CN117946432A - Method for preparing graphene polyimide composite film by spraying - Google Patents
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- CN117946432A CN117946432A CN202410115699.XA CN202410115699A CN117946432A CN 117946432 A CN117946432 A CN 117946432A CN 202410115699 A CN202410115699 A CN 202410115699A CN 117946432 A CN117946432 A CN 117946432A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 122
- 238000000034 method Methods 0.000 title claims abstract description 77
- 239000002131 composite material Substances 0.000 title claims abstract description 59
- 229920001721 polyimide Polymers 0.000 title claims abstract description 53
- 239000004642 Polyimide Substances 0.000 title claims abstract description 51
- 238000005507 spraying Methods 0.000 title claims abstract description 38
- 239000002002 slurry Substances 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 239000004952 Polyamide Substances 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 19
- 229920002647 polyamide Polymers 0.000 claims abstract description 19
- 239000002243 precursor Substances 0.000 claims abstract description 19
- 230000009435 amidation Effects 0.000 claims abstract description 18
- 238000007112 amidation reaction Methods 0.000 claims abstract description 18
- 238000000576 coating method Methods 0.000 claims abstract description 14
- 239000011248 coating agent Substances 0.000 claims abstract description 13
- 238000007590 electrostatic spraying Methods 0.000 claims abstract description 13
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 15
- 239000012298 atmosphere Substances 0.000 claims description 12
- 239000011261 inert gas Substances 0.000 claims description 12
- 239000012528 membrane Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 239000006255 coating slurry Substances 0.000 claims description 2
- 229920003169 water-soluble polymer Polymers 0.000 claims 1
- 239000006185 dispersion Substances 0.000 abstract description 17
- 238000001035 drying Methods 0.000 abstract description 12
- 239000007788 liquid Substances 0.000 abstract description 10
- 239000012299 nitrogen atmosphere Substances 0.000 description 16
- 238000005087 graphitization Methods 0.000 description 10
- 238000004321 preservation Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 7
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 238000009775 high-speed stirring Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000011268 mixed slurry Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000010008 shearing Methods 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 230000017525 heat dissipation Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229960002887 deanol Drugs 0.000 description 2
- 239000012972 dimethylethanolamine Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000000750 progressive effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a method for preparing a graphene polyimide composite film by using a spraying mode. Wherein the method comprises the following steps: coating spraying slurry containing graphene oxide and polyamic acid into a precursor film by adopting an electrostatic spraying mode; and carrying out low-temperature heat treatment and amidation treatment on the precursor film to obtain the graphene polyimide composite film. According to the method, graphene oxide dispersion liquid and polyimide precursor solution can be rapidly and uniformly sprayed into a film, and certain groups of graphene oxide and polyamide acid can be crosslinked in the drying film forming process, so that the film forming strength is higher, a large amount of latent heat release in the low-temperature heat treatment process can be avoided to a certain extent, and the pretreated film is amidated and thermally reduced and graphitized at a low temperature to prepare the graphene polyimide composite film with high heat conductivity and high strength.
Description
Technical Field
The invention relates to the technical field of graphene polyimide composite films, in particular to a method for preparing a graphene polyimide composite film in a spraying mode.
Background
Graphene is a two-dimensional nanomaterial with single-layer carbon atoms arranged in a hexagonal honeycomb structure in an sp 2 hybridization orbit, has excellent heat conduction, electric conduction, mechanical, optical and other properties, and is considered to be an ideal functional material. Polyimide is a high molecular material with high heat resistance, high strength and high modulus, and is widely applied to the fields of aerospace, electronics, optics and the like. The graphene polyimide composite film is a film material formed by compounding graphene and polyimide, has the excellent performances of graphene and polyimide, and is suitable for the fields of heat dissipation, electromagnetic shielding, flexible electronics, optical devices and the like.
