CN1750176A - Method for preparing carbon containing nano tube conductive powder - Google Patents
Method for preparing carbon containing nano tube conductive powder Download PDFInfo
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- CN1750176A CN1750176A CNA2004100407048A CN200410040704A CN1750176A CN 1750176 A CN1750176 A CN 1750176A CN A2004100407048 A CNA2004100407048 A CN A2004100407048A CN 200410040704 A CN200410040704 A CN 200410040704A CN 1750176 A CN1750176 A CN 1750176A
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Abstract
This invention relates to a preparation method for conductive powder containing carbon nm tube which takes inorganic powder as the carrier uniformly loading VIII group metallic particles to contact with enough carbon gas to generate carbon nm tubes at home position on the inorganic powder by the chemical gas-phase deposition reaction to get the conductive powder with carbon nm tubes. Its volume resistivity is less than 50 Omega cm controlled by controlling the growing volume of carbon nm tubes. The inorganic powder for depositing carbon nm tubes can be mica, graphite, black carbon, SiO2, TiO2 ZnO, conductive mica powder, diatom and scale stone.
Description
Technical field:
The present invention relates to a kind of preparation method of carbon nanotubes conductive powder body, particularly be reflected at uniform deposition carbon nano-tube on the inorganic particle, belong to field of inorganic chemical engineering by catalytic chemical gaseous phase deposition.
Background technology:
Along with the raising of development of technology, expanding economy and people's living standard, the harm of static also highlights day by day.Over surplus in the of nearly 10 year, the misoperation of electronic and electrical equipment (as cause) causes accident many times because the interference of static and harm, caused great economic loss, particularly petroleum storage tank, owing to inadequately serious fire explosion once took place to antistatic processing understanding is not enough with paying attention to.
Static conductive coating is a kind of functional coating that develops rapidly in recent years, is mainly used in the harm of eliminating static.Because production equipment is simple, easy construction, characteristics such as with low cost, static conductive coating has obtained being extensive use of.
Conductive functional filler is a static conductive coating important composition composition.Traditional conductive functional filler has carbon black, graphite, silver, copper, aluminium, nickel metal powder, is restricted when using but these conductive functional fillers all have certain defective.Conductive black or graphite are black, and conductivity is better, but strong coloring force, difficult dispersion, and especially the goods color is very black, absorb sunlight or infrared light easily and cause that heating expands.Though various metal dust conductivity are strong, beyond the desilver, aluminium, nickel, the easy oxidation of copper powders may, corrosion-resistant.So urgent wish that exploitation is of light color, good conductivity, chemical stability height, conductive functional filler that cost is low.
Carbon nano-tube is a kind of tubular structure nano-carbon material, is found by Japanese NEC Electronic Speculum expert Iijima in 1991.Carbon nano-tube has good electric conductivity and chemical stability, and has filamentary structure.When the preparation static conductive coating, add very a spot of carbon nano-tube and just can reach the requirement of leading static.Because of addition is few, its color is covered easily, is easy to obtain light tone product, also help the design of other performance of static conductive coating simultaneously, but the modulation space is big.
Carbon nano-tube is a monodimension nanometer material, and diameter is in nano-scale range, and length is in the micro-meter scale scope, and draw ratio is generally more than 1000.Because special structural form twines mutually between the carbon nano-tube, be difficult to disperse, serviceability is unsatisfactory.
In order to solve the scattering problem of carbon nano-tube in coating, patent (the application number: 200410021990.3) proposed following thinking: at first in the aqueous solution or other organic solvent, even carbon nanotube is disperseed of Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences's application, form the suspension of carbon nano-tube, under brute force stirs, other micron particles is joined in the carbon nano tube suspension then, filter after stirring certain hour, filtrate recycles after reclaiming, and promptly obtains composite conductive powder after the filter cake oven dry.The composite granule of the method gained has good result of use in coating, but needs ultrasonic wave to disperse in the preparation process, and operations such as filtration are loaded down with trivial details relatively.
