CN112760082A - High-thermal-conductivity graphene film and preparation method thereof - Google Patents
High-thermal-conductivity graphene film and preparation method thereof Download PDFInfo
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- CN112760082A CN112760082A CN202110203482.0A CN202110203482A CN112760082A CN 112760082 A CN112760082 A CN 112760082A CN 202110203482 A CN202110203482 A CN 202110203482A CN 112760082 A CN112760082 A CN 112760082A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052802 copper Inorganic materials 0.000 claims abstract description 19
- 239000010949 copper Substances 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 238000012546 transfer Methods 0.000 claims abstract description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000007769 metal material Substances 0.000 claims abstract description 6
- 229910052709 silver Inorganic materials 0.000 claims abstract description 6
- 239000004332 silver Substances 0.000 claims abstract description 6
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 3
- 239000010408 film Substances 0.000 claims description 50
- 238000009713 electroplating Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000007731 hot pressing Methods 0.000 claims description 7
- 238000005245 sintering Methods 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 239000011889 copper foil Substances 0.000 claims description 4
- 238000005096 rolling process Methods 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 3
- 239000010432 diamond Substances 0.000 claims description 3
- 229910003460 diamond Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 238000007747 plating Methods 0.000 claims description 2
- 239000012774 insulation material Substances 0.000 claims 1
- 238000000465 moulding Methods 0.000 claims 1
- 239000010409 thin film Substances 0.000 claims 1
- 239000010410 layer Substances 0.000 description 20
- 230000000694 effects Effects 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 230000017525 heat dissipation Effects 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000002490 spark plasma sintering Methods 0.000 description 2
- -1 401W/mK Chemical compound 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Cooling Or The Like Of Semiconductors Or Solid State Devices (AREA)
Abstract
A high-thermal-conductivity graphene film and a preparation method thereof are disclosed, and the principle is as follows: the high-heat-conduction-material nanoscale sheet (such as metal such as copper and silver or silicon carbide non-metallic materials) is filled in the middle of the graphene sheet layer and is tightly combined with the graphene sheet, so that air between the graphene sheet layers can be reduced, the number of graphene sheet layers per unit thickness can be increased, the horizontal heat conduction capability can be improved, phonon heat transfer between the graphene sheet layers can be enhanced, and the heat conduction capability perpendicular to the graphene film direction can be greatly improved.
Description
Technical Field
The invention relates to the technical field of graphene film preparation, in particular to a method for manufacturing a graphene heat dissipation film.
Background
With the rapid development of information technology, the power consumption of chips is increasing day by day, the rapid derivation of heat plays a decisive role in the normal operation of the chips, and a heat management solution with high efficiency and low cost is of great importance. With the trend toward light weight, thinness and flexibility of integrated circuits and durable consumer electronics, the use of heat dissipation films with high thermal conductivity will gradually become an effective means for achieving efficient thermal management of electronic components.
The theory of solid state heat conduction is that the thermal conductivity of a material depends on both the electron thermal conductivity and the phonon thermal conductivity of the material. The theory of electron heat transfer states that the higher the electrical conductivity of a material, the higher the thermal conductivity, e.g., silver is the least resistive metal and the best conductive metal material, and according to the theory of phonon heat transfer, the higher the hardness of the material, the higher the elastic modulus, the better the thermal conductivity, e.g., diamond is the most hard and the best conductive non-metallic material.
The single-layer graphene has extremely low resistance, extremely excellent thermal performance in the layer, and electron coincidenceTheory of heat transfer. The theoretical value of the in-layer thermal conductivity of the single-layer graphene is as high as 6000W/mK, and the in-layer thermal conductivity of the single-layer graphene and the multi-layer graphene measured by actual experiments is respectively about 5000W/mK and 3000W/mK. However, single-layer graphene is very thin and cannot be used alone in life. If single graphene sheets are simply stacked together, there is no SP between the carbon atoms between the sheets2The hybrid C-C bond structure and a large amount of air exist among layers, so that the heat conduction capability in the vertical direction is greatly limited, and the vertical heat conduction coefficient is generally in single digit. In many inventions, a hot pressing method is adopted to prepare the graphene film, but because the melting point of graphene per se is more than 3000 ℃, and the graphene has extremely high yield strength, graphene layers cannot be fused and combined together, and the graphene layers still rebound after the hot pressing pressure is removed, so that the graphene layers are filled with air, and the heat conduction capability of the graphene film in the vertical direction is greatly influenced.
The patent of Changzhou Fuhe Tech company with application number 2020102487563 (heat conducting film, heat conducting gasket and preparation method) proposes a method of pressing a graphene film in a direction perpendicular to the film by using a die to form a three-dimensional transverse convex-concave structure, and then filling the graphene film with a heat conducting material, so that the prepared graphene heat dissipation film has a good transverse heat transfer effect (the maximum heat conducting coefficient is 52W/mk in the direction perpendicular to the film). However, the thermal conductivity coefficient of the graphene film in the direction perpendicular to the film is 8 times lower than that of copper, the preparation of a rolling die with a nano-scale structure is not easy, the strength of the graphene is 200 times that of steel, and the graphene film is deformed by pressure and is difficult.
