CN113800504A - Continuous graphene heat-conducting film preparation method - Google Patents
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002002 slurry Substances 0.000 claims abstract description 28
- 239000011248 coating agent Substances 0.000 claims abstract description 22
- 238000000576 coating method Methods 0.000 claims abstract description 22
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- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000011229 interlayer Substances 0.000 claims description 5
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 4
- 229930003268 Vitamin C Natural products 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
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- GWTCIAGIKURVBJ-UHFFFAOYSA-L dipotassium;dodecyl phosphate Chemical compound [K+].[K+].CCCCCCCCCCCCOP([O-])([O-])=O GWTCIAGIKURVBJ-UHFFFAOYSA-L 0.000 claims description 2
- 238000007765 extrusion coating Methods 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
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- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 2
- ONJQDTZCDSESIW-UHFFFAOYSA-N polidocanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO ONJQDTZCDSESIW-UHFFFAOYSA-N 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
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- -1 defoaming in vacuum Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 51
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/24—Thermal properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
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Abstract
The invention discloses a preparation method of a continuous graphene heat-conducting film, which comprises the following steps: preparing graphene oxide slurry with the viscosity of 10000-50000 mPa.S; dispersing the graphene oxide slurry, defoaming in vacuum, and coating; drying after coating is finished to obtain a dried GO membrane coil; rewinding the GO membrane coiled material and the base membrane; and (3) respectively carrying out heat treatment on the rewound composite membrane through an oven, a carbonization furnace and a graphite film furnace, and then calendering to obtain the composite membrane with proper thickness. The continuous graphene heat-conducting film preparation method can be used for manufacturing continuous graphene film coiled materials, and is appropriate in thickness and good in heat conductivity; the method has the advantages of simple production process, good process stability, remarkably improved production efficiency and capacity, and reduced cost.
Description
Technical Field
The invention belongs to the technical field of graphene heat-conducting films, and particularly relates to a continuous preparation method of a graphene heat-conducting film.
Background
With the rapid development of modern microelectronic technology, electronic devices (such as notebook computers, mobile phones, tablet computers, notebook computers and the like) become increasingly ultra-thin and portable, the internal power density of the electronic devices is obviously improved due to the structure, and heat generated in operation is not easy to discharge and is easy to accumulate quickly to form high temperature. On the other hand, high temperatures can reduce the performance, reliability, and service life of electronic devices. Therefore, the current electronic industry puts higher and higher requirements on heat dissipation materials serving as core components of a thermal control system, and an efficient heat-conducting and light material is urgently needed to rapidly transfer heat out and ensure normal operation of electronic equipment. In addition, plasma-facing materials for solid rocket engine throat liners and nuclear fusion reactors are required to have high-efficiency heat-conducting properties.
Graphene is a novel two-dimensional carbon material formed by hexagonal close packing of carbon atoms in a plane. Graphene, the thinnest material known in the world at present, has received worldwide attention because of its unique and excellent physicochemical properties since its discovery in 2004, and its discoverer has gained much of the honor of the 2010 nobel prize on physics. The graphene heat-conducting film also has the advantages of excellent mechanical property, low density, small thermal expansion coefficient and the like, and is considered to be a high-efficiency heat-conducting material with great development potential.
The current industrialized heat conduction materials are mainly metal materials (such as copper and aluminum), natural graphite and artificial graphite films, the metal materials are generally pressed into products with different thicknesses, and the products are called copper foils or aluminum foils, and the products are characterized by high density, hard surfaces and difficult contact with a heat dissipation interface. And the thermal conductivity coefficient is lower and can only reach 200- & lt 400 & gt 400 w.m/k. The natural graphite heat-conducting film has the advantages of low price, wide application, capability of being made into materials with various thicknesses, low heat conductivity coefficient, poor physical properties and easiness in wrinkling and powder falling. The raw material of the artificial graphite heat-conducting film is a polyimide film, and the artificial graphite heat-conducting film has the advantages of higher heat-conducting coefficient which can reach 1000-1800w.m/k, but the manufacturing process pollutes the environment, the application range is lower, and the thickness of a general product is lower than 80 microns.
