CN100554577C - The preparation of carbon nano tube/acrylic carbon fiber composite carbon fiber paper and purposes - Google Patents
The preparation of carbon nano tube/acrylic carbon fiber composite carbon fiber paper and purposes Download PDFInfo
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- CN100554577C CN100554577C CNB2006101183166A CN200610118316A CN100554577C CN 100554577 C CN100554577 C CN 100554577C CN B2006101183166 A CNB2006101183166 A CN B2006101183166A CN 200610118316 A CN200610118316 A CN 200610118316A CN 100554577 C CN100554577 C CN 100554577C
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Abstract
The invention discloses a kind of preparation and purposes of carbon nano tube/acrylic carbon fiber composite carbon fiber paper, comprise the steps: (1), flooded 1-3 hour, be washed to neutrality with activator with acrylonitrile base carbon fiber and CNT; (2) take by weighing acrylonitrile base carbon fiber and the CNT of handling, put into beater and pull an oar,, fully mix, add adhesive with the carbon fiber slurries with the dispersant wiring solution-forming; (3) adopt conventional wet papermaking technology can obtain described carbon fiber reinforce plastic paper.Can be used for antistatic packaging material, planar exothermic material, new forms of energy and electrochemical field and equip material, high-quality acoustical material and environmental-protection material with material, electromagnetic shielding material, modern weapons.The carbon fiber paper material that the present invention makes has fine electric conductivity; The CNT that adds can improve its electric conductivity and pliability.
Description
Technical field
The present invention relates to a kind of electric conductivity preferably that has, the preparation and the purposes of the new type functional carbon fiber paper of voidage and hydrophobic performance particularly relate to a kind of preparation and purposes of carbon nano tube/acrylic carbon fiber composite carbon fiber paper.
Background technology
20th century particularly entered the seventies, since the successful Application of fuel cell in space travel, the appearance of worldwide energy crisis, and an urgent demand of environmental protection and sustainable development makes people step up to seek cleaning new forms of energy efficiently.Fuel cell system is the clean energy resource dynamical system of new generation that is with historically new significance, and is chosen as one of 21 century change human lives " ten big science and technology " by U.S.'s " epoch " weekly.International energy circle prediction: fuel cell will become after waterpower, firepower nuclear energy the 4th generation TRT, and after steam engine, internal combustion engine the 3rd generation dynamical system; Fuel cells applications is very extensive, demonstrates out wide application prospect at aspects such as electric automobile, power station, portable power supply, submarine, navigation, Aero-Space.
Generally speaking, the unit of present domestic development Proton Exchange Membrane Fuel Cells (PEMFC) is a lot, according to incompletely statistics, the Dalian Chemistry and Physics Institute of the Chinese Academy of Sciences is arranged, institute should be changed in Changchun, the organic institute in Shanghai, Shanghai space research institute, Tianjin power supply research institute, Tsing-Hua University, Xiamen University, Fudan University, Shanghai Communications University etc.At present these domestic PEMFC research units all are to use the carbon fiber paper of Japanese TORAY company, Germany technology company (SGL) or Canadian Ballard company basically.Domestic considerably less, the used gas diffusion layer material dependence on import of unit to the research of PEMFC associated materials.And carbon fiber paper is as the pith of gas diffusion layers, with regard to carbon fiber paper, the research level of China lags far behind abroad, research still is in laboratory stage, can not provide large-area carbon fiber paper, the device and the equipment that also do not have serialization to produce, the resistivity of material, pore-size distribution, aspects such as intensity can't satisfy the actual use of PEMFC needs.
Can't satisfy conduction, heat conduction, hydrophobic and stability requirement fully simultaneously at having carbon fiber paper both at home and abroad now, particularly carbon fiber paper fragility is big, lacks flexibility, and is easily destroyed in the process of preparation electrode.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation and purposes of carbon nano tube/acrylic carbon fiber composite carbon fiber paper, to remedy the deficiencies in the prior art or defective, meets the demands of production and living.
