CN109181654A - A kind of graphene-based composite heat conduction film and preparation method thereof and its application - Google Patents
A kind of graphene-based composite heat conduction film and preparation method thereof and its application Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of graphene-based composite heat conduction film, include the following steps: that (1) crystalline flake graphite is added in oxidant solutions and carries out ultrasonic agitation removing, then it is stirred after laruyl alcohol sodium sulfovinate and dodecyl sulphate monoethanolamine being added, it carries out microwave irradiation processing again later, obtains graphene oxide solution；(2) hollow nano carbon microsphere is taken, in the mixed solvent is scattered in, is then heated to reflux, obtains the modified hollow nano carbon microsphere in surface；(3) it in the graphene oxide solution for being added to modified Nano carbon ball, stirs evenly；Obtained mixed solution is sprayed in flexible substrate using hot spray process, deposition obtains graphene composite thin film；(4) graphene composite thin film is restored；(5) the graphene-based laminated film that reduction obtains is calcined to get the graphene composite heat conduction film.Graphene-based composite heat conduction film excellent thermal conductivity produced by the present invention, stability is good, has a extensive future.
Description
Technical field
The invention belongs to grapheme material and its applied technical fields, and in particular to a kind of graphene-based composite heat conduction film and
Preparation method and its application.
Background technique
With the development of science and technology electronic equipment is gradually to small miniaturization, component integration, lightening, performance efficiencyization hair
Exhibition, however electronic equipment can generate amount of heat in the process of running, if in time cannot effectively export heat, not only will affect
Its stability, and its service life can be greatly shortened, thus heat sink material must be used to improve heat transfer efficiency, eliminate heat
Point aggregation, Quick diffusing heat reduce device temperature, run its persistent high efficiency.Traditional heat-dissipating density of material is big, thermal conductivity is low
And processing is complicated, it is difficult to meet modern cooling requirements, there is an urgent need to a kind of materials of low close high thermal conductivity to realize for heat dissipation
Demand.
Graphene (Graphene) be one kind by carbon atom with sp2It is in honeycomb lattice that hybridized orbit, which forms hexangle type,
The single layer flat film that (honeycomb crystal lattice) is arranged to make up, the two-dimentional material of only one carbon atom thickness
Material.It is but also most hard nano material that graphene, which is currently most thin in the world, it is almost fully transparent, only absorption 2.3%
Light；Thermal coefficient is up to 5300W/mK, is higher than carbon nanotube and diamond, its electron mobility is more than under room temperature
15000cm2/ (Vs), but it is higher than carbon nanotubes or silicon crystal, and resistivity about 10-6Ω cm, it is lower than copper or silver, be
The smallest material of world resistivity.Graphene has so excellent physical and chemical performance, oneself is gradually available for transparent conductive film,
Nano electron device (transistor, transistor circuit interconnect memory semiconductor), conductive ink are solar battery, clang battery, super
The fields such as capacitor, sensor and biological medicine.
Chinese patent CN104592950A is by graphene microchip and high molecular polymer mixing film forming be carbonized and then stone
The graphene-based polymer bond's film of high thermal conductivity is made in inkization processing.Chinese patent CN104264146A functionalization graphene solution
It is thermally conductive that the electrically conducting transparent based on functionalization graphene is made in 1000-2800 DEG C of high-temperature process after coating film forming is dry on matrix
Film.Chinese patent CN105523547A passes through graphene oxide solution film forming, electronation, high temperature reduction and high pressure compacting etc.
Step obtains super flexible high thermal conductivity graphene film.The graphene oxide of pre-treatment is coated on by Chinese patent CN105110794A
It is carbonized in PET film, is graphitized obtained graphene film.Chinese patent CN105502368A is by graphene oxide on matrix
Graphitization processing, which rolls and removes matrix, after knifing obtains graphene film.Oxidation is aoxidized stone by Chinese patent CN104085143A
On a flexible substrate, graphene thermally conductive film then is made by reduction method in black alkene solution spraying.
However above-mentioned graphene thermally conductive film still has several drawbacks and defect, for example thermal conductivity is insufficient, spray coating method also needs
To reinforce by binder with the bond strength of substrate etc., therefore, develop a kind of high thermal conductivity, the stable graphene of performance
Film has a very important significance.
Summary of the invention
The purpose of the present invention is to provide a kind of graphene-based composite heat conduction film and preparation method thereof, the preparation method techniques
Simply, condition is controllable, can effectively reduce the cohesion between graphene, and reduces the internal flaw of graphene, obtained production
Moral character can be stablized, and heat dissipation performance is excellent.
