CN103896249B - Spherical Carbon nanotube group and its production and use - Google Patents
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- CN103896249B CN103896249B CN201410114240.4A CN201410114240A CN103896249B CN 103896249 B CN103896249 B CN 103896249B CN 201410114240 A CN201410114240 A CN 201410114240A CN 103896249 B CN103896249 B CN 103896249B
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Abstract
A kind of Spherical Carbon nanotube group and its production and use, this Spherical Carbon nanotube group is to be placed in slewing by CNT, make the CNT of unordered winding be agglomerated into the group of intertexture in order by rotation and formed, the particle diameter of described group is 0.1～3 micron, is shaped as spherical or rod.Preparation method includes: by CNT with abrasive media in grinding machine for grinding, the powder that shape glomerate CNT group is constituted；Or the milling apparatus grinding through non-grinding medium, forms the powder that CNT group is constituted；Or CNT is carried out gases at high pressure impact comminution through airslide disintegrating mill, form the powder that CNT group is constituted.This Spherical Carbon nanotube group can be used as lithium battery, macromolecular material, coating, the conductive agent of paint, thermal conducting agent.The Spherical Carbon nanotube group preparation process of the present invention is simple, has excellent dispersive property, can be directly appended in matrix material, and stable in properties is homogeneous, is easily formed conductive network.
Description
[technical field]
The present invention relates to CNT, particularly relate to a kind of Spherical Carbon nanotube group and preparation side thereof
Method and purposes.
[background technology]
CNT is outstanding conductive agent, and it typically has a size of 2～100 nanometers, length up to 10～
50 microns.CNT is not only able to play the effect of wire in conductive network, but also has double
Electric layer effect and the high-rate characteristics of ultracapacitor.Meanwhile, the heat conductivility that CNT is good has
It is beneficial to heat radiation during battery charging and discharging, reduces the polarization of battery, improve the high temperature performance of battery, prolong
The life-span of long battery.Macromolecular material and coating, paint add amounts of carbon black 1/10 carbon nanometer
Pipe, i.e. can reach the conduction state of carbon black.
Sheem et al. (Journal of Power Sources 2006,158,1425-1430) is right
Compare multi-walled carbon nano-tubes and the impact on lithium ion battery of traditional conductive black, it was found that nothing
Opinion is in capacitance and cycle-index, and multi-walled carbon nano-tubes is the most significantly better than conductive black.But,
Due to the Van der Waals force that CNT is the strongest so that be mutually wrapped in one between CNT
Rise, it is difficult to be evenly dispersed in material, thus have impact on the performance of the physical property of CNT own.
Therefore, how to prepare the carbon nanotube product being easily dispersed and become the master limiting its commercial application
Want obstacle.At present, the scattering problem solving CNT mainly has chemically and physically two kinds of methods.Its
In, mostly chemical method is to be aoxidized by strong acid.Due to strong acid meeting this body structure of destroying carbon nanometer tube, make
The impaired performance of CNT or inefficacy, and due to operation complexity, easily to factors such as environments,
It is allowed to be difficult to industrialized production.The materials such as current macromolecular material, coating, paint are mainly applied
This type of CNT.Physical method is then to carry out wet grinding process by sand mill, is prepared as conduction
Slurry, although dispersion effect is preferable, but the amount of the dispersant wherein added is big affects sending out of electric conductivity
Waving, be allowed to resistance and become big, and the shelf-life is short, current lithium battery produces main this series products of application.
[summary of the invention]
Present invention seek to address that the problems referred to above, and provide a kind of preparation process simple, there is excellent dividing
Dissipating performance, can be directly appended in matrix material without adding dispersant, stable in properties is homogeneous, easily
Form the Spherical Carbon nanotube group of network.
The present invention also aims to provide the preparation method of a kind of Spherical Carbon nanotube group.
The present invention also aims to provide the purposes of described Spherical Carbon nanotube group.
For achieving the above object, the present invention provides a kind of Spherical Carbon nanotube group, this Spherical Carbon nanometer
Pipe group is carbon nanotube dust to be placed in slewing, is made the carbon nanometer of unordered winding by rotation
Pipe is agglomerated into the group of intertexture in order and is formed, and the particle diameter of described group is 0.1～3 micron, is shaped as
Spherical or rod.
Described spherical CNT group is spheroidal or elliposoidal.
Described slewing is grinder or airslide disintegrating mill.
Described grinder is ball mill or sand mill.
