CN108503383A - A kind of preparation method of the graphene composite film of high thermal conductivity - Google Patents

A kind of preparation method of the graphene composite film of high thermal conductivity Download PDF

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CN108503383A
CN108503383A CN201810352536.8A CN201810352536A CN108503383A CN 108503383 A CN108503383 A CN 108503383A CN 201810352536 A CN201810352536 A CN 201810352536A CN 108503383 A CN108503383 A CN 108503383A
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thermal conductivity
preparation
composite film
high thermal
graphene composite
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CN108503383B (en
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韩金玲
吕振瑞
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Xiamen Chengyu Industrial Co.,Ltd.
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韩金玲
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Abstract

Graphene is due to its excellent physicochemical characteristics, it is with a wide range of applications in every field, in heat conduction field, since it has the thermal coefficient of up to 3500 W/mK, heat conduction field is used to it to be also widely used, the technical program introduces plasma ablator during preparing high heat conduction graphite film and carries out ablation processes to the polyimide composite film of preparation for the first time, greatly shorten the carbonized graphite time, so that the carbonized graphite alkene in original technique is reduced to a step, improving one step of high temperature ablation realizes the carbonized graphite processing of Kapton and the reduction of graphene oxide, so that final product shows very excellent heat conductivility.

Description

A kind of preparation method of the graphene composite film of high thermal conductivity
Technical field
The invention belongs to high-heat-conductive composite material preparation fields, and in particular to a kind of graphene compound macromolecular polymer High heat conduction technology of thin film material preparation field.
Background technology
With the continuous development of electronic industry, the integrated level of electronic product is higher and higher, at the same time, the heat that chip generates Amount also increased dramatically, and due to the miniaturization of product so that the unit heat density of product inevitably increases sharply, and traditional This is increasingly difficult to using the physics radiating mode such as copper pipe, aluminium flake to meet actual demand, such as copper pipe or aluminium commercial at present Its thermal coefficient of piece is only respectively 380 W/mK and 200W/mK, and its density is 8.96g/cm respectively3And 2.7g/cm3, this The rapid cooling that cannot not only solve the problems, such as electronic device also limits the lighting development of electronic device, and development is a kind of as a result, Low-density, the copper pipe and aluminium flake that the material substitution of high thermal conductivity is traditional have the sustainable development of current entire electronic industry Important meaning.
Graphite film has attracted the sight of large quantities of researchers due to having good thermal conductivity and lower density, and by In the layer structure of graphite so that it has apparent anisotropy in heat conduction, this is greatly different from current traditional material Material, if its thermal coefficient in the horizontal direction is up to 1500-3000W/mK, the thermal coefficient of vertical direction is only its horizontal direction 1 percent, and its density more can be down to 1-2g/cm3, these excellent performances so that graphite film is latent with huge application Power.
In this regard, Chinese patent CN105235307A discloses a kind of heat conducting film graphite composite material, and disclose a kind of use In the heat conducting film graphite composite material of various electronic equipment dissipating heat occasions；Its structure includes from top to bottom PET back-adhesive films, metal foil Layer, heat-conducting silicone grease, graphite film, acrylic compounds glue and release film open up aperture and perforation simultaneously on metal foil layer and graphite film respectively It corresponds, metal foil layer, which is affixed to merge with PET back-adhesive films, is provided with metal foil layer protrusion, first by PI films through carbon when preparation Change and graphitization is made the laggard eleven punch 11 of graphite film, form graphite film perforation, then metal foil layer perforated and to form metal foil layer and passes through Hole, then will be compound with the graphite film of smearing acrylic compounds glue after the coated with thermally conductive silicone grease of metal foil layer side, then is pasted with release film It closes, is finally bonded the metal foil layer other side with PET back-adhesive films, composite material is made by rubber roller compacting.Chinese patent CN103011141A discloses a kind of manufacturing method of high heat conduction graphite film, it is using Kapton as raw material, warp Two processes of carbonization and graphitization are crossed, technical process is as follows：A. select Kapton as raw material, in each strata Graphite paper is sandwiched between imide membrane；B. by be separated with graphite paper it is cross layered after Kapton be put into retort It is carbonized in nitrogen or ar gas environment, 1000 DEG C -1400 DEG C of carburizing temperature, time control was at -6 hours 1 hour；C. it is carbonized laggard Row graphitization, graphitization are also to be carried out in nitrogen or ar gas environment, and temperature is controlled at 2500 DEG C to 3000 DEG C or so, and control exists Within 12 hours.Although above-mentioned heat conducting film is all to be graphite film, have very high thermal coefficient, due to it uses Polyimides is film base material, this makes the process that polyimides is changed into graphite film complex, needs first to be carbonized It is graphitized again afterwards, this continuous time consumption and energy consumption, and the product controllability prepared is worse, is unfavorable for large-scale production.
