CN104891472A

CN104891472A - Synthetizing method of straight line type carbon nanometer tubes

Info

Publication number: CN104891472A
Application number: CN201510235071.4A
Authority: CN
Inventors: 孙晓刚; 庞志鹏; 岳立福; 吴小勇; 聂艳艳; 刘珍红
Original assignee: Nanchang University
Current assignee: Nanchang University
Priority date: 2015-05-11
Filing date: 2015-05-11
Publication date: 2015-09-09

Abstract

The invention relates to a synthetizing method of straight line type carbon nanometer tubes. The synthetizing method comprises the following steps: (1) sufficiently dissolving ferrocene of which the granules are 20-300 microns in a benzene solution in the gravimetric volume (g/ml) ratio of 1:10-50; (2) jetting a ferrocene-benzene solution into the synthetizing furnace from the top of a vertical synthetizing furnace by using an atomizer with 3-6 holes and by using hydrogen as a carrier, besides, injecting nitrogen into the synthetizing furnace from the top of the synthetizing furnace, wherein the inlet pressure intensity of the hydrogen and the inlet pressure intensity of the nitrogen are respectively controlled to be 0.1-0.6 MPa and 0.1-0.6 MPa, and the flow speed ratio is 2:1; controlling the temperature of a carbon nanometer tube growing region of the vertical synthetizing furnace to be 1200-1400 DEG C, and maintaining a temperature gradient from top to bottom sequentially be 900-1200 DEG C, 1200-1400 DEG C, and 900-1200 DEG C. The straight line type carbon nanometer tubes are produced by increasing and controlling the movement speed of catalyst granules. The synthetizing method disclosed by the invention has the advantages that the technology is simple, the raw material sources are extensive, and the production efficiency is high, so that the synthetizing method is suitable for large-scale industrial production.

Description

A kind of synthetic method of linear pattern carbon nanotube

Technical field

The invention belongs to chemistry and field of functional materials, relate to the synthetic method of carbon nanotube.

Background technology

At present, the main manufacture methods of carbon nanotube is: direct current arc method, laser ablation method and chemical Vapor deposition process.Direct current arc method and laser ablation method cannot realize scale operation (gram quantity level), can only meet the needs of laboratory study on a small quantity, be not suitable for suitability for industrialized production, and chemical Vapor deposition process can prepare the carbon nanotube of industrial application magnitude.

The carbon nanotube pattern that conventional chemical vapor sedimentation is produced bends, be wound around mutually, purity and degree of crystallinity not high, make the structure properties of carbon nanotube itself not good enough, be difficult to disperse simultaneously, hinder its application in the industry.Fig. 1, Fig. 2 demonstrate, the microscopic appearance figure of conventional carbon nanotube.Can find out that carbon nanotube also exists a large amount of bending and wrapping phenomenas with reference to Fig. 1, Fig. 2.Therefore, fundamentally solve the bending and reunion in carbon nanotube growth process, just seem particularly crucial.

The reactor of carbon nanotube synthesis is the important factor determining carbon nanotube pattern, due to the special growth pattern of carbon nanotube, according to synthetic methods such as fixation reaction bed, mobile response beds, carbon nanotube is in process of growth, internal stress can not get release, hinder carbon nano tube growth, easily cause further reunion.Therefore, the growth reactor of carbon nanotube must provide sufficient growing space.In the process that carbon nanotube is formed, the temperature of Reaktionsofen, atmosphere all produce material impact to the pattern of carbon nanotube and quality, and the air-flow guiding in Reaktionsofen also has the effect of guiding to the growth of carbon nanotube.Therefore, in carbon nanotube building-up process, the control for this series of parameters determines pattern and the quality of carbon nanotube.

Summary of the invention

The object of the invention is to overcome the deficiencies in the prior art, by controlling the growth conditions of carbon nanotube, proposing a kind of synthetic method of linear pattern carbon nanotube.

The present invention is achieved by the following technical solutions.

Synthetic method of the present invention, as follows.

(1) by the ferrocene of particle between 20 ~ 300 microns by weight volume (g/ml) than being dissolved in benzole soln for 1:10 ~ 50, through magnetic agitation to after fully dissolving, filtering and removing undissolvable particle.

(2) ferrocene-benzole soln configured being used 3 ~ 6 hole spraying guns, is that carrier is injected into synthetic furnace from vertical synthetic furnace top jet with hydrogen, regulates furnace atmosphere from synthetic furnace top nitrogen injection simultaneously.Wherein the pressure that passes into of hydrogen and nitrogen controls at 0.1 ~ 0.6MPa and 0.1 ~ 0.6MPa respectively, and both velocity ratios maintain 2:1.

The temperature in vertical synthetic furnace carbon nano tube growth district controls at 1200 DEG C ~ 1400 DEG C, and keeps thermograde to be from top to bottom followed successively by: 900 DEG C ~ 1200 DEG C, 1200 DEG C ~ 1400 DEG C, 900 DEG C ~ 1200 DEG C.

Linear pattern carbon nanotube is a kind of high-crystallinity carbon nanotube of one-dimentional structure.The present invention abandons using solid catalyst in conventional carbon nanotube synthesis technique and catalyzer keeps actionless technique, carrys out production linear pattern carbon nanotube by improving and controlling granules of catalyst movement velocity.Another feature of the present invention is, contrast traditional technology, the production technique of carbon nanotube of the present invention, the production efficiency of carbon nanotube significantly improves, the synthesis of linear pattern carbon nanotube can complete within the time in 5-10 second, and traditional technology synthesizing carbon nanotubes at least needs the time of 1-2 hour could be complete.

