金属氧化物/碳纳米管复合材料的制备及性能研究
摘要
碳纳米管(CNTs)基复合纳米材料不仅具有一般复合材料的共性,而且由于其独特的物理、化学性质,使得此类复合材料具有不同于其他材料的特殊性质。本文通过不同的方法制备了Fe3O4/CNTs、Cu2O/CNTs和NiO/CNTs纳米复合材料,重点研究了处理温度、表面活性剂、反应条件等因素对产物结构和形貌等的影响,并测试了这些纳米复合材料的磁性能和电化学性能。
在160℃下用乙二醇作还原剂合成了Fe3O4/CNTs复合材料,随后对其进行煅烧处理。CNTs上的Fe3O4纳米颗粒由非晶转变成单晶,且颗粒尺寸及其分布范围也均随着煅烧温度的升高而增大。在室温下这些纳米复合材料表现出超顺磁性。
在240℃下用二甘醇作为溶剂和还原剂,醋酸纳(NaAc)为表面活性剂制备出了Fe3O4/CNTs复合材料。随着NaAc量的增加,Fe3O4纳米颗粒在CNTs上的分布更加均匀,且晶粒有长大趋势,Fe3O4的负载量也在增加,将其作为锂离子电池负极材料表现出良好的循环性能。
通过化学溶液法合成了Cu2O/CNTs复合材料,反应温度对复合材料影响较大。低于70℃时,产物为Cu2O和CNTs两相；高于70℃时,产生了单质Cu。在复合材料中,Cu2O以CNTs为基体自组装成网状结构,作为锂离子电池负极材料,其可逆容量为200 mAh g-1,在30次循环后仍保持了首次容量的80%。
以二甘醇作为溶剂首先合成前驱体,经煅烧后制备出NiO/CNTs复合材料,研究了煅烧温度对复合材料的影响。沉积在CNTs上的NiO颗粒形貌均匀,尺寸在30 nm以下；升高煅烧温度,能改善其结晶性。将其用作电容器电极材料,煅烧温度在300℃时的产物具有双电层效应；煅烧温度为400℃和500℃时则产生法拉第准电容效应。
Carbon nanotubes(CNTs)-based nanocomposites usually have the general properties of component materials and they would typically present unique properties different from their counterpart because of the unique physical and chemical properties of CNTs. Fe3O4/CNTs, Cu2O/CNTs and NiO/CNTs nanocomposites have been successfully synthesized by different methods in this thesis. The influence on the structure and morphology of the composites were intensively researched under different annealing temperatures, amounts of surfactant and reaction conditions.
The precursor of Fe3O4/CNTs nanocomposites was fabricated using ethylene glycol as reductant at 160℃. The precursor was subsequently annealed under different temperatures in an inert atmosphere. The phase of Fe3O4 transformed from amorphous phase into single crystalline after calcination. The average size of Fe3O4 nanoparticles increased with increasing annealing temperature. Meanwhile, the size distribution of nanoparticles became wide with the increasing temperature. Magnetic hysteresis loop measurements revealed that Fe3O4/CNTs nanocomposites displayed superparamagnet-ic behavior under room temperature.
Fe3O4/CNTs nanocomposites were also synthesized using diethylene glycol as reductant and sodium acetate (NaAc) as surfactant at 240℃. With the increasing amount of NaAc, the loading of Fe3O4 nanoparticles on the CNTs surface increased and the size of nanoparticles had a trend to growing. Electrochemical properties of the products were measured and the results showed that the products presented good cycling performance.
Cu2O/CNTs nanocomposites were fabricated by solution method at different temperatures. When the temperature was below 70℃, the product was a two-phase composite including Cu2O and CNTs. As it was higher than 70℃, the product would contain metallic Cu. These Cu2O nanoparticles were agglomerated and deposited on the external surface of CNTs. The electrochemical tests proved that the reversible capacity of the product is 200 mAh g-1 and it still remained 80% of first capacity after 30 cycles.