At present, the traditional graphene heat dissipation film uses graphene oxide as a raw material, the graphene oxide is dispersed into water according to a certain proportion, a proper additive is added, a certain dispersion, homogenization and defoaming process is carried out to prepare graphene oxide slurry, a tape casting method is adopted for coating, and an oven is used for drying to form the film. And carrying out low-temperature heat treatment, thermal reduction, graphitization and other processes on the obtained graphene oxide film to obtain the graphene film. In the traditional method, graphene oxide is used as a raw material, so that the viscosity of slurry is high, the requirement on the coating process is high on film forming uniformity, and a large amount of impurities are required to be discharged in the pretreatment process of the graphene oxide film, so that the pretreatment process is complicated along with a large amount of heat release. The graphene film with high thermal conductivity can be obtained after high-temperature thermal reduction and graphitization of the film obtained by pretreatment, the graphitization temperature is generally higher than 3000 ℃, higher energy consumption and time are required, and the cost is high.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing a graphene polyimide composite film by spraying, which can rapidly and uniformly spray graphene oxide dispersion liquid and polyimide precursor solution into a film, and then prepare the graphene polyimide composite film with high heat conductivity and high strength through low temperature heat treatment and amidation treatment.
According to one aspect of the present invention, there is provided a method for preparing a graphene polyimide composite film by spraying, comprising:
Coating spraying slurry containing graphene oxide and polyamic acid into a precursor film by adopting an electrostatic spraying mode; and carrying out low-temperature heat treatment and amidation treatment on the precursor film to obtain the graphene polyimide composite film.
According to the technical scheme, graphene oxide dispersion liquid and polyimide precursor solution can be rapidly and uniformly sprayed into the film, and graphene oxide and polyamide acid can be subjected to crosslinking of a certain group in the electrostatic spraying and drying film forming processes, so that the film forming strength is higher, a large amount of latent heat release in the low-temperature heat treatment process can be avoided to a certain extent, and the pretreated film is subjected to amidation and thermal reduction and low-temperature graphitization to prepare the graphene polyimide composite film with high heat conductivity and high strength.
In some embodiments, in the spray coating slurry,
Solute: the solid content range of the graphene oxide is 3.5% -7%; the polyamide acid solid content range is as follows: 1% -5%;
solvent: n, N-dimethylformamide.
In the above technical scheme, the solvent can also be N, N-dimethylacetamide and dimethylethanolamine, but the two solvents are relatively expensive. The raw material is graphene oxide, so that the graphene oxide can be well dispersed in a solvent, and the cost of other dispersion modes is higher. Surfactants may also be used for dispersion, but they introduce new impurities that affect the thermal conductivity, and require higher drying and heat treatment requirements and also result in higher costs. Further, by the formula and the proportion, the viscosity of the slurry is moderate, about 8000-10000, so that the graphene oxide and the polyamide acid can be well dispersed, and the slurry spraying is facilitated.
In some embodiments, the precursor film has a thickness of 10-100 μm.
In the above technical solution, the thickness of the precursor film is determined by the spraying process, and is controlled within the range which is favorable for forming thinner films in subsequent processing, and is optimally 80-100 μm.
In some embodiments, the low temperature heat treatment process parameters are as follows:
preserving heat for 6-12 hours at the temperature of 110-130 ℃ in inert gas atmosphere;
preserving the temperature for 6-12 hours in the inert gas atmosphere at 290-310 ℃.
In the technical scheme, the principle of the sectional treatment is that a great amount of heat and corrosive gas can be discharged when the graphene oxide is treated to decompose oxygen-containing groups at high temperature in amidation treatment, and the groups are required to be removed at low temperature, so that damage and danger to a film caused by heat release are avoided. Particularly, the thickness of the film in the scheme is too thin because the graphene film is not suitable for being manufactured to be below 20 microns, and the graphene film is easy to crack in the pretreatment process. The method adopts electrostatic spraying to prepare the film with the thickness of 10 micrometers, and if the film is not treated in the method, the film is easy to damage. Meanwhile, in consideration of the fact that graphene oxide groups and polyamide acid generate a certain degree of crosslinking reaction during dispersion, groups on the graphene oxide treated at 110-130 ℃ can be released in a small molecular form, the graphene oxide is further released at 290-310 ℃, and the film is prevented from being damaged to the minimum degree in a progressive mode. It should be noted that, both temperature sections have release groups, and the graphene film releases heat while in the pretreatment process, and with the expansion of graphene, the direct temperature rise to 290-310 ℃ can lead to the heat release at the low temperature stage to be concentrated at 300 ℃, the heat cannot be effectively dissipated, and the film can burn out.
