CN103922303B - Spherical Carbon nanotube coacervate and its production and use - Google Patents
Spherical Carbon nanotube coacervate and its production and use Download PDFInfo
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Abstract
A kind of Spherical Carbon nanotube coacervate and its production and use, Spherical Carbon nanotube coacervate is reunited through rotating in rotating equipment by some Spherical Carbon nanotube groups, the particle diameter of this coacervate is 3～50 microns, shape is spherical or clavate, Spherical Carbon nanotube group is the group that by rotating, carbon nanotube dust is gathered into intertexture in order and is formed, the particle diameter of group is 0.1～3 micron, and shape is spherical or clavate. Preparation method comprises: carbon nanotube and grinding medium are placed in grinding machine for grinding, and being formed by multiple particle diameter is 0.1～3 micron, and shape is spherical or the powder body of the carbon nanotube group of clavate formation; The grinding machine for grinding that the powder body of the carbon nanotubes group of preparation is placed in non-grinding medium, being formed by multiple particle diameter is 3～50 microns, the powder body that the carbon nanotube coacervate that shape is spherical is formed. This Spherical Carbon nanotube coacervate can be used as lithium cell, macromolecular material, coating, the conductive agent of paint or thermal conducting agent.
Description
[technical field]
The present invention relates to carbon nanotube, particularly relate to a kind of Spherical Carbon nanotube coacervate and its production and use.
[background technology]
Carbon nanotube is outstanding conductive agent, and its size is generally 2��100 nanometers, and length can reach 10��50 microns. Carbon nanotube not only can play the effect of wire in conductive network, but also has the high magnification characteristic of electrostatic double layer effect and ultracapacitor. Meanwhile, the heat conductivility that carbon nanotube is good is conducive to heat radiation during battery charging and discharging, reduces the polarization of battery, it is to increase the high temperature performance of battery, extends the life-span of battery. Macromolecular material and coating, paint add amounts of carbon black 1/10 carbon nanotube, the conduction state of carbon black can be reached.
The people such as Sheem (JournalofPowerSources2006,158,1425-1430) compared for multi-walled carbon nano-tubes and traditional graphitized carbon black to the impact of lithium ion battery, found that, no matter in electrical capacity and cycle index, multi-walled carbon nano-tubes is all significantly better than graphitized carbon black. But, due to the Van der Waals force that carbon nanotube is stronger each other so that be mutually intertwined between carbon nanotube, it is difficult to evenly be distributed in material, thus have impact on the performance of the physicals of carbon nanotube own. Therefore, how to prepare the carbon nanotube product being easy to dispersion and become the major obstacle limiting its commercial application. At present, the scattering problem solving carbon nanotube mainly contains chemistry and physics two kinds of methods. Wherein, mostly chemical process is to be oxidized by strong acid. Due to strong acid meeting this body structure of destroying carbon nanometer tube, make impaired performance or the inefficacy of carbon nanotube, and due to complicated operation, easily to factors such as environment pollute, make it to be difficult to realize suitability for industrialized production. This type of carbon nanotube mainly applied by the materials such as current macromolecular material, coating, paint. Physical method is then carry out wet grinding process by sand mill, is prepared into electrocondution slurry, although dispersion effect is better, but the amount of the dispersion agent wherein added affects greatly the performance of conductivity, making it resistance and become big, and the quality guaranteed period is short, current lithium cell produces main this series products of application.
[summary of the invention]
The present invention is intended to solve the problem, and provides a kind of preparation process simple, has excellent dispersing property, can directly add to without the need to adding dispersion agent and solvent in body material, stable in properties equal, easily forms the Spherical Carbon nanotube coacervate of conductive network.
The present invention also aims to provide the preparation method of a kind of Spherical Carbon nanotube coacervate.
The present invention also aims to provide the purposes of described Spherical Carbon nanotube coacervate.