To achieve the above object, preparation process adopted by the present invention are as follows:
A kind of preparation method of graphene-based composite heat conduction film, includes the following steps:
(1) preparation of graphene oxide solution: by crystalline flake graphite be added the in the mixed solvent of the concentrated sulfuric acid and potassium permanganate into
Row ultrasonic agitation removing, stirs a period of time after laruyl alcohol sodium sulfovinate and dodecyl sulphate monoethanolamine is then added, it
It carries out microwave irradiation processing a period of time again afterwards, is eventually adding after deionized water washing filters and obtains graphene oxide solution；
(2) preparation of modified Nano carbon ball: hollow nano carbon microsphere is taken, ethylene glycol monomethyl ether and ethyl acetate are scattered in
In the mixed solvent, be then heated to reflux 3-5h, after the reaction was completed, be centrifuged, wash, modified hollow in surface is obtained by filtration receiving
Rice carbon ball；
(3) modified Nano carbon ball prepared by step (2) is added in the graphene oxide solution of step (1), stirring is equal
It is even；Mixed solution obtained above is sprayed in flexible substrate using hot spray process later, it is multiple that deposition obtains graphene oxide
Close film；
(4) graphene composite thin film of step (3) is restored, obtains graphene-based laminated film；
(5) the graphene-based laminated film that step (4) reduction obtains is warming up to 600-1000 with the rate of 1-3 DEG C/min
DEG C heat preservation 2-4h, is cooled to room temperature later up to the graphene composite heat conduction film.
Preferably, the mass ratio of the concentrated sulfuric acid, potassium permanganate and crystalline flake graphite is 3-6:150-250:10-40 in step (1)；
The additional amount of laruyl alcohol sodium sulfovinate and dodecyl sulphate monoethanolamine is the 0.5-3% of crystalline flake graphite quality.
Preferably, the time of ultrasonic agitation removing is 0.5-3h in step (1), and the power of microwave irradiation is 700-900W,
Time is 5-15min.
Preferably, the diameter of nano carbon microsphere described in step (2) is 10-40nm, the quality of nano carbon microsphere and mixed solvent
Volume ratio g/mL is 1:40-80；The volume ratio of in the mixed solvent ethylene glycol monomethyl ether and ethyl acetate is 1:1.
Preferably, in step (3) modified Nano carbon ball additional amount be graphene oxide solution 5-10%.
Preferably, the height sprayed when thermal spraying in step (3) is from substrate 50-70cm, and the temperature of spraying is 80-160
℃。
Preferably, method graphene composite thin film restored in step (4) are as follows: vacuum tube furnace is used,
At a high temperature of 1000 DEG C, it is passed through H2It is restored, obtains graphene-based laminated film.
Preferably, the flexible substrate is copper foil or aluminium foil.
In addition, the present invention is also claimed by the preparation-obtained graphene-based composite heat conduction film of the preparation method.
Compared with prior art, the invention has the benefit that
(1) present invention carries out ultrasound removing to crystalline flake graphite by strong oxidation first and obtains graphene oxide, then
To the secondary removing of microwave radiation after graphene oxide progress functional group modification, thinner graphene can be obtained by 2 removings,
And since the introducing of the functional groups such as hydroxyl, carboxyl can be effectively improved the dispersibility and spraying of graphene oxide in a solvent
The uniformity of liquid on substrate；
(2) nano carbon microsphere is added in graphene oxide solution and forms composite spraying liquid by the present invention, on the one hand utilizes carbon ball
High thermal conductivity enhances the heat-sinking capability of graphene, and another aspect carbon ball can be distributed in graphene due to its small-size effect
Piece interlayer the thermal conducting path of graphene can be made unimpeded, form the heat conduction network of stable and uniform, improve heat transfer efficiency；
(3) present invention can effectively repair the defect of graphene by carrying out high-temperature process to graphene-based composite membrane, into one
Step promotes the thermal conducting path of graphene-based composite material, promotes its stability.
