CN116375472A - Super-thick polyimide-based graphite film and preparation method thereof - Google Patents
Super-thick polyimide-based graphite film and preparation method thereof Download PDFInfo
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- CN116375472A CN116375472A CN202310178185.4A CN202310178185A CN116375472A CN 116375472 A CN116375472 A CN 116375472A CN 202310178185 A CN202310178185 A CN 202310178185A CN 116375472 A CN116375472 A CN 116375472A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 229920001721 polyimide Polymers 0.000 title claims abstract description 76
- 239000004642 Polyimide Substances 0.000 title claims abstract description 54
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 52
- 239000010439 graphite Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims description 78
- 229910021389 graphene Inorganic materials 0.000 claims description 57
- 239000004744 fabric Substances 0.000 claims description 42
- 229920000642 polymer Polymers 0.000 claims description 34
- 239000004952 Polyamide Substances 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 22
- 229920002647 polyamide Polymers 0.000 claims description 22
- 238000005266 casting Methods 0.000 claims description 18
- 229920005575 poly(amic acid) Polymers 0.000 claims description 16
- 238000003763 carbonization Methods 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 3
- 238000010000 carbonizing Methods 0.000 claims description 3
- 150000004985 diamines Chemical class 0.000 claims description 3
- 239000002798 polar solvent Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000005187 foaming Methods 0.000 abstract description 7
- 238000011161 development Methods 0.000 abstract description 3
- 238000004377 microelectronic Methods 0.000 abstract description 3
- 238000005087 graphitization Methods 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 230000007547 defect Effects 