CN105047940A - Preparation method of carbon nanotube film - Google Patents
Preparation method of carbon nanotube film Download PDFInfo
- Publication number
- CN105047940A CN105047940A CN201510330909.8A CN201510330909A CN105047940A CN 105047940 A CN105047940 A CN 105047940A CN 201510330909 A CN201510330909 A CN 201510330909A CN 105047940 A CN105047940 A CN 105047940A
- Authority
- CN
- China
- Prior art keywords
- carbon nanotube
- carbon nano
- tube
- preparation
- nanotube film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of a carbon nanotube film. The method comprises the following steps: (1), putting carbon nanotubes into a graphitization furnace, vacuumizing and heating the carbon nanotubes to over 2800 DEG C, carrying out heat preservation for a period of time, and then cooling the carbon nanotubes to a room temperature; (2), with the carbon nanotubes in the step (1), a dispersing agent, a binder and an N-methyl-2-pyrrolidinone solution as raw materials, carrying out ultrasonic treatment, high-speed shearing or ball-milling and the like to prepare a carbon nanotube suspension; (3), dropwise adding the carbon nanotube suspension in the step (2) on a paved base, drying the carbon nanotube suspension at 65 DEG C and separating the base; and (4), putting the carbon nanotube film in the step (3) in a vacuum furnace and heating the carbon nanotube film with the furnace to 1300-1500 DEG C for carbonization, carrying out heat preservation for 0.5-2 hours, cooling the carbon nanotube film to the room temperature and taking out the carbon nanotube film. The carbon nanotube film prepared by the method is about 10-20[mu]m in thickness; the base is relatively easy to separate; through high-temperature carbonization and modification, the carbon nanotube film has relatively good usability, is capable of replacing an aluminum foil and a copper foil as a current collector in a lithium ion battery, can be independently used as an anode, and has relatively high initial specific capacity.
Description
Technical field
The invention belongs to technical field of nano material.
Background technology
Carbon nano-tube film is one of them of derivatizing carbon nanotubes product, is a kind of environmentally friendly, nontoxic, harmless basic material.Because carbon nano-tube film has flexible, therefore can be used for transparent conductive film, make the parts of the high cost such as flexible display, touch-screen modern electronic product.Carbon nano-tube film density is low in addition, quality light, good conductivity, also can be used as battery afflux liquid, reduces electrode integral weight, promotes the energy density of battery.
The preparation method of current carbon nano-tube film comprises: chemical vapour deposition technique, and solution/be filtered into embrane method, LBL self-assembly masking method, electrophoresis, silk screen print method etc.Wherein chemical gaseous phase directly grows in substrate, and all the other prepare membrane process indirectly for powder.The technique preparing carbon nano-tube film is more, be referred in " preparation method of carbon nano-tube film " of application number 200910309105.4 a kind of by ultrasonic, stir or high-pressure homogeneous process making carbon nano tube dispersion liquid, then suction filtration is deposited on filter membrane, dispersant is removed with removing liquid, finally combine with substrate and carbon nano-tube film, isolate the method for carbon nano-tube film.Application number: 201110311780.8 devise a kind of carbon nano-tube film manufacturing equipment, can obtain carbon nano-tube film continuously in enormous quantities.Application number: 201210304671.8 manufacture method and the carbon nanotube film plate that relate to a kind of carbon nanotube film plate.
Carbon nano-tube is One-dimensional nanoreticular carbon materials, and its draw ratio and specific area are comparatively large, and thus carbon nano-tube also has better absorption property.But also therefore the large multiple pileup of carbon nano-tube adsorbs, is mutually intertwined, and makes the scattering problem of carbon nano-tube become a large difficult point.But crystal whisker-shaped carbon nanotube is the good carbon nano-tube of a kind of linear pattern, greatly reduces the difficulty of dispersion comparatively speaking, the preparation of carbon nano tube dispersion liquid is more prone to.
In addition, in order to study some electronic installations relevant with carbon nano-tube film and equipment (ultracapacitor and affluxion body in lithium ion batteries) in some electrochemistry experiments, need fast and prepare in a large number carbon nano-tube film with meet from need, based on this, be developed particularly one and prepare carbon nano-tube film method simply, fast.
Summary of the invention
The object of the invention is in order to can simpler and easy, quick, prepare carbon nano-tube film efficiently, propose a kind of novel method preparing carbon nano-tube film, and carried out modified film process, improve the serviceability of carbon nano-tube film with this.
Carbon nano-tube film preparation method of the present invention, can regulate thickness and the density of carbon nano tube structure film, possesses certain intensity to ensure integrality when it uses simultaneously.
The present invention is achieved by the following technical solutions, and concrete steps comprise as follows.