Detailed description of the invention
Fig. 1 is the SEM figure of graphene-based composite heat conduction film prepared by the embodiment of the present invention 1.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
Embodiment 1
A kind of preparation method of graphene-based composite heat conduction film, includes the following steps:
(1) preparation of graphene oxide solution: the mixing that the 1g concentrated sulfuric acid and 40g potassium permanganate is added in 2g crystalline flake graphite is molten
Ultrasonic agitation removing 1h is carried out in agent, after 0.01g laruyl alcohol sodium sulfovinate 0.01g dodecyl sulphate monoethanolamine then is added
0.5h is stirred, carries out microwave irradiation processing a period of time 10min again later, is eventually adding after deionized water washing filters and obtains oxygen
Graphite alkene solution；
(2) preparation of modified Nano carbon ball: taking the nano carbon microsphere that 0.2g is hollow, be scattered in 5mL ethylene glycol monomethyl ether and
The in the mixed solvent of 5mL ethyl acetate, is then heated to reflux 4h, after the reaction was completed, it is centrifuged, washs, surface modification is obtained by filtration
Hollow nano carbon microsphere；
(3) modified Nano carbon ball prepared by step (2) is added in the graphene oxide solution of step (1), stirring is equal
It is even；Mixed solution obtained above is sprayed on copper foil substrate using hot spray process later, it is multiple that deposition obtains graphene oxide
Close film；The height sprayed when thermal spraying is from substrate 60cm, and the temperature of spraying is 120 DEG C；
(4) H is passed through at a high temperature of 1000 DEG C using vacuum tube furnace2It is restored, obtains graphene-based THIN COMPOSITE
Film；
(5) the graphene-based laminated film that step (4) reduction obtains is warming up to 800 DEG C of heat preservations with the rate of 2 DEG C/min
3h is cooled to room temperature later up to the graphene composite heat conduction film.
Embodiment 2
A kind of preparation method of graphene-based composite heat conduction film, includes the following steps:
(1) preparation of graphene oxide solution: the mixing that the 1g concentrated sulfuric acid and 40g potassium permanganate is added in 2g crystalline flake graphite is molten
Ultrasonic agitation removing 1h is carried out in agent, after 0.01g laruyl alcohol sodium sulfovinate 0.01g dodecyl sulphate monoethanolamine then is added
0.5h is stirred, carries out microwave irradiation processing a period of time 10min again later, is eventually adding after deionized water washing filters and obtains oxygen
Graphite alkene solution；
(2) preparation of modified Nano carbon ball: taking the nano carbon microsphere that 0.15g is hollow, is scattered in 4.5mL ethylene glycol monomethyl ether
With the in the mixed solvent of 4.5mL ethyl acetate, it is then heated to reflux 4h, after the reaction was completed, it is centrifuged, washs, surface is obtained by filtration
Modified hollow nano carbon microsphere；
(3) modified Nano carbon ball prepared by step (2) is added in the graphene oxide solution of step (1), stirring is equal
It is even；Mixed solution obtained above is sprayed on copper foil substrate using hot spray process later, it is multiple that deposition obtains graphene oxide
Close film；The height sprayed when thermal spraying is from substrate 60cm, and the temperature of spraying is 100 DEG C；
(4) H is passed through at a high temperature of 1000 DEG C using vacuum tube furnace2It is restored, obtains graphene-based THIN COMPOSITE
Film；
(5) the graphene-based laminated film that step (4) reduction obtains is warming up to 1000 DEG C of heat preservations with the rate of 2 DEG C/min
3h is cooled to room temperature later up to the graphene composite heat conduction film.
Embodiment 3
A kind of preparation method of graphene-based composite heat conduction film, includes the following steps:
(1) 2g crystalline flake graphite the preparation of graphene oxide solution: is added to the mixing of the 0.6g concentrated sulfuric acid and 20g potassium permanganate
Ultrasonic agitation removing 1h is carried out in solvent, and 0.02g laruyl alcohol sodium sulfovinate 0.02g dodecyl sulphate monoethanolamine is then added
After stir 0.5h, carry out again later microwave irradiation processing a period of time 10min, be eventually adding deionized water washing filter after obtain
Graphene oxide solution；
(2) preparation of modified Nano carbon ball: taking the nano carbon microsphere that 0.2g is hollow, be scattered in 5mL ethylene glycol monomethyl ether and
The in the mixed solvent of 5mL ethyl acetate, is then heated to reflux 4h, after the reaction was completed, it is centrifuged, washs, surface modification is obtained by filtration
Hollow nano carbon microsphere；
(3) modified Nano carbon ball prepared by step (2) is added in the graphene oxide solution of step (1), stirring is equal
It is even；Mixed solution obtained above is sprayed on copper foil substrate using hot spray process later, it is multiple that deposition obtains graphene oxide
Close film；The height sprayed when thermal spraying is from substrate 70cm, and the temperature of spraying is 160 DEG C；
(4) H is passed through at a high temperature of 1000 DEG C using vacuum tube furnace2It is restored, obtains graphene-based THIN COMPOSITE
Film；
(5) the graphene-based laminated film that step (4) reduction obtains is warming up to 800 DEG C of heat preservations with the rate of 2 DEG C/min
4h is cooled to room temperature later up to the graphene composite heat conduction film.
