CN1962429A - Preparation method of pure nano-carbon tube film - Google Patents
Preparation method of pure nano-carbon tube film Download PDFInfo
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- CN1962429A CN1962429A CN 200610022327 CN200610022327A CN1962429A CN 1962429 A CN1962429 A CN 1962429A CN 200610022327 CN200610022327 CN 200610022327 CN 200610022327 A CN200610022327 A CN 200610022327A CN 1962429 A CN1962429 A CN 1962429A
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Abstract
The invention discloses a preparing method of pure-carbon nanometer pipe film, which comprises the following steps: adopting electric spinning method or solution spinning method; spraying composite solution of carbon nanometer pipe and dispersant on the receiving board; heating to volatilize dispersant; or removing dispersant through distilled water.
Description
Affiliated technical field
The present invention relates to a kind of preparation of nano material, relate in particular to a kind of preparation method of pure nano-carbon tube film.
Background technology
Carbon nanotube finds that in 1991 carbon nanotube is divided into multi-walled carbon nano-tubes (also claiming Baji-tube) and Single Walled Carbon Nanotube by Japanese Electronic Speculum expert Iijima.Because all there is application prospects by its carbon nano-tube film that forms in the carbon nanotube particular structure aspect support of the catalyst, semiconductor material, an emission, opto-electronic device, the energy storage.For example carbon nano-tube film is when the electrode materials, has degree of crystallinity height, good conductivity, specific surface area greatly, pore size distribution is concentrated within the specific limits, and advantage such as pore size is controlled.
The preparation method of existing carbon nano-tube film has: one, adopt chemical Vapor deposition process, catalystic pyrolysis etc., carbon nanotube promptly is grown on the matrix with the form of film in preparation process, its shortcoming is: preparation process needs catalyzer, high temperature action, the preparation process complexity, and film growth is on matrix, film can not be peeled off use separately, has limited its use range.Two, adopt common paint-on technique carbon nanomaterial to be coated on the matrix by binding agent, its shortcoming is: preparation process is loaded down with trivial details, in conjunction with not firm, drying course in the later stage, easily make the film cracking, and, make the composition of the pure nano-carbon tube film that makes impure, the degradation of pure nano-carbon tube film owing to added binding agent.
Summary of the invention
Purpose of the present invention just provides a kind of preparation method of pure nano-carbon tube film, and its preparation process is simple, and cost of manufacture is low, and the pure nano-carbon tube film material that makes conducts electricity very well, internal resistance is low, the utilization ratio height of carbon nanotube.
The present invention realizes that the technical scheme that its goal of the invention adopts is: a kind of preparation method of pure nano-carbon tube film, and its way is: adopt electrical spinning method or solution spray method, the mixed solution of carbon nanotube and dispersion agent is injected on the dash receiver; Make the dispersion agent volatilization by heating then, or remove dispersion agent, get final product with distilled water wash.
Electrical spinning method is the spining technology under electric field action, its principle of work is: the mixed solution of carbon nanotube and dispersion agent is joined in the syringe, be connected with power supply by the metal electrode that places liquid then, the liquid of syringe spout end is subjected to the acting in conjunction of surface tension and electrical forces; Along with voltage increases, strength of electric field increases, the same sex electric charge in the solution is forced to accumulate in the drop surface, and the solution of end gradually becomes taper by semisphere, when critical electric field power surpasses surface tension, charged liquid fails to be convened for lack of a quorum and goes out from the spout end-fire, is ejected on the dash receiver of receiving trap, forms film.
The solution spray method be utilize high pressure with spouting of liquid on dash receiver, form film.
Compared with prior art, the invention has the beneficial effects as follows: adopt electrical spinning method or solution spray method, the mixed solution of carbon nanotube and dispersion agent is injected on the dash receiver, carbon nanotube is under the effect of high-voltage or high pressure, carbon nanotube produces nano effect, combines closely mutually and the film that forms.In conjunction with tight, film forming properties is good each other for carbon nanotube, and film is not easy to crack, and can peel off independent use from dash receiver, and use range is wide.Need not to sneak into materials such as binding agent in the carbon nano-tube film that makes, the composition of carbon nano-tube film is pure, carbon nanomaterial utilization ratio height, and specific surface area is big, and chemical property is good.
The carbon nano-tube film that adopts the inventive method to make is used to make electrode for capacitors, and its internal resistance is low, good conductivity, electrochemistry capacitance height.
Above-mentioned dispersion agent is N, the mixed solution of one or more in dinethylformamide, sodium dodecyl benzenylsulfonate, lithium dodecyl sulfate, 2-methyl cellosolve, propylene carbonate, trolamine, Tri sodium Phosphate, the polyacrylic acid; The mass ratio of carbon nanotube and dispersion agent is 1: 1～1000.