Summary of the invention:
The objective of the invention is to realize the evenly compound of carbon nano-tube and inorganic particle, the carbon nanotubes conductive powder body that obtained performance is good by simple procedure.
The present invention is achieved through the following technical solutions: the VII family metallic of uniform distribution of at least one on inorganic particle, under 550-1000 ℃ of temperature, pass through chemical vapour deposition reaction, on inorganic particle, deposit equally distributed carbon nano-tube, promptly obtain the conductive powder body of carbon nanotubes.
Can realize that easily nano level VIII family's metallic or nano level VIII family metal oxide load on the inorganic particle uniformly by liquid phase method among the present invention, this is the general way of condition restriction such as a kind of shape that can not be subjected to powder, specific surface, granular size.For example, be dispersant and solvent with ethanol, Fe, the Co of dissolving aequum, the nitrate of Ni add the used inorganic particle of deposition of carbon nanotubes simultaneously.Drip alkaline solution then in above-mentioned mixture, for example ammoniacal liquor, ammonium hydrogencarbonate, carbonic acid ammonia etc.The amount of control ethanol is much larger than the amount of basic species, and dropping is very slow, filters then, and the oxidate that just can make nano level Fe, Co, Ni is on the object powder.Can be in fluidized state by in ebullated bed, making the object powder in addition, feed organo-metallic compound simultaneously, on inorganic particle, deposit VIIII family metal nanoparticle.
The dispersion of metal on inorganic particle of VIII family is to realize easily, amount and length that the amount by control VIII family metal and the time length of reaction just can controlling carbon nanotube, thus control the conductive capability of conductive network.Because draw ratio that carbon nano-tube is bigger and good conductive capability, addition seldom just can reach the effect of leading static.For example, the titanium oxide specific insulation that contains 10% carbon nano-tube can reach 3 Ω cm.
The conducting powder of the present invention preparation is compared the purification step of having removed carbon nano-tube mutually to the preparation of the preparation of a carbon nano-tube and conducting powder process that permeates.Well-known is that the carbon nano-tube that has just prepared generally contains carriers such as silica, aluminium oxide, magnesium oxide, need consume a large amount of acid and loaded down with trivial details operation in order to remove carrier, both uneconomical also not environmental protection.Inorganic particle of the present invention plays carrier in preparation in the conducting powder, plays the effect of filler in adding coating to, does not need to remove, and multiple advantage is permeated, and has originality.
The problem of the dispersion difficulty the when conductive powder body of the present invention's preparation has avoided general carbon nano-tube to use.Carbon nano-tube has very big draw ratio, and this helps the formation of conductive network, but is unfavorable for the dispersion of carbon nano-tube.Carbon nano-tube has bigger surface energy simultaneously, has the tendency of reunion.For dispersing Nano carbon tubes general need ultrasonic wave, ball milling, there is difficult problem of amplifying in this in suitability for industrialized production, also need the surfactant of consume expensive simultaneously.The diameter of carbon nano-tube and growth position are that diameter and position by VIII family metal determined in the present invention, method provided by the invention just can obtain the even dispersion of carbon nano-tube on inorganic particle by the even dispersion of VIII family metal on inorganic particle.
Inorganic particle of the present invention can be present existing conductive powder body, as conductive mica powder, conductive titanate dioxide, conduction silicon dioxide, conductive zinc oxide, graphite, semiconductor oxide tin-antimony oxide, also can be inorganic particles such as nonconducting mica powder, titanium dioxide, silicon dioxide, zinc oxide.
Description of drawings
Accompanying drawing is the stereoscan photograph of the conductive mica powder of embodiment 1 gained, and to the covering on the mica sheet of even carbon nanotube, diameter is mostly at 15-35nm as seen from the figure, and length is about 1000nm.