Embodiment 4
A kind of preparation method of graphene-based composite heat conduction film, includes the following steps:
(1) 2g crystalline flake graphite the preparation of graphene oxide solution: is added to the mixing of the 0.6g concentrated sulfuric acid and 24g potassium permanganate
Ultrasonic agitation removing 1h is carried out in solvent, and 0.02g laruyl alcohol sodium sulfovinate 0.02g dodecyl sulphate monoethanolamine is then added
After stir 0.5h, carry out again later microwave irradiation processing a period of time 10min, be eventually adding deionized water washing filter after obtain
Graphene oxide solution；
(2) preparation of modified Nano carbon ball: taking the nano carbon microsphere that 0.2g is hollow, be scattered in 5mL ethylene glycol monomethyl ether and
The in the mixed solvent of 5mL ethyl acetate, is then heated to reflux 4h, after the reaction was completed, it is centrifuged, washs, surface modification is obtained by filtration
Hollow nano carbon microsphere；
(3) modified Nano carbon ball prepared by step (2) is added in the graphene oxide solution of step (1), stirring is equal
It is even；Mixed solution obtained above is sprayed in aluminum substrates using hot spray process later, it is multiple that deposition obtains graphene oxide
Close film；The height sprayed when thermal spraying is from substrate 60cm, and the temperature of spraying is 120 DEG C；
(4) H is passed through at a high temperature of 1000 DEG C using vacuum tube furnace2It is restored, obtains graphene-based THIN COMPOSITE
Film；
(5) the graphene-based laminated film that step (4) reduction obtains is warming up to 800 DEG C of heat preservations with the rate of 2 DEG C/min
3h is cooled to room temperature later up to the graphene composite heat conduction film.
Embodiment 5
A kind of preparation method of graphene-based composite heat conduction film, includes the following steps:
(1) preparation of graphene oxide solution: the mixing that the 1g concentrated sulfuric acid and 40g potassium permanganate is added in 2g crystalline flake graphite is molten
Ultrasonic agitation removing 1h is carried out in agent, after 0.01g laruyl alcohol sodium sulfovinate 0.01g dodecyl sulphate monoethanolamine then is added
0.5h is stirred, carries out microwave irradiation processing a period of time 10min again later, is eventually adding after deionized water washing filters and obtains oxygen
Graphite alkene solution；
(2) preparation of modified Nano carbon ball: taking the nano carbon microsphere that 0.1g is hollow, be scattered in 3mL ethylene glycol monomethyl ether and
The in the mixed solvent of 3mL ethyl acetate, is then heated to reflux 4h, after the reaction was completed, it is centrifuged, washs, surface modification is obtained by filtration
Hollow nano carbon microsphere；
(3) modified Nano carbon ball prepared by step (2) is added in the graphene oxide solution of step (1), stirring is equal
It is even；Mixed solution obtained above is sprayed in aluminum substrates using hot spray process later, it is multiple that deposition obtains graphene oxide
Close film；The height sprayed when thermal spraying is from substrate 50cm, and the temperature of spraying is 100 DEG C；
(4) H is passed through at a high temperature of 1000 DEG C using vacuum tube furnace2It is restored, obtains graphene-based THIN COMPOSITE
Film；
(5) the graphene-based laminated film that step (4) reduction obtains is warming up to 900 DEG C of heat preservations with the rate of 2 DEG C/min
3h is cooled to room temperature later up to the graphene composite heat conduction film.
