CN1277937A - 一种大量制备单壁纳米碳管的氢弧放电方法 - Google Patents
一种大量制备单壁纳米碳管的氢弧放电方法 Download PDFInfo
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Abstract
一种大量制备单壁纳米碳管的氢弧放电方法,采用阴、阳极在压力气氛下电弧放电的方式,阳极为由石墨、催化剂混合物组成的消耗阳极,催化剂选自铁、钴、镍、钇中的一种或多种,加入量为2.5~5.0at%,其特征在于:(1)反应气氛为50~400乇氢气;(2)阴极与阳极间成30~80°的角度;(3)构成阳极的反应物中加入0.5~1at%的硫或固体硫化物作生长促进剂。本发明可以半连续地低成本、大量、高纯度地生产单壁纳米管。
Description
本发明涉及纳米碳管的制备技术,特别提供了一种在氢气压力下电弧放电大量生产单壁纳米碳管的方法。
纳米碳管自1991年被发现以来,已在全世界范围内引起了各国学者的广泛关注和极大兴趣。理论计算表明纳米碳管具有极高的强度和弹性模量,被称为超级纤维,可用于高级复合材料的增强体;纳米碳管具有独特的电子带结构,是理想的一维量子导线;此外,纳米碳管用作发射极、吸波材料、储氢材料等也极具潜力。正是因为具有众多的优异性能和广阔的应用前景,纳米碳管激起了科学家们的极大研究热情。大量制备出高纯度的纳米碳管是对其进行结构观察、性能测试以及进一步研究和应用的前提,所以纳米碳管的制备至关重要。近年来,纳米碳管的制备一直处于发展和进步之中。多壁纳米碳管(MWNT)的合成技术已较为成熟,并可以实现定向生长,单壁纳米碳管(SWNT)的制备方法则主要有电弧法、激光法和炭氢化合物催化分解法等。传统的电弧法是在充有一定压力惰性气体的反应室内,在两根石墨电极棒间通过高频或接触起弧产生高温,蒸发石墨电极,同时在催化剂的作用下碳原子结构重排,可以制得单壁纳米碳管。1993年日本学者Iijima就是用这种方法首次获得了单壁纳米碳管,但其含量很低。1997年,C.Journet等人通过变换催化剂种类及调整反应器内气体压力的方法,取得了较好的结果。其实验条件为:反应气氛660乇氦气;阴极和阳极分别是一根石墨棒,其尺寸为阴极Φ16×40mm,阳极Φ16×100mm,又在阳极棒中间钻有一个Φ3.5×40mm深的孔,孔中充填催化剂(钇、镍)和石墨粉的混合物;阴极和阳极垂直相对,其间距为~3mm,反应时间为~2分钟。获得产物有以下几种形态:a.在反应室内壁上生成大量的橡胶状烟炙;b.在阴极与器壁间形成的网状结构;c.在阴极末端形成的柱状沉积物;d.在柱状沉积物周围出现的一个多孔、轻质环状物。其中胶状烟炙中含单壁纳米碳管最少,而环状物中纳米碳管的含量最高(体积百分含量~80%),此后没有采用电弧法制备单壁纳米碳管获得新进展的相关报道。传统电弧法制备单壁纳米碳管存在着以下缺陷:受电极及反应器尺寸的限制,产量有限;无法实现连续生产;无定形炭等杂质的含量较高。
本发明的目的在于提供一种大量制备单壁纳米碳管的氢弧放电方法,其可以半连续地低成本、大量、高纯度地生产单壁纳米管。
本发明提供了一种大量制备单壁纳米碳管的氢弧放电方法,采用阴、阳极在压力气氛下电弧放电的方式,阳极为由石墨、催化剂混合物组成的消耗阳极,催化剂选自铁、钴、镍、钇中的一种或多种,加入量为2.5~5.0 at%,其特征在于:
(1)反应气氛为50~400乇氢气;
(2)阴极与阳极间成30~80°的角度;
(3)构成阳极的反应物中加入0.5~1 at%的硫或固体硫化物作生长促进剂。
本发明中所述阳极可以为一石墨盘,其上钻孔,孔内填充石墨粉与催化剂生长促进剂的混合物;或者所述阳极为由石墨粉、催化剂、含硫生长促进剂混合物压制成型的原料靶。
此外,本发明氢气氛中可以加入氩气,加入量不超过20vol%。