The precursor of NiO/CNTs was first synthesized with diethylene glycol as solvent. Then, the NiO/CNTs nanocomposites were obtained by calcining the precursor under high temperatures. The size of the NiO nanoparticles coated on CNTs was smaller than 30 nm. The crystallinity NiO nanoparticles was imporved with increasing the annealing temperature. Electrochemical results showed that when the calcination temperature at 300℃the product had obvious effect of electric double layer and that the products showed the effects of Faraday as the calcination temperature were 400℃and 500℃.
在160℃下用乙二醇作还原剂合成了Fe3O4/CNTs复合材料,随后对其进行煅烧处理。CNTs上的Fe3O4纳米颗粒由非晶转变成单晶,且颗粒尺寸及其分布范围也均随着煅烧温度的升高而增大。在室温下这些纳米复合材料表现出超顺磁性。
在240℃下用二甘醇作为溶剂和还原剂,醋酸纳(NaAc)为表面活性剂制备出了Fe3O4/CNTs复合材料。随着NaAc量的增加,Fe3O4纳米颗粒在CNTs上的分布更加均匀,且晶粒有长大趋势,Fe3O4的负载量也在增加,将其作为锂离子电池负极材料表现出良好的循环性能。
通过化学溶液法合成了Cu2O/CNTs复合材料,反应温度对复合材料影响较大。低于70℃时,产物为Cu2O和CNTs两相；高于70℃时,产生了单质Cu。在复合材料中,Cu2O以CNTs为基体自组装成网状结构,作为锂离子电池负极材料,其可逆容量为200 mAh g-1,在30次循环后仍保持了首次容量的80%。
以二甘醇作为溶剂首先合成前驱体,经煅烧后制备出NiO/CNTs复合材料,研究了煅烧温度对复合材料的影响。沉积在CNTs上的NiO颗粒形貌均匀,尺寸在30 nm以下；升高煅烧温度,能改善其结晶性。将其用作电容器电极材料,煅烧温度在300℃时的产物具有双电层效应；煅烧温度为400℃和500℃时则产生法拉第准电容效应。
Carbon nanotubes(CNTs)-based nanocomposites usually have the general properties of component materials and they would typically present unique properties different from their counterpart because of the unique physical and chemical properties of CNTs. Fe3O4/CNTs, Cu2O/CNTs and NiO/CNTs nanocomposites have been successfully synthesized by different methods in this thesis. The influence on the structure and morphology of the composites were intensively researched under different annealing temperatures, amounts of surfactant and reaction conditions.
The precursor of Fe3O4/CNTs nanocomposites was fabricated using ethylene glycol as reductant at 160℃. The precursor was subsequently annealed under different temperatures in an inert atmosphere. The phase of Fe3O4 transformed from amorphous phase into single crystalline after calcination. The average size of Fe3O4 nanoparticles increased with increasing annealing temperature. Meanwhile, the size distribution of nanoparticles became wide with the increasing temperature. Magnetic hysteresis loop measurements revealed that Fe3O4/CNTs nanocomposites displayed superparamagnet-ic behavior under room temperature.
Fe3O4/CNTs nanocomposites were also synthesized using diethylene glycol as reductant and sodium acetate (NaAc) as surfactant at 240℃. With the increasing amount of NaAc, the loading of Fe3O4 nanoparticles on the CNTs surface increased and the size of nanoparticles had a trend to growing. Electrochemical properties of the products were measured and the results showed that the products presented good cycling performance.
Cu2O/CNTs nanocomposites were fabricated by solution method at different temperatures. When the temperature was below 70℃, the product was a two-phase composite including Cu2O and CNTs. As it was higher than 70℃, the product would contain metallic Cu. These Cu2O nanoparticles were agglomerated and deposited on the external surface of CNTs. The electrochemical tests proved that the reversible capacity of the product is 200 mAh g-1 and it still remained 80% of first capacity after 30 cycles.