Comparative example 1
A kind of preparation method of graphene-based composite heat conduction film, includes the following steps:
(1) preparation of graphene oxide solution: the mixing that the 1g concentrated sulfuric acid and 40g potassium permanganate is added in 2g crystalline flake graphite is molten
Ultrasonic agitation removing 1h is carried out in agent, after 0.01g laruyl alcohol sodium sulfovinate 0.01g dodecyl sulphate monoethanolamine then is added
0.5h is stirred, carries out microwave irradiation processing a period of time 10min again later, is eventually adding after deionized water washing filters and obtains oxygen
Graphite alkene solution；
(2) it will be sprayed on copper foil substrate, deposited using hot spray process in the graphene oxide solution of step (1) preparation
To graphene composite thin film；The height sprayed when thermal spraying is from substrate 60cm, and the temperature of spraying is 120 DEG C；
(3) H is passed through at a high temperature of 1000 DEG C using vacuum tube furnace2It is restored, obtains graphene film；
(4) graphene film that step (3) reduction obtains is warming up to 800 DEG C of heat preservation 3h with the rate of 2 DEG C/min, later
It is cooled to room temperature up to the graphene composite heat conduction film.
Comparative example 2
A kind of preparation method of graphene-based composite heat conduction film, includes the following steps:
(1) preparation of graphene oxide solution: the mixing that the 1g concentrated sulfuric acid and 40g potassium permanganate is added in 2g crystalline flake graphite is molten
Ultrasonic agitation removing 1h is carried out in agent, after 0.01g laruyl alcohol sodium sulfovinate 0.01g dodecyl sulphate monoethanolamine then is added
0.5h is stirred, is eventually adding after deionized water washing filters and obtains graphene oxide solution；
(2) preparation of modified Nano carbon ball: taking the nano carbon microsphere that 0.2g is hollow, be scattered in 5mL ethylene glycol monomethyl ether and
The in the mixed solvent of 5mL ethyl acetate, is then heated to reflux 4h, after the reaction was completed, it is centrifuged, washs, surface modification is obtained by filtration
Hollow nano carbon microsphere；
(3) modified Nano carbon ball prepared by step (2) is added in the graphene oxide solution of step (1), stirring is equal
It is even；Mixed solution obtained above is sprayed on copper foil substrate using hot spray process later, it is multiple that deposition obtains graphene oxide
Close film；The height sprayed when thermal spraying is from substrate 60cm, and the temperature of spraying is 120 DEG C；
(4) H is passed through at a high temperature of 1000 DEG C using vacuum tube furnace2It is restored, obtains graphene-based THIN COMPOSITE
Film；
(5) the graphene-based laminated film that step (4) reduction obtains is warming up to 800 DEG C of heat preservations with the rate of 2 DEG C/min
3h is cooled to room temperature later up to the graphene composite heat conduction film.
Performance test
The performance of the graphene heat conducting film of embodiment 1-5 and comparative example 1-2 is measured, as a result such as the following table 1:
| Thermal conductivity (W/mK) | Tensile strength (MPa) | Film thickness (μm) | |
| Embodiment 1 | 1930 | 84 | 15-22 |
| Embodiment 2 | 1895 | 86 | 16-24 |
| Embodiment 3 | 1916 | 92 | 18-22 |
| Embodiment 4 | 1925 | 90 | 16-25 |
| Embodiment 5 | 1933 | 87 | 15-24 |
| Comparative example 1 | 1219 | 70 | 20-28 |
| Comparative example 2 | 1458 | 80 | 38-56 |
It is obvious to a person skilled in the art that invention is not limited to the details of the above exemplary embodiments, Er Qie
In the case where without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by appended power
Benefit requires rather than above description limits, it is intended that all by what is fallen within the meaning and scope of the equivalent elements of the claims
Variation is included within the present invention.
In addition, it should be understood that although this specification is described in terms of embodiments, but not each embodiment is only wrapped
Containing an independent technical solution, this description of the specification is merely for the sake of clarity, and those skilled in the art should
It considers the specification as a whole, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art
The other embodiments being understood that.
Claims (9)
1. a kind of preparation method of graphene-based composite heat conduction film, which comprises the steps of:
(1) preparation of graphene oxide solution: the in the mixed solvent that the concentrated sulfuric acid and potassium permanganate is added in crystalline flake graphite is surpassed
Sound stirring removing, stirs a period of time, Zhi Houzai after laruyl alcohol sodium sulfovinate and dodecyl sulphate monoethanolamine is then added
Microwave irradiation processing a period of time is carried out, is eventually adding after deionized water washing filters and obtains graphene oxide solution；
(2) preparation of modified Nano carbon ball: taking hollow nano carbon microsphere, is scattered in the mixed of ethylene glycol monomethyl ether and ethyl acetate
In bonding solvent, it is then heated to reflux 3-5h, after the reaction was completed, is centrifuged, washs, the modified hollow nano-sized carbon in surface is obtained by filtration
Ball；
(3) modified Nano carbon ball prepared by step (2) is added in the graphene oxide solution of step (1), is stirred evenly；It
Mixed solution obtained above is sprayed in flexible substrate using hot spray process afterwards, deposition obtains graphene oxide THIN COMPOSITE
Film；
(4) graphene composite thin film of step (3) is restored, obtains graphene-based laminated film；
(5) the graphene-based laminated film that step (4) reduction obtains is warming up to 600-1000 DEG C of guarantor with the rate of 1-3 DEG C/min
Warm 2-4h is cooled to room temperature later up to the graphene composite heat conduction film.