In order to solve the problems of the technologies described above, one of the technical solution adopted in the present invention is: a kind of preparation method of carbon nano tube/acrylic carbon fiber composite carbon fiber paper comprises the steps:
(1) mass fraction that will account for compound is that the acrylonitrile base carbon fiber of 98-99% and the mass fraction that accounts for compound are the CNT of 1-2%, with activator dipping 1-3 hour, is washed till neutrality with distilled water again; Described activator is NaOH solution, H
3PO
4Solution, HNO
3Solution or H
2SO
4In the solution one or more.
(2) take by weighing acrylonitrile base carbon fiber and the carbon mano-tube composite of handling through step (1), putting into beater pulls an oar, with mass fraction is the dispersant wiring solution-forming of the 0.5%-2% of compound quality, the slurries that mix with carbon fiber and CNT fully mix, and fixedly the mass percent concentration of slurries is 10%-30%; After making beating is finished, add adhesive, the mass fraction of adhesive is the 1%-15% of compound quality.
(3) adopt conventional wet papermaking technology, copy to get at pattern and copy sheet on the device, vacuumize after processing of 15% ptfe emulsion and carbonization, obtains described carbon fiber reinforce plastic paper.
As optimized technical scheme: the electric conductivity of described acrylonitrile base carbon fiber is 0.01-0.05 Ω cm, and length is 1-10mm.
Described CNT is a multi-walled carbon nano-tubes, and diameter is 20nm, and draw ratio is 200.
Described dispersant is one or more in polyacrylamide solution, polyethylene glycol oxide or the glycerine.
Described adhesive is one or more in polyvinyl alcohol, modified starch or the water soluble phenol resin.
In order to solve the problems of the technologies described above, two of the technical solution adopted in the present invention is: a kind of application of carbon nano tube/acrylic carbon fiber composite carbon fiber paper can be used for antistatic packaging material, planar exothermic material, new forms of energy and electrochemical field and equips material, high-quality acoustical material and environmental-protection material with material, electromagnetic shielding material, modern weapons.
Details are as follows for purposes of the present invention:
One antistatic packaging material
The carbon fiber paper of different resistance values has different use, and resistivity is 10
7-10
4The carbon fiber paper of Ω cm has antistatic property, is used for the packaging material of the electronic device of the antistatic requirement of needs.
Two planar exothermic materials
Resistivity is 10
4-10
-1The carbon fiber paper of Ω cm is commonly used for planar exothermic material.Planar exothermic material is by the voltage that uses, and can divide conventional voltage (380,220 and 110V) and safe voltage (36,12 and 6V), can be divided into rigidity and flexible two classes by the insulating materials type, and rigidity adopts fiberglass more, and flexibility mostly is textiles.These planar exothermic materials are used more and more wide in industrial and agricultural production, low-temperature industrial container heat tracing for example, and the heating of agricultural greenhouse, owing to be the corrosion-resistant heater of low-temperature insulation, so can be directly to the plant root soil heating, than more economizing energy by the air heat transfer.In Russia and Northern Europe, the planar exothermic material of carbon fiber paper is widely used in family's heating, and it combines planar exothermic material with wall, carpet, combine with workmanship, this advantage of utilizing the radiation low temperature heating mode to have comfortable power saving.
And high-performance carbon fibre paper can book and softness, and resistivity is low, and for the flexible planar exothermic material exploitation under the safe voltage provides assurance, and the planar exothermic material of this flexibility all has sizable market at family's heating, body-care numerous areas.For example China has developed electric blanket, footwarmer, joint hot compress band, hot compress waist support etc.
