CN105047940B - A kind of preparation method of carbon nano-tube film - Google Patents
A kind of preparation method of carbon nano-tube film Download PDFInfo
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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Abstract
A kind of preparation method of carbon nano-tube film, includes the following steps：（1）Carbon nanotube is placed in graphitizing furnace, vacuumize and is warming up to 2800 DEG C or more, heat preservation a period of time postcooling to room temperature；（2）With step（1）Carbon nanotube, dispersant, binding agent and N methylpyrrolidone solutions for raw material, by ultrasound, high speed shear or ball milling etc., prepare carbon nanotube suspension；（3）By step（2）Carbon nanotube suspension be added dropwise in the substrate of tiling, 65 DEG C drying, un-mixing bases bottom；（4）By step（3）Carbon nano-tube film be placed in vacuum drying oven and be warming up to 1,300 1500 DEG C of carbonizations with stove, 0.5 2h of heat preservation is cooled to room temperature taking-up.Carbon nano-tube film thickness prepared by the present invention is easier to un-mixing bases bottom at 10 20 μm or so；It is modified through high temperature cabonization, there is better performance；In lithium ion battery, aluminium foil copper foil can be replaced also there can be higher initial specific capacities separately as cathode as collector.
Description
Technical field
The invention belongs to technical field of nano material.
Background technology
Carbon nano-tube film is one of derivatizing carbon nanotubes product, is a kind of environmentally friendly, nontoxic, harmless
Basic material.Since carbon nano-tube film has the characteristics that flexible, it can be used for transparent conductive film, be made soft
The component of the high costs modern electronic products such as property display, touch screen.In addition carbon nano-tube film density is low, light weight, conduction
Property it is good, can also be used as battery afflux liquid, reduce electrode overall weight, promote the energy density of battery.
The preparation method of carbon nano-tube film includes at present：Chemical vapour deposition technique and solution/embrane method is filtered into, layer by layer
Self assembly method method, electrophoresis, silk screen print method etc..Wherein chemical gaseous phase is directly to be grown in substrate, remaining is between powder
Connect preparation membrane process.The technique for preparing carbon nano-tube film is more, application number 200910309105.4 " carbon nano-tube film
One kind is referred in preparation method ", carbon nano tube dispersion liquid is made by ultrasound, stirring or high-pressure homogeneous processing, then suction filtration is heavy
It forms sediment on filter membrane, removes dispersant with removing liquid, be finally combined with substrate and carbon nano-tube film, isolate carbon nano-tube film
Method.Application number：201110311780.8 devising a kind of carbon nano-tube film manufacturing equipment, carbon continuously can in high volume be made
Nano-tube film.Application number：201210304671.8 relate to the manufacturing method and carbon nanotube of a kind of carbon nanotube film plate
Thin web.
Carbon nanotube is One-dimensional nanoreticular carbon materials, and draw ratio and specific surface area are larger, thus carbon nanotube also have compared with
Good absorption property.But also therefore the big multiple pileup of carbon nanotube adsorbs, is mutually intertwined so that the scattering problem of carbon nanotube
Into a big difficulty.But crystal whisker-shaped carbon nanotube is a kind of preferable carbon nanotube of linear type, is comparatively greatly reduced
The difficulty of dispersion so that the preparation of carbon nano tube dispersion liquid is more prone to.
In addition, in order to study some and the relevant electronic device of carbon nano-tube film and equipment in some electrochemistry experiments
（Ultracapacitor and affluxion body in lithium ion batteries）, need to prepare quickly and largely carbon nano-tube film to meet from need, based on this,
Be developed particularly it is a kind of simple, quickly prepare carbon nano-tube film method.
Invention content
The purpose of the invention is to can it is eased, quick, efficiently prepare carbon nano-tube film, it is proposed that Yi Zhongxin
The method that type prepares carbon nano-tube film, and modified film processing has been carried out, the performance of carbon nano-tube film is improved with this.
Carbon nano-tube film preparation method of the present invention can adjust the thickness and density of carbon nano tube structure film,
Certain intensity is provided simultaneously with to ensure integrality during its use.
The present invention is achieved by the following technical solutions, and specific steps include as follows.
（1）Carbon nanotube is subjected to graphitization processing.
Carbon nanotube is placed in graphitizing furnace, vacuumize and is warming up to 2800 DEG C or more, heat preservation a period of time postcooling
To room temperature.Purpose is to eliminate carbon nanotube defect, improves crystallinity and purifying carbon nano-tube.
（2）With the carbon nanotube of graphitization processing, dispersant, binding agent and N-Methyl pyrrolidone（NMP）Solution is original
Material by ultrasound, high speed shear or ball milling etc., prepares carbon nanotube suspension.
Carbon nanotube suspension of the present invention pressed 5-10 by carbon nanotube, dispersant and NMP before this:1-1.5:84-
100 mass ratio is configured to dispersion liquid, then presses 90-100 by dispersion liquid and binding agent:1-1.2 mass ratio be formulated.