2. the preparation method of graphene-based composite heat conduction film according to claim 1, which is characterized in that dense sulphur in step (1)
The mass ratio of acid, potassium permanganate and crystalline flake graphite is 3-6:150-250:10-40；Laruyl alcohol sodium sulfovinate and dodecyl sulphate
The additional amount of monoethanolamine is the 0.5-3% of crystalline flake graphite quality.
3. the preparation method of graphene-based composite heat conduction film according to claim 1, which is characterized in that ultrasonic in step (1)
The time of stirring removing is 0.5-3h, and the power of microwave irradiation is 700-900W, time 5-15min.
4. the preparation method of graphene-based composite heat conduction film according to claim 1, which is characterized in that described in step (2)
The diameter of nano carbon microsphere is 10-40nm, and the mass volume ratio g/mL of nano carbon microsphere and mixed solvent is 1:40-80；Mixed solvent
The volume ratio of middle ethylene glycol monomethyl ether and ethyl acetate is 1:1.
5. the preparation method of graphene-based composite heat conduction film according to claim 1, which is characterized in that modified in step (3)
The additional amount of nano carbon microsphere is the 5-10% of graphene oxide solution.
6. the preparation method of graphene-based composite heat conduction film according to claim 1, which is characterized in that thermal jet in step (3)
The height sprayed when painting is from substrate 50-70cm, and the temperature of spraying is 80-160 DEG C.
7. the preparation method of graphene-based composite heat conduction film according to claim 1, which is characterized in that oxygen in step (4)
The method that graphite alkene laminated film is restored are as follows: H is passed through at a high temperature of 1000 DEG C using vacuum tube furnace2It is gone back
Original obtains graphene-based laminated film.
8. the preparation method of graphene-based composite heat conduction film according to claim 1, which is characterized in that the flexible substrate is
Copper foil or aluminium foil.
9. a kind of preparation-obtained graphene-based composite heat conduction film of any one of claim 1-8 preparation method.
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| CN109852835A (en) * | 2019-01-23 | 2019-06-07 | 南京工业大学 | A kind of preparation method of graphene/copper nanocomposite |
| CN111908460A (en) * | 2020-07-06 | 2020-11-10 | 深圳市展旺新材料科技有限公司 | Preparation method of highly ordered and compact graphene heat-conducting film |
| CN111944497A (en) * | 2019-05-16 | 2020-11-17 | 常州第六元素材料科技股份有限公司 | Graphene oxide composite carbon source mixture and preparation method thereof, graphene heat-conducting film and preparation method thereof |
| CN114772583A (en) * | 2022-05-05 | 2022-07-22 | 黄河科技学院 | Carbon nanotube/graphene modified metal/oxide nano energetic composite film |
| CN115182022A (en) * | 2021-04-01 | 2022-10-14 | 浙江正泰电器股份有限公司 | Compound dispersant and preparation method thereof, and mixed electroplating solution and preparation method thereof |
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| CN111944497B (en) * | 2019-05-16 | 2022-02-22 | 常州第六元素材料科技股份有限公司 | Graphene oxide composite carbon source mixture and preparation method thereof, graphene heat-conducting film and preparation method thereof |
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| CN115182022A (en) * | 2021-04-01 | 2022-10-14 | 浙江正泰电器股份有限公司 | Compound dispersant and preparation method thereof, and mixed electroplating solution and preparation method thereof |
| CN114772583A (en) * | 2022-05-05 | 2022-07-22 | 黄河科技学院 | Carbon nanotube/graphene modified metal/oxide nano energetic composite film |
| CN114772583B (en) * | 2022-05-05 | 2023-09-08 | 黄河科技学院 | Carbon nano tube/graphene modified metal/oxide nano energetic composite film |
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