The above-mentioned carbon nanotube and the mixed solution of dispersion agent are that the step by ultra-sonic dispersion forms homodisperse mixed solution.Can make blending dispersion more even like this, in the film that makes, being more evenly distributed of carbon nanotube, film performance is better.
When above-mentioned employing electrical spinning method sprayed, the dash receiver of employing was the conduction dash receiver that metal or graphite constitute.
The present invention is further detailed explanation below in conjunction with the drawings and specific embodiments.
Description of drawings
200 times of opticmicroscope figure of the pure nano-carbon tube film that Fig. 1 makes for the method that adopts the embodiment of the invention one.
Fig. 2 schemes for 10000 times the electronic scanning micro-(SEM) of the pure nano-carbon tube film that the method that adopts the embodiment of the invention one makes.
Fig. 3 is 200 times opticmicroscope figure of the carbon nano-tube film that adopts common coating method and make.
Embodiment
Embodiment one
A, at room temperature in 1: 500 ratio of mass ratio with multi-wall carbon nano-tube tube material and N, dinethylformamide solution thorough mixing carries out ultra-sonic dispersion then, makes the solution homodisperse.
B, mixing solutions being joined the electrospinning silk with in the syringe, place aluminium foil at distance spinning nozzle 15cm place as dash receiver, is jet velocity 0.1mL/s, a spray time 1h of 30KV, mixed solution with the voltage-regulation of syringe.
C, the film that makes is dry in the vacuum environment of 200 ℃ of temperature promptly makes pure nano-carbon tube film.
Fig. 1,2 illustrates, and the micro-image of the carbon nano-tube film that this example makes is clear, illustrates by its film surface smoothly, and the uneven phenomenon of no concave-convex not have to occur the crack that causes because of reasons such as oven dry yet.Fig. 3 illustrates, and adopts the optical microscopic image of the carbon nano-tube film that common coating method makes fuzzy in some scope, and some cracks occur, the film that adopts common paint-on technique to obtain is described, apply not only inhomogeneous, uneven, and the oven dry after the crack has also appearred.
This routine pure nano-carbon tube film both can directly use as the material of making electrode for capacitors, also film can be peeled off from aluminium foil, and other uses it for anything else.
Embodiment two
The making method of method that this is routine and embodiment one is basic identical, different only be: carbon nanotube is a Single Walled Carbon Nanotube, and dispersion agent is a trolamine, and the mass ratio of Single Walled Carbon Nanotube and trolamine is 1: 1000.Mixed solution directly mixes together without supersound process.The film that makes is put into distilled water and is soaked, and removes the trolamine dispersion agent.
Embodiment three
The making method of method that this is routine and embodiment one is basic identical, different only be: dispersion agent is a sodium dodecyl benzenylsulfonate, and the mass ratio of Single Walled Carbon Nanotube and sodium dodecyl benzenylsulfonate is 1: 1, and dash receiver is that nickel material is made.
Embodiment four
The making method of method that this is routine and embodiment one is basic identical, different only be: dispersion agent is a lithium dodecyl sulfate, and the mass ratio of multi-walled carbon nano-tubes and lithium dodecyl sulfate is 1: 50.Dash receiver is that ag material constitutes.
Embodiment five
The making method of method that this is routine and embodiment one is basic identical, different only be: dispersion agent is a 2-methyl cellosolve, and the mass ratio of multi-walled carbon nano-tubes and 2-methyl cellosolve is 1: 100.Dash receiver is the graphite dash receiver.
Embodiment six
The making method of method that this is routine and embodiment one is basic identical, different only be: dispersion agent is Tri sodium Phosphate, polyacrylic acid and N, the mixed solution of dinethylformamide (volume ratio is 1: 1: 1), the mass ratio of multi-walled carbon nano-tubes and mixed solution is 1: 500.Dash receiver is the stainless steel dash receiver.
Embodiment seven
This routine method is to adopt the solution spray method, with Single Walled Carbon Nanotube and propylene carbonate by after the mixing of 1: 200 mass ratio, become uniform mixed solution through ultra-sonic dispersion, inject the syringe of solution spray method then, mixed solution is expelled on the glass dash receiver by syringe.Remove dispersion agent by distilled water wash then, get final product.
Embodiment eight
The making method of method that this is routine and embodiment seven is basic identical, different only be: dispersion agent is a Tri sodium Phosphate, and dash receiver is the copper coin material.