(1) carbon nano-tube is carried out graphitization processing.
Carbon nano-tube is placed in graphitizing furnace, vacuumizes and be warming up to more than 2800 DEG C, after insulation a period of time, be cooled to room temperature.Object eliminates carbon nano-tube defect, improves degree of crystallinity and purifying carbon nano-tube.
(2) with the carbon nano-tube of graphitization processing, dispersant, binding agent and 1-METHYLPYRROLIDONE (NMP) solution for raw material, through ultrasonic, high speed shear or ball milling etc., preparation carbon nanotube suspension.
Carbon nanotube suspension of the present invention was mixed with dispersion liquid by carbon nano-tube, dispersant and NMP by the mass ratio of 5-10:1-1.5:84-100 before this, then it is formulated to press the mass ratio of 90-100:1-1.2 by dispersion liquid and binding agent.
Described Carbon nano-tube dispersant refers to the one in neopelex (SDBS) or lauryl sodium sulfate (SDS) plasma dispersant.
Described binding agent is one or more in Kynoar (PVDF), carboxymethyl cellulose (CMC) and butadiene-styrene rubber (SBR).
(3) drip in the substrate of tiling by the carbon nanotube suspension made, 65 DEG C of oven dry, just can obtain carbon nano-tube film at the bottom of last un-mixing bases.
Described substrate refers to the one in flexible plastic film, Copper Foil or aluminium foil three kinds of materials.
It is wetting that method at the bottom of described un-mixing bases refers to by water or alcohol, clamps base material one jiao, start oppositely slowly to pull, at the bottom of final un-mixing bases with tweezers.
(4) modification of carbon nano-tube film, is placed in carbon nano-tube film in vacuum furnace and is warming up to 1300-1500 DEG C of carbonization with stove, insulation 0.5-2h, is cooled to room temperature and takes out.
Carbon nano-tube film thickness prepared by the present invention, at about 10-20 μm, is easier at the bottom of un-mixing bases.Through high temperature cabonization modification, remove impurity in carbon nano-tube film, make carbon nano-tube film have better serviceability.In lithium ion battery, aluminium foil Copper Foil can be replaced to use as collector, also separately as negative discharge, higher initial specific capacities can be had.
Accompanying drawing explanation
Fig. 1 is embodiment carbon nano-tube film figure.
Fig. 2 is embodiment carbon nano-tube film when doing lithium ion battery negative, the charge and discharge electrograph of battery under 0.1c multiplying power.Wherein, 1 is first time discharge curve, and 2 is second time discharge curve, and 3 is third time discharge curve.
Embodiment
The present invention is described further by following examples.
Embodiment of the present invention carbon nano-tube used is prepared by Chinese patent ZL201210067937.1, ZL201210304345.7.
Embodiment 1.
(1) graphitization processing.With crucible, carbon nano-tube is loaded, to be placed in graphitizing furnace and to vacuumize, being slowly warming up to 2800 DEG C.Insulation 24h, is cooled to room temperature and takes out.
(2) carbon nanotube suspension preparation.The carbon nano-tube of graphitization processing, SDBS dispersant, NMP are taken with the mass ratio of 5:1:84 and is placed in beaker, with sealed membrane sealing, more ultrasonic 1h, then change closed container high speed shear 1h, be made into dispersion liquid.Dispersion liquid and PVDF binding agent are prepared with the mass ratio of 95:1.1, shear 2h in closed container high speed, preparation carbon nanotube suspension.
(3) on a glass, first use alcohol dampening surface, the aluminium foil of cleaning is sprawled on it, and fits tightly.Surrounding narrow limit transparent rubberized fabric is adjacent to fixing, surrounds enclosing square.Middle dropping carbon nanotube suspension, 65 DEG C of oven dry.
(4) after dried, with water-wet, clamp corner gently with tweezers, oppositely slowly pull, to be separated aluminum foil substrate.
(5) carbon nano-tube film is placed in vacuum furnace and is warming up to 1300 DEG C of carbonizations with stove, insulation 1.5h, be cooled to room temperature and take out.
Embodiment 2.
(1) graphitization processing.With crucible, carbon nano-tube is loaded, to be placed in graphitizing furnace and to vacuumize, being slowly warming up to 2900 DEG C.Insulation 30h, is cooled to room temperature and takes out.
(2) carbon nanotube suspension preparation.The carbon nano-tube of graphitization processing, SDS dispersant, NMP are taken with the mass ratio of 6:1.1:90 and is placed in beaker, with sealed membrane sealing, more ultrasonic 1h, then change closed container high speed shear 1h, be made into dispersion liquid.Dispersion liquid and SBR binding agent are prepared with the mass ratio of 90:1, ball milling 4h in closed container, preparation carbon nanotube suspension.