The specific embodiment mode
Embodiment 1:
Get 65.66 gram nickel nitrates and be dissolved in the mixed solution that contains 350ml water, 100ml ethanol, stir and obtain settled solution, add 300 gram mica powders again, stir half an hour, stand-by.147.427 gram carbonic hydroammonium are dissolved in the 850ml water.The aqueous solution that contains carbonic hydroammonium, be added drop-wise in the stand-by mixture recited above, the control dropping time is half an hour, 55 ℃ of reaction temperatures.After dripping, mixture slaking 3 hours is filtered, washing, drying, 500 ℃ of roasting half an hour.Get the baked mica powder of 100 grams and put into the quartz ampoule of diameter 10cm, logical nitrogen emptying air is in 700 ℃ of methane gas reaction half an hour that feed 80l/h, logical nitrogen cooling.The specific insulation of gained powder is 5 Ω cm.Make an addition to acrylic resin, wherein conductive powder body accounts for 20%, normal temperature self-drying, and surface resistivity is 10
4-10
6Ω/mouth, rinses that to be coated with effect the same entirely at spraying, roller coat.Conductive powder body to gained carries out sem test, can be observed the uniform distribution of carbon nano-tube at mica surface, and length is shorter.
Embodiment 2:
Get 90 gram ferric nitrates and be dissolved in and contain 350ml water, in the mixed solution of 100 gram ethanol, stir and obtain settled solution, add 300 gram titanium dioxides again, stir half an hour, stand-by.147.427 gram carbonic hydroammonium are dissolved in the 850ml water.The aqueous solution that contains carbonic hydroammonium, be added drop-wise in the stand-by mixture recited above, the control dropping time is half an hour, 55 ℃ of reaction temperatures.After dripping, mixture slaking 3 hours is filtered, washing, drying, 500 ℃ of roasting half an hour.Get the baked mica powder that contains the nanoscale nickel oxide of 100 grams and put into the quartz ampoule of diameter 10cm, logical nitrogen purge is in 700 ℃ of methane gas reaction half an hour that feed 80l/h, logical nitrogen cooling.The specific insulation of gained powder is 6 Ω cm.
Embodiment 3:
Get the silicon dioxide of 100 gram average diameters, be added in the 500 gram distilled water, add Co (NO at 50nm
3)
2.6H
2O 15.0g stirs in 80 ℃ of evaporates to dryness, in 100 ℃ of dryings 12 hours, again through 300 ℃ of roastings silicon oxide catalyst of cobalt oxide that just obtained uniform load in 4 hours.Get this catalyst 10 grams, put into the quartz ampoule that diameter is 5cm, logical nitrogen emptying.Be warmed up to 750 ℃, feed methane and hydrogen volume ratio and be 1: 1 gaseous mixture, reacted 1 hour, obtain the light grey product of carbon nanotubes.Burn the 2 hours a spot of amorphous carbon in place to go through 400 ℃ of dry airs again, weighing at last obtains containing the combined oxidation silicon filler of 5% carbon nano-tube.Measuring its specific insulation is 18.7 Ω .cm.Get this composite granule and observe under transmission electron microscope, find the scope of gained carbon nano-tube diameter at 5-60nm, length is 0.5 micron-100 microns scope.Growing from silicon oxide surface of gained even carbon nanotube forms uniform network.Get this composite granule and be filled in the E-51 epoxy resin, make conductive powder body weight account for whole macromolecule ratio 20%, disperse, film, record surface resistivity 10 through colloid mill
6Ω/mouth.
Claims (8)
1. the preparation method of a carbon nanotubes conductive powder body is to be core with the inorganic particle, by realizing the coated with carbon nanotube at the inorganic powder surface in-situ growing carbon nano tube.It is characterized in that:
(1) with the inorganic particle is carrier, uniformly at least a VIII of load family metallic;
(2) on inorganic particle, deposit equally distributed carbon nano-tube at 550-1000 ℃ by chemical vapour deposition reaction, obtain the conductive powder body of carbon nanotubes.
2. according to the method for claim 1, the metal that it is characterized in that load on the inorganic particle is Co, Ni, Fe and composition thereof.