本发明与现有技术的区别在于:传统电弧法是以氦气作为介质气体,且采用较高压力(660乇)。本发明用氢气作为介质,其价格远比氦气低廉,而且气体压力较低(50~400乇),这就大大地降低了成本。同时,氢自身的一些特性也有利于单壁纳米碳管的合成:氢气的热导率高,对等离子流有较好的冷却效果,能产生较大的温度梯度,利于单壁纳米碳管的生长;氢气可以选择性地刻蚀反应中生成的无定形碳(生成烷烃),提高产物质量;氢还能促进金属催化剂的蒸出,并防止其被毒化等,起弧电流低,可大幅降低能耗。
对制备装置的改进则提供了大量、半连续生产单壁纳米碳管的可能性。本发明阳极与阴极构成一角度,从而带来在反应过程中气体的流动,使特大反应室成为可能,本发明反应室是圆柱形的,直径600mm,高400mm,大的反应室容积对于大量制备轻质、大相对体积的单壁纳米碳管是十分必要的。在阳极圆盘上挖孔蓄装反应物,使得石墨粉与催化剂的蒸出更加均匀,阳极的可转动性使本发明能够实现制备的半连续化,而将反应原料粉末压制成型制成原料靶后,操作更为方便。
含硫生长促进剂的加入极为关键。没有含硫生长促进剂存在的情况下,几乎没有单壁纳米碳管生成;而只要加入适当数量的含硫生长促进剂,就能获得大量、高纯度的纳米碳管。
总之,本发明选用氢气替代氦气作为介质气体制备单壁纳米碳管,既能降低成本又可以提高产物质量;通过改进实验装置,实现了制备的半连续化,在半小时内可以制得产物约1.0g。氢弧放电半连续法制备单壁纳米碳管具有连续性好、成本低、大量、高纯度等特点,有着良好的商业化生产应用前景。
下面结合附图详述本发明。
附图1为氢弧放电半连续、大量制备单壁纳米碳管的装置示意图I。
附图2为氢弧放电半连续、大量制备单壁纳米碳管的装置示意图II。
附图3为制备单壁纳米碳管的扫描电镜照片。
附图4为制备单壁纳米碳管的透射电镜照片。
附图5为制备单壁纳米碳管的拉曼测试图谱。
实施例1
装置如附图1。
在阳极圆盘的一个孔中填充反应物2.0g,其中含有2.6at%Ni,0.7at%Fe,0.7at%Co,0.75at%FeS,其余成分为石墨粉。反应器内充入200乇氢气,起弧电流为150A直流,两电极间保持~2mm的距离,反应时间3分钟,获薄膜状及网状产物计180毫克。
实施例2
装置如附图1。
在阳极圆盘的一个孔中填充反应物2.0g,其中含有2.6at% Ni,1.0 at% Co,0.75at%FeS,其余成分为石墨粉。反应器内充入200乇氢气,起弧电流为150A直流,两电极间保持~2mm的距离,反应时间3分钟,获薄膜状及网状产物计165毫克。
实施例3
装置如附图1。
在阳极圆盘的一个孔中填充反应物2.0g其中含有2.6at%Ni,1.0at% Y,0.75at%FeS,其余成分为石墨粉。反应器内充入200乇氢气,起弧电流为150A直流,两电极间保持~2mm的距离,反应时间3分钟,获薄膜状及网状产物计175毫克。
实施例4
装置如附图1。
在阳极圆盘的一个孔中填充反应物2.0g,其中含有2.6at%Ni,1.0at%Fe,0.75at%FeS,其余成分为石墨粉。反应器内充入200乇氢气,起弧电流为150A直流,两电极间保持~2mm的距离,反应时间3分钟,获薄膜状及网状产物计160毫克。
实施例5
装置如附图1。
在阳极圆盘的一个孔中填充反应物2.0g,其中含有2.6at%Ni,0.7at% Fe,0.7at%Co,1.0at%S,其余成分为石墨粉。反应器内充入200乇氢气,起弧电流为150A直流,两电极间保持~2mm的距离,反应时间3分钟,获薄膜状及网状产物计170毫克。
实施例6
装置如附图1。
在阳极圆盘的一个孔中填充反应物2.0g,其中含有2.6at%Ni,0.7at%Fe,0.7at% Co,0.75at%FeS,其余成分为石墨粉。反应器内充入200乇氢气和50乇氩气,起弧电流为150A直流,两电极间保持~2mm的距离,反应时间3分钟,获薄膜状及网状产物计170毫克。
实施例7
装置如附图1。
在阳极圆盘的一个孔中填充反应物2.0g,其中含有2.6at%Ni,0.7at%Fe,0.7at%Co,0.75at%FeS,其余成分为石墨粉。反应器内充入300乇氢气,起弧电流为150A直流,两电极间保持~2mm的距离,反应时间3分钟,获薄膜状及网状产物计175毫克。
实施例8
装置如附图1。