Present invention also offers the preparation method of described Spherical Carbon nanotube group, the method includes as follows
Step:
A, CNT and abrasive media are placed in grinder in the ratio of 0.1～1:0.1～10；
B, by CNT with there being the grinder of abrasive media to grind 1 with the linear velocity of 2～50 meter per seconds
Minute～20 hours, being formed is 0.1～3 micron by multiple particle diameters, is shaped as spherical or rod carbon and receives
The powder that mitron group is constituted.
In another program of the present invention, the preparation method of described Spherical Carbon nanotube group includes as follows
Step:
C, the CNT accounting for milling apparatus volume 30～90% is placed in the grinder of non-grinding medium；
D, the grinder of CNT non-grinding medium is ground 1 minute～20 hours, described in grind
The linear velocity of grinding machine is 5～50 meter per seconds, and being formed by multiple particle diameters is 0.1～3 micron, is shaped as ball
The powder that the CNT group of shape or rod is constituted.
In the yet another aspect of the present invention, the preparation method of described Spherical Carbon nanotube group includes as follows
Step
E, CNT is sent into airslide disintegrating mill, the charging rate of CNT is 1～100 kilogram/
Hour, charging air pressure is 0.7～1.0Mpa；
F, by CNT in airslide disintegrating mill with 2～the high pressure of the throughput of 10 cubes ms/h
Gas carries out discharging after impact comminution, and i.e. obtaining by multiple particle diameters is 0.1～3 micron, is shaped as spherical
Or the powder that the CNT group of rod is constituted.
Described abrasive media is material and equivalently-sized Single Medium, or material and different mixed of size
Closing medium, wherein, the particle diameter of described Single Medium is 0.1～50mm.
Abrasive media is the combination of one or more in zirconium silicate pearl, zirconium dioxide pearl or steel ball.
Present invention also offers the purposes of described Spherical Carbon nanotube group, this Spherical Carbon nanotube base
Group can be used as lithium battery, macromolecular material, coating, the conductive agent of paint, thermal conducting agent.
The contribution of the present invention is, it efficiently solves CNT dispersiveness present in prior art
Difference, needs strong acid oxidation and uses the problems such as dispersant.The Spherical Carbon nanotube group of the present invention
Material is owing to being agglomerated into orbicule, thus has excellent dispersing characteristic, and it can be directly appended to matrix
In material, thus reduce or without adding dispersant, thus be greatly expanded its range of application, optimize
With improve production technology, and can significantly save the energy.The spherical knot of the CNT group of the present invention
Structure is easily formed conductive network, therefore can preferably play the performance of CNT.In actual applications,
This CNT group directly can make lithium battery electrocondution slurry through short time high-speed stirred, therefore
Greatly reduce jitter time.The preparation method technique of the present invention is simple, it is easy to implements and pushes away on a large scale
Wide application, and low production cost.The CNT group of the present invention is of many uses, and it can be applicable to
In lithium battery, macromolecular material, coating, paint, as can homodisperse conductive agent and thermal conducting agent.
[accompanying drawing explanation]
Fig. 1 is the micro-scanning of powder by there being the carbon nanotubes group obtained by medium milling equipment
Figure.
Fig. 2 is by the micro-scanning of powder without the carbon nanotubes group obtained by medium milling equipment
Figure.
Fig. 3 is the powder micro-scanning figure by the carbon nanotubes group obtained by airslide disintegrating mill.
The electrocondution slurry micro-scanning figure that Fig. 4 is made up of CNT group.
[detailed description of the invention]
The following example is further explanation of the present invention, and the present invention does not constitute any limit
System.
CNT in the present invention can be in known SWCN or multi-walled carbon nano-tubes
Any one.
Embodiment 1
It is 600 grams by the multi-walled carbon nano-tubes of 160 grams and weight, the zirconium pearl of a diameter of 5 millimeters and weight
Being 600 grams, the blending agent of the zirconium pearl of a diameter of 1 millimeter puts into the planetary ball mill of 3 liters simultaneously
In tank, the linear velocity of ball mill is 5 meter per seconds, milling time 5 hours, obtain containing multiple a diameter of 1～
3 microns, it is shaped as the powder of axiolitic CNT group, the volume of CNT group in powder
Content is 30～40%, and the micro-scanning figure of this CNT group powder is as shown in Figure 1.