(3) on a glass, first use alcohol dampening surface, the Copper Foil of cleaning is sprawled on it, and fits tightly.Surrounding narrow limit transparent rubberized fabric is adjacent to fixing, surrounds enclosing square.Carbon nanotube suspension is dripped, 65 DEG C of oven dry in rectangle.
(4) after dried, with alcohol dampening, corner is clamped gently with tweezers, to oppositely slowly pulling, at the bottom of un-mixing bases.
(5) carbon nano-tube film is placed in vacuum furnace and is warming up to 1450 DEG C of carbonizations with stove, insulation 0.5h, be cooled to room temperature and take out.
Embodiment 3.
(1) graphitization processing.With crucible, carbon nano-tube is loaded, to be placed in graphitizing furnace and to vacuumize, being slowly warming up to 3000 DEG C.Insulation 25h, is cooled to room temperature and takes out.
(2) carbon nanotube suspension preparation.The carbon nano-tube of graphitization processing, SDBS dispersant, NMP are taken with the mass ratio of 10:1.3:100 and is placed in beaker, with sealed membrane sealing, more ultrasonic 2h, then change closed container high speed shear 1.5h, be made into dispersion liquid.Dispersion liquid and CMC binding agent are prepared with the mass ratio of 93:1.2, shear 3h in closed container high speed, preparation carbon nanotube suspension.
(3) on a glass, first use alcohol dampening surface, the flexible plastic film of cleaning is sprawled on it, and fits tightly.Surrounding narrow limit transparent rubberized fabric is adjacent to fixing, surrounds enclosing square.Carbon nanotube suspension is dripped, 65 DEG C of oven dry in rectangle.
(4) after dried, with alcohol dampening, corner is clamped gently with tweezers, to oppositely slowly pulling, at the bottom of un-mixing bases.
(5) carbon nano-tube film is placed in vacuum furnace and is warming up to 1460 DEG C of carbonizations with stove, insulation 1h, be cooled to room temperature and take out.
Claims (4)
1. a preparation method for carbon nano-tube film, is characterized in that comprising the steps:
(1) carbon nano-tube is placed in graphitizing furnace, vacuumizes and be warming up to more than 2800 DEG C, after insulation a period of time, be cooled to room temperature;
(2) with the carbon nano-tube of step (1), dispersant, binding agent and 1-METHYLPYRROLIDONE solution for raw material, through ultrasonic, high speed shear or ball milling etc., preparation carbon nanotube suspension;
Described carbon nanotube suspension is first mixed with dispersion liquid by carbon nano-tube, dispersant and 1-METHYLPYRROLIDONE by the mass ratio of 5-10:1-1.5:84-100, then it is formulated to press the mass ratio of 90-100:1-1.2 by dispersion liquid and binding agent;
(3) drip in the substrate of tiling by the carbon nanotube suspension of step (2), 65 DEG C of oven dry, just can obtain carbon nano-tube film at the bottom of last un-mixing bases;
(4) carbon nano-tube film of step (3) is placed in vacuum furnace and is warming up to 1300-1500 DEG C of carbonization with stove, insulation 0.5-2h, be cooled to room temperature and take out.
2. the preparation method of carbon nano-tube film according to claim 1, is characterized in that described dispersant refers to the one in neopelex or lauryl sodium sulfate ionic dispersants.
3. the preparation method of carbon nano-tube film according to claim 1, is characterized in that described binding agent is one or more in Kynoar, carboxymethyl cellulose and butadiene-styrene rubber.
