CN105514434A - Preparation method of whisker-shaped carbon nano tube film - Google Patents
Preparation method of whisker-shaped carbon nano tube film Download PDFInfo
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- CN105514434A CN105514434A CN201610034108.1A CN201610034108A CN105514434A CN 105514434 A CN105514434 A CN 105514434A CN 201610034108 A CN201610034108 A CN 201610034108A CN 105514434 A CN105514434 A CN 105514434A
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- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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
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- 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
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- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- 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 whisker-shaped carbon nano tube film. The preparation method comprises the following steps: graphitizing a whisker-shaped carbon nano tube; performing ball-milling to obtain tiny dense powder; with one or two of ethyl alcohol, deionized water, N-methyl-2-pyrrolidone and acetone as a solvent and the carbon nano tube as a base material, adding a binder and a dispersant, and mixing slurry, thereby preparing suspension; with any one of glass, aluminum foil, copper foil and a plastic film as a substrate, coating the surface of the substrate with the suspension, drying, and performing film separation; immersing in ethyl alcohol and deionized water, and separating a film through heat flow in water bath; and performing carbonization, then graphitizing, and compacting a product, thereby obtaining the carbon nano tube film. The carbon nano tube film has certain flexibility and strength, and has thickness of 10-100 micron meters. The carbon nano tube film can be used as a negative electrode of a lithium ion battery independently, and also as positive and negative collectors of a lithium ion battery, wherein the specific discharge capacity of a button battery is more than or equal to 2000mAh/g and the reversible capacity of the battery is more than or equal to 1000mAh/g.
Description
Technical field
The invention belongs to field of nanometer technology, relate to a kind of preparation method of crystal whisker-shaped carbon nanotube film.
Background technology
Carbon nano-tube tensile strength is 100 times of steel, and density but only has 1/6th of steel, have good mechanical performance, and carbon nano-tube also has advantage in conductive and heat-conductive.Therefore, carbon nano-tube is often applied in the technical field of composite materials such as conduction, heat conduction.
Early stage old-fashioned carbon nano-tube is due to the limitation of catalyst and manufacture method, the carbon nano-tube of preparation mostly is bending winding-type, need the process such as acidified or microwave to carry out purifying, disperseing, and carbon nano-tube is numerous in knee defect, degree of crystallinity is low, and degree of graphitization is low.Old-fashioned carbon nano-tube is serious owing to being wound around in addition, and difficulties in dispersion.
Carbon nano-tube has excellent electric conductivity, can be used as the conductive additive of anode material for lithium-ion batteries or uses as negative pole separately.But during separately as negative pole, need first film forming.But film-forming process respectively has short length, based on the preparation technology of lithium ion battery, be developed particularly a kind of preparation method of novel crystal whisker-shaped carbon nanotube film, be convenient to simple film forming fast, carry out lithium ion battery test.
Summary of the invention
In order to more rapid, efficient, in enormous quantities film forming, this invention exploits a kind of novel method preparing crystal whisker-shaped carbon nanotube film, to prepare film fast in enormous quantities, substitute Copper Foil and aluminium foil and copper-carbon nano-tube compound film, aluminium-carbon nano-tube compound film, battery shielded film as lithium ion battery negative, affluxion body in lithium ion batteries.
Crystal whisker-shaped carbon nanotube film prepared by the present invention has the advantages such as thickness is adjustable, film forming simple, film forming area is large, demoulding is easy, and film has certain pliability, is convenient to mobile taking.
The present invention is achieved by the following technical solutions.
Of the present invention is a kind of new type whisker shape carbon nano-tube film film build method, comprises the following steps.
(1) crystal whisker-shaped carbon nanotube (CNTs) is put into graphitizing furnace, 3000 ~ 3500 DEG C, insulation 10-64h, carries out graphitization processing.
(2) the carbon nano-tube 200r/min ball milling 2-5h that graphitization processing is good, becomes tiny closely knit powder.