Spark Plasma Sintering (SPS for short) is also called Plasma activated Sintering (PAS for short), which is a technology for preparing functional materials by instantly melting high-melting-point substances by adopting electric arcs at the temperature of over ten thousand ℃, has the distinct characteristics of high temperature rise speed, short Sintering time, controllable tissue structure, energy conservation, environmental protection and the like, can be used for preparing metal materials, ceramic materials and composite materials, and can also be used for preparing nano-block materials, amorphous block materials, gradient materials and the like.
Aiming at the key problems, the invention provides a novel method for constructing the graphene film with high thermal conductivity.
Disclosure of Invention
A high-thermal-conductivity graphene film and a preparation method thereof are disclosed, and the principle is as follows: the high-heat-conduction-material nanoscale sheet (such as metal such as copper and silver or silicon carbide non-metallic materials) is filled in the middle of the graphene sheet layer and is tightly combined with the graphene sheet, so that air between the graphene sheet layers can be reduced, the number of graphene sheet layers per unit thickness of graphene can be increased, the horizontal heat conduction capability can be improved, the phonon heat transfer between the graphene sheet layers can be enhanced, and the heat conduction capability perpendicular to the graphene film direction can be improved.
According to the principle of the invention, the high-thermal-conductivity graphene film and the preparation method comprise the following three steps.
1. Electroplating metal: and (3) putting the three-dimensional graphene thick film into metal ion electroplating liquid for electroplating, plating metal (copper or silver high-heat-conductivity material) on the graphene sheet, and controlling the electroplating time to obtain the required thickness of the electroplated metal layer.
2. Surface pasting: two pieces of smooth copper foils (or other high-thermal-conductivity material films) with proper thicknesses are respectively pasted on two surfaces of the electroplated graphene thick film.
3. Hot pressing treatment: and (3) putting the three-dimensional graphene thick film coated with the copper foil (or other materials) on a vacuum hot press or a plasma sintering machine, pressurizing and heating, preserving heat for a certain time, and naturally cooling.
Preferably, in the electroplating metal, the metal ions can be one or more metal ions to form an electroplating alloy layer, so that the composite material with special functions is prepared.
Preferably, in the surface application, a high-insulation high-heat-conduction material film, such as an aluminum oxide film, a diamond film and a mica film, is adopted, so that an insulating heat dissipation film with high heat conductivity can be obtained.
Preferably, in the hot pressing treatment, a rolling and rolling mode is adopted, so that air between graphene sheets can be eliminated to the greatest extent, and a good heat conduction effect is obtained.
Alternatively, the preparation process can also be that copper is plated on the graphene sheet firstly, then the copper-plated graphene sheet is heated to be above the melting point of copper, and then hot-press forming or plasma pressure sintering is carried out, and then cooling is carried out to obtain the graphene.
Drawings
Fig. 1 is a SEM image of the three-dimensional graphene foam after copper electroplating according to the present invention.
FIG. 2 is a SEM image of the cross-sectional structure of the finished membrane of the present invention.
Detailed Description
According to the principle of the invention, the high-thermal-conductivity graphene film and the preparation method thereof have the following examples:
example 1
Preparing the three-dimensional graphene by adopting a template method or a freezing method, and controlling the density to be less than 0.2 g/cc. And (2) taking three-dimensional graphene foam with the thickness of 2 mm as a cathode, putting the three-dimensional graphene foam into copper sulfate electroplating solution with the concentration of 10g/L, controlling the current density to be 0.2-0.5A/dm2, the pH value to be 8 and the temperature to be 30 ℃, and forming a copper coating with the thickness of 3-30 nanometers on the surface of the three-dimensional graphene within 1-10 minutes.
And (2) putting the copper-plated graphene foam into a plasma sintering machine, introducing hydrogen or inert gas to remove air, pressurizing to 1 ton, rapidly heating to a temperature above the melting point of copper (1084 ℃), pressurizing to 2 tons, keeping for more than 20 seconds, fully filling liquid copper into gaps among graphene sheets, removing air in the gaps, naturally cooling to room temperature, and thus obtaining the graphene film with the thickness of 50-100 microns. As a large amount of air between the graphene sheet layers is replaced by the nano-scale copper layer, the heat conductivity coefficient of the graphene sheet layers perpendicular to the graphene film direction exceeds the heat conductivity coefficient of copper, namely 401W/mK, and the highest heat conductivity coefficient reaches 626W/mK, so that the enhancement effect of the three-dimensional graphene network on the heat conductivity of copper can be understood. Due to the good adhesion effect between the copper sheet layer and the graphene sheet layer, the number of graphene layers in unit thickness is increased by more than 1 time compared with the number of graphene film sheets prepared by a common hot-pressing method, the horizontal heat conductivity coefficient in the sheet is up to 3373W/mK, which is about 2 times of that of the graphene film prepared by the common hot-pressing method, and the theoretical analysis and calculation are matched.
The foregoing has described the general principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited by the foregoing examples, and the foregoing examples and descriptions are only illustrative of the application of the principles of the present invention, and various changes and modifications may be made without departing from the principles of the present invention by merely changing the sequence of process steps or by combining and dividing various process steps and adjusting parameters.
Claims (7)
1. A high-thermal-conductivity graphene film and a preparation method thereof are disclosed, and the principle is as follows: the high-heat-conduction-material nanoscale sheet (such as metal such as copper and silver or silicon carbide non-metallic materials) is filled in the middle of the graphene sheet layer and is tightly combined with the graphene sheet, so that air between the graphene sheet layers can be reduced, the number of graphene sheet layers per unit thickness of the graphene film is increased, the horizontal heat conduction capability is improved, phonon heat transfer between the graphene sheet layers is enhanced, and the heat conduction capability perpendicular to the graphene film direction is improved.
2. The graphene film with high thermal conductivity and the preparation method of the graphene film with high thermal conductivity according to claim 1, wherein the graphene film with high thermal conductivity comprises the following three steps:
(1) electroplating metal: putting the three-dimensional graphene thick film into metal ion electroplating solution for electroplating, plating metal (copper or silver high-heat-conduction material) on the graphene sheet, and controlling the electroplating time to obtain the required thickness of the electroplated metal layer;
(2) surface pasting: two pieces of smooth copper foils (or other high-thermal-conductivity material films) with certain thickness are respectively pasted on two sides of the electroplated graphene thick film;
(3) hot pressing treatment: and (3) putting the three-dimensional graphene thick film coated with the copper foil (or other materials) on a vacuum hot press or a plasma sintering machine, pressurizing and heating, preserving heat for a certain time, and naturally cooling.
3. The plated metal according to claim 2, wherein the metal is one or more metal ions to form a plated alloy layer, thereby preparing a composite material having a specific function.
4. The surface application of claim 2, wherein a thin film of high thermal conductivity and high insulation material, such as aluminum oxide film, diamond film, mica film, is used to obtain an insulating and heat dissipating film with high thermal conductivity.
5. The autoclave process of claim 2, wherein rolling is preferred to minimize air entrapment between graphene sheets.
6. The graphene film with high thermal conductivity and the preparation method of the graphene film as claimed in claim 1, wherein the preparation process selected again is to plate copper on the graphene sheet, heat the graphene sheet plated with copper to a temperature higher than the melting point of copper, then carry out hot press molding or plasma pressure sintering, and then cool the graphene sheet.
7. The use of one or a combination of the preceding claims 1 to 6 in a method for the preparation of graphene films.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110203482.0A CN112760082A (en) | 2021-02-23 | 2021-02-23 | High-thermal-conductivity graphene film and preparation method thereof |
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| CN202110203482.0A CN112760082A (en) | 2021-02-23 | 2021-02-23 | High-thermal-conductivity graphene film and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113351201A (en) * | 2021-06-04 | 2021-09-07 | 武汉氢能与燃料电池产业技术研究院有限公司 | Thin film catalyst, precious metal/graphene composite thin film, and preparation method and application thereof |
| CN113510979A (en) * | 2021-07-15 | 2021-10-19 | 常州富烯科技股份有限公司 | Graphene composite heat-conducting gasket and preparation method thereof |
| CN114990535A (en) * | 2022-05-09 | 2022-09-02 | 北京石墨烯技术研究院有限公司 | Graphene film composite material and preparation method and application thereof |
| CN115367744A (en) * | 2022-09-14 | 2022-11-22 | 上海大学 | Secondary-formed high-thermal-conductivity graphene thick film and preparation method thereof |
-
2021
- 2021-02-23 CN CN202110203482.0A patent/CN112760082A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113351201A (en) * | 2021-06-04 | 2021-09-07 | 武汉氢能与燃料电池产业技术研究院有限公司 | Thin film catalyst, precious metal/graphene composite thin film, and preparation method and application thereof |
| CN113510979A (en) * | 2021-07-15 | 2021-10-19 | 常州富烯科技股份有限公司 | Graphene composite heat-conducting gasket and preparation method thereof |
| CN113510979B (en) * | 2021-07-15 | 2022-08-30 | 常州富烯科技股份有限公司 | Graphene composite heat conduction gasket and preparation method thereof |
| CN114990535A (en) * | 2022-05-09 | 2022-09-02 | 北京石墨烯技术研究院有限公司 | Graphene film composite material and preparation method and application thereof |
| CN114990535B (en) * | 2022-05-09 | 2024-01-19 | 北京石墨烯技术研究院有限公司 | Graphene film composite material and preparation method and application thereof |
| CN115367744A (en) * | 2022-09-14 | 2022-11-22 | 上海大学 | Secondary-formed high-thermal-conductivity graphene thick film and preparation method thereof |
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