Three new forms of energy and electrochemical field material
Resistivity is 10
-2-10
-3The carbon fiber paper of Ω cm belongs to high-performance carbon fibre paper, is referred to as the high conductivity carbon fiber paper usually, in new forms of energy and electrochemical field just in wide popularization and application.The green energy resource fuel cell more and more is subjected to people's attention.It is to utilize the same fuel of airborne oxygen (hydrogen) to become electric energy under the acting in conjunction of proton diffusion barrier and catalyst, discharges accessory substance hot water simultaneously.Require electrode material to have following performance in the entire reaction: 1. enough chemical stabilities, corrosion-resistant; 2. porous; The hole that sufficient amount promptly will be arranged is with the supply of assurance fuel gas and the discharge of water byproduct; Also a great deal of micropore should be arranged simultaneously,, improve generating efficiency to guarantee that chemical reaction fully carries out; 3. electric conductivity: have low resistance, reduce the battery in-fighting.Scientist confirms that through multiple exploration high-performance carbon fibre paper can satisfy above-mentioned performance requirement.And compare with former material with carbon element electrode, also have that volume is little, light weight, efficient advantages of higher.Now, the gas diffusion layers electrode material with high-performance carbon fibre paper making Proton Exchange Membrane Fuel Cells (PEMFC) has obtained the approval of each fuel cell manufacturers, thereby has obtained very fast development.
Four electromagnetic shielding materials
Electromagnetic harm more and more causes people's attention.In general, have the good electrical conductivity and the material of magnetic conductivity, electromagnetic wave had function of shielding, people carbon fiber mixed in plastics, make the plastic shell of tool electro-magnetic screen function.The goods that utilize high-performance carbon fibre paper to make function of shielding have more characteristic, and the someone proposes carbon fiber paper is attached to glass fiber reinforced plastic surface or frosting, makes the case with electro-magnetic screen function with it, and perhaps material saving more more can keep the original mechanical performance of case.Perhaps, make ultra-thin porous shielding case with paper impregnating resin, moulding.
Five modern weaponss equipment material
Carbon fiber paper with carbon fiber and other absorbing material combination are made is expected to use on stealthy weapon.The U.S. has used the lethal bomb of " microwave bomb " microwave bomb right and wrong in 1991 Gulf War and Kosovo War in 1999, it fills graphite and carbon fiber, after the blast they is spread to the space, to destroy enemy radar defense system and communication system.The author thinks that the carbon fiber in the bomb contains carbon fiber paper probably, because paper has more floatability, the time of staying is longer in the space.
Six high-quality acoustical materials
With the cone of carbon fiber paper making loudspeaker, be the patent of each famous brand advanced audio, this is that light weight has higher sensitivity because carbon fiber cone density is little.The soniferous speed of carbon fiber is fast, is 11.17km/s according to the carbon determination fiber, and xylon is 1.45km/s, and this is beneficial to the minimizing distortion factor, sound clarity, and acoustics is splendid.
Seven environmental-protection materials
Carbon fiber paper with adsorption filtration function has wide purposes in environmental protection and chemical industry, as air freshener, air conditioner, anti-poison respirator, protective clothing, chemical filtration device etc.
In a word, high-performance carbon fibre paper as the purposes of functional material be far above above-mentioned some, its many performances are still waiting us and go understanding, go developing, for example in all conglomeraties such as electrochemical field, environmental protection, space flight, metallurgy, the energy and building materials, all exist extensive potential market.
The invention has the beneficial effects as follows: the carbon fiber paper material that the present invention makes has fine electric conductivity; The CNT that adds can improve its electric conductivity and pliability; The novel carbon fiber paper of final products, electric conductivity, pliability and hydrophobic performance all obviously are better than traditional carbon fibres paper.The application of this carbon fiber paper is very extensive simultaneously.
The specific embodiment
Below in conjunction with specific embodiment the present invention is further elaborated.
Embodiment 1
Acrylonitrile base carbon fiber is cut off, and getting its distribution of lengths is 2mm20%, 4mm20%, and 6mm20%, 8mm20%, 10mm20%, carbon fiber are 98% of compound quality mark;
Multi-walled carbon nano-tubes is 2% of a compound quality mark, uses its compound of activator NaOH solution impregnation 1 hour simultaneously, is washed till neutrality with distilled water again;
With the dispersant polyacrylamide solution carbon fiber and CNT are dispersed in the aqueous solution, the polyacrylamide consumption is 1% of a compound quality mark, adds adhesive polyethylene alcohol simultaneously, and its mass fraction is 5% of a compound;
Utilize the wet papermaking principle just can make carbon fiber paper;
Carbon fiber paper being placed in the vacuum drying oven dry, is 15% polytetrafluoroethylsolution solution (PTFE) processing again with concentration: will obtain to such an extent that carbon fiber paper carries out carbonization treatment and obtains described high-performance carbon fibre paper.
Utilize some performance indications of the carbon fiber paper that this example makes as follows:
Unit Weight 0.009g/cm
2, thickness 0.2mm, voidage 85%, density 0.45g/cm
3, resistivity 0.06 Ω cm, TENSILE STRENGTH 40N/cm.
Embodiment 2
Acrylonitrile base carbon fiber is cut off, and getting its distribution of lengths is 1mm20%, 3mm20%, and 5mm20%, 7mm20%, 9mm20%, carbon fiber are 99% of compound quality mark;
Multi-walled carbon nano-tubes is 1% of a compound quality mark, uses activator H simultaneously
3PO
4Its compound of solution impregnation is washed till neutrality with distilled water after 3 hours again;
With the dispersant polyethylene oxide solutions carbon fiber and CNT are dispersed in the aqueous solution, the polyethylene glycol oxide consumption is 2% of a compound quality mark, adds the adhesive water soluble phenol resin simultaneously, and its mass fraction is 1% of a compound;
Utilize the wet papermaking principle just can make carbon fiber paper;
Carbon fiber paper is placed on drying in the vacuum drying oven, is 15% polytetrafluoroethylsolution solution (PTFE) processing with concentration: will obtain to such an extent that carbon fiber paper carries out carbonization treatment again; Just can obtain high-performance carbon fibre paper.
Utilize some performance indications of the novel carbon fiber paper that this example makes as follows:
Unit Weight 0.0138g/cm
2, thickness 0.3mm, voidage 75%, density 0.46g/cm
3, resistivity 0.04 Ω cm, TENSILE STRENGTH 55N/cm.
Embodiment 3
Acrylonitrile base carbon fiber is cut off, and getting its distribution of lengths is 2mm20%, 4mm20%, and 6mm20%, 8mm20%, 10mm20%, carbon fiber are 90% of compound quality mark;
Multi-walled carbon nano-tubes is 5% of a compound quality mark, uses activator HNO simultaneously
3Its compound of solution impregnation 2 hours is washed till neutrality with distilled water again;
With the dispersant glycerite carbon fiber and CNT are dispersed in the aqueous solution, the glycerine consumption is 0.5% of a compound quality mark, adds the adhesive modified starch simultaneously, and its mass fraction is 15% of a compound;
Utilize the wet papermaking principle just can make carbon fiber paper;
Carbon fiber paper being placed in the vacuum drying oven dry, is 15% polytetrafluoroethylsolution solution (PTFE) processing again with concentration: will obtain to such an extent that carbon fiber paper carries out carbonization treatment and obtains described high-performance carbon fibre paper.
Utilize some performance indications of the carbon fiber paper that this example makes as follows:
Unit Weight 0.009g/cm
2, thickness 0.3mm, voidage 80%, density 0.45g/cm
3, resistivity 0.05 Ω cm, TENSILE STRENGTH 45N/cm.