With the pure nano-carbon tube film that embodiment one makes, directly make electric chemical super capacitor electrode and electrical condenser thereof, prove that its chemical property is superior:
The aluminium foil of the band pure nano-carbon tube film that embodiment one is made adopts existing electrode for capacitors manufacturing technology, makes disk shape electrode (2 * 10
-4m
2), as the positive and negative electrode of ultracapacitor, be every utmost point layer, in argon gas glove box kind, with the LiClO of 0.1mol/L with U.S. Celgard2400 film
4(is that 1: 1 ethyl-carbonate and diethyl carbonate is solvent with volume ratio) soaks into behind utmost point layer and positive and negative electrode as electrolytic solution, the aluminium foil dash receiver face of positive and negative electrode is opposing, and having the one side of carbon nano-tube film relative, the middle embedding every utmost point layer promptly is assembled into button-shaped electric chemical super capacitor.
Performance test: with the constant current density is 3.5A/m
2, the scope of discharging and recharging is that the charge and discharge mode of 0-2.5V is tested its electrochemical behavior at the DC-5 cell tester.Reversible capacity is a benchmark with its discharge curve, by formula C=(I * t)/U calculate (in, C represents the electrochemistry capacitance of material; I represents the constant electric current; T represents discharge time; The voltage range of U representative discharge).
Test result shows: under 0.2mA constant current charge-discharge pattern, the single electrode capacity of this electrical condenser is 32F/g in organic electrolyte, the single electrode of the electrical condenser 24F/g of the electrode that makes than prior art exceeds 25%, and its circulation and conductivity have all had very big improvement in addition.
Concrete processing condition of the present invention can be determined according to the prior art and the film thickness of spraying formation that requires.Usually injecting time is that 0.0003-10h, injection flow velocity are that the distance of 0.0001-10mL/s, spinning nozzle and dash receiver is that the voltage of 0.1-100cm, electric spinning method is that the pressure of 0.1-1000KV, solution method is 0.1-100MPa; The thickness of the carbon nano-tube film that makes is 0.1-1000 μ m.
The spinning nozzle of electrical spinning method and solution spray method can be level and vertically places, and dash receiver can be shapes such as flat board, rotating disk or cylinder.Obviously, the dash receiver effect that solution spray method of the present invention is adopted is: block and receive the mixed solution of injection, and make the carbon nanotube in the mixed solution form film thereon.Therefore, dash receiver can be not any smooth sheet material with carbon nanotube generation chemical reaction.And the effect of the dash receiver that electrical spinning method of the present invention adopted, except the above effect identical with the solution spray method, also as another electrode of electric spinning device high voltage appearance, mixed solution is produced sucking action, absorb charged mixed solution, make it be deposited on the dash receiver surface, therefore, it is generally the sheet material of conduction.
Dispersion agent of the present invention can be by kind, purposes and the thickness of the carbon nano-tube film of making, and selects blending ratio between corresponding single dispersion agent or mixed dispersant and dispersion agent thereof for use according to prior art knowledge, so that carbon nanotube homodisperse better.
The present invention is after being injected into mixed solution on the dash receiver with high-voltage or high pressure, and the dispersion agent on the dash receiver obviously also can use the pairing solvent of these dispersion agents that its dissolving, washing are removed except that available distilled water wash is removed.
Claims (4)
1, a kind of preparation method of pure nano-carbon tube film, its way is: adopt electrical spinning method or solution spray method, the mixed solution of carbon nanotube and dispersion agent is injected on the dash receiver; Make the dispersion agent volatilization by heating then, or remove dispersion agent, get final product with distilled water wash.
2, the preparation method of pure nano-carbon tube film according to claim 1, it is characterized in that: described dispersion agent is N, the mixed solution of one or more in dinethylformamide, sodium dodecyl benzenylsulfonate, lithium dodecyl sulfate, 2-methyl cellosolve, propylene carbonate, trolamine, Tri sodium Phosphate, the polyacrylic acid; The mass ratio of carbon nanotube and dispersion agent is 1: 1～1000.
3, the preparation method of pure nano-carbon tube film according to claim 1 and 2 is characterized in that: the mixed solution of described carbon nanotube and dispersion agent forms homodisperse mixed solution by the step of ultra-sonic dispersion.