Invention content
Based on the above issues, applicant is by for a long time in the further investigation of function nano Material Field, it is proposed that as follows Technical solution proposes a kind of simple for process, repeatability height, and heat conducting film obtained is compared to existing to solve the technical problem Heat conducting film have higher thermal coefficient film technology of preparing scheme.
In recent years, graphene is with a wide range of applications due to its excellent physicochemical characteristics in every field, Heat conduction field, since it has the thermal coefficient of up to 3500 W/mK, heat conduction field is used for it also extensive research, Shen It asks someone, according to from the correlative study in field of graphene, to be introduced into high molecular polymer, pass through a kind of simple side Method prepares rapidly the graphene composite film of high thermal conductivity.
In order to enable those skilled in the art further to understand the technical solution of applicant, applicant is to the technology Scheme is described in detail as follows：
A kind of preparation method of the graphene composite film of high thermal conductivity, includes the following steps：
Step 1, amine substance is added in organic solvent and anhydride substance is several, stir evenly, until being completely dissolved, obtain solution A；
Step 2, several single-layer graphene oxides are taken, in dispersion in solution, the ultrasound 5-10min under 30-60 DEG C of ultrasound condition, Obtain orange-yellow graphene oxide colloidal dispersion B；
Step 3, it is stirred continuously in 50-80 DEG C of water-bath, the dispersion liquid B in the solution A and step 2 in step 1 is mixed Uniformly, stable block copolymer systems C is formed；
Step 4, the mold of the polytetrafluoroethylene (PTFE) Jing Guo pre-treatment is placed in an oven, into the Teflon mould The block copolymer systems C being added in step 3 is several, and solidification drying is carried out at 50-300 DEG C；Obtain desciccate D；
Step 5, desciccate D in step 4 is subjected to ablation with plasma ablator, after 30-70S, you can obtain one kind The graphene composite film of high thermal conductivity.
Further, the organic solvent described in step 1 includes in acetone, N,N-Dimethylformamide, dimethyl sulfoxide It is one or more of.
Further, the amine substance described in step 1 includes p-phenylenediamine, m-phenylene diamine (MPD), dichloro benzidine One or more of.
Further, the anhydride substance described in step 1 includes pyromellitic acid anhydride, diphenyl ether tetracarboxylic dianhydride, connection One or more of benzene tertacarbonic acid's dianhydride.
Further, the molar ratio of the amine substance described in step 1 and anhydride substance is 1:1-2.
Further, the single-layer graphene oxide described in step 2, from pioneer's nano material, piece diameter is 0.5-5 for buying Micron, thickness 0.8-1.2nm.
Further, the single-layer graphene oxide described in step 2, a concentration of 0.05-0.1mg/ml.
Further, the Teflon mould described in step 4 can have any shape, and the oven temperature is 80-100 degrees Celsius, drying time 0.5-1h.
Further, the pre-treatment described in step 4 refers to spraying Teflon mould using releasing agent.
