CN106082186B - A kind of heat conduction film and preparation method thereof of graphene-nanometer carbon/carbon-copper composite material - Google Patents
A kind of heat conduction film and preparation method thereof of graphene-nanometer carbon/carbon-copper composite material Download PDFInfo
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- CN106082186B CN106082186B CN201610404290.5A CN201610404290A CN106082186B CN 106082186 B CN106082186 B CN 106082186B CN 201610404290 A CN201610404290 A CN 201610404290A CN 106082186 B CN106082186 B CN 106082186B
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/32—Thermal properties
Abstract
The invention discloses heat conduction films of a kind of graphene-nanometer carbon/carbon-copper composite material and preparation method thereof, the heat conduction film is combined by copper nano particles and multi-layer graphene, the copper particle diameter is in Nano grade, it is evenly distributed between graphene layer, the fault location in graphene is filled up, and is connected upper layer and lower layer graphene.The heat conduction film can effectively increase its longitudinal thermal conductivity, can be used for dissipation from electronic devices while keeping lateral high heat conductance characteristic.
Description
Technical field
The invention belongs to technical field of heat transfer, and in particular to a kind of heat conduction film of graphene-nanometer carbon/carbon-copper composite material and
Preparation method.
Background technology
With the continuous improvement of the integrated level of electronic chip, packaging density and working frequency, chip heat flow density is rapid
Increase, brings great challenge to chip cooling, heat dissipation problem has influenced electronic product, high-power electrical, aviation boat
The development in the fields such as it.In order to solve the above problem, it is more excellent to find performance in addition to being optimized to Thermal Design of Electronic Equipments by people
Good heat dissipation film also becomes an important breakthrough mouth.
Graphene is presently found most thin, most hard, the strongest novel nano-material of conductive and heat-conductive ability, graphene hair
So far now, the performances such as calorifics, mechanics and electricity obtain the research of more and more scholars.Scientist estimates mono-layer graphite at room temperature
The transverse thermal conductivity of alkene is up to 5300W/ (mK), but single-layer graphene thickness only has 0.335nm or so.Multi-layer graphene interlayer
Be also easy to produce sliding because Van der Waals force is only existed, keep its longitudinal thermal conductivity not high, due to its transverse thermal conductivity of phon scattering with
The increase of the number of plies and reduce rapidly, limit its heat dissipation film applications application.Scientists have been carried out to graphite in recent years
Alkene composite material makes and the multinomial research of various performances develops heat conductivility using the heat conductivility that graphene is excellent
Good graphene composite material has important realistic meaning.
Invention content
Goal of the invention：In order to overcome the deficiencies in the prior art, it is compound that the present invention provides a kind of graphene-Nanometer Copper
Heat conduction film of material and preparation method thereof can be applied to the high thermal conductivity graphite alkene membrane structure of dissipation from electronic devices.
Technical solution：To achieve the above object, the technical solution adopted by the present invention is：
A kind of heat conduction film of graphene-nanometer carbon/carbon-copper composite material, is combined by copper particle with multi-layer graphene, described
Copper particle diameter is evenly distributed in Nano grade between two adjacent graphene layers.Copper particle fills up the defect in graphene
Place, and it is connected upper layer and lower layer graphene.
Further, the thickness of the heat conduction film of gained is 50 μm -100 μm, and transverse thermal conductivity is in 600W/mK at room temperature
More than.
Further, a diameter of 35nm-120nm of the copper particle.
The preparation method of the heat conduction film of above-mentioned graphene-nanometer carbon/carbon-copper composite material, includes the following steps：
1) graphene oxide film is prepared；
2) electro deposition oxidation graphene film is prepared on the graphene oxide film using electroplating technology；
3) it is dried in vacuo, anneals, restore the electro deposition oxidation graphene film and form graphene-Nanometer Copper THIN COMPOSITE
Film；
4) it hot pressing and anneals.
Further, the specific method that the step 1) prepares graphene oxide film is：
1-1) natural flaky graphite powder is added in the mixture containing concentrated nitric acid sodium and the freezing concentrated sulfuric acid；
Potassium permanganate 1-2) is added, and stirs mixture；
It 1-3) is gradually added into hydrogen peroxide solution and removes remaining potassium permanganate；
1-4) mixture is diluted and centrifuged, obtains graphene oxide；
1-5) graphene oxide is cleaned with hydrochloric acid solution and deionized water；
1-6) filtered under vacuum is dehydrated to obtain graphene oxide film.
Further, the step 2) prepares electro deposition oxidation stone using electroplating technology on the graphene oxide film
Black alkene film, concrete technology are：It adds graphene oxide into and carries out ultrasonic disperse in deionized water, electrophoresis is carried out in electroplating bath
Deposition, specially electro-deposition 180s under conditions of 20V constant pressures, during electrolysis, the copper sheet as anode loses electronics
Bivalent cupric ion is formed, the dark film of gel, that is, electro deposition oxidation graphene film is formed in anode surface.
Further, the specific method of the step 3) is：The electro deposition oxidation graphene film is put into atmosphere furnace
Middle drying, is put into atmosphere furnace later, is passed through nitrogen, is heated to 300 DEG C with the rate of 6 DEG C/min, constant temperature is logical after 10 minutes
Entering hydrogen, then corresponding temperature is warming up to the rate of 8 DEG C/min, is heat-treated by hydrogen annealing, the defect of graphene is repaired,
The bivalent cupric ion formed in the electroplating process of step 2) is reduced into nano copper particle and moves to graphene oxide
Graphene-Nanometer Copper laminated film is formed in interlayer.
Further, the technique of the hydrogen annealing is to be separately heated to 400 DEG C, 500 DEG C, 650 DEG C and 700 DEG C.Annealing
The thermal polymerization of temperature and copper ion and copper nano particles form related, copper particle diameter size increase with annealing temperature raising,
But the too conference of copper particle leads to the decline of thermal conductivity, therefore annealing temperature section is scheduled on 400 DEG C -700 DEG C.
Further, the step 4) uses hot-pressing technique, specially pressure 30MPa to heat up with the rate of 10 DEG C/min
To 800 DEG C, constant temperature 30min, then natural cooling.Hot pressing makes to contact between copper nano particles and graphene closer, makes simultaneously
The distance for obtaining composite material interlayer with multi-layer structure reduces, and contact is closer.
Further, the step 4) uses annealing technology, is warming up to the rate of 10 DEG C/min in the atmosphere of nitrogen
300 DEG C, constant temperature 1h, then natural cooling.Heat treatment mode using annealing is reduced and is lacked to eliminate the thermal stress of film
It falls into.
Advantageous effect：The heat conduction film and preparation method thereof of graphene provided by the invention-nanometer carbon/carbon-copper composite material, can be with
While keeping lateral high heat conductance characteristic, effectively increase its longitudinal thermal conductivity, the small-sized electronic device that can be used for
Heat dissipation.
Description of the drawings
Fig. 1 is the preparation method flow diagram of the present invention.
Specific implementation mode
The present invention is further described below in conjunction with the accompanying drawings.
It is a kind of preparation method of the heat conduction film of graphene-nanometer carbon/carbon-copper composite material as shown in Figure 1, utilizes physics or change
Method prepares graphene oxide, then prepares electro deposition oxidation graphene on graphene oxide film using electroplating technology
Film is formed graphene-Nanometer Copper laminated film with hydrogen annealing redox graphene, and is received using annealing temperature control copper
The diameter of rice grain.Make to contact between copper nano particles and graphene using hot-pressing technique it is closer, while make have
The distance of the composite material interlayer of multilayered structure reduces, and contact is closer.Film is finally eliminated using the heat treatment mode of annealing
Thermal stress, reduce defect.
Embodiment
A kind of preparation method of the heat conduction film of graphene-nanometer carbon/carbon-copper composite material, preparation process flow chart is as follows, specifically
For：The natural flaky graphite powder of 2.0g is added to the mixture of the concentrated sulfuric acid containing 1.0g concentrated nitric acids sodium and 92ml freezings
In.9.0g potassium permanganate is added, and stirs mixture.Then it is gradually added into hydrogen peroxide solution and removes remaining potassium permanganate,
Mixture is diluted and centrifuged again, the graphene oxide of gained is cleaned with hydrochloric acid solution and deionized water.It is put into atmosphere furnace
Filtered under vacuum is dehydrated.
It adds graphene oxide into and carries out ultrasonic disperse in deionized water, electrophoretic deposition is carried out in electroplating bath.In 20V perseverances
Electro-deposition 180s under conditions of pressure, anode surface form the dark film of gel (GO-EPD), are then dried in vacuo in atmosphere furnace.
GO-EPD films carry out high-temperature hydrogen annealing processing in atmosphere furnace, are separately heated to 400,500,650 and 700 DEG C,
Copper particle diameter size increases with annealing temperature and is increased.The film of preparation is put into hot press hot pressing, pressure 30MPa, with 10
DEG C/rate of min is warming up to 800 DEG C, constant temperature 30min, then natural cooling.It is put into later in atmosphere furnace in the atmosphere of nitrogen
300 DEG C, constant temperature 1h are warming up to the rate of 10 DEG C/min, then natural cooling.
Due to only existing weak interaction force Van der Waals force between graphene layer, longitudinal heat conduction is leveraged, this implementation
The heat conduction film for graphene-nanometer carbon/carbon-copper composite material that example obtains, because in many Nanometer Coppers of Intercalation reaction of graphene
Grain, the higher copper nano particles of one side thermal conductivity ratio take part in the heat conduction of interlayer, on the other hand hot-pressing technique are used to make copper
Between nano particle and graphene, the contact of composite material interlayer it is closer, therefore this structure can increase longitudinal thermal conductivity
Rate.Meanwhile this structure does not destroy the highly thermally conductive characteristic of transverse direction that graphene itself has, transverse thermal conductivity can reach 600W/
MK or more, is higher than the 500W/mK of existing commercial thermal conductivity film, and thermal conductivity at least improves 20%.Film thickness is in 50-100 μ
Between m, it can be used for the heat dissipation of electronic device.
The above is only a preferred embodiment of the present invention, it should be pointed out that：For the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (6)
1. a kind of heat conduction film of graphene-nanometer carbon/carbon-copper composite material, it is characterised in that：It is compound by copper particle and multi-layer graphene
It forms, the copper particle diameter is evenly distributed in Nano grade between two adjacent graphene layers；The heat conduction film of gained
Thickness is 50 μm -100 μm, and transverse thermal conductivity is in 600W/mK or more at room temperature.
2. the heat conduction film of graphene according to claim 1-nanometer carbon/carbon-copper composite material, it is characterised in that：The copper
A diameter of 35nm-120nm of grain.
3. the preparation method of the heat conduction film of graphene according to claim 1-nanometer carbon/carbon-copper composite material, feature exist
In：Include the following steps：
1）Prepare graphene oxide film；
2）Electro deposition oxidation graphene film is prepared on the graphene oxide film using electroplating technology；Electroplating technology is specific
For：Electro deposition oxidation graphene film is prepared on the graphene oxide film, concrete technology is：It adds graphene oxide into
Ultrasonic disperse is carried out in deionized water, electrophoretic deposition is carried out in electroplating bath, specially electro-deposition under conditions of 20 V constant pressures
180 s, during electrolysis, the copper sheet as anode, which loses, electronically forms bivalent cupric ion, and gel is formed in anode surface
The dark film of shape, that is, electro deposition oxidation graphene film
3）Vacuum drying, annealing restore the electro deposition oxidation graphene film and form graphene-Nanometer Copper laminated film；
4）Hot pressing is simultaneously annealed；Hot-pressing technique is specially：Pressure 30MPa is warming up to 800 DEG C, constant temperature with the rate of 10 DEG C/min
30min, then natural cooling；Annealing technology is specially：300 DEG C are warming up to the rate of 10 DEG C/min in the atmosphere of nitrogen,
Constant temperature 1h, then natural cooling.
4. the preparation method of the heat conduction film of graphene according to claim 3-nanometer carbon/carbon-copper composite material, feature exist
In：The step 1）The specific method for preparing graphene oxide film is：
1-1）Natural flaky graphite powder is added in the mixture containing concentrated nitric acid sodium and the freezing concentrated sulfuric acid；
1-2）Potassium permanganate is added, and stirs mixture；
1-3）It is gradually added into hydrogen peroxide solution and removes remaining potassium permanganate；
1-4）Mixture is diluted and centrifuged, graphene oxide is obtained；
1-5）The graphene oxide is cleaned with hydrochloric acid solution and deionized water；
1-6）Filtered under vacuum is dehydrated to obtain graphene oxide film.
5. the preparation method of the heat conduction film of graphene according to claim 3-nanometer carbon/carbon-copper composite material, feature exist
In：The step 3）Specific method be：The electro deposition oxidation graphene film is put into drying in atmosphere furnace, is put into later
In atmosphere furnace, be passed through nitrogen, 300 DEG C be heated to the rate of 6 DEG C/min, constant temperature is passed through hydrogen after 10 minutes, then with 8 DEG C/
The rate of min is warming up to corresponding temperature, is heat-treated by hydrogen annealing, and the defect of graphene is repaired, step 2）Galvanizer
The bivalent cupric ion formed during skill, which is reduced into nano copper particle and moves in the interlayer of graphene oxide, forms graphite
Alkene-Nanometer Copper laminated film.
6. the preparation method of the heat conduction film of graphene according to claim 5-nanometer carbon/carbon-copper composite material, feature exist
In：The technique of the hydrogen annealing is to be separately heated to 400 DEG C, 500 DEG C, 650 DEG C and 700 DEG C.
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| WO2019047164A1 (en) * | 2017-09-08 | 2019-03-14 | 深圳大学 | Preparation method for graphene oxide |
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| CN109811175A (en) * | 2019-03-26 | 2019-05-28 | 重庆大学 | A kind of graphene-method of manufacturing carbon/carbon-copper composite material |
| CN110117810B (en) * | 2019-06-10 | 2021-03-30 | 广西师范大学 | Method for preparing modified graphene oxide aluminum composite heat conduction material through electrophoresis |
| CN110344099A (en) * | 2019-07-18 | 2019-10-18 | 桂林电子科技大学 | A kind of preparation method of high thermal conductivity graphene composite thin film material |
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| CN114096118B (en) * | 2021-11-03 | 2023-05-02 | 武汉华星光电半导体显示技术有限公司 | Heat radiating fin, manufacturing method thereof and electronic device |
| CN113860888A (en) * | 2021-11-04 | 2021-12-31 | 四川恒力盛泰石墨烯科技有限公司 | Preparation method of graphene heat dissipation film for electronic equipment |
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| CN105624445B (en) * | 2016-01-06 | 2017-10-27 | 昆明理工大学 | A kind of graphene strengthens the preparation method of Cu-base composites |
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Effective date of registration: 20200103 Address after: Yudaojie Qinhuai District of Nanjing City, Jiangsu Province, No. 29 210000 Co-patentee after: BEIJING INSTITUTE OF ELECTRONIC SYSTEM ENGINEERING Patentee after: Nanjing University of Aeronautics and Astronautics Address before: Yudaojie Qinhuai District of Nanjing City, Jiangsu Province, No. 29 210000 Patentee before: Nanjing University of Aeronautics and Astronautics |
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