Claims (6)
1. the preparation method of a carbon nano tube/acrylic carbon fiber composite carbon fiber paper is characterized in that, comprises the steps:
(1) mass fraction that will account for compound is that the acrylonitrile base carbon fiber of 98-99% and the mass fraction that accounts for compound are the CNT of 1-2%, with activator dipping 1-3 hour, is washed till neutrality with distilled water again; Described activator is NaOH solution, H
3PO
4Solution, HNO
3Solution or H
2SO
4In the solution one or more;
(2) take by weighing acrylonitrile base carbon fiber and the carbon mano-tube composite of handling through step (1), putting into beater pulls an oar, with mass fraction is the dispersant wiring solution-forming of the 0.5%-2% of compound quality, the slurries that mix with carbon fiber and CNT fully mix, and fixedly the mass percent concentration of slurries is 10%-30%; After making beating is finished, add adhesive, the mass fraction of adhesive is the 1%-15% of compound quality;
(3) adopt conventional wet papermaking technology, copy to get at pattern and copy sheet on the device, vacuumize after 15% polytetrafluoroethylsolution solution processing and carbonization, obtains described carbon fiber reinforce plastic paper.
2, the preparation method of carbon fiber reinforce plastic paper according to claim 1 is characterized in that, the electric conductivity of described acrylonitrile base carbon fiber is 0.01-0.05 Ω cm, and length is 1-10mm.
3, the preparation method of carbon fiber reinforce plastic paper according to claim 1 is characterized in that, described CNT is a multi-walled carbon nano-tubes, and diameter is 20nm, and draw ratio is 200.
4, the preparation method of carbon fiber reinforce plastic paper according to claim 1 is characterized in that, described dispersant is one or more in polyacrylamide solution, polyethylene glycol oxide or the glycerine.
5, the preparation method of carbon fiber reinforce plastic paper according to claim 1 is characterized in that, described adhesive is one or more in polyvinyl alcohol, modified starch or the water soluble phenol resin.
6, a kind of purposes of carbon fiber reinforce plastic paper as claimed in claim 1 is characterized in that, is used for antistatic packaging material, new forms of energy and electrochemical field material, electromagnetic shielding material.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102146641B (en) * | 2011-01-12 | 2013-11-06 | 中南大学 | Process for manufacturing modified carbon fiber paper by adopting carbon nanotube implanting method |
| CN102182100B (en) * | 2011-04-12 | 2012-08-29 | 武汉赛洋暖通设备有限公司 | Carbon fiber heating paper and preparation method thereof |
| CN102561109A (en) * | 2011-12-20 | 2012-07-11 | 南昌大学 | Method for preparing carbon nano tube conductive paper |
| CN105297524B (en) * | 2014-05-26 | 2018-05-22 | 昆明纳太科技有限公司 | Across scale fibrous paper and its wet method pulping method |
| JPWO2016203746A1 (en) * | 2015-06-19 | 2018-04-05 | 日本ゼオン株式会社 | Conductive nonwoven fabric and method for producing the same |
| CN105332277B (en) * | 2015-10-30 | 2017-10-24 | 深圳市联兴商贸实业有限公司 | A kind of special sepiolite fibre of papermaking and preparation method thereof |
| CN106917319A (en) * | 2015-12-24 | 2017-07-04 | 成都新柯力化工科技有限公司 | A kind of papermaking Special high-strength flexibility sepiolite fibre and preparation method thereof |
| CN107141777A (en) * | 2017-04-20 | 2017-09-08 | 常州可赛成功塑胶材料有限公司 | A kind of preparation method of composite conducting engineering plastics |
| CN109003730B (en) * | 2018-09-10 | 2020-05-19 | 江西克莱威纳米碳材料有限公司 | Anti-electromagnetic interference and anti-fracture data line |
| CN114566655A (en) * | 2020-11-27 | 2022-05-31 | 国家能源投资集团有限责任公司 | Carbon nanotube/carbon fiber paper composite electrode material, preparation method thereof and all-vanadium redox flow battery |
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Non-Patent Citations (2)
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| 碳纤维材料与碳纤维纸. 黄鸿.中华纸业，第25卷第5期. 2004 |
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