The Carbon nano-tube dispersant refers to neopelex（SDBS）Or lauryl sodium sulfate（SDS）
One kind in plasma dispersant.
The binding agent is Kynoar（PVDF）, carboxymethyl cellulose（CMC）And butadiene-styrene rubber（SBR）In one
Kind is two or more.
（3）The carbon nanotube suspension made is added dropwise in the substrate of tiling, 65 DEG C of drying are finally separating substrate just
Carbon nano-tube film can be made.
The substrate refers to one kind in three kinds of flexible plastic film, copper foil or aluminium foil materials.
The method at the un-mixing bases bottom refers to the wetting by water or alcohol, and one jiao of base material is clamped with tweezers,
Start reversely slowly to pull, be finally recovered substrate.
（4）The modification of carbon nano-tube film, carbon nano-tube film is placed in vacuum drying oven and is warming up to 1300- with stove
1500 DEG C of carbonizations, keep the temperature 0.5-2h, are cooled to room temperature taking-up.
Carbon nano-tube film thickness prepared by the present invention is easier to un-mixing bases bottom at 10-20 μm or so.Through high temperature cabonization
It is modified, impurity in carbon nano-tube film is removed, makes carbon nano-tube film that there is better performance.In lithium ion battery,
It can be used instead of aluminium foil copper foil as collector, can also have higher initial specific capacities separately as negative discharge.
Description of the drawings
Fig. 1 is embodiment carbon nano-tube film figure.
When Fig. 2 does negative electrode of lithium ion battery for embodiment carbon nano-tube film, the charge and discharge electrograph of battery under 0.1c multiplying powers.Its
In, 1 is first time discharge curve, and 2 be second of discharge curve, and 3 be third time discharge curve.
Specific embodiment
The present invention is described further by following embodiment.
Carbon nanotube used in the embodiment of the present invention is Chinese patent ZL201210067937.1, ZL201210304345.7
Prepared.
Embodiment 1.
（1）Graphitization processing.Carbon nanotube is loaded with crucible, be placed in graphitizing furnace and is vacuumized, is slowly heated up
To 2800 DEG C.Heat preservation for 24 hours, is cooled to room temperature taking-up.
（2）It is prepared by carbon nanotube suspension.By the carbon nanotube of graphitization processing, SDBS dispersants, NMP with 5:1:84
Mass ratio, which weighs, to be placed in beaker, is sealed with sealed membrane, then ultrasound 1h, then changes closed container high speed shear 1h, is fabricated to dispersion
Liquid.Dispersion liquid and PVDF binding agents are with 95:1.1 mass ratio is prepared, and is sheared 2h in closed container high speed, is prepared carbon nanotube
Suspension.
（3）On a glass, first clean aluminium foil is sprawled thereon, and fit closely with alcohol dampening surface.Surrounding is used
Narrow side transparent rubberized fabric is adjacent to fixation, surrounds enclosing square.Carbon nanotube suspension, 65 DEG C of drying are added dropwise in centre.
（4）It after dried, is soaked with water, corner is gently clamped with tweezers, reversely slowly pulled, to detach aluminum foil substrate.
（5）Carbon nano-tube film is placed in vacuum drying oven and is warming up to 1300 DEG C of carbonizations with stove, 1.5h is kept the temperature, is cooled to room temperature
It takes out.
Embodiment 2.
（1）Graphitization processing.Carbon nanotube is loaded with crucible, be placed in graphitizing furnace and is vacuumized, is slowly heated up
To 2900 DEG C.30h is kept the temperature, is cooled to room temperature taking-up.
（2）It is prepared by carbon nanotube suspension.By the carbon nanotube of graphitization processing, SDS dispersants, NMP with 6:1.1:90
Mass ratio weigh and be placed in beaker, sealed with sealed membrane, then ultrasound 1h, then change closed container high speed shear 1h, make ingredient
Dispersion liquid.Dispersion liquid and SBR binding agents are with 90:1 mass ratio is prepared, the ball milling 4h in closed container, and it is suspended to prepare carbon nanotube
Liquid.
（3）On a glass, first clean copper foil is sprawled thereon, and fit closely with alcohol dampening surface.Surrounding is used
Narrow side transparent rubberized fabric is adjacent to fixation, surrounds enclosing square.Carbon nanotube suspension, 65 DEG C of drying are added dropwise in rectangle.
（4）After dried, with alcohol dampening, corner is gently clamped with tweezers, to reversely slowly pulling, with un-mixing bases bottom.
（5）Carbon nano-tube film is placed in vacuum drying oven and is warming up to 1450 DEG C of carbonizations with stove, 0.5h is kept the temperature, is cooled to room temperature
It takes out.
Embodiment 3.
（1）Graphitization processing.Carbon nanotube is loaded with crucible, be placed in graphitizing furnace and is vacuumized, is slowly heated up
To 3000 DEG C.25h is kept the temperature, is cooled to room temperature taking-up.