Further, the volume of liquid in polytetrafluoroethylene (PTFE) can be determined in step 4 according to the thickness of required heat conducting film.
Further, the plasma ablator described in step 5 is that ablation, ablation process are carried out at 2100-3000 DEG C In object to be ablated horizontally or vertically moved with the speed of 1-5mm/s.
Further, further include in step 5 by the film cooled to room temperature after ablation, then use hot pressing machine into Row rolling, to improve the flexibility of product.
So-called plasma ablator is the machine for referring to generate plasma torch in the present invention.
Compared with prior art, the present invention has following advantageous effects：
1, the present invention introduces polyimides of the plasma ablator to preparation during preparing high heat conduction graphite film for the first time Composite membrane carries out ablation processes, greatly shortens the carbonized graphite time.
2, due to the use of plasma ablator so that originally the carbonized graphite alkene in technique is reduced to a step, not only simple Change preparation process, also saved energy consumption, improves the production efficiency of product.
3, graphene is introduced in the Kapton of preparation, due to being the very high mono-layer graphite oxide of quality Alkene, with preferable dispersibility, improving one step of high temperature ablation realizes at the carbonized graphite of Kapton The reduction of reason and graphene oxide so that final product shows very excellent heat conductivility.
Specific implementation mode
With reference to specific embodiment, the present invention is described in further detail, it is described be explanation of the invention simultaneously It is not to limit, any without prejudice to present inventive concept, the simple deformation done belongs to claimed Range.
Embodiment 1
M-phenylene diamine (MPD) is added in n,N-Dimethylformamide and pyromellitic acid anhydride is several, stirs evenly, until be completely dissolved, Obtain solution A；1g single-layer graphene oxides are taken, are dispersed in the solution of 10ml, the ultrasound 10min under 40 DEG C of ultrasound condition, Obtain orange-yellow graphene oxide colloidal dispersion B；Be stirred continuously in 50 DEG C of water-bath, by step 1 solution A and Dispersion liquid B in step 2 is uniformly mixed, and forms stable block copolymer systems C；The polytetrafluoro that will be crossed by releasing agent spray treatment The mold of ethylene is placed in an oven, and the block copolymer systems C being added in step 3 into the Teflon mould is several, It carries out curing dry 0.5h at 100 DEG C；Obtain desciccate D；Desciccate D in step 4 is burnt with plasma ablator Erosion, at 2500 DEG C after 70S ablations, you can obtain a kind of graphene composite film of high thermal conductivity, wait for heat conducting film nature After being cooled to room temperature, rolling process is carried out using hot pressing machine, obtains final products.
It is tested by universal tensile instrument, when bending radius is 2mm, by 20,000 uninterrupted follow-on tests, system of the present invention Standby heat conducting film is not broken, and is had extraordinary flexibility, is carried out the test of thermal conductivity to it, find its horizontal direction Thermal conductivity is up to 2300W/mK.
Embodiment 2
P-phenylenediamine is added in n,N-Dimethylformamide and pyromellitic acid anhydride is several, wherein p-phenylenediamine and equal benzene The molar ratio of tetracarboxylic acid dianhydride is 10:11, it stirs evenly, until being completely dissolved, obtains solution A；0.1g single-layer graphene oxides are taken, It is dispersed in the solution of 10ml, the ultrasound 10min under 40 DEG C of ultrasound condition obtains orange-yellow graphene oxide colloidal dispersions Liquid B；It is stirred continuously in 50 DEG C of water-bath, the dispersion liquid B in the solution A and step 2 in step 1 is uniformly mixed, formed Stable block copolymer systems C；In an oven by the mold placement for the polytetrafluoroethylene (PTFE) crossed by releasing agent spray treatment, to described Teflon mould in be added step 3 in block copolymer systems C it is several, carry out curing dry 1h at 100 DEG C；Obtain drying Product D；Desciccate D in step 4 is subjected to ablation with plasma ablator, at 2800 DEG C after 70S ablations, you can It is rolled to a kind of graphene composite film of high thermal conductivity using hot pressing machine after the heat conducting film cooled to room temperature Processing, obtains final products.