Present invention process is simple, and raw material sources are extensive, and production efficiency is high, is suitable for large-scale commercial production.

Carbon nanotube of the present invention: as the conductive additive of lithium ion battery; For the manufacture of carbon nanotube conductive thin film; For the manufacture of electromagnetic shielding and absorbing material; As positive and negative electrode and the afflux pole of lithium ion battery; For Field Emission Display emtting electrode.

Accompanying drawing explanation

Fig. 1 is the SEM figure of conventional carbon nanotube.

Fig. 2 is the TEM figure of conventional carbon nanotube.

Fig. 3 is that the present invention synthesizes linear pattern carbon nanotube SEM and schemes.

Fig. 4 is that the present invention synthesizes linear pattern carbon nanotube TEM and schemes.

Fig. 5 is the TGA collection of illustrative plates that the present invention synthesizes linear pattern carbon nanotube.Wherein, X-coordinate is temp cel (degree Celsius), and left ordinate scale is DTA (μ V) (differential thermal analysis), and right ordinate scale is TG (%) (thermogravimetric analysis).

Fig. 6 is the XRD figure spectrum that the present invention synthesizes linear pattern carbon nanotube.

Embodiment

The present invention will be described further by following examples.

Embodiment 1.

1) getting the ferrocene of 10 grams of granular sizes between 100 ~ 200 microns is dissolved in 300 milliliters of benzole solns, for subsequent use after filtering.

2) the above-mentioned ferrocene-benzole soln peristaltic pump prepared is injected in spraying gun, simultaneously by hydrogen and nitrogen respectively with the pressure of 0.2MPa and 0.2MPa, flow velocity 24L/min and 12L/min imports 3 hole spraying guns.

3) solution after atomization sprays implantation temperature gradient and is 1000 DEG C from top to bottom, 1300 DEG C, synthesizing carbon nanotubes in the vertical synthetic furnace of 1000 DEG C.

4) carbon nanotube synthesized, at the bottom deposit of synthetic furnace, takes out after cooling.

Embodiment 2.

1) getting the ferrocene of 10 grams of granular sizes between 200 ~ 300 microns is dissolved in 100 milliliters of benzole solns, for subsequent use after filtering.

2) the above-mentioned ferrocene-benzole soln peristaltic pump prepared is injected in spraying gun, simultaneously by hydrogen and nitrogen respectively with the pressure of 0.1MPa and 0.3MPa, flow velocity 12L/min and 6L/min imports 6 hole spraying guns.

3) solution after atomization sprays implantation temperature gradient and is 900 DEG C from top to bottom, 1200 DEG C, synthesizing carbon nanotubes in the vertical synthetic furnace of 900 DEG C.

Embodiment 3.

1) getting the ferrocene of 10 grams of granular sizes between 50 ~ 100 microns is dissolved in 400 milliliters of benzole solns, for subsequent use after filtering.

2) the above-mentioned ferrocene-benzole soln peristaltic pump prepared is injected in spraying gun, simultaneously by hydrogen and nitrogen respectively with the pressure of 0.2MPa and 0.3MPa, flow velocity 18L/min and 9L/min imports 5 hole spraying guns.

3) solution after atomization sprays implantation temperature gradient and is 1100 DEG C from top to bottom, 1400 DEG C, synthesizing carbon nanotubes in the vertical synthetic furnace of 1100 DEG C.

Embodiment 4.

1) getting the ferrocene of 10 grams of granular sizes between 200 ~ 300 microns is dissolved in 300 milliliters of benzole solns, for subsequent use after filtering.

2) the above-mentioned ferrocene-benzole soln peristaltic pump prepared is injected in spraying gun, simultaneously by hydrogen and nitrogen respectively with the pressure of 0.1MPa and 0.2MPa, flow velocity 28L/min and 14L/min imports 4 hole spraying guns.

3) solution after atomization sprays implantation temperature gradient and is 1000 DEG C from top to bottom, 1400 DEG C, synthesizing carbon nanotubes in the vertical synthetic furnace of 1000 DEG C.

Synthetic materials contrasts: Fig. 1, Fig. 2 are SEM, TEM figure of conventional carbon nanotube, can find out in figure that carbon nanotube exists to reunite and be wound around, Fig. 3, Fig. 4 are SEM, TEM figure of present method synthesizing carbon nanotubes, can find out in figure that carbon nanotube is linear pattern, caliber is smooth, even, and atomic arrangement is fine and close.Fig. 5 is the TGA curve of present method synthesis linear pattern carbon nanotube, can find out that the purity of linear pattern carbon nanotube is 99.8% in figure.Fig. 6 is the XRD figure spectrum of present method synthesis linear pattern carbon nanotube, and can find out in figure that (002) peak of carbon nanotube is sharp-pointed and narrow, the degree of graphitization of carbon nanotube reaches 97.25%, has very high degree of crystallinity.

Claims

1. a synthetic method for linear pattern carbon nanotube, is characterized in that as follows:

(1) by the ferrocene of particle between 20 ~ 300 microns by weight volume (g/ml) than being dissolved in benzole soln for 1:10 ~ 50, through magnetic agitation to after fully dissolving, filtering and removing undissolvable particle;

(2) ferrocene-benzole soln configured is used 3 ~ 6 hole spraying guns, be that carrier is injected into synthetic furnace from vertical synthetic furnace top jet with hydrogen, regulate furnace atmosphere from synthetic furnace top nitrogen injection simultaneously, wherein the pressure that passes into of hydrogen and nitrogen controls at 0.1 ~ 0.6MPa and 0.1 ~ 0.6MPa respectively, and both velocity ratios maintain 2:1;