3. according to the method for claim 1, the mass percent that it is characterized in that the metal of load and carrier is 0.5: 100-30: 100.
4. according to the method for claim 3, the mass percent that it is characterized in that the metal of load and carrier is 1: 100-5: 100.
5. according to the method for claim 1, it is characterized in that gained carbon nano-tube diameter is at 0.4nm-400nm.
6. according to the method for right 1, it is characterized in that described carrier is mica, graphite, carbon black, silicon dioxide, titanium dioxide, zinc oxide, conductive mica powder, diatomite, wollastonite.
7. according to the method for claim 1, it is characterized in that the carried metal element is by infusion process, coprecipitation, the realization of Metalorganic chemical vapor deposition method.
8. according to the method for claim 1, the reaction temperature that it is characterized in that described deposition of carbon nanotubes is 600-850 ℃.
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| CNA2004100407048A CN1750176A (en) | 2004-09-17 | 2004-09-17 | Method for preparing carbon containing nano tube conductive powder |
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Cited By (16)
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| CN100369809C (en) * | 2004-12-14 | 2008-02-20 | 中国科学院物理研究所 | Carbon wool ball material and its preparation method and uses |
| CN100388392C (en) * | 2005-06-20 | 2008-05-14 | 浙江大学 | Conducting powder by using laminar soilicate mineral as basal body, and preparation method |
| CN100400469C (en) * | 2006-11-21 | 2008-07-09 | 浙江大学 | Process of preparing carbon nanotube/nanometer zinc oxide sphere heterojunction |
| CN101182098B (en) * | 2007-11-30 | 2010-11-03 | 福州大学 | Technology for preparing nano-carbon tube-silica dioxide gel glass |
| CN101578023B (en) * | 2008-05-09 | 2011-04-06 | 富港电子（东莞）有限公司 | Element protection method of electronic product |
| CN102074279A (en) * | 2010-12-30 | 2011-05-25 | 北京工业大学 | Preparation method of multihole-structure-characterized conducting diatomaceous earth |
| CN102211184A (en) * | 2011-05-23 | 2011-10-12 | 浙江大学 | Method for preparing tin nanometer rod completely covered by carbon nanometer tube |
| CN102558917A (en) * | 2011-12-30 | 2012-07-11 | 苏州工业园区润佳工程塑料有限公司 | Wrapped conducting nano material, conducting nano composite material and preparation method for wrapped conducting nano material and conducting nano composite material |
| CN103502148A (en) * | 2011-02-14 | 2014-01-08 | 国立大学法人九州大学 | Layered compound-metal particle composite and production method therefor, and suspension, film and flexible solar cell using same |
| CN105273445A (en) * | 2015-05-08 | 2016-01-27 | 苏州第一元素纳米技术有限公司 | Nano carbon composite diatomite and preparation method therefor |
| CN103183353B (en) * | 2011-12-29 | 2017-03-08 | 中国科学院成都有机化学有限公司 | A kind of conductive mica powder and preparation method thereof |
| JPWO2015133474A1 (en) * | 2014-03-05 | 2017-04-06 | 積水化学工業株式会社 | Conductive filler, method for producing conductive filler, and conductive paste |
| CN106947290A (en) * | 2017-03-31 | 2017-07-14 | 合肥悦兰信息技术有限公司 | The preparation method of colored silicon-dioxide powdery material |
| CN108430755A (en) * | 2015-11-20 | 2018-08-21 | 琳得科株式会社 | Sheet material, heater and heat generating device |
| CN108448122A (en) * | 2018-03-21 | 2018-08-24 | 青岛大学 | A kind of preparation method of carbon-nitrogen nano tube package nano metal particles |
| CN114195126A (en) * | 2020-10-26 | 2022-03-18 | 武汉新碳科技有限公司 | Preparation method of composite nano-carbon material and composite nano-material |