It is tested by universal tensile instrument, when bending radius is 2mm, by 20,000 uninterrupted follow-on tests, system of the present invention Standby heat conducting film is not broken, and is had extraordinary flexibility, is carried out the test of thermal conductivity to it, find its horizontal direction Thermal conductivity is up to 2150W/mK.
Embodiment 3
P-phenylenediamine is added in n,N-Dimethylformamide and pyromellitic acid anhydride is several, wherein m-phenylene diamine (MPD) and equal benzene The molar ratio of tetracarboxylic acid dianhydride is 1:1, it stirs evenly, until being completely dissolved, obtains solution A；0.5g single-layer graphene oxides are taken, point It is dispersed in the solution of 10ml, the ultrasound 10min under 40 DEG C of ultrasound condition obtains orange-yellow graphene oxide colloidal dispersion B；It is stirred continuously in 50 DEG C of water-bath, the dispersion liquid B in the solution A and step 2 in step 1 is uniformly mixed, formed steady Fixed block copolymer systems C；In an oven by the mold placement for the polytetrafluoroethylene (PTFE) crossed by releasing agent spray treatment, to described The block copolymer systems C being added in step 3 in Teflon mould is several, carries out curing dry 1h at 100 DEG C；Obtain dry production Object D；Desciccate D in step 4 is subjected to ablation with plasma ablator, at 2800 DEG C after 70S ablations, you can obtain A kind of graphene composite film of high thermal conductivity carries out rolling after the heat conducting film cooled to room temperature using hot pressing machine Reason, obtains final products.
It is tested by universal tensile instrument, when bending radius is 2mm, by 20,000 uninterrupted follow-on tests, system of the present invention Standby heat conducting film is not broken, and is had extraordinary flexibility, is carried out the test of thermal conductivity to it, find its horizontal direction Thermal conductivity is up to 2300W/mK.
Embodiment 4
P-phenylenediamine is added in dimethyl sulfoxide and pyromellitic acid anhydride is several, wherein m-phenylene diamine (MPD) and Pyromellitic Acid two The molar ratio of acid anhydride is 10:12, it stirs evenly, until being completely dissolved, obtains solution A；0.1g single-layer graphene oxides are taken, are dispersed in In the solution of 10ml, the ultrasound 10min under 40 DEG C of ultrasound condition obtains orange-yellow graphene oxide colloidal dispersion B； It is stirred continuously in 50 DEG C of water-bath, the dispersion liquid B in the solution A and step 2 in step 1 is uniformly mixed, is formed stable Block copolymer systems C；The mold for the polytetrafluoroethylene (PTFE) crossed by releasing agent spray treatment is placed in an oven, to described poly- four The block copolymer systems C being added in step 3 in vinyl fluoride mold is several, carries out curing dry 1h at 100 DEG C；Obtain desciccate D； Desciccate D in step 4 is subjected to ablation with plasma ablator, at 2800 DEG C after 70S ablations, you can obtain one kind The graphene composite film of high thermal conductivity carries out rolling process using hot pressing machine, obtains after the heat conducting film cooled to room temperature To final products.
It is tested by universal tensile instrument, when bending radius is 2mm, by 20,000 uninterrupted follow-on tests, system of the present invention Standby heat conducting film is not broken, and is had extraordinary flexibility, is carried out the test of thermal conductivity to it, find its horizontal direction Thermal conductivity is up to 2200W/mK.
Comparative example 1
Other steps are same as Example 1, difference lies in carrying out ablation without using plasma ablator, but use conventional elder generation Graphited processing mode after carbonization, the thermal conductivity of graphene composite film obtained is also in 2000 W/mK or more, this proof Serious decline will not be caused to influence the performance of product using plasma ablator.