Embodiment 2
It is 600 grams by the multi-walled carbon nano-tubes of 160 grams and weight, the zirconium pearl of a diameter of 5 millimeters and weight
Being 600 grams, the blending agent of the zirconium pearl of a diameter of 1 millimeter puts into the planetary ball mill of 3 liters simultaneously
In tank, the linear velocity of ball mill is 5 meter per seconds, milling time 19 hours, obtain containing multiple a diameter of 1～
3 microns, it is shaped as the powder of axiolitic CNT group, the volume of CNT group in powder
Content is 50～60%.
Embodiment 3
It is 400 grams by multi-walled carbon nano-tubes and weight that volume is 300 milliliters, the list of a diameter of 1 millimeter
The zirconium pearl of one medium puts into the sand mill tank of 1 liter, the wherein dispersion impeller of sand mill and the gap of cylinder
Being 5 millimeters, the linear velocity of dispersion impeller is 15 meter per seconds, milling time 1 hour, obtain containing multiple directly
Footpath is 1～3 micron, is shaped as the powder of axiolitic CNT group, CNT base in powder
The volume content of group is 30～40%, and the micro-scanning figure of this CNT group powder is as shown in Figure 2.
Embodiment 4
It is 400 grams by multi-walled carbon nano-tubes and weight that volume is 300 milliliters, the list of a diameter of 1 millimeter
The zirconium pearl of one medium puts into the sand mill tank of 1 liter, the wherein dispersion impeller of sand mill and the gap of cylinder
Being 5 millimeters, dispersion impeller linear velocity is 25 meter per seconds, and milling time 6 hours obtains containing multiple diameters
It is 1～3 micron, is shaped as the powder of axiolitic CNT group, CNT group in powder
Volume content be 60～70%.
Embodiment 5
The multi-walled carbon nano-tubes that volume is 800 milliliters is put into the tank of sand mill without medium of 1 liter, wherein
The dispersion impeller of sand mill and the gap of cylinder are 3 millimeters, and dispersion impeller linear velocity is 50 meter per seconds, grind
3 minutes time, obtain, containing multiple a diameter of 1～3 micron, being shaped as axiolitic CNT group
Powder, in powder, the volume content of CNT group is 70～80%.
Embodiment 6
The multi-walled carbon nano-tubes that volume is 800 milliliters is put into the tank of sand mill without medium of 1 liter, wherein
The dispersion impeller of sand mill and the gap of cylinder are 5 millimeters, and dispersion impeller linear velocity is 50 meter per seconds, grind
10 minutes time, obtain, containing multiple a diameter of 1～3 micron, being shaped as axiolitic CNT base
The powder of group, in powder, the volume content of CNT group is 80～90%.
Embodiment 7
Multi-walled carbon nano-tubes is sent in the airslide disintegrating mill of stream pressure 0.8Mpa, airslide disintegrating mill
Charging rate is 40 kgs/hour；It is 10 to stand with, throughput by CNT in airslide disintegrating mill
The gases at high pressure of square m/h carry out impact comminution 0.5 hour, obtain containing multiple a diameter of 1～3 micro-
Rice, is shaped as the powder of axiolitic CNT group, and in powder, the volume of CNT group contains
Amount is 40～50%, and the micro-scanning figure of this CNT group powder is as shown in Figure 3.
Embodiment 8
By CNT group obtained in embodiment 1,2,3,4,5,6,7 respectively with solvent N～
Methyl pyrrolidone is mixed in stirring container mutually by the weight ratio of 5:95, the linear velocity of stirring container
Being 5 meter per seconds, at the uniform velocity stirring 5 minutes, is respectively prepared leading of serial number 1,2,3,4,5,6,7
Plasma-based material, coating is prepared as electrode slice, then surveys its resistivity, and compares resistance size and disperse all
Even property, data such as table 1:
Table 1
Comparative example 1
By the common CNT that processes without this law and solvent N～methyl pyrrolidone by the weight of 5:95
Amount mixes mutually than in stirring container, and the linear velocity of stirring container is 5 meter per seconds, at the uniform velocity stirring 5 minutes,
Making electrocondution slurry, coating is prepared as electrode slice, then surveys its resistivity, the results are shown in Table 1.
Above-mentioned test result shows, in the case of same dispersing technology, and the CNT group of the present invention
Resistivity is little and narrow range, illustrate that dispersity is uniform, be easier to than untreated CNT
Dispersion.
Comparative example 2:
The common CNT processed without this law is being stirred by the weight ratio of 3:97 with base material polyethylene
Mixing mutually in container, through mill the temperature of 165 DEG C mixing 5 minutes, pulling-on piece surveyed sheet resistance, knot
Fruit is shown in Table 2.