In some embodiments, the amidation treatment process parameters are as follows:
The temperature is 700-1000 ℃, the temperature is kept for 6-12 hours under the inert gas atmosphere, the temperature is 1500-2000 ℃, and the temperature is kept for 12-24 hours under the inert gas atmosphere.
In the technical scheme, the 700-1000 ℃ is imidization of polyamide acid, and the composite membrane structure is reconstructed at the temperature to obtain the reduced graphene composite membrane with an ideal structure. The composite film can be further graphitized at 1500-2000 ℃ to enhance the heat conducting property. The process aims to utilize the toughness of the polyimide film and the graphene to compound at the temperature of 700-1000 ℃, so that the toughness of the graphene in the heat treatment process can be increased, the compound film is not easy to become brittle, the sample yield is increased in the treatment process, and the film can be thinned. Because the general graphene film is not suitable for being made to be below 20 microns thick and is too thin, the graphene film is easy to crack in the pretreatment process, the method can be used for making the film with the thickness of 10 microns by adopting electrostatic spraying, and the toughness of the film is enhanced by introducing polyimide, so that the graphene film cannot crack in the heat treatment process. Further, under the condition of 1500-2000 ℃, the film is further graphitized, the graphitization temperature of pure graphene is generally required to reach 3000 ℃, the graphitization temperature of the composite film is only required to reach about 2000 ℃, the heat preservation time is relatively short, and the energy consumption of heat treatment is greatly reduced.
According to another aspect of the present invention, a graphene polyimide composite film is provided, which is prepared by the method for preparing a graphene polyimide composite film by spraying.
According to the technical scheme, the graphene oxide dispersion liquid and the polyimide precursor solution can be rapidly and uniformly sprayed into the film, and certain groups of graphene oxide and polyamide acid can be crosslinked in the drying film forming process, so that the film forming strength is higher, a large amount of latent heat release in the low-temperature heat treatment process can be avoided to a certain extent, and the pretreated film is subjected to amidation and thermal reduction and is subjected to low-temperature graphitization to prepare the graphene polyimide composite film with high heat conductivity and high strength.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic flow chart of an embodiment of a method for preparing a graphene polyimide composite film by spraying;
fig. 2 is an XRD spectrum of a graphene polyimide composite film according to an embodiment of the present invention.
Detailed Description
The invention is described in further detail below with reference to the drawings and examples. It is specifically noted that the following examples are only for illustrating the present invention, but do not limit the scope of the present invention. Likewise, the following examples are only some, but not all, of the examples of the present invention, and all other examples, which a person of ordinary skill in the art would obtain without making any inventive effort, are within the scope of the present invention.
The invention provides a method for preparing a graphene polyimide composite film by using a spraying mode, which can be used for rapidly and uniformly spraying graphene oxide dispersion liquid and polyimide precursor solution into a film, and preparing the graphene polyimide composite film with high heat conductivity and high strength through low-temperature heat treatment and amidation treatment.
One of the embodiments
Referring to fig. 1, fig. 1 is a schematic flow chart of an embodiment of a method for preparing a graphene polyimide composite film by spraying according to the present invention. It should be noted that, if there are substantially the same results, the method of the present invention is not limited to the flow sequence shown in fig. 1. As shown in fig. 1, the method comprises the steps of:
S101: coating spraying slurry containing graphene oxide and polyamic acid into a precursor film by adopting an electrostatic spraying mode;
s102: and carrying out low-temperature heat treatment and amidation treatment on the precursor film to obtain the graphene polyimide composite film.
In the embodiment, the method can be used for rapidly and uniformly spraying graphene oxide dispersion liquid and polyimide precursor solution into a film, and the graphene oxide and polyamide acid can be crosslinked by a certain group in the drying film forming process, so that the film forming strength is higher, a large amount of latent heat release in the low-temperature heat treatment process can be avoided to a certain extent, and the pretreated film is subjected to amidation and thermal reduction and is subjected to low-temperature graphitization to prepare the graphene polyimide composite film with high heat conductivity and high strength.
In this embodiment, in the spray slurry, the solute: the solid content range of the graphene oxide is 3.5% -7%; the polyamide acid solid content range is as follows: 1% -5%; solvent: n, N-dimethylformamide. The solvent may also be N, N-dimethylacetamide, dimethylethanolamine, but both are relatively expensive. The raw material is graphene oxide, so that the graphene oxide can be well dispersed in a solvent, and the cost of other dispersion modes is higher. Surfactants may also be used for dispersion, but they introduce new impurities that affect the thermal conductivity, and require higher drying and heat treatment requirements and also result in higher costs. Further, by the formula and the proportion, the viscosity of the slurry is moderate, about 8000-10000, so that the graphene oxide and the polyamide acid can be well dispersed, and the slurry spraying is facilitated.
In this embodiment, the precursor film has a thickness of 10 to 100 μm. The precursor film thickness is determined by the spray coating process and is controlled within this range to facilitate thinner films, optimally 80-100 μm. In the embodiment, the spraying process is that the slurry injection speed is 500-1000mL/min, the running speed of a coater is 0.2-1.5m/min, and the drying temperature is 65-85 ℃. The thickness of the film obtained under the process is between 10 and 100 mu m.
In this embodiment, the low temperature heat treatment process parameters are as follows: preserving heat for 6-12 hours in an inert gas atmosphere at 120 ℃; preserving the temperature for 6-12 hours in an inert gas atmosphere at 300 ℃. The principle of the sectional treatment is that a great amount of heat and corrosive gas can be discharged when the graphene oxide is treated to decompose oxygen-containing groups at high temperature of amidation treatment, and the groups need to be removed at low temperature, so that damage and danger to a film caused by heat release are avoided. Particularly, the thickness of the film in the scheme is too thin because the graphene film is not suitable for being manufactured to be below 20 microns, and the graphene film is easy to crack in the pretreatment process. The method adopts electrostatic spraying to prepare the film with the thickness of 10 micrometers, and if the film is not treated in the method, the film is easy to damage. Meanwhile, in consideration of the fact that graphene oxide groups and polyamide acid generate a certain degree of crosslinking reaction during dispersion, groups on the graphene oxide treated at 110-130 ℃ can be released in a small molecular form, the graphene oxide is further released at 290-310 ℃, and the film is prevented from being damaged to the minimum degree in a progressive mode. It should be noted that, both temperature sections have release groups, and the graphene film releases heat while in the pretreatment process, and with the expansion of graphene, the direct temperature rise to 290-310 ℃ can lead to the heat release at the low temperature stage to be concentrated at 300 ℃, the heat cannot be effectively dissipated, and the film can burn out.
In this embodiment, the amidation treatment process parameters are as follows: the temperature is 700-1000 ℃, the temperature is kept for 6-12 hours under the inert gas atmosphere, the temperature is 1500-2000 ℃, and the temperature is kept for 12-24 hours under the inert gas atmosphere. The 700-1000 ℃ is imidization of polyamide acid, and the composite membrane structure is reconstructed at the temperature to obtain the reduced graphene composite membrane with an ideal structure. The composite film can be further graphitized at 1500-2000 ℃ to enhance the heat conducting property. The process aims to utilize the toughness of the polyimide film and the graphene to compound at the temperature of 700-1000 ℃, so that the toughness of the graphene in the heat treatment process can be increased, the compound film is not easy to become brittle, the sample yield is increased in the treatment process, and the film can be thinned. Because the general graphene film is not suitable for being made to be below 20 microns thick and is too thin, the graphene film is easy to crack in the pretreatment process, the method can be used for making the film with the thickness of 10 microns by adopting electrostatic spraying, and the toughness of the film is enhanced by introducing polyimide, so that the graphene film cannot crack in the heat treatment process. Further, under the condition of 1500-2000 ℃, the film is further graphitized, the graphitization temperature of pure graphene is generally required to reach 3000 ℃, the graphitization temperature of the composite film is only required to reach about 2000 ℃, the heat preservation time is relatively short, and the energy consumption of heat treatment is greatly reduced.