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2004
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Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100369809C (en) * | 2004-12-14 | 2008-02-20 | 中国科学院物理研究所 | Carbon wool ball material and its preparation method and uses |
| CN100388392C (en) * | 2005-06-20 | 2008-05-14 | 浙江大学 | Conducting powder by using laminar soilicate mineral as basal body, and preparation method |
| CN100400469C (en) * | 2006-11-21 | 2008-07-09 | 浙江大学 | Process of preparing carbon nanotube/nanometer zinc oxide sphere heterojunction |
| CN101182098B (en) * | 2007-11-30 | 2010-11-03 | 福州大学 | Technology for preparing nano-carbon tube-silica dioxide gel glass |
| CN101578023B (en) * | 2008-05-09 | 2011-04-06 | 富港电子（东莞）有限公司 | Element protection method of electronic product |
| CN102074279A (en) * | 2010-12-30 | 2011-05-25 | 北京工业大学 | Preparation method of multihole-structure-characterized conducting diatomaceous earth |
| CN103502148B (en) * | 2011-02-14 | 2015-07-22 | 国立大学法人九州大学 | Layered compound-metal particle composite and production method therefor, and suspension, film and flexible solar cell using same |
| CN103502148A (en) * | 2011-02-14 | 2014-01-08 | 国立大学法人九州大学 | Layered compound-metal particle composite and production method therefor, and suspension, film and flexible solar cell using same |
| US9035169B2 (en) | 2011-02-14 | 2015-05-19 | Kyushu University | Layered compound-metal particle composite and production method therefor, and suspension, film and flexible solar cell using same |
| CN102211184A (en) * | 2011-05-23 | 2011-10-12 | 浙江大学 | Method for preparing tin nanometer rod completely covered by carbon nanometer tube |
| CN102211184B (en) * | 2011-05-23 | 2013-01-02 | 浙江大学 | Method for preparing tin nanometer rod completely covered by carbon nanometer tube |
| CN103183353B (en) * | 2011-12-29 | 2017-03-08 | 中国科学院成都有机化学有限公司 | A kind of conductive mica powder and preparation method thereof |
| CN102558917B (en) * | 2011-12-30 | 2014-08-06 | 苏州润佳工程塑料股份有限公司 | Wrapped conducting nano material, conducting nano composite material and preparation method for wrapped conducting nano material and conducting nano composite material |
| CN102558917A (en) * | 2011-12-30 | 2012-07-11 | 苏州工业园区润佳工程塑料有限公司 | Wrapped conducting nano material, conducting nano composite material and preparation method for wrapped conducting nano material and conducting nano composite material |
| JPWO2015133474A1 (en) * | 2014-03-05 | 2017-04-06 | 積水化学工業株式会社 | Conductive filler, method for producing conductive filler, and conductive paste |
| US10639713B2 (en) | 2014-03-05 | 2020-05-05 | Sekisui Chemical Co., Ltd. | Conductive filler, method for manufacturing conductive filler, and conductive paste |
| CN105273445A (en) * | 2015-05-08 | 2016-01-27 | 苏州第一元素纳米技术有限公司 | Nano carbon composite diatomite and preparation method therefor |
| CN108430755A (en) * | 2015-11-20 | 2018-08-21 | 琳得科株式会社 | Sheet material, heater and heat generating device |
| CN106947290A (en) * | 2017-03-31 | 2017-07-14 | 合肥悦兰信息技术有限公司 | The preparation method of colored silicon-dioxide powdery material |
| CN108448122A (en) * | 2018-03-21 | 2018-08-24 | 青岛大学 | A kind of preparation method of carbon-nitrogen nano tube package nano metal particles |
| CN114195126A (en) * | 2020-10-26 | 2022-03-18 | 武汉新碳科技有限公司 | Preparation method of composite nano-carbon material and composite nano-material |
| WO2022089671A1 (en) * | 2020-10-26 | 2022-05-05 | 武汉新碳科技有限公司 | Preparation method for composite nano-carbon material and composite nanomaterial |
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