For achieving the above object, the present invention provides a kind of Spherical Carbon nanotube coacervate, this Spherical Carbon nanotube coacervate is reunited through rotating in rotating equipment by some Spherical Carbon nanotube groups, the particle diameter of this coacervate is 3��50 microns, shape is spherical or clavate, described Spherical Carbon nanotube group is that carbon nanotube dust is placed in rotating equipment, the carbon nanotube of unordered winding is made to be gathered into the group of intertexture in order and formed by rotating, the particle diameter of described group is 0.1��3 micron, and shape is spherical or clavate.
Described spherical carbon nanotube coacervate and spherical carbon nanotube group are spheroidal or elliposoidal.
Rotating equipment for the formation of Spherical Carbon nanotube group is shredder or micronizer mill, and described shredder is ball mill or sand mill.
Rotating equipment for the formation of Spherical Carbon nanotube coacervate is sand mill.
Present invention also offers the preparation method of described Spherical Carbon nanotube coacervate, the method comprises the steps:
A, carbon nanotube and grinding medium are placed in shredder in the ratio of 0.1��1:0.1��10;
B, by CNT (carbon nano-tube), with having, the shredder of grinding medium grinds 1 minute��20 hours with the linear velocity of 2��50 meters/second, and being formed by multiple particle diameter is 0.1��3 micron, and shape is spherical or the powder body that forms of the carbon nanotube group of clavate;
The powder body of c, the carbon nanotubes group accounting for shredder volume 30��90% prepared by step b is placed in the shredder of non-grinding medium, grind 3 minutes��20 hours, the linear velocity of described grinding plant is 5��50 meters/second, being formed by multiple particle diameter is 3��50 microns, and shape is spherical or the powder body of the carbon nanotube coacervate of clavate formation.
In another program of the present invention, the preparation method of described Spherical Carbon nanotube coacervate comprises the steps:
D, the shredder that the carbon nanotube accounting for grinding plant volume 30��90% is placed in non-grinding medium;
E, shredder by CNT (carbon nano-tube) non-grinding medium grind 1 minute��20 hours, and the linear velocity of described shredder is 5��50 meters/second, and being formed by multiple particle diameter is 0.1��3 micron, and shape is spherical or the powder body that forms of the carbon nanotube group of clavate;
The powder body of f, the carbon nanotubes group accounting for shredder volume 30��90% prepared by step e is placed in the shredder of non-grinding medium, grind 3 minutes��20 hours, the linear velocity of described grinding plant is 5��50 meters/second, being formed by multiple particle diameter is 3��50 microns, and shape is spherical or the powder body of the carbon nanotube coacervate of clavate formation.
In a scheme again of the present invention, the preparation method of described Spherical Carbon nanotube coacervate comprises the steps:
G, carbon nanotube being sent into micronizer mill, the input speed of carbon nanotube is 1��100 kg/hour, and charging air pressure is 0.7��1.0Mpa;
H, with the high pressure gas of the airshed of 2��10 cubes ms/h, carbon nanotube being carried out discharging after impact grinding in micronizer mill, namely obtaining by multiple particle diameter is 0.1��3 micron, and shape is spherical or the powder body that forms of the carbon nanotube group of clavate;
The powder body of i, the carbon nanotubes group accounting for shredder volume 30��90% prepared by step h is placed in the shredder of non-grinding medium, grind 3 minutes��20 hours, the linear velocity of described grinding plant is 5��50 meters/second, being formed by multiple particle diameter is 3��50 microns, and shape is spherical or the powder body of the carbon nanotube coacervate of clavate formation.
The Ji Li of aforesaid method is, carbon nanotube is when rotating equipment high speed rotates, between carbon nanotube, original unordered winding state is broken, carbon nanotube is assembled agglomerating by orderly arrangement and intertexture under high speed rotating state, form aggregate that is spherical or clavate, this kind of aggregate makes carbon nanotube can be disperseed quickly when practical application, thus improves service efficiency.
Described grinding medium is the single medium that material and size are identical, or material and the different blending agent of size, and the particle diameter of described single medium is 0.1��50mm.
Described grinding medium is the combination of one or more in zirconium silicate pearl, zirconium dioxide pearl, titanium dioxide aluminium pill or steel ball.