4. the preparation method of carbon nano-tube film according to claim 1, is characterized in that described substrate refers to the one in flexible plastic film, Copper Foil or aluminium foil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510330909.8A CN105047940B (en) | 2015-06-16 | 2015-06-16 | A kind of preparation method of carbon nano-tube film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510330909.8A CN105047940B (en) | 2015-06-16 | 2015-06-16 | A kind of preparation method of carbon nano-tube film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105047940A true CN105047940A (en) | 2015-11-11 |
| CN105047940B CN105047940B (en) | 2018-06-08 |
Family
ID=54454315
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510330909.8A Active CN105047940B (en) | 2015-06-16 | 2015-06-16 | A kind of preparation method of carbon nano-tube film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105047940B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN106298260A (en) * | 2016-09-13 | 2017-01-04 | 南昌大学 | A kind of preparation method of fluorinated carbon material super-capacitor pole piece |
| CN106396680A (en) * | 2016-09-07 | 2017-02-15 | 南昌大学 | Preparation method of flexible ultrathin carbon nanotube paper |
| CN106564878A (en) * | 2016-11-07 | 2017-04-19 | 南昌大学 | Preparation method for carbon nano tube heat conducting film |
| CN107946553A (en) * | 2017-10-25 | 2018-04-20 | 温州大学 | High graphitization three dimensional carbon nanotubes graphene composite material and its preparation and application |
| CN110611029A (en) * | 2019-09-04 | 2019-12-24 | 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| JP2010105909A (en) * | 2008-09-30 | 2010-05-13 | Nippon Chemicon Corp | High-density carbon nanotube assembly and method for producing the same |
| CN103015256A (en) * | 2012-12-11 | 2013-04-03 | 肖辉 | Carbon nanofiber paper and preparation method thereof |
-
2015
- 2015-06-16 CN CN201510330909.8A patent/CN105047940B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| JP2010105909A (en) * | 2008-09-30 | 2010-05-13 | Nippon Chemicon Corp | High-density carbon nanotube assembly and method for producing the same |
| CN103015256A (en) * | 2012-12-11 | 2013-04-03 | 肖辉 | Carbon nanofiber paper and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 庞志鹏等: "碳纳米管导电纸制备及其电磁屏蔽性能研究", 《人工晶体学报》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN106298260A (en) * | 2016-09-13 | 2017-01-04 | 南昌大学 | A kind of preparation method of fluorinated carbon material super-capacitor pole piece |
| CN106564878A (en) * | 2016-11-07 | 2017-04-19 | 南昌大学 | Preparation method for carbon nano tube heat conducting film |
| CN107946553A (en) * | 2017-10-25 | 2018-04-20 | 温州大学 | High graphitization three dimensional carbon nanotubes graphene composite material and its preparation and application |
| 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 |
| CN110611029A (en) * | 2019-09-04 | 2019-12-24 | 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 |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105047940B (en) | 2018-06-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105047940A (en) | Preparation method of carbon nanotube film | |
| Zhang et al. | High performance flexible supercapacitors based on porous wood carbon slices derived from Chinese fir wood scraps | |
| Chen et al. | Nitrogen and sulfur co-doped porous carbon fibers film for flexible symmetric all-solid-state supercapacitors | |
| CN102436934B (en) | Composite nanometer carbon paper and preparation method thereof | |
| CN102351165A (en) | Large-area freestanding carbon nanotube paper and preparation method thereof | |
| Ma et al. | Ultra-thick wood biochar monoliths with hierarchically porous structure from cotton rose for electrochemical capacitor electrodes | |
| Hu et al. | Encapsulating V2O3 nanorods into carbon core-shell composites with porous structures and large specific surface area for high performance solid-state supercapacitors | |
| CN107275587B (en) | A kind of lithium ion silicon-carbon composite cathode material and preparation method thereof | |
| CN104192836B (en) | The solution hot preparation method of self-supporting porous graphene base film | |
| CN103569997A (en) | Preparation method for flexible graphene-modified knittable carbon nanofiber | |
| CN106941167A (en) | A kind of porous composite negative pole material of lithium ion battery and preparation method thereof | |
| CN103456520B (en) | A kind of preparation method and applications of graphene/carbon nanotube composite film | |
| CN102074683A (en) | Porous carbon nanofiber anode material for lithium ion battery and preparation method thereof | |
| Yang et al. | Metallic layered germanium phosphide GeP 5 for high rate flexible all-solid-state supercapacitors | |
| CN107946553B (en) | High-graphitization three-dimensional carbon nanotube graphene composite material and preparation and application thereof | |
| CN103578771A (en) | Graphene thin film and preparation method and application thereof | |
| CN104726965B (en) | A kind of preparation method of flexible high connductivity three-dimensional communication hollow carbon fiber | |
| CN106992288A (en) | A kind of antimony/carbon nano-fiber flexible material and its preparation method and application | |
| Moreno et al. | Lithium battery using sulfur infiltrated in three-dimensional flower-like hierarchical porous carbon electrode | |
| CN108666580A (en) | A kind of polymer three-dimensional collector, preparation method and application | |
| Qin et al. | Design and fabrication of Co 3 V 2 O 8 nanotubes by electrospinning as a high-performance anode for lithium-ion batteries | |
| CN113629249A (en) | Preparation method of MXene-based supported platinum catalyst applied to lithium-sulfur battery anode | |
| CN110668438A (en) | Novel porous carbon electrode material for capacitive deionization technology and application thereof | |
| CN107500263B (en) | Preparation method of rice hull derived hard carbon, obtained material and application thereof | |
| CN109003827B (en) | Preparation method and application of spongy graphene/nickel-cobalt sulfide composite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |