CN116426251A - Fluorinated graphene composite heat conducting film and preparation method thereof - Google Patents
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- 239000002131 composite material Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 83
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 73
- 239000002002 slurry Substances 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000003763 carbonization Methods 0.000 claims abstract description 11
- 238000005087 graphitization Methods 0.000 claims abstract description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 10
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- 238000000265 homogenisation Methods 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
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- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
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- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a fluorinated graphene composite heat-conducting film and a preparation method thereof, wherein the preparation method comprises the following steps: adding graphite oxide and graphite fluoride into water according to a target mass ratio, and homogenizing to prepare a graphene fluoride/graphene oxide composite slurry with target solid content; coating the fluorinated graphene/graphene oxide composite slurry on a substrate, drying and rolling; performing heat treatment on the rolled film to form a fluffy fluorinated graphene/graphene composite film; and carrying out vacuum flattening treatment on the fluffy fluorinated graphene/graphene composite film to obtain the fluorinated graphene composite heat-conducting film. According to the invention, a proper amount of graphene oxide is introduced into the fluorinated graphene, and interaction of graphene sheets is enhanced by virtue of hydrogen bond, so that the film forming property of the fluorinated graphene is improved, and the addition of the proper amount of graphene oxide can improve the integral heat conductivity of the film and simultaneously maintain the insulativity of the film after subsequent carbonization and graphitization.
Description
Technical Field
The invention belongs to the technical field of graphene heat conduction films, and particularly relates to a fluorinated graphene composite heat conduction film and a preparation method thereof.
Background
With the development of mobile phones towards high performance and miniaturization, the heat productivity of the chip is increased, the mobile phones are limited by a small space, and heat is easy to gather to form hot spots, so that the chips cannot work normally, and therefore materials with higher transverse heat conductivity are adopted for uniform heating.
For a 4G mobile phone, the material is usually an artificial graphite heat dissipation film which is prepared by taking a polyimide film as a raw material through carbonization, graphitization and calendaring processes, is limited by the polyimide film raw material, has a limited thickness of the artificial graphite heat dissipation film (less than 100 microns), and cannot cope with higher heat productivity of a 5G mobile phone chip. Because the process and the raw materials are different, the graphene heat dissipation film breaks through the limitation of thickness, and can meet the requirement of uniform heating of a 5G mobile phone chip, so that the graphene heat dissipation film is widely applied.
Although graphene heat conducting films have gained acceptance by cell phone manufacturers and are widely used in 5G cell phones, the excellent electrical conductivity of graphene itself also results in poor electrical insulation, limiting its application to more scenes. Although some insulating nanomaterials such as boron nitride (chem. Mater.,2016,28,1049-1057), insulating oxides (Compos.Sci.Technol., 2016,137,16;ACS Appl.Mater.Interfaces.,2015,7,14397), and the like can be introduced to achieve insulation by blocking the formation of a graphene conductive network, the thermal conductivity of the thin film is significantly reduced.
The fluorinated graphene has good electrical insulation and can maintain the theoretical thermal conductivity exceeding 1800W/mK. Therefore, the heat conductive film prepared from the fluorinated graphene has high heat conductivity and electrical insulation in theory, however, the interaction force of the fluorinated graphene sheets is weak, and the film forming property is poor.
The Chinese patent with application number 201910166347.6 reports a flexible and electrically insulating fluorinated graphene composite heat-conducting film and preparation and application thereof, wherein the fluorinated graphene composite film consists of fluorinated graphene nano-sheets and polyvinyl alcohol. According to the preparation method, the film forming property of the fluorinated graphene is improved by taking the composite polyvinyl alcohol as a binder, however, the thermal conductivity of the polyvinyl alcohol is poor, so that the thermal conductivity (thermal conductivity) of the composite film is only 61.3W/mK at the highest, and the heat dissipation requirement of the mobile phone cannot be met.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to provide the fluorinated graphene composite heat-conducting film and the preparation method thereof, so as to overcome the defect that the fluorinated graphene composite heat-conducting film in the prior art cannot achieve both higher film forming property and higher heat conductivity.
In order to solve the problems, the invention provides a preparation method of a fluorinated graphene composite heat conducting film, which comprises the following steps:
s100, adding graphite oxide and graphite fluoride into water according to a target mass ratio, and homogenizing to prepare a graphene fluoride/graphene oxide composite slurry with target solid content;
s200, coating the fluorinated graphene/graphene oxide composite slurry on a substrate, drying and rolling;
s300, performing heat treatment on the rolled film to form a fluffy fluorinated graphene/graphene composite film;
s400, carrying out vacuum flattening treatment on the fluffy fluorinated graphene/graphene composite film to obtain the fluorinated graphene composite heat-conducting film.
In some embodiments, in said step S100,
the target mass ratio is (0.05-0.2): 1, a step of; and/or, the target solids content is 1wt% to 5wt%.
In some embodiments, in the step S100, the homogenization is performed in the following manner:
after graphite oxide and graphite fluoride are added into water according to a target mass ratio, ultrasonic treatment is carried out for 10-30 minutes, then stirring is carried out for 30-60 minutes in a stirring device, and then the mixture is processed for 10-30 minutes by a homogenizer under the pressure of 50-500 MPa.
In some embodiments, in the step S200, the coated fluorinated graphene/graphene oxide composite slurry is dried at 50-90 ℃ through a tunnel furnace.
In some embodiments, in said step S300,
the conditions of the heat treatment are as follows: treating in a carbonization furnace at 1300-1500 ℃ for 2-6 hours, and then treating in a graphitization furnace at 2850-3000 ℃ for 6-10 hours.
In some embodiments, in the step S400, the vacuum platen press process specifically includes:
and stacking a smooth mirror surface stainless steel sheet between every two fluffy fluorinated graphene/graphene composite films in a mould, and vacuumizing and pressing for 5-30 minutes under the pressure of 50-500 tons by a vacuum platen press.
The invention also provides the fluorinated graphene composite heat-conducting film, which is prepared by adopting the preparation method of the fluorinated graphene composite heat-conducting film.
In some embodiments, the fluorinated graphene composite thermally conductive film has an in-plane thermal conductivity of 150-300W/mK.
In some embodiments, the fluorinated graphene composite thermally conductive film consists of fluorinated graphene and graphene, the mass ratio of fluorinated graphene to graphene being 1: (0.05-0.2).
In some embodiments, the fluorinated graphene composite thermally conductive film has a volume resistivity of 1×10 11 -1×10 14 Ω·cm。
According to the fluorinated graphene composite heat conducting film and the preparation method thereof, proper amount of graphene oxide is introduced into the fluorinated graphene, and interaction of graphene sheets is enhanced by means of hydrogen bonding, so that film forming property of the fluorinated graphene is improved, and the addition of the proper amount of graphene oxide can improve integral heat conductivity of the film and keep insulativity of the film after subsequent carbonization and graphitization (heat treatment process). Experiments prove that the fluorinated graphene composite heat-conducting film prepared by the preparation method disclosed by the invention has excellent film forming property, the insulativity is not obviously reduced, and the in-plane thermal conductivity reaches 150-300W/mK, so that the improvement is obvious.
Drawings
Fig. 1 is a step diagram of a preparation method of a fluorinated graphene composite heat conducting film according to an embodiment of the present invention.
Detailed Description
Referring to fig. 1, according to an embodiment of the present invention, there is provided a method for preparing a fluorinated graphene composite heat conductive film, including the steps of:
s100, adding graphite oxide and graphite fluoride into water according to a target mass ratio, and homogenizing to prepare a graphene fluoride/graphene oxide composite slurry with target solid content;
s200, coating the fluorinated graphene/graphene oxide composite slurry on a substrate, drying and rolling, wherein in the process, C-F bonds in the fluorinated graphene interact with oxygen-containing functional groups (-C00H, -OH, -C-O-C and the like) of the graphene oxide to form hydrogen bonds, so that the film forming property of the fluorinated graphene is improved;
s300, performing heat treatment on the rolled film to form a fluffy fluorinated graphene/graphene composite film, wherein graphene oxide in the film can be reduced to graphene through heat treatment, and lattice defects are repaired;
s400, carrying out vacuum flattening treatment on the fluffy fluorinated graphene/graphene composite film, and improving the density to obtain the fluorinated graphene composite heat-conducting film.
According to the technical scheme, proper amount of graphene oxide is introduced into the fluorinated graphene, interaction of graphene sheets is enhanced by means of hydrogen bond action, so that film forming property of the fluorinated graphene is improved, and the addition of the proper amount of graphene oxide can improve integral heat conductivity of the film and keep insulativity of the film after subsequent carbonization and graphitization (heat treatment process). Experiments prove that the fluorinated graphene composite heat-conducting film prepared by the preparation method disclosed by the invention has excellent film forming property, the insulativity is not obviously reduced, and the in-plane thermal conductivity reaches 150-300W/mK, so that the improvement is obvious.
In step S100, the target mass ratio is (0.05-0.2): 1, the effect of improving the film forming property of the fluorinated graphene is not obvious due to the fact that the content of the oxidized graphene is too low, and the insulating property is obviously reduced due to the fact that the content of the oxidized graphene is too high; the target solids content is preferably 1wt% to 5wt%, the solids content is too low, the viscosity is too low to be coated, the solids content is too high, and the viscosity is too high to be coated.
In step S100, homogenization is performed as follows:
after graphite oxide and graphite fluoride are added into water according to a target mass ratio, ultrasonic treatment is carried out for 10-30 minutes, then stirring is carried out for 30-60 minutes in a stirring device (such as a double planetary vacuum stirrer), and then the mixture is treated for 10-30 minutes by a high-pressure homogenizer under the pressure of 50-500 MPa, so that the dispersion stability of the mixture is improved.
In step S200, the coated fluorinated graphene/graphene oxide composite slurry is dried at 50-90 ℃ through a tunnel furnace.
In step S300, the conditions of the heat treatment are: treating in a carbonization furnace at 1300-1500 ℃ for 2-6 hours, and then treating in a graphitization furnace at 2850-3000 ℃ for 6-10 hours.
In some embodiments, in step S400, the vacuum platen press process specifically includes:
and stacking a piece of mirror smooth stainless steel sheet between every two fluffy fluorinated graphene/graphene composite films in a mould, and vacuumizing and pressing for 5-30 minutes under the pressure of 50-500 tons by a vacuum flat press.
According to the embodiment of the invention, the fluorinated graphene composite heat-conducting film is prepared by adopting the preparation method of the fluorinated graphene composite heat-conducting film, and the in-plane thermal conductivity of the prepared fluorinated graphene composite heat-conducting film is 150-300W/mK; volume resistivity of 1X 10 11 -1×10 14 Ω·cm。
In some embodiments, the fluorinated graphene composite heat conducting film consists of fluorinated graphene and graphene, the mass ratio of fluorinated graphene to graphene being 1: (0.05-0.2).
The preparation method of the fluorinated graphene composite heat conducting film of the present invention is further described below in connection with several examples and comparative examples.
Example 1:
step 1-pulping: graphite oxide and graphite fluoride are mixed according to the mass ratio of 0.05:1 adding the mixture into water, carrying out ultrasonic treatment for 10 minutes, stirring for 60 minutes in a double-planetary vacuum stirrer, and then treating for 10 minutes under the pressure of 100MPa by a high-pressure homogenizer, so as to improve the dispersion stability of the mixture and prepare fluorinated graphene/graphene oxide composite slurry with the solid content of 5 weight percent;
step 2-coating: coating the composite slurry on a substrate, drying at 70 ℃ through a tunnel furnace, and winding;
step 3-heat treatment: placing the rolled film in a carbonization furnace to be treated for 2 hours at 1500 ℃, and then treating the film in a graphitization furnace to be treated for 6 hours at 3000 ℃ to obtain a fluffy fluorinated graphene/graphene composite film;
step 4-vacuum flattening: and stacking a smooth mirror surface stainless steel sheet between every two fluffy graphene fluoride/graphene composite films in a grinding tool, vacuumizing and pressing for 5 minutes under the pressure of 500 tons by a vacuum flat press, and improving the density to obtain a finished product of the graphene fluoride composite heat conducting film.
The fluorinated graphene composite heat conduction film is tested by a thermogravimetric analyzer, and the mass ratio of the fluorinated graphene to the graphene is 1:0.05; the thermal conductivity of the material is 150W/mK through the test of a laser thermal conductivity coefficient tester; the volume resistivity of the material is 1X 10 after being tested by a high resistance meter 14 Ω·cm。
Example 2:
step 1-pulping: graphite oxide and graphite fluoride are mixed according to the mass ratio of 0.1:1 adding the mixture into water, carrying out ultrasonic treatment for 10 minutes, stirring for 60 minutes in a double-planetary vacuum stirrer, and then treating for 10 minutes under the pressure of 100MPa by a high-pressure homogenizer, so as to improve the dispersion stability of the mixture and prepare fluorinated graphene/graphene oxide composite slurry with the solid content of 5 weight percent;
step 2-coating: coating the composite slurry on a substrate, drying at 70 ℃ through a tunnel furnace, and winding;
step 3-heat treatment: placing the rolled film in a carbonization furnace to be treated for 2 hours at 1500 ℃, and then treating the film in a graphitization furnace to be treated for 6 hours at 3000 ℃ to obtain a fluffy fluorinated graphene/graphene composite film;
step 4-vacuum flattening: and stacking a smooth mirror surface stainless steel sheet between every two fluffy graphene fluoride/graphene composite films in a grinding tool, vacuumizing and pressing for 5 minutes under the pressure of 500 tons by a vacuum flat press, and improving the density to obtain a finished product of the graphene fluoride composite heat conducting film.
The fluorinated graphene composite heat conduction film is tested by a thermogravimetric analyzer, and the mass ratio of the fluorinated graphene to the graphene is 1:0.1; the thermal conductivity of the material is 200W/mK through the test of a laser thermal conductivity coefficient tester; through the test of a high resistance meter, the volume resistance of the alloy isThe rate is 4.5X10 12 Ω·cm。
Example 3:
step 1-pulping: graphite oxide and graphite fluoride are mixed according to the mass ratio of 0.2:1 adding the mixture into water, carrying out ultrasonic treatment for 10 minutes, stirring for 60 minutes in a double-planetary vacuum stirrer, and then treating for 10 minutes under the pressure of 100MPa by a high-pressure homogenizer, so as to improve the dispersion stability of the mixture and prepare fluorinated graphene/graphene oxide composite slurry with the solid content of 5 weight percent;
step 2-coating: coating the composite slurry on a substrate, drying at 70 ℃ through a tunnel furnace, and winding;
step 3-heat treatment: placing the rolled film in a carbonization furnace to be treated for 2 hours at 1500 ℃, and then treating the film in a graphitization furnace to be treated for 6 hours at 3000 ℃ to obtain a fluffy fluorinated graphene/graphene composite film;
step 4-vacuum flattening: and stacking a smooth mirror surface stainless steel sheet between every two fluffy graphene fluoride/graphene composite films in a grinding tool, vacuumizing and pressing for 5 minutes under the pressure of 500 tons by a vacuum flat press, and improving the density to obtain a finished product of the graphene fluoride composite heat conducting film.
The fluorinated graphene composite heat conduction film is tested by a thermogravimetric analyzer, and the mass ratio of the fluorinated graphene to the graphene is 1:0.2; the thermal conductivity of the material is 300W/mK through the test of a laser thermal conductivity coefficient tester; the volume resistivity of the material is 1X 10 after being tested by a high resistance meter 11 Ω·cm。
Comparative example 1:
example 1 reported in the Chinese patent with reference to application number 201910166347.6
Step 1: commercial graphite fluoride powder is dispersed in isopropanol, ultrasonic treatment is carried out on a water bath ultrasonic instrument for 24 hours (250W), and then the mixed dispersion liquid is centrifuged for 10 minutes at a rotating speed of 3000rpm, so that the peeled graphite fluoride nano-sheets are obtained.
Step 2: weighing 40mg of the fluorinated graphene obtained in the step 1, dispersing in 200ml of water, adding 0.05ml of 6wt% polyvinyl alcohol (molecular weight 145 kg/mol) aqueous solution, and carrying out ultrasonic treatment for 30min to obtain uniformly dispersed fluorinated graphene dispersion; and then pouring the dispersion liquid into a decompression filtering device of a mixed acetate filter membrane, and uniformly depositing the fluorinated graphene nano sheets layer by layer to obtain the fluorinated graphene composite heat-conducting membrane.
The relevant data for each of the above examples and comparative examples are summarized in the following table:
from the data, the invention can enhance interaction of graphene sheets by introducing a proper amount of graphene oxide into the fluorinated graphene and enhancing film forming property of the fluorinated graphene through hydrogen bonding, and the addition of the proper amount of graphene oxide can improve integral thermal conductivity of the film and maintain insulativity of the film after subsequent carbonization and graphitization.
It will be readily appreciated by those skilled in the art that the above advantageous ways can be freely combined and superimposed without conflict.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention. The foregoing is merely a preferred embodiment of the present invention, and it should be noted that it will be apparent to those skilled in the art that modifications and variations can be made without departing from the technical principles of the present invention, and these modifications and variations should also be regarded as the scope of the invention.
Claims (10)
1. The preparation method of the fluorinated graphene composite heat-conducting film is characterized by comprising the following steps of:
s100, adding graphite oxide and graphite fluoride into water according to a target mass ratio, and homogenizing to prepare a graphene fluoride/graphene oxide composite slurry with target solid content;
s200, coating the fluorinated graphene/graphene oxide composite slurry on a substrate, drying and rolling;
s300, performing heat treatment on the rolled film to form a fluffy fluorinated graphene/graphene composite film;
s400, carrying out vacuum flattening treatment on the fluffy fluorinated graphene/graphene composite film to obtain the fluorinated graphene composite heat-conducting film.
2. The method according to claim 1, wherein in the step S100,
the target mass ratio is (0.05-0.2): 1, a step of; and/or, the target solids content is 1wt% to 5wt%.
3. The method according to claim 1, wherein in the step S100, the homogenization is performed by:
after graphite oxide and graphite fluoride are added into water according to a target mass ratio, ultrasonic treatment is carried out for 10-30 minutes, then stirring is carried out for 30-60 minutes in a stirring device, and then the mixture is processed for 10-30 minutes by a homogenizer under the pressure of 50-500 MPa.
4. The method according to claim 1, wherein in the step S200, the coated fluorinated graphene/graphene oxide composite slurry is dried at 50-90 ℃ through a tunnel furnace.
5. The method according to claim 1, wherein, in the step S300,
the conditions of the heat treatment are as follows: treating in a carbonization furnace at 1300-1500 ℃ for 2-6 hours, and then treating in a graphitization furnace at 2850-3000 ℃ for 6-10 hours.
6. The method according to claim 1, wherein in the step S400, the vacuum platen press process specifically includes:
and stacking a smooth mirror surface stainless steel sheet between every two fluffy fluorinated graphene/graphene composite films in a mould, and vacuumizing and pressing for 5-30 minutes under the pressure of 50-500 tons by a vacuum platen press.
7. A fluorinated graphene composite heat conducting film, characterized in that the fluorinated graphene composite heat conducting film is prepared and formed by adopting the preparation method of the fluorinated graphene composite heat conducting film according to any one of claims 1 to 6.
8. The fluorinated graphene composite thermally conductive film according to claim 7, wherein the fluorinated graphene composite thermally conductive film has an in-plane thermal conductivity of 150 to 300W/mK.
9. The fluorinated graphene composite heat conducting film according to claim 7, wherein the fluorinated graphene composite heat conducting film is composed of fluorinated graphene and graphene, and the mass ratio of the fluorinated graphene to the graphene is 1: (0.05-0.2).
10. The fluorinated graphene composite heat conductive film according to claim 7, wherein the fluorinated graphene composite heat conductive film has a volume resistivity of 1 x 10 11 -1×10 14 Ω·cm。
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