Present invention also offers the purposes of described Spherical Carbon nanotube coacervate, this Spherical Carbon nanotube coacervate can be used as lithium cell, macromolecular material, coating, the conductive agent of paint or thermal conducting agent.
The contribution of the present invention is, it is poor that it efficiently solves in prior art the carbon nanotube dispersed existed, it is necessary to the problems such as strong acid oxidation and use dispersion agent dispersion. The Spherical Carbon nanotube group material of the present invention is owing to being agglomerated into spherule, thus there is excellent dispersing characteristic, it can directly add in body material, thus reduce or without the need to adding dispersion agent, thus its range of application is greatly extended, optimize and improve production technique, and can remarkable save energy. The ball-like structure of the carbon nanotube group of the present invention is easy to form conductive network, therefore can better play the performance of carbon nanotube. In actual applications, this carbon nanotube group directly can make lithium cell electrocondution slurry through short period of time high-speed stirring, therefore greatly reduces jitter time. Preparation method's technique of the present invention is simple, is easy to implement and large-scale promotion application, and low production cost. The carbon nanotube coacervate purposes of the present invention is extensive, and it can be applicable in lithium cell, macromolecular material, coating, paint, as the conductive agent that can evenly disperse and thermal conducting agent.
[accompanying drawing explanation]
Fig. 1 is by without the carbon nanotube coacervate microscan figure obtained by medium grinder.
Fig. 2 is by without carbon nanotube coacervate another microscan figure obtained by medium grinder.
Fig. 3 is the electrocondution slurry microscan figure being made up of carbon nanotube coacervate.
[embodiment]
The following example is further explanation of the present invention, the present invention is not constituted any limitation.
Carbon nanotube in the present invention can be any one in known Single Walled Carbon Nanotube or multi-walled carbon nano-tubes.
Embodiment 1
Be the multi-walled carbon nano-tubes of 100 grams and weight by weight it it is 200 grams, diameter is the ball mill tank that the zirconium pearl of the single medium of 1 millimeter puts into 1 liter, wherein the linear velocity of ball mill is 5 meters/second, milling time 1 hour, obtaining containing multiple diameter is 1��3 micron, shape is the powder body of the carbon nanotube group of ellipsoid shape, and in powder body, the volume content of carbon nanotube group is 30��40%.
It is the 3 minutes grinding machine for grinding time that the powder body of the carbon nanotubes group of 100 grams is placed in non-grinding medium by prepared weight, wherein the dispersion impeller of sand mill and the gap of cylinder are 3 millimeters, dispersion impeller linear velocity is 50 meters/second, being formed by multiple particle diameter is 3��50 microns, the powder body that the carbon nanotube coacervate that shape is spherical is formed, in powder body, the volume content of carbon nanotube coacervate is 80��90%. The microscan figure of this carbon nanotube-based cooking starch body is as shown in Figure 1 and Figure 2.
Embodiment 2
The multi-walled carbon nano-tubes that weight is 100 grams is put into the sand mill tank of 1 liter, wherein the dispersion impeller of sand mill and the gap of cylinder are 5 millimeters, dispersion impeller linear velocity is 50 meters/second, milling time 19 hours, obtaining containing multiple diameter is 1��3 micron, shape is the powder body of the carbon nanotube group of ellipsoid shape, and in powder body, the volume content of carbon nanotube group is 80��90%.
It is the 3 minutes grinding machine for grinding time that the powder body of the carbon nanotubes group of 100 grams is placed in non-grinding medium by prepared weight, wherein the dispersion impeller of sand mill and the gap of cylinder are 3 millimeters, dispersion impeller linear velocity is 50 meters/second, being formed by multiple particle diameter is 3��50 microns, the powder body that the carbon nanotube coacervate that shape is spherical is formed, in powder body, the volume content of carbon nanotube coacervate is 50��70%.
Embodiment 3
Spherical Carbon nanotube coacervate obtained in embodiment 1,2 is mixed mutually by the weight ratio of 5:95 with solvent N��methyl-2-pyrrolidone respectively in stirred vessel, the linear velocity of stirred vessel is 5 meters/second, at the uniform velocity stir 5 minutes, making the electrocondution slurry that sequence number is 1,2 respectively, the microscan figure of this electrocondution slurry is as shown in Figure 3. The coating of obtained electrocondution slurry being prepared into electrode slice, then surveys its resistivity, and compare resistance size and dispersing uniformity, data are such as table 1.
Comparative example 1
The common carbon nanotube processed without this method is mixed mutually by the weight ratio of 5:95 with solvent N��methyl-2-pyrrolidone in stirred vessel, the linear velocity of stirred vessel is 5 meters/second, at the uniform velocity stir 5 minutes, make electrocondution slurry, the coating of obtained electrocondution slurry is prepared into electrode slice, then survey its resistivity, the results are shown in Table 1.
Table 1
| Sequence number | 1 | 2 | Comparative example 1 |
| Electrical resistivity range/�� .cm | 1.2��1.6 | 1.3��1.7 | 1.6��8.5 |
Above-mentioned test result shows, when same dispersing technology, the resistivity of the carbon nanotube group of the present invention is little and narrow range, illustrates that dispersion state is even, is easier to dispersion than untreated carbon nanotube.
Embodiment 4
Spherical Carbon nanotube coacervate obtained in embodiment 1,2 is mixed mutually by the weight ratio of 3:97 with solvent polyethylene in stirred vessel, through mill the temperature of 165 DEG C mixing 5 minutes, formed and draw sheet 1,2, survey surface resistivity, relatively resistance size and dispersing uniformity, data are such as table 2.
Comparative example 2:
The common carbon nanotube processed without this method is mixed mutually by the weight ratio of 3:97 with matrix polyethylene in stirred vessel, through mill the temperature of 165 DEG C mixing 5 minutes, is formed and draw sheet, survey surface resistivity, the results are shown in Table 2.
Table 2
| Sequence number | 1 | 2 | Comparative example 2 |
| Resistance range/�� | 100��120 | 100��125 | 120��550 |
Above-mentioned test result shows, when same dispersing technology, the resistivity of the carbon nanotube group of the present invention is little and narrow range, illustrates that dispersion state is even, is easier to dispersion than untreated carbon nanotube.
Although by above embodiment to invention has been announcement, but protection scope of the present invention is not limited thereto, when not deviateing present inventive concept, the distortion done by above each component, replacement etc. are all by the right falling into the present invention.
Claims (6)
1. the preparation method of a Spherical Carbon nanotube coacervate, it is characterized in that, this Spherical Carbon nanotube coacervate is reunited through rotating in rotating equipment by some Spherical Carbon nanotube groups, the particle diameter of this coacervate is 3��50 microns, shape is spherical, described Spherical Carbon nanotube group is that carbon nanotube dust is placed in rotating equipment, the carbon nanotube of unordered winding is made to be gathered into the group of intertexture in order and formed by rotating, the particle diameter of described group is 0.1��3 micron, shape is spherical
The making method of described Spherical Carbon nanotube coacervate comprises following a, b, step c or d, e, f step or g, h, i step:
A, carbon nanotube and grinding medium are placed in shredder in the ratio of 0.1��1:0.1��10;
B, by carbon nanotube, with having, the shredder of grinding medium grinds 1 minute��20 hours with the linear velocity of 2��50 meters/second, and being formed by multiple particle diameter is 0.1��3 micron, the powder body that the carbon nanotube group that shape is spherical is formed;
The powder body of c, the carbon nanotubes group accounting for shredder volume 30��90% step (b) prepared is placed in the shredder of non-grinding medium, grind 3 minutes��20 hours, the linear velocity of described grinding plant is 5��50 meters/second, being formed by multiple particle diameter is 3��50 microns, the powder body that the carbon nanotube coacervate that shape is spherical is formed;
D, the shredder that the carbon nanotube accounting for grinding plant volume 30��90% is placed in non-grinding medium;
E, shredder by carbon nanotube non-grinding medium grind 1 minute��20 hours, and the linear velocity of described shredder is 5��50 meters/second, and being formed by multiple particle diameter is 0.1��3 micron, the powder body that the carbon nanotube group that shape is spherical is formed;
The powder body of f, the carbon nanotubes group accounting for shredder volume 30��90% step (e) prepared is placed in the shredder of non-grinding medium, grind 3 minutes��20 hours, the linear velocity of described grinding plant is 5��50 meters/second, being formed by multiple particle diameter is 3��50 microns, the powder body that the carbon nanotube coacervate that shape is spherical is formed;
G, carbon nanotube being sent into micronizer mill, the input speed of carbon nanotube is 1��100 kg/hour, and charging air pressure is 0.7��1.0MPa;
H, with the high pressure gas of the airshed of 2��10 cubes ms/h, carbon nanotube being carried out discharging after impact grinding in micronizer mill, namely obtaining by multiple particle diameter is 0.1��3 micron, the powder body that the carbon nanotube group that shape is spherical is formed;
The powder body of i, the carbon nanotubes group accounting for shredder volume 30��90% step (h) prepared is placed in the shredder of non-grinding medium, grind 3 minutes��20 hours, the linear velocity of described grinding plant is 5��50 meters/second, being formed by multiple particle diameter is 3��50 microns, the powder body that the carbon nanotube coacervate that shape is spherical is formed.
2. the preparation method of Spherical Carbon nanotube coacervate as claimed in claim 1, it is characterised in that, described Spherical Carbon nanotube coacervate and Spherical Carbon nanotube group are spheroidal or elliposoidal.
3. the preparation method of Spherical Carbon nanotube coacervate as claimed in claim 1, it is characterised in that, described shredder is ball mill or sand mill.
4. the preparation method of Spherical Carbon nanotube coacervate as claimed in claim 3, it is characterised in that, the rotating equipment for the formation of Spherical Carbon nanotube coacervate is sand mill.
5. the preparation method of Spherical Carbon nanotube coacervate as claimed in claim 1, it is characterised in that, described grinding medium is the single medium that material and size are identical, or material and the different blending agent of size, and the particle diameter of described single medium is 0.1��50mm.
6. the preparation method of Spherical Carbon nanotube coacervate as claimed in claim 1, it is characterised in that, described grinding medium is the combination of one or more in zirconium silicate pearl, zirconium dioxide pearl or steel ball.
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| GB2566267B (en) * | 2017-09-06 | 2021-02-17 | Peratech Holdco Ltd | Agglomerating nano-particles |
| CN110684392B (en) * | 2019-09-29 | 2022-05-06 | 佛山宜可居新材料有限公司 | Multi-wall carbon nano tube composite conductive material, preparation method and product thereof |
| CN113399093B (en) * | 2021-07-30 | 2023-08-11 | 深圳陶陶科技有限公司 | Method for preparing spheroidic powder by mechanical crushing method and spheroidic powder |
| CN114361427A (en) * | 2021-12-28 | 2022-04-15 | 深圳市纳米港有限公司 | Method for coating silicon cathode material with carbon nano tube |
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| JP2005239531A (en) * | 2004-01-27 | 2005-09-08 | Shimizu Corp | Spheric carbon nanotube aggregate, its manufacturing method and method for manufacturing composite material |
| CN1730386A (en) * | 2005-06-17 | 2006-02-08 | 华东师范大学 | Process for preparing nanometer carbon particles |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005239531A (en) * | 2004-01-27 | 2005-09-08 | Shimizu Corp | Spheric carbon nanotube aggregate, its manufacturing method and method for manufacturing composite material |
| CN1730386A (en) * | 2005-06-17 | 2006-02-08 | 华东师范大学 | Process for preparing nanometer carbon particles |
Non-Patent Citations (2)
| Title |
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| Ball milling effect on the structure of single-wall carbon nanotubes;N.Pierard et al.;《Carbon》;20040408;第42卷;第1691–1697页 * |
| Effect of grinding speed changes on dispersibility of the treated multi-walled carbon nanotubes in aqueous solution and its thermal characteristics;B. Munkhbayar et al.;《Chemical Engineering and Processing》;20120702;第61卷;第36–41页 * |
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