4, the preparation method of pure nano-carbon tube film according to claim 1 is characterized in that: when described employing electrical spinning method sprayed, the dash receiver of employing was the conduction dash receiver that metal or graphite constitute.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2006100223274A CN100420626C (en) | 2006-11-27 | 2006-11-27 | Preparation method of pure nano-carbon tube film |
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| CNB2006100223274A CN100420626C (en) | 2006-11-27 | 2006-11-27 | Preparation method of pure nano-carbon tube film |
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| CN1962429A true CN1962429A (en) | 2007-05-16 |
| CN100420626C CN100420626C (en) | 2008-09-24 |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101407312B (en) * | 2007-10-10 | 2011-01-26 | 鸿富锦精密工业（深圳）有限公司 | Apparatus and method for preparing carbon nano-tube film |
| CN102515558A (en) * | 2011-11-21 | 2012-06-27 | 江西理工大学 | Method for preparing transparent conductive carbon nano tube film with combination method |
| CN103105123A (en) * | 2011-11-14 | 2013-05-15 | 雅马哈株式会社 | Strain sensor |
| CN103262176A (en) * | 2010-09-30 | 2013-08-21 | 可隆工业株式会社 | Manufacturing method of electrode substrate |
| CN104282444A (en) * | 2014-09-07 | 2015-01-14 | 复旦大学 | Stretchable line-shaped super capacitor with carbon nano tube/polyaniline composite materials as counter electrodes and manufacturing method of stretchable line-shaped super capacitor |
| CN104685316A (en) * | 2012-09-28 | 2015-06-03 | 阪东化学株式会社 | Capacitance-type sensor sheet, method for manufacturing capacitance-type sensor sheet, and sensor |
| US9476782B2 (en) | 2013-05-10 | 2016-10-25 | Yamaha Corporation | Strain sensor |
| CN106115656A (en) * | 2016-06-22 | 2016-11-16 | 嘉兴学院 | A kind of preparation method of carbon nano-tube film |
| CN109761222A (en) * | 2017-11-09 | 2019-05-17 | 北京华碳元芯电子科技有限责任公司 | The method for removing carbon nano tube surface dispersing agent using being evaporated in vacuo |
| CN109761223A (en) * | 2017-11-09 | 2019-05-17 | 北京华碳元芯电子科技有限责任公司 | The method for removing carbon nano-tube film surface organic dispersing agent |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1303260C (en) * | 2004-04-23 | 2007-03-07 | 清华大学 | Process for preparing carbon nano tube film through electrophoresis deposition |
| CN1660692A (en) * | 2005-02-01 | 2005-08-31 | 上海纳晶科技有限公司 | Method for preparing film made from compound Nano carbon fiber |
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2006
- 2006-11-27 CN CNB2006100223274A patent/CN100420626C/en not_active Expired - Fee Related
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101407312B (en) * | 2007-10-10 | 2011-01-26 | 鸿富锦精密工业（深圳）有限公司 | Apparatus and method for preparing carbon nano-tube film |
| CN103262176A (en) * | 2010-09-30 | 2013-08-21 | 可隆工业株式会社 | Manufacturing method of electrode substrate |
| US9212895B2 (en) | 2011-11-14 | 2015-12-15 | Yamaha Corporation | Flexible strained sensor with protective coating |
| CN103105123A (en) * | 2011-11-14 | 2013-05-15 | 雅马哈株式会社 | Strain sensor |
| CN103105123B (en) * | 2011-11-14 | 2017-08-04 | 雅马哈株式会社 | Strain transducer |
| CN102515558A (en) * | 2011-11-21 | 2012-06-27 | 江西理工大学 | Method for preparing transparent conductive carbon nano tube film with combination method |
| CN102515558B (en) * | 2011-11-21 | 2013-12-04 | 江西理工大学 | Method for preparing transparent conductive carbon nano tube film with combination method |
| CN104685316A (en) * | 2012-09-28 | 2015-06-03 | 阪东化学株式会社 | Capacitance-type sensor sheet, method for manufacturing capacitance-type sensor sheet, and sensor |
| CN104685316B (en) * | 2012-09-28 | 2017-11-03 | 阪东化学株式会社 | Capacitance type sensor chip, the manufacture method of capacitance type sensor chip and sensor |
| US9476782B2 (en) | 2013-05-10 | 2016-10-25 | Yamaha Corporation | Strain sensor |
| CN104282444A (en) * | 2014-09-07 | 2015-01-14 | 复旦大学 | Stretchable line-shaped super capacitor with carbon nano tube/polyaniline composite materials as counter electrodes and manufacturing method of stretchable line-shaped super capacitor |
| CN106115656A (en) * | 2016-06-22 | 2016-11-16 | 嘉兴学院 | A kind of preparation method of carbon nano-tube film |
| CN109761222A (en) * | 2017-11-09 | 2019-05-17 | 北京华碳元芯电子科技有限责任公司 | The method for removing carbon nano tube surface dispersing agent using being evaporated in vacuo |
| CN109761223A (en) * | 2017-11-09 | 2019-05-17 | 北京华碳元芯电子科技有限责任公司 | The method for removing carbon nano-tube film surface organic dispersing agent |
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| CN100420626C (en) | 2008-09-24 |
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