At present, the conventional preparation methods of the graphene heat conduction film mainly include a CVD method and a coating heat treatment method. The CVD method for preparing the single-layer or single-bit-layer graphene film has the advantages of complete crystals, no defects, high thermal conductivity which can exceed 2000w.m/k, but is difficult to form thicker graphene layers which are generally not more than 1 micron thick, so that the CVD method is not suitable for commercial heat-conducting films. Meanwhile, the graphene film prepared by CVD can be used only by transferring the graphene film from a metal substrate to a required substrate, which further limits the commercial application of the method. The coating heat treatment method comprises the process flows of preparing slurry, coating, removing impurities, carrying out heat treatment, rolling and the like, wherein after the slurry is coated into a coil, the coil is cut into sheets, and then the subsequent treatment is carried out. The whole production flow is complex, the process stability is poor, and the performance is unstable. The process difficulty is that high-solid stably dispersed slurry is prepared, and a graphene crystal structure which is arranged in a flat and ordered manner is obtained after heat treatment, so that high heat-conducting property can be obtained; in addition, methods such as a spin coating method, an LB membrane method, solution casting, and a tape casting method are often used in a laboratory to prepare the graphene thin film, but these laboratory methods have a complex process and limited productivity, and are not suitable for mass production of the graphene heat-conducting film.
At present, all graphene heat-conducting film preparation processes are not continuous, products are sheets, the productivity and the manufacturing cost of the graphene heat-conducting film are seriously influenced by the problem, and the popularization of the products is not facilitated.
Disclosure of Invention
The invention aims to overcome the defects, provides a continuous preparation method of a graphene heat-conducting film, can prepare a continuous graphene film coiled material,
in order to realize the purpose, the invention is realized by the following technical scheme:
a preparation method of a continuous graphene heat conduction film comprises the following steps:
preparing graphene oxide slurry, wherein the solid content is 5% -7%, and the viscosity is 10000-50000 mPa.S; preferably 30000 mpa.s;
dispersing the graphene oxide slurry, then carrying out vacuum defoaming, coating and drying to obtain a dried GO membrane coil;
rewinding the GO membrane coiled material and the base membrane;
and (3) respectively carrying out impurity removal and heat treatment on the rewound composite film through an oven, a carbonization furnace and a graphite film furnace, then carrying out calendering, and pressing to 40-200 mu m.
Preferably, the graphene oxide slurry comprises the following components in parts by weight:
100 parts of graphene oxide, 1400-2000 parts of deionized water, 1-3 parts of a dispersing agent, 5-8 parts of a reducing agent and 30-60 parts of a pH regulator.
Preferably, the dispersant can be sodium dodecyl sulfate and potassium dodecyl phosphate in anionic surfactant, or one of polyvinyl alcohol, nonylphenol polyoxyethylene ether TX-10 and fatty alcohol polyoxyethylene ether AEO-9 in nonionic surfactant.
Preferably, the reducing agent may be one of hydrohalic acid, sodium borohydride or vitamin C.
Preferably, the pH adjuster may be ammonia or sodium hydroxide solution.
Preferably, the vacuum negative pressure of the vacuum defoaming is 300-400 pa.
Preferably, the coating is a doctor blade or extrusion coating mode, and the thickness of the wet film after the coating is finished is 5-6 mm.
Preferably, the temperature for drying after coating is not higher than 90 ℃, so as to avoid other chemical reactions of the slurry.
Preferably, the GO membrane coiled material is divided into one roll of 50-200 meters, preferably one roll of 100 meters.
Preferably, the GO membrane coiled material and the base membrane are rewound, and the interlayer spacing is controlled to be 50-100 microns; the base film is a natural graphite film or a polyimide film, and the thickness of the base film is 30-50 mu m.
Preferably, the temperatures of the oven, the carbonization furnace and the graphite film furnace for heat treatment are respectively room temperature to 400 ℃, 400 to 1000 ℃ and 1000 to 3000 ℃, wherein the first step mainly comprises water removal, the second step comprises removing macromolecular fragments and other non-carbon elements, the third step comprises further removing the non-carbon elements and carrying out rearrangement crystallization.
Compared with the prior art, the invention has the beneficial effects that:
the continuous preparation method of the graphene heat-conducting film, provided by the invention, is used for preparing the graphene oxide slurry with high solid content and stable dispersion, and can be used for preparing continuous graphene film coiled materials.
The thickness of the graphene heat-conducting film prepared by the invention can reach 300 micrometers, the heat conductivity coefficient can reach 1500W/M.K, and the graphene heat-conducting film has good mechanical property and bending resistance.
Detailed Description
Preferred embodiments of the present invention will be described in more detail with reference to specific examples.
Example 1
A preparation method of a continuous graphene heat conduction film comprises the following steps:
(1) preparing graphene oxide slurry, dispersing 10 kg of graphene oxide dry powder into 185 kg of deionized water, adding 0.1 kg of sodium dodecyl sulfate, 0.5 kg of vitamin C and 5 kg of ammonia water to obtain 5% solid content graphene oxide slurry, and dispersing at high speed in the preparation process, wherein the linear speed is more than 50m/s, so as to prepare the slurry with the viscosity of 30000 mPa.S;
(2) dispersing the slurry by a homogenizer, defoaming by a vacuum defoaming machine, and carrying out vacuum negative pressure of 300 pa;
(3) injecting the defoamed slurry into a coating tank, and coating by a scraper, wherein the thickness of a wet film is 5 mm;
(4) drying in an oven after coating is finished, wherein the temperature of the oven is not higher than 90 ℃, and obtaining a dried GO membrane;
(5) dividing the GO film into a roll of 100 meters, rewinding the roll with the natural graphite film on a rewinding machine, and controlling the interlayer spacing to be 50-100 mu m;
(6) carrying out heat treatment on the rewound composite film in a high-temperature oven, a carbonization furnace and a graphite film furnace respectively, wherein the temperatures are room temperature to 400 ℃, 400 ℃ to 1000 ℃ and 1000 ℃ to 3000 ℃;
(7) on a calender, to a thickness of 100 μm.
Through detection, the heat conduction coefficient of the heat conduction film is 1480W/M.K, and the 180-degree bending resistant times exceed 1 ten thousand.
Example 2
A preparation method of a continuous graphene heat conduction film comprises the following steps:
(1) preparing graphene oxide slurry, dispersing 10 kg of graphene oxide dry powder into 150 kg of deionized water, adding 0.2 kg of sodium dodecyl sulfate, 0.6 kg of vitamin C and 4 kg of sodium hydroxide solution to obtain 6% solid content graphene oxide slurry, and dispersing at high speed in the preparation process, wherein the linear speed is more than 50m/s to prepare slurry with the viscosity of 40000 mPa.S;
(2) dispersing the slurry by a homogenizer, defoaming by a vacuum defoaming machine, and carrying out vacuum negative pressure of 300 pa;
(3) injecting the defoamed slurry into a coating tank, and coating by a scraper, wherein the thickness of a wet film is 8 mm;
(4) drying in an oven after coating is finished, wherein the temperature of the oven is not higher than 90 ℃, and obtaining a dried GO membrane;
(5) dividing the GO film into a roll of 100 meters, rewinding the roll with the natural graphite film on a rewinding machine, and controlling the interlayer spacing to be 50-100 mu m;
(6) carrying out heat treatment on the rewound composite film in a high-temperature oven, a carbonization furnace and a graphite film furnace respectively, wherein the temperatures are room temperature to 400 ℃, 400 ℃ to 1000 ℃ and 1000 ℃ to 3000 ℃;
(7) on a calender, to a thickness of 200 μm.
The heat conduction coefficient of the heat conduction film is 1500W/M.K through detection, and the 180-degree bending resistant times exceed 1 ten thousand.
Example 3
A preparation method of a continuous graphene heat conduction film comprises the following steps:
(1) preparing graphene oxide slurry, dispersing 10 kg of graphene oxide dry powder into 150 kg of deionized water, adding 0.2 kg of sodium dodecyl sulfate, 0.06 kg of hydroiodic acid and 3 kg of ammonia water to obtain 4.6% solid content graphene oxide slurry, and dispersing at high speed in the preparation process, wherein the linear speed is more than 50m/s, so as to prepare the slurry with the viscosity of 50000 mPa.S;
(2) dispersing the slurry by a homogenizer, defoaming by a vacuum defoaming machine, and carrying out vacuum negative pressure of 300 pa;
(3) injecting the defoamed slurry into a coating tank, and coating by a scraper, wherein the thickness of a wet film is 8 mm;
(4) drying in an oven after coating is finished, wherein the temperature of the oven is not higher than 90 ℃, and obtaining a dried GO membrane;
(5) dividing the GO film into a roll of 100 meters, rewinding the roll with the natural graphite film on a rewinding machine, and controlling the interlayer spacing to be 50-100 mu m;
(6) carrying out heat treatment on the rewound composite film in a high-temperature oven, a carbonization furnace and a graphite film furnace respectively, wherein the temperatures are room temperature to 400 ℃, 400 ℃ to 1000 ℃ and 1000 ℃ to 3000 ℃;
(7) on a calender, to a thickness of 300 μm.
The heat conduction film is detected to have the heat conduction coefficient of 1460W/M.K, and the 180-degree bending resistant times exceed 1 ten thousand.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and technical principles of the described embodiments, and such modifications and variations should also be considered as within the scope of the present invention.
Claims (10)
1. A preparation method of a continuous graphene heat conduction film is characterized by comprising the following steps:
preparing graphene oxide slurry, wherein the solid content is 2% -8%, and the viscosity is 10000-50000 mPa.S;
dispersing the graphene oxide slurry, then carrying out vacuum defoaming, coating and drying to obtain a dried GO membrane coil;
rewinding the GO membrane coiled material and the base membrane;
and (3) respectively carrying out impurity removal and heat treatment on the rewound composite film through an oven, a carbonization furnace and a graphite film furnace, and then carrying out calendering.
2. The method for preparing the continuous graphene thermal conductive film according to claim 1, wherein the graphene oxide slurry comprises the following components in parts by weight:
100 parts of graphene oxide, 1400-2000 parts of deionized water, 1-3 parts of a dispersing agent, 5-8 parts of a reducing agent and 30-60 parts of a pH regulator.
3. The method for preparing the continuous graphene thermal conductive film according to claim 2, wherein the dispersant is one of sodium dodecyl sulfate and potassium dodecyl phosphate in anionic surfactant, or polyvinyl alcohol, nonylphenol polyoxyethylene ether TX-10 and fatty alcohol polyoxyethylene ether AEO-9 in nonionic surfactant.
4. The method for preparing the continuous graphene thermal conductive film according to claim 2, wherein the reducing agent is one of halogen acid, sodium borohydride or vitamin C.
5. The method for preparing the continuous graphene thermal conductive film according to claim 1, wherein vacuum negative pressure of the vacuum defoaming is 300-400 pa.
6. The method for preparing the continuous graphene thermal conductive film according to claim 1, wherein the coating is performed by a doctor blade or an extrusion coating method, and the thickness of the wet film after the coating is completed is 5-6 mm.
7. The method according to claim 1, wherein the temperature for drying after coating is not higher than 90 ℃.
8. The preparation method of the continuous graphene heat-conducting film according to claim 1, wherein the GO film coil is divided into 50-200 m rolls.
9. The continuous graphene thermal conductive film preparation method according to claim 1, wherein the GO film coil and the base film are rewound, and the interlayer distance is controlled to be 50-100 μm.
10. The method for preparing the continuous graphene thermal conductive film according to claim 1, wherein the temperatures for the heat treatment in the oven, the carbonization furnace and the graphite film formation furnace are respectively room temperature to 400 ℃, 400 ℃ to 1000 ℃, and 1000 ℃ to 3000 ℃.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114590803A (en) * | 2022-03-04 | 2022-06-07 | 浙江道明超导科技有限公司 | Manufacturing process of graphene heat dissipation film coiled material |
| CN115872396A (en) * | 2022-11-30 | 2023-03-31 | 江苏斯迪克新材料科技股份有限公司 | Graphene heat-conducting film and preparation method thereof |
| CN115893399A (en) * | 2022-10-24 | 2023-04-04 | 深瑞墨烯科技(福建)有限公司 | Composite film, preparation method thereof and electronic equipment |
| CN117263175A (en) * | 2023-09-28 | 2023-12-22 | 科泽新材料股份有限公司 | High-solid-content graphene oxide slurry, graphene oxide heat-conducting film and preparation method |
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| US20140227164A1 (en) * | 2011-09-23 | 2014-08-14 | Suk Tai Chang | Production method for a graphene thin film |
| US20150044565A1 (en) * | 2013-08-08 | 2015-02-12 | Yanbo Wang | Anode active material-coated graphene sheets for lithium batteries and process for producing same |
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| JP2024535402A (en) * | 2022-03-04 | 2024-09-30 | 浙江道明超導科技有限公司 | Manufacturing process of graphene heat dissipation film coil material |
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| CN115893399A (en) * | 2022-10-24 | 2023-04-04 | 深瑞墨烯科技(福建)有限公司 | Composite film, preparation method thereof and electronic equipment |
| CN115872396A (en) * | 2022-11-30 | 2023-03-31 | 江苏斯迪克新材料科技股份有限公司 | Graphene heat-conducting film and preparation method thereof |
| CN117263175A (en) * | 2023-09-28 | 2023-12-22 | 科泽新材料股份有限公司 | High-solid-content graphene oxide slurry, graphene oxide heat-conducting film and preparation method |
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