Comparative example 2
Other steps are same as Example 1, difference lies in the graphene oxide for using traditional Hummers methods to prepare, from final From the point of view of the thermal conductivity of product, performance is obviously not so good as using the good of single-layer graphene oxide, this also illustrates the property of the composite heat conduction film There can be prodigious relationship with the quality of graphene.

Claims (10)

1. a kind of preparation method of the graphene composite film of high thermal conductivity, which is characterized in that include the following steps：
Step 1, amine substance is added in organic solvent and anhydride substance is several, stir evenly, until being completely dissolved, obtain solution A；
Step 2, several single-layer graphene oxides are taken, in dispersion in solution, the ultrasound 5-10min under 30-60 DEG C of ultrasound condition, Obtain orange-yellow graphene oxide colloidal dispersion B；
Step 3, it is stirred continuously in 50-80 DEG C of water-bath, the dispersion liquid B in the solution A and step 2 in step 1 is mixed Uniformly, stable block copolymer systems C is formed；
Step 4, the mold of the polytetrafluoroethylene (PTFE) Jing Guo pre-treatment is placed in an oven, into the Teflon mould The block copolymer systems C being added in step 3 is several, and solidification drying is carried out at 50-300 DEG C；Obtain desciccate D；
Step 5, desciccate D in step 4 is subjected to ablation with plasma ablator, after 30-70S, you can obtain one kind The graphene composite film of high thermal conductivity.
2. a kind of preparation method of the graphene composite film of high thermal conductivity according to claim 1, it is characterised in that：Also wrap It includes the film cooled to room temperature after ablation, is then rolled using hot pressing machine.
3. according to a kind of preparation method of the graphene composite film of high thermal conductivity described in claim 1, it is characterised in that：Step 1 Described in organic solvent include one or more of acetone, N,N-Dimethylformamide, dimethyl sulfoxide.
4. according to a kind of preparation method of the graphene composite film of high thermal conductivity described in claim 1, it is characterised in that：Step 1 Described in amine substance include one or more of p-phenylenediamine, m-phenylene diamine (MPD), dichloro benzidine.
5. according to a kind of preparation method of the graphene composite film of high thermal conductivity described in claim 1, it is characterised in that：Step 1 Described in anhydride substance include pyromellitic acid anhydride, diphenyl ether tetracarboxylic dianhydride, one kind in biphenyltetracarboxylic dianhydride or It is several.
6. according to a kind of preparation method of the graphene composite film of high thermal conductivity described in claim 1, it is characterised in that：Step 1 Described in amine substance and anhydride substance molar ratio be 1:1-2.
7. according to a kind of preparation method of the graphene composite film of high thermal conductivity described in claim 1, it is characterised in that：Step 2 Described in single-layer graphene oxide, piece diameter be 0.5-5 microns, thickness 0.8-1.2nm；The mono-layer graphite oxide Alkene, a concentration of 0.05-0.1mg/ml.
8. according to a kind of preparation method of the graphene composite film of high thermal conductivity described in claim 1, it is characterised in that：Step 4 Described in Teflon mould can have any shape, the oven temperature is 80-100 degrees Celsius, and drying time is 0.5-1h；The pre-treatment refers to spraying Teflon mould using releasing agent.
9. a kind of preparation method of the graphene composite film of high thermal conductivity described in claim 1, it is characterised in that：In step 5 The plasma ablator is that ablation is carried out at 2100-3000 DEG C, horizontal or vertical with the speed of 1-5mm/s in ablation process Object to be ablated is moved in translation.
10. the graphene composite film of high thermal conductivity prepared by preparation method described in claim 1, it is characterised in that：This is compound Film so keeps good flexibility when bending radius is 2mm, by 20,000 bending successors, and its thermal conductivity is more than 2000 W/ mK。
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