The precursor of NiO/CNTs was first synthesized with diethylene glycol as solvent. Then, the NiO/CNTs nanocomposites were obtained by calcining the precursor under high temperatures. The size of the NiO nanoparticles coated on CNTs was smaller than 30 nm. The crystallinity NiO nanoparticles was imporved with increasing the annealing temperature. Electrochemical results showed that when the calcination temperature at 300℃the product had obvious effect of electric double layer and that the products showed the effects of Faraday as the calcination temperature were 400℃and 500℃.
引文
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[2]J.P. Cheng, X.B. Zhang, F. Liu, J.P. Tu, Y. Ye, Y.J. Ji and C.P. Chen. Synthesis of Carbon Nanotubes Filled with Fe3C Nanowires by CVD with Titanate Modified Palyg orskite as Catalyst. Carbon,2003,41:1965-1970.
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[6]Dresselhaus M.S., Dressseelhaus G. and Saito R. Physics of carbon nanotubes. Carbon,1995, 33:883-890.
[7]Liu M. and Cowley J.M. Structures of carbon nanotubes studied by HRTEM and nanodiffraction. Ultramicroscopy,1994,53:333-342.
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[9]C. Liu, H.T. Cong, F. Li,P.H. Tan, H.M. Cheng, K. Lu and B.L. Zhou. Semi-continuous synthesis of single-walled carbon nanotubes by a hydrogen arc discharge. Carbon,1999,37: 1865.
[10]Thess A, Lee R, Nikolaev P, Dai H, Petit P, Rober J, Xu C, Lee Y, Kim S, Rinzler A, Colbert D, Scuseria G, Tomanek D, Fischer J and Smalley R. Crystalline Ropes of Metallic Carbon nanotubes. Science,1996,273:483-487.
[11]Ivanov V, Nagy JB, Lambin P, Lucas A, Zhang XB, Zhang XF, Bernaerts D, Tendeloo GV, Amelinckx S. and Landuyt JV. The study of carbon nanotubes produced by catalyticd method. Chemical Physics letters,1994,223:329-335.
[12]Hsu WK, Trasobares S, Terrones H, Terrones M, Grobert N, Zhu YQ, Li WZ, Escudero R, Hare JP, Kroto HW and Walton DRM. Electrolytic formation of carbon sheathed mixed Sn-Pb nanowires. Chemistry of Materials,1999,11:1747-1751.
[13]Vander Wal RL, Ticich TM and Curtis VE. Diffusion flame synthesis of single-walled carbon nanotubes. Chemical Physics Letters,2000,323:217-223.
[14]Libera J, and Gogotsi Y. Hydrothermal synthesis of graphite tubes using Ni catalyst. Carbon, 2001,39:1307-1318.
[15]Huang J.Y., Yasuda H. and Mori H. Highly curved carbon nanostructures produced by ball-milling. Chemical Physics Letters,1999,303:130-134.
[16]卢怡,朱珍平,刘振宇.催化剂对爆炸法合成碳纳米管的影响.新型炭材料,2004,19：1-6.
[17]Lee DC, Mikulec FV and Korgel BA. Carbon nanotube synthesis in supercritical toluene.the Journal of the American Chemical Society,2004,126:4951-4957.
[18]T.Guo, P. Nikolaev, A.G. Andrew, D.Tomanek, D.T. Colbert and R.E. Smalley. Self-Assembly of Tubular Fullerenes. Journal of Physical Chemistry,1995,99:10694.
[19]Ajayan P M, Ebbesen T W, Ichihashi T, et al. Opening carbon nanotubes with oxygen and implications for filling. Nature,1993,362:522-525.
[20]J.W. Minonire, B.l.Dunlap and C.T. White. Are fullerene tubules metallic. Physical Review letters,1992,68:631.
[21]R.A. Jiahi, J. Bragin and L. Lou. Electronic structure of short and long carbon nanotubes form first principles. Physical Review B,1999,59:9862.
[22]韦进全,张先锋,王昆林.碳纳米管宏观体[M].北京：清华大学出版社,2006.
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