X. G. Electrochemical capacitance of NiO/Ru0.35V0.65O2 asymmetric electrochemical capacitors. J. Power Sources 2007, 173, 606–612.
Nam, K. W.; Kim, K. B. A study of the preparation of NiOx electrode via electrochemical route for supercapacitor applications and their charge storage mechanism. J. Electrochem. Soc. 2002, 149, A346–A354.
Xing, W.; Li, F.; Yan, Z. F.; Lu, G. Q. Synthesis and electrochemical properties of mesoporous nickel oxide. J. Power Sources 2004, 134, 324–330.
Hu, C. Q.; Gao, Z. H.; Yang, X. R. Synthesis of mesoporous NiO with crystalline walls by a simple sol-gel route. J. Sol Gel Sci. Technol. 2007, 44, 171–176.
Yan, H. W.; Blanford, C. F.; Holland, B. T.; Parent, M.; Smyrl, W. H.; Stein, A. A chemical synthesis of periodic macroporous NiO and metallic Ni. Adv. Mater. 1999, 11, 1003–1006.
Wang, Y. G.; Xia, Y. Y. Electrochemical capacitance characterization of NiO with ordered mesoporous structure synthesized by template SBA-15. Electrochim. Acta 2006, 51, 3223–3227.
Yuan, C. Z.; Su, L. H.; Gao, B.; Zhang, X. G. Enhanced electrochemical stability and storage of MnO2/carbon nanotubes composite modified by polyaniline coating layer in acidic electrolytes. Electrochim. Acta 2008, 53, 7039–7047.
Lei, Y.; Fournier, C.; Pascal, J. L.; Favier, F. Mesoporous carbon-manganese oxide composite as negative electrode material for supercapacitors. Micropor. Mesopor. Mater. 2008, 110, 167–176.
Li, J.; Yang, Q. M.; Zhitomirsky, I. Nickel foam-based manganese dioxide-carbon nanotube composite electrodes for electrochemical supercapacitors. J. Power Sources 2008, 185, 1569–1574.
Park, J. H.; Park, O. O.; Shin, K. H.; Jin, C. S.; Kim, J. H. An electrochemical capacitor based on a Ni(OH)2/activated carbon composite electrode. Electrochem. Solid-State Lett. 2002, 5, H7–H10.
Conway, B. E. Electrochemical Supercapacitors: Scientific Fundamentals and Technological Applications. Kluwer Acdemic/Plenum: New York, 1999.
Wang, D. W.; Li, F.; Liu, M.; Lu, G. Q.; Cheng, H. M. 3D aperiodic hierarchical porous graphitic carbon material for high-rate electrochemical capacitive energy storag. Angew. Chem. Int. Ed. 2008, 47, 373–376.
Nam, K. W.; Lee, E. S.; Kim, J. H.; Lee, Y. H.; Kim, K. B. Synthesis and electrochemical investigations of Ni1−x O thin films and Ni1−x O on three-dimensional carbon substrates for electrochemical capacitors. J. Electrochem. Soc. 2005, 152, A2123–A2129.
Gao, B.; Yuan, C. Z.; Su, L. H.; Chen, S. Y.; Zhang, X. G. High dispersion and electrochemical capacitive performance of NiO on benzenesulfonic functionalized carbon nanotubes. Electrochim. Acta 2009, 54, 3561–3567.
Zhang, H.; Cao, G. P.; Wang, Z. D.; Yang, Y. S.; Shi, Z. A.; Gu, Z. S. Growth of manganese oxide nanoflowers on vertically-aligned carbon nanotube arrays for high-rate electrochemical capacitive energy storage. Nano Lett. 2008, 8, 2664 2668.
Ye, J. S.; Cui, H. F.; Liu, X.; Lim, T. M.; Zhang, W. D.; Sheu, F. S. Preparation and characterization of aligned carbon nanotube-ruthenium oxide nanocomposites for supercapacitors. Small 2005, 1, 560–565.
Zhang, M. N.; Su, L.; Mao, L. Q. Surfactant functionalization of carbon nanotubes (CNTs) for layer-by-layer assembling of CNT multi-layer films and fabrication of gold nanoparticle/CNT nanohybrid. Carbon 2006, 44, 276–283.
Gong, K. P.; Yu, P.; Su, L.; Xiong, S. X.; Mao, L. Q. Polymer-assisted synthesis of manganese dioxide/carbon nanotube nanocomposite with excellent electrocatalytic activity toward reduction of oxygen. J. Phys. Chem. C 2007, 111, 1882–1887.
Chen, L.; Yuan, C. Z.; Dou, H.; Gao, B.; Chen, S. Y.; Zhang, X. G. Synthesis and electrochemical capacitance of core-shell poly (3,4-ethylenedioxythiophene)/poly(sodium 4-styrenesulfonate)-modified multiwalled carbon nanotube nanompocites. Electrochim. Acta 2009, 54, 2335–2341.
O’Connell, M. J.; Boul, P.; Ericson, L. M.; Huffman, C.; Wang, Y. H.; Haroz, E.; Kuper, C.; Tour, J.; Ausman K. D.; Smalley, R. E. Reversible water-solubilization of singlewalled carbon nanotubes by polymer wrapping. Chem. Phys. Lett. 2001, 342, 265–271.
Correa-Duarte, M. A.; Perez-Juste, J.; Sanchez-Iglesias, A.; Giersig, M.; Liz-Maran, L. M. Aligning Au nanorods by using carbon nanotubes as templates. Angew. Chem. Int. Ed. 2005, 44, 4375 4378.
Lou, X. W.; Deng, D.; Lee, J. Y.; Archer, L. A. Thermal formation of mesoporous single-crystal Co3O4 nanoneedles and their lithium storage properties. J. Mater. Chem. 2008, 18, 4397 4401.
Zhou, W.; Yao, M.; Guo, L.; Li, Y. M.; Li, J. H.; Yang, S. H. Hydrazine-liked convergent self-assembly of sophisticated concave polyhedrons of β-Ni(OH)2 and NiO from nanoplate building blocks. J. Am. Chem. Soc. 2009, 131, 2959–2964.
Matos, J. R.; Kruk, M.; Mercuri, L. P.; Jaroniec, M.; Zhao, L.; Kamiyama, T.; Terasaki, O.; Pinnavaia, T. J.; Liu, Y. Ordered mesoporous silica with large cage-like pores: Structural identification and pore connectivity design by controlling the synthesis temperature and time. J. Am. Chem. Soc. 2003, 125, 821–829.
Grosso, D.; Illia, G.; Crepaldi, E. L.; Charleux, B.; Sanchez, C. Nanocrystalline transition-metal oxide spheres with controlled multi-scale porosity. Adv. Funct. Mater. 2003, 13, 37–42.
Su, L. H.; Zhang, X. G.; Liu, Y. Electrochemical performance of Co-Al layered double hydroxide nanosheets mixed with multiwall carbon nanotubes. J. Solid State Electrochem. 2008, 12, 1129–1134.
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Yuan, C., Xiong, S., Zhang, X. et al. Template-free synthesis of ordered mesoporous NiO/poly(sodium-4-styrene sulfonate) functionalized carbon nanotubes composite for electrochemical capacitors. Nano Res. 2, 722–732 (2009). https://doi.org/10.1007/s12274-009-9079-7
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DOI: https://doi.org/10.1007/s12274-009-9079-7