在阳极圆盘的一个孔中填充反应物2.0g,其中含有2.6at%Ni,0.7at%Fe,0.7at%Co,0.75at%FeS,其余成分为石墨粉。反应器内充入200乇氢气和50乇氩气,起弧电流为150A直流,两电极间保持~2mm的距离,反应时间3分钟,获薄膜状及网状产物计167毫克。
实施例9
装置如附图1。
在阳极圆盘的五个孔中各填充反应物2.0g,其中含有2.6at%Ni,0.7at%Fe,0.7at%Co,0.75at%FeS,其余成分为石墨粉。反应器内充入200乇氢气,超弧电流为150A直流,两电极间保持~2mm的距离,每个孔反应时间3分钟,之后更换反应室内气体,旋转阳极圆盘,蒸发下一个孔内的反应物。总反应时间30分钟,计获得薄膜状及网状产物计940毫克。
实施例10
装置如附图2。
将2.6at%Ni,0.7at%Fe,0.7at%Co,0.75at%FeS,和石墨粉的混合物充分混合均匀并压制成型,制成反应物圆盘作为阳极。反应器内充入200乇氢气,起弧电流为150A直流,两电极间保持~2mm的距离。每反应3分钟后,更换反应室内气体,旋转阳极圆盘,蒸发另一处的反应物。总反应时间30分钟,计获得薄膜状及网状产物980毫克。
Claims (4)
1.一种大量制备单壁纳米碳管的氢弧放电方法,采用阴、阳极在压力气氛下电弧放电的方式,阳极为由石墨、催化剂混合物组成的消耗阳极,催化剂选自铁、钴、镍、钇中的一种或多种,加入量为2.5~5.0at%,其特征在于:
(1)反应气氛为50~400乇氢气;
(2)阴极与阳极间成30~80°的角度;
(3)构成阳极的反应物中加入0.5~1 at%的硫或固体硫化物作生长促进剂。
2.按照权利要求1所述大量制备单壁纳米碳管的氢弧放电方法,其特征在于:所述阳极为一石墨盘,其上钻孔,孔内填充石墨粉与催化剂生长促进剂的混合物。
3.按照权利要求1所述大量制备单壁纳米碳管的氢弧放电方法,其特征在于:所述阳极为由石墨粉、催化剂、含硫生长促进剂混合物压制成型的原料靶。
4.按照权利要求1所述大量制备单壁纳米碳管的氢弧放电方法,其特征在于:氢气氛中加入氩气,加入量不超过20vol%。
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US09/588,568 US6517800B1 (en) | 1999-06-16 | 2000-06-07 | Production of single-walled carbon nanotubes by a hydrogen arc discharge method |
EP00305131A EP1061044B1 (en) | 1999-06-16 | 2000-06-16 | Production of single-walled carbon nanotubes |
AT00305131T ATE330905T1 (de) | 1999-06-16 | 2000-06-16 | Herstellung von einwandigen kohlenstoffnanoröhren |
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CN102459073A (zh) * | 2009-06-11 | 2012-05-16 | 同和控股(集团)有限公司 | 碳纳米管及其制造方法 |
CN102459073B (zh) * | 2009-06-11 | 2014-05-14 | 同和控股(集团)有限公司 | 碳纳米管及其制造方法 |
CN102530918A (zh) * | 2012-01-09 | 2012-07-04 | 中国科学院金属研究所 | 一种具有小管束尺寸的单/双壁碳纳米管结构的制备方法 |
CN102530918B (zh) * | 2012-01-09 | 2013-08-07 | 中国科学院金属研究所 | 一种具有小管束尺寸的单/双壁碳纳米管结构的制备方法 |
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