In order to better prove the creativity of the scheme, the scheme provides the following four specific examples for illustration:
Specific example 1
(1) Dispersing graphene oxide powder and polyamide acid dispersion liquid in DMF solvent through high-speed stirring and shearing to obtain graphene oxide slurry; the solid content of graphene oxide in the obtained slurry was 3.5%, and the solid content of polyamic acid was 5%.
(2) And spraying the obtained mixed slurry on a coating machine in an electrostatic spraying mode, wherein the spraying process is that the slurry injection speed is 500mL/min, the coating machine running speed is 0.2m/min, and the drying temperature is 65 ℃. The resulting composite film had a thickness of 50. Mu.m.
(3) The obtained graphene oxide polyamic acid composite membrane is subjected to low-temperature pretreatment, and is kept at 120 ℃ for 6 hours under nitrogen atmosphere and 300 ℃ for 6 hours under nitrogen atmosphere
(4) And carrying out high-temperature amidation thermal reduction on the film obtained by pretreatment to obtain the graphene polyimide composite film, wherein the specific parameters are 700 ℃, the heat preservation is carried out for 6 hours under nitrogen atmosphere, the temperature is 1500 ℃, and the heat preservation is carried out for 12 hours under nitrogen atmosphere.
Specific example 2
(1) Dispersing graphene oxide powder and polyamide acid dispersion liquid in DMF solvent through high-speed stirring and shearing to obtain graphene oxide slurry; the solid content of graphene oxide in the obtained slurry was 7%, and the solid content of polyamic acid was 1%.
(2) And spraying the obtained mixed slurry on a coating machine in an electrostatic spraying mode, wherein the spraying process is that the slurry injection speed is 1000mL/min, the coating machine running speed is 0.2m/min, and the drying temperature is 75 ℃. The resulting composite film had a thickness of 100. Mu.m.
(3) The obtained graphene oxide polyamide acid composite membrane is subjected to low-temperature pretreatment, and is kept at 120 ℃ for 12 hours under nitrogen atmosphere and 300 ℃ for 12 hours under nitrogen atmosphere
(4) And carrying out high-temperature amidation thermal reduction on the film obtained by pretreatment to obtain the graphene polyimide composite film, wherein the specific parameters are 1000 ℃, the heat preservation is carried out for 12 hours under the nitrogen atmosphere, and the heat preservation is carried out for 24 hours under the nitrogen atmosphere at 2000 ℃.
Specific example 3
(1) Dispersing graphene oxide powder and polyamide acid dispersion liquid in DMF solvent through high-speed stirring and shearing to obtain graphene oxide slurry; the solid content of graphene oxide in the obtained slurry was 5%, and the solid content of polyamic acid was 2%.
(2) And spraying the obtained mixed slurry on a coating machine in an electrostatic spraying mode, wherein the spraying process is that the slurry injection speed is 800mL/min, the coating machine running speed is 1m/min, and the drying temperature is 70 ℃. The resulting composite film had a thickness of 30. Mu.m.
(3) The obtained graphene oxide polyamide acid composite membrane is subjected to low-temperature pretreatment, and is kept at 120 ℃ for 10 hours under nitrogen atmosphere and 300 ℃ for 10 hours under nitrogen atmosphere
(4) And carrying out high-temperature amidation thermal reduction on the film obtained by pretreatment to obtain the graphene polyimide composite film, wherein the specific parameters are 800 ℃, the heat preservation is carried out for 10 hours under the nitrogen atmosphere, the heat preservation is carried out for 1800 hours under the nitrogen atmosphere.
Specific example 4
(1) Dispersing graphene oxide powder and polyamide acid dispersion liquid in DMF solvent through high-speed stirring and shearing to obtain graphene oxide slurry; the solid content of graphene oxide in the obtained slurry was 6%, and the solid content of polyamic acid was 4%.
(2) And spraying the obtained mixed slurry on a coating machine in an electrostatic spraying mode, wherein the spraying process is that the slurry injection speed is 500mL/min, the coating machine running speed is 1.5m/min, and the drying temperature is 85 ℃. The resulting composite film had a thickness of 10. Mu.m.