(3) get one or both in ethanol, deionized water, 1-METHYLPYRROLIDONE (NMP) or acetone as solvent, the CNTs that ball milling is good is stock, and adding additives and dispersant, size mixing, and is configured to the suspension of 2 ~ 5% solid contents.
(4) in glass, aluminium foil, Copper Foil, plastic film, uniform suspension, as substrate, is coated in its surface, controls thickness by any one.After oven dry, carry out thin film separation process.
(5) 1 ~ 10h, then tepidarium 10 ~ 30min is soaked, by water-bath hot-fluid by thin film separation with ethanol, deionized water.
(6), after masking, carbonize at 1300 ~ 2000 DEG C, then 3000 ~ 3500 DEG C of graphitizations, take out compacting, make the carbon nano-tube film with certain pliability and intensity.
Binding agent described in step (3) be butadiene-styrene rubber (SBR), carboxymethyl cellulose (CMC), Kynoar (PVDF) one or more.
Dispersant described in step (3) is one or both in detergent alkylate sulphur sodium (SDBS) or lauryl sodium sulfate (SDS).
The ratio of sizing mixing described in step (3) is carbon nano-tube: binding agent: dispersant is by 81 ~ 96:2 ~ 9:2 ~ 10 mass ratio.
The crystal whisker-shaped carbon nanotube used in the present invention is through chemical vapour deposition technique (CVD) preparation, and it is good that carbon nano-tube (CNTs) has linearity, and impurity is few, degree of crystallinity is high, the advantage that degree of graphitization is high, and after more than 3000 DEG C graphitization processing, more than 99% purity can be reached.Compared to old-fashioned carbon nano-tube, linear pattern crystal whisker-shaped carbon nanotube has the advantages that more easily disperse.
Crystal whisker-shaped carbon nanotube film prepared by the present invention has certain pliability and intensity, thickness 10 ~ 100 μm.Finished film can use as lithium ion battery negative separately, and also can be used as lithium ion cell positive and negative current collector and substitute Copper Foil and aluminium foil uses, button cell specific discharge capacity is at more than 2000mAh/g, and reversible capacity is at more than 1000mAh/g.
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) get 100g crystal whisker-shaped carbon nanotube, 3000 DEG C of graphitizing furnace inside holding 20h, take out.
(2) carbon nano-tube 200r/min ball milling 4h, to tiny closely knit powder.
(3) take NMP as solvent, carbon nano-tube (CNTs) is stock, is the configuration of 91:5:4 mass ratio, regulates solid content to be 4%, high speed shear 2h, slurrying by CNTs:PVDF:SDS.
(4) select aluminium foil to be base material, get slurries 10ml, apply into 5x8cm
2region, 50 DEG C of oven dry, aluminium foil forms carbon nano-tube film.
(5) aluminium foil is placed in deionized water solution and soaks 8h, then soak 20min in tepidarium, by the hot water stream of flowing, CNTs is separated with aluminium foil, take out positive empty oven dry.
(6) by the CNTs film 1600 DEG C charing of preparation, then 3000 DEG C of graphitizations, take out compacting, make and there is certain pliability and the carbon nano-tube film of intensity.
Embodiment 2.
(1) get 100g crystal whisker-shaped carbon nanotube, 3300 DEG C of graphitizing furnace inside holding 16h, take out.
(2) carbon nano-tube 200r/min ball milling 3h, to tiny closely knit powder.
(3) take ethanol as solvent, carbon nano-tube (CNTs) is stock, is the configuration of 96:2:2 mass ratio, regulates solid content to be 2%, high speed shear 1h, slurrying by CNTs:PVDF:SDBS.
(4) select glass to be base material, get slurries 10ml, apply into 5x8cm
2region, 50 DEG C of oven dry, film forming.
(5) glass modules is placed in ethanolic solution and soaks 5h, then soak 30min in tepidarium, by the hot water stream of flowing, CNTs is separated with glass, careful taking-up is dried.
(6) by the CNTs film 1300 DEG C charing of preparation, then 3300 DEG C of graphitizations, take out compacting, make and there is certain pliability and the carbon nano-tube film of intensity.
Embodiment 3.
(1) get 100g crystal whisker-shaped carbon nanotube, 3500 DEG C of graphitizing furnace inside holding 12h, take out.
(2) carbon nano-tube 200r/min ball milling 2h, to tiny closely knit powder.
(3) take deionized water as solvent, carbon nano-tube (CNTs) is stock, is the configuration of 81:4.5:4.5:10 mass ratio, regulates solid content to be 3%, high speed shear 3h, slurrying by CNTs:CMC:SBR:SDBS.
(4) select Copper Foil to be base material, get slurries 10ml, apply into 5x8cm
2region, 50 DEG C of oven dry, film forming.
(5) Copper Foil module is placed in deionized water solution and soaks 8h, then soak 30min in tepidarium, by the hot water stream of flowing, CNTs is separated with glass, careful taking-up is dried.
(6) the CNTs film 1800 DEG C charing will prepared, then 3500 DEG C of graphitizations, take out compacting, makes to make to have certain pliability and the carbon nano-tube film of intensity.
Claims (1)
1. a preparation method for crystal whisker-shaped carbon nanotube film, is characterized in that comprising the following steps:
(1) crystal whisker-shaped carbon nanotube is put into graphitizing furnace, 3000 ~ 3500 DEG C, insulation 10-64h, carries out graphitization processing;
(2) the carbon nano-tube 200r/min ball milling 2-5h that graphitization processing is good, becomes tiny closely knit powder;
(3) get one or both in ethanol, deionized water, 1-METHYLPYRROLIDONE or acetone as solvent, the carbon nano-tube that ball milling is good is stock, and adding additives and dispersant, size mixing, and is configured to the suspension of 2 ~ 5% solid contents;
(4) in glass, aluminium foil, Copper Foil, plastic film, uniform suspension, as substrate, is coated in its surface, controls thickness by any one; After oven dry, carry out thin film separation process;
(5) 1 ~ 10h, then tepidarium 10 ~ 30min is soaked, by water-bath hot-fluid by thin film separation with ethanol, deionized water;
(6), after masking, carbonize at 1300 ~ 2000 DEG C, then 3000 ~ 3500 DEG C of graphitizations, take out compacting, make pure crystal whisker-shaped carbon nanotube film;
Binding agent described in step (3) be butadiene-styrene rubber, carboxymethyl cellulose, Kynoar one or more;
Dispersant described in step (3) is one or both in detergent alkylate sulphur sodium or lauryl sodium sulfate;
The ratio of sizing mixing described in step (3) is carbon nano-tube: binding agent: dispersant is by 81 ~ 96:2 ~ 9:2 ~ 10 mass ratio.
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| CN201610034108.1A CN105514434A (en) | 2016-01-19 | 2016-01-19 | Preparation method of whisker-shaped carbon nano tube film |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106299552A (en) * | 2016-10-19 | 2017-01-04 | 南昌大学 | The preparation method of graphitized carbon nano pipe flexible membrane lithium-air battery |
| CN106367696A (en) * | 2016-09-09 | 2017-02-01 | 南昌大学 | Preparation method for crystal whisker carbon nano tubes coated with aluminum oxide/magnesium matrix composite semi-solid billets |
| CN106374113A (en) * | 2016-10-31 | 2017-02-01 | 南昌大学 | Method for preparing lithium-sulfur battery by taking graphitized carbon nanotube flexible film as current collector of lithium-sulfur battery |
| CN106396680A (en) * | 2016-09-07 | 2017-02-15 | 南昌大学 | Preparation method of flexible ultrathin carbon nanotube paper |
| CN106399872A (en) * | 2016-09-09 | 2017-02-15 | 南昌大学 | Preparation method for whisker carbon nanotube/aluminum matrix composite semisolid blank coated with aluminum oxide |
| CN106450493A (en) * | 2016-11-07 | 2017-02-22 | 南昌大学 | Method for preparing foldable batteries with flexible films with graphitized carbon nano-tubes |
| CN106449154A (en) * | 2016-11-09 | 2017-02-22 | 南昌大学 | Supercapacitor taking low-dimensional carbon material thin films as electrode slices and preparation method |
| CN106564878A (en) * | 2016-11-07 | 2017-04-19 | 南昌大学 | Preparation method for carbon nano tube heat conducting film |
| CN109786722A (en) * | 2019-02-26 | 2019-05-21 | 苏州第一元素纳米技术有限公司 | The preparation method of electrochemical active material |
| CN111350097A (en) * | 2020-03-30 | 2020-06-30 | 江西克莱威纳米碳材料有限公司 | Preparation method of heating film |
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| CN102557010A (en) * | 2012-03-05 | 2012-07-11 | 南昌大学 | Synthesis method of crystal whisker-shaped carbon nanotube |
| CN105047940A (en) * | 2015-06-16 | 2015-11-11 | 南昌大学 | Preparation method of carbon nanotube film |
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- 2016-01-19 CN CN201610034108.1A patent/CN105514434A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102557010A (en) * | 2012-03-05 | 2012-07-11 | 南昌大学 | Synthesis method of crystal whisker-shaped carbon nanotube |
| CN105047940A (en) * | 2015-06-16 | 2015-11-11 | 南昌大学 | Preparation method of carbon nanotube film |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106396680A (en) * | 2016-09-07 | 2017-02-15 | 南昌大学 | Preparation method of flexible ultrathin carbon nanotube paper |
| CN106367696B (en) * | 2016-09-09 | 2018-01-12 | 南昌大学 | A kind of preparation method of whisker CNT/magnesium-base composite material semi-solid state blank of coating alumina |
| CN106367696A (en) * | 2016-09-09 | 2017-02-01 | 南昌大学 | Preparation method for crystal whisker carbon nano tubes coated with aluminum oxide/magnesium matrix composite semi-solid billets |
| CN106399872A (en) * | 2016-09-09 | 2017-02-15 | 南昌大学 | Preparation method for whisker carbon nanotube/aluminum matrix composite semisolid blank coated with aluminum oxide |
| 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 |
| CN106299552A (en) * | 2016-10-19 | 2017-01-04 | 南昌大学 | The preparation method of graphitized carbon nano pipe flexible membrane lithium-air battery |
| CN106374113A (en) * | 2016-10-31 | 2017-02-01 | 南昌大学 | Method for preparing lithium-sulfur battery by taking graphitized carbon nanotube flexible film as current collector of lithium-sulfur battery |
| CN106564878A (en) * | 2016-11-07 | 2017-04-19 | 南昌大学 | Preparation method for carbon nano tube heat conducting film |
| CN106450493A (en) * | 2016-11-07 | 2017-02-22 | 南昌大学 | Method for preparing foldable batteries with flexible films with graphitized carbon nano-tubes |
| CN106449154A (en) * | 2016-11-09 | 2017-02-22 | 南昌大学 | Supercapacitor taking low-dimensional carbon material thin films as electrode slices and preparation method |
| CN109786722A (en) * | 2019-02-26 | 2019-05-21 | 苏州第一元素纳米技术有限公司 | The preparation method of electrochemical active material |
| CN109786722B (en) * | 2019-02-26 | 2021-05-11 | 苏州第一元素纳米技术有限公司 | Method for producing electrochemically active material |
| CN111350097A (en) * | 2020-03-30 | 2020-06-30 | 江西克莱威纳米碳材料有限公司 | Preparation method of heating film |
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Application publication date: 20160420 |