Table 2
Above-mentioned test result shows, in the case of same dispersing technology, and the CNT base of the present invention
Group resistivity is little and narrow range, illustrate that dispersity uniformly, is more easy to than untreated CNT
In dispersion.
Although being disclosed the present invention by above example, but protection scope of the present invention is not
It is confined to this, under conditions of without departing from present inventive concept, deformation that above each component is done, replaces
Change etc. and all will fall within the claims of the present invention.
Claims (5)
1. the preparation method of a Spherical Carbon nanotube group, it is characterised in that the method includes as follows
A, b step or c, Step d or e, f step:
A, CNT and abrasive media are placed in grinder in the ratio of 0.1～1:0.1～10；
B, by CNT with there being the grinder of abrasive media to grind 1 with the linear velocity of 2～50 meter per seconds
Minute～20 hours, being formed is 0.1～3 micron by multiple particle diameters, is shaped as spherical or rod carbon and receives
The powder that mitron group is constituted；
C, the CNT accounting for milling apparatus volume 30～90% is placed in the grinder of non-grinding medium；
D, the grinder of CNT non-grinding medium is ground 1 minute～20 hours, described in grind
The linear velocity of grinding machine is 5～50 meter per seconds, and being formed by multiple particle diameters is 0.1～3 micron, is shaped as ball
The powder that the CNT group of shape or rod is constituted；
E, CNT is sent into airslide disintegrating mill, the charging rate of CNT is 1～100 kilogram/
Hour, charging air pressure is 0.7～1.0MPa；
F, by CNT in airslide disintegrating mill with 2～the high pressure of the throughput of 10 cubes ms/h
Gas carries out discharging after impact comminution, and i.e. obtaining by multiple particle diameters is 0.1～3 micron, is shaped as spherical
Or the powder that the CNT group of rod is constituted.
2. the preparation method of Spherical Carbon nanotube group as claimed in claim 1, it is characterised in that
Described spherical CNT group is spheroidal or elliposoidal.
3. the preparation method of Spherical Carbon nanotube group as claimed in claim 1, it is characterised in that
Described grinder is ball mill or sand mill.
4. the preparation method of Spherical Carbon nanotube group as claimed in claim 1, it is characterised in that
Described abrasive media is material and equivalently-sized Single Medium, or material and the different mixing of size are situated between
Matter, wherein, the particle diameter of described Single Medium is 0.1～50mm.
5. the preparation method of Spherical Carbon nanotube group as claimed in claim 4, it is characterised in that
Described abrasive media is the combination of one or more in zirconium silicate pearl, zirconium dioxide pearl or steel ball.
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| CN107994232B (en) * | 2017-11-23 | 2020-07-03 | 深圳市清新电源研究院 | Carrier material for lithium-sulfur battery |
| 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 |
| CN114068933A (en) * | 2021-10-28 | 2022-02-18 | 诺瑞(深圳)新技术有限公司 | Carbon nano tube conductive agent and preparation method and application thereof |
| 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 |
| CN115304056B (en) * | 2022-07-21 | 2024-01-26 | 青岛泰联新材料有限公司 | Granular carbon nano tube and preparation method thereof |
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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 |
| CN1696053A (en) * | 2004-05-14 | 2005-11-16 | 中国科学院成都有机化学有限公司 | Method for truncating Nano carbon tubes |
| CN1730386A (en) * | 2005-06-17 | 2006-02-08 | 华东师范大学 | Process for preparing nanometer carbon particles |
| JP2006143532A (en) * | 2004-11-19 | 2006-06-08 | Shimizu Corp | Method of improving dispersibility of carbon nanotube |
| CN101873993A (en) * | 2007-07-11 | 2010-10-27 | 御国色素株式会社 | Granulated and the manufacture method of carbon nanotube |
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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 |
| CN1696053A (en) * | 2004-05-14 | 2005-11-16 | 中国科学院成都有机化学有限公司 | Method for truncating Nano carbon tubes |
| JP2006143532A (en) * | 2004-11-19 | 2006-06-08 | Shimizu Corp | Method of improving dispersibility of carbon nanotube |
| CN1730386A (en) * | 2005-06-17 | 2006-02-08 | 华东师范大学 | Process for preparing nanometer carbon particles |
| CN101873993A (en) * | 2007-07-11 | 2010-10-27 | 御国色素株式会社 | Granulated and the manufacture method of carbon nanotube |
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