(3) The obtained graphene oxide polyamic acid composite membrane is subjected to low-temperature pretreatment, and is kept at 120 ℃ for 8 hours under nitrogen atmosphere and at 300 ℃ for 12 hours under nitrogen atmosphere
(4) And carrying out high-temperature amidation thermal reduction on the film obtained by pretreatment to obtain the graphene polyimide composite film, wherein the specific parameters are 900 ℃, the heat preservation is carried out for 12 hours under nitrogen atmosphere, and the heat preservation is carried out for 18 hours under nitrogen atmosphere at 1900 ℃.
The thermal conductivity of the obtained graphene polyimide composite film is shown in the following table 1,
Table 1 thermal conductivity of graphene polyimide composite films of specific examples 1 to 4
| Sample of | Thermal conductivity W.m -1·K-1 | Peel force gF |
| Specific example 1 | 1170 | 12.5 |
| Specific example 2 | 1250 | 15.2 |
| Specific example 3 | 1080 | 14.3 |
| Specific example 4 | 1320 | 13.1 |
| Graphene film | 1280 | 10.4 |
| PI film | 980 | 12.3 |
As shown in the table, the thermal conductivity of the composite film obtained by the process is quite higher than that of the traditional PI thermal conductive film, and the stripping force is higher than that of the graphene film, so that the composite film has better processing performance and more application scenes compared with the graphene film. The film of example 4 was brittle, but had a high solid content and a high density, and the film had a high thermal conductivity, since 80 to 100 μm was excellent in film formation quality, and the thermal conductivity was related to the density. Of the above comparisons, the combination effect of specific example 2 was the best. Referring to fig. 2, it can be seen from the XRD spectrum that the film prepared in this embodiment is a heat dissipation composite film mainly composed of graphene, and the general characteristics of graphene are shown.
Second embodiment
A graphene polyimide composite film is prepared by the method for preparing the graphene polyimide composite film in a spraying mode.
In this example, the film prepared by the method of one of the examples is specific to the properties of high thermal conductivity and high strength. The specific principles and advantages have been described in detail in one of the embodiments and are not repeated herein.
The foregoing description is only a partial embodiment of the present invention, and is not intended to limit the scope of the present invention, and all equivalent devices or equivalent processes using the descriptions and the drawings of the present invention or directly or indirectly applied to other related technical fields are included in the scope of the present invention.
Claims (6)
1. The method for preparing the graphene polyimide composite film by using a spraying mode is characterized by comprising the following steps of:
Coating spraying slurry containing graphene oxide and polyamic acid into a precursor film by adopting an electrostatic spraying mode; and carrying out low-temperature heat treatment and amidation treatment on the precursor film to obtain the graphene polyimide composite film.
2. The method for preparing the graphene polyimide composite membrane by using a spraying mode according to claim 1, wherein the method comprises the following steps of,
In the spray-coating slurry, the water-soluble polymer,
Solute: the solid content range of the graphene oxide is 3.5% -7%; the polyamide acid solid content range is as follows: 1% -5%;
solvent: n, N-dimethylformamide.
3. The method for preparing the graphene polyimide composite membrane by using a spraying mode according to claim 1, wherein the method comprises the following steps of,
The precursor film has a thickness of 10-100 μm.
4. The method for preparing the graphene polyimide composite membrane by using a spraying mode according to claim 1, wherein the method comprises the following steps of,
The low-temperature heat treatment process parameters are as follows:
preserving heat for 6-12 hours at the temperature of 110-130 ℃ in inert gas atmosphere;
preserving the temperature for 6-12 hours in the inert gas atmosphere at 290-310 ℃.
5. The method for preparing the graphene polyimide composite membrane by using a spraying mode according to claim 1, wherein the method comprises the following steps of,
The amidation treatment process parameters are as follows:
the temperature is 700-1000 ℃, the temperature is kept for 6-12 hours under the inert gas atmosphere, the temperature is 1500-2000 ℃, and the temperature is kept for 12-24 hours under the inert gas atmosphere.
6. A graphene polyimide composite film, characterized in that the graphene polyimide composite film is prepared by a method for preparing the graphene polyimide composite film by a spraying mode according to any one of claims 1 to 5.
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