（2）It is prepared by carbon nanotube suspension.By the carbon nanotube of graphitization processing, SDBS dispersants, NMP with 10:1.3:
100 mass ratio, which weighs, to be placed in beaker, is sealed with sealed membrane, then ultrasound 2h, then changes closed container high speed shear 1.5h, is made
Into dispersion liquid.Dispersion liquid and CMC binding agents are with 93:1.2 mass ratio is prepared, and is sheared 3h in closed container high speed, is prepared carbon
Nanotube suspension.
（3）On a glass, first clean flexible plastic film is sprawled thereon, and closely paste with alcohol dampening surface
It closes.Surrounding is adjacent to fixation with narrow side transparent rubberized fabric, surrounds enclosing square.Carbon nanotube suspension, 65 DEG C of drying are added dropwise in rectangle.
（4）After dried, with alcohol dampening, corner is gently clamped with tweezers, to reversely slowly pulling, with un-mixing bases bottom.
（5）Carbon nano-tube film is placed in vacuum drying oven and is warming up to 1460 DEG C of carbonizations with stove, 1h is kept the temperature, is cooled to room temperature and takes
Go out.
Claims (4)
1. a kind of preparation method of carbon nano-tube film, it is characterized in that including the following steps：
（1）Carbon nanotube is placed in graphitizing furnace, vacuumize and is warming up to 2800 DEG C or more, heat preservation a period of time postcooling is extremely
Room temperature；
（2）With step（1）Carbon nanotube, dispersant, binding agent and N-Methyl pyrrolidone solution for raw material, by ultrasound,
High speed shear or ball milling prepare carbon nanotube suspension；
The carbon nanotube suspension is first by 5-10 by carbon nanotube, dispersant and N-Methyl pyrrolidone:1-1.5:84-
100 mass ratio is configured to dispersion liquid, then presses 90-100 by dispersion liquid and binding agent:1-1.2 mass ratio be formulated；
（3）By step（2）Carbon nanotube suspension be added dropwise in the substrate of tiling, 65 DEG C drying, be finally separating substrate
Carbon nano-tube film is made；
（4）By step（3）Carbon nano-tube film be placed in vacuum drying oven and be warming up to 1300-1500 DEG C of carbonization, heat preservation 0.5- with stove
2h is cooled to room temperature taking-up.
2. the preparation method of carbon nano-tube film according to claim 1, it is characterized in that the dispersant refers to 12
One kind in sodium alkyl benzene sulfonate or lauryl sodium sulfate ionic dispersants.
3. the preparation method of carbon nano-tube film according to claim 1, it is characterized in that the binding agent is to gather inclined fluorine
One or more of ethylene, carboxymethyl cellulose and butadiene-styrene rubber.
4. the preparation method of carbon nano-tube film according to claim 1, it is characterized in that the substrate refers to flexible modeling
Expect one kind in film, copper foil or aluminium foil.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105514434A (en) * | 2016-01-19 | 2016-04-20 | 南昌大学 | Preparation method of whisker-shaped carbon nano tube film |
| CN106006601A (en) * | 2016-05-11 | 2016-10-12 | 赵社涛 | Pretreatment method of carbon nano tube for chemical power supply |
| CN106396680A (en) * | 2016-09-07 | 2017-02-15 | 南昌大学 | Preparation method of flexible ultrathin carbon nanotube paper |
| CN106298260B (en) * | 2016-09-13 | 2019-04-12 | 南昌大学 | A kind of preparation method of fluorinated carbon material super-capacitor pole piece |
| CN106219519A (en) * | 2016-09-13 | 2016-12-14 | 南昌大学 | A kind of preparation method of high-graphitized CNT ultra-thin heat-conductivity conducting thin film |
| CN106564878A (en) * | 2016-11-07 | 2017-04-19 | 南昌大学 | Preparation method for carbon nano tube heat conducting film |
| CN107946553B (en) * | 2017-10-25 | 2021-03-26 | 温州大学 | High-graphitization three-dimensional carbon nanotube graphene composite material and preparation and application thereof |
| CN110611029B (en) * | 2019-09-04 | 2022-01-18 | 北京华碳元芯电子科技有限责任公司 | Method for preparing carbon nano tube film by printing method |
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| CN103015256A (en) * | 2012-12-11 | 2013-04-03 | 肖辉 | Carbon nanofiber paper and preparation method thereof |
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| JP5604843B2 (en) * | 2008-09-30 | 2014-10-15 | 日本ケミコン株式会社 | High-density carbon nanotube aggregate and method for producing the same |
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| CN1598141A (en) * | 2004-08-20 | 2005-03-23 | 中国科学院山西煤炭化学研究所 | Carbon fibre paper and its mfg. method |
| CN103015256A (en) * | 2012-12-11 | 2013-04-03 | 肖辉 | Carbon nanofiber paper and preparation method thereof |
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| Title |
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| 碳纳米管导电纸制备及其电磁屏蔽性能研究;庞志鹏等;《人工晶体学报》;20141031;第43卷(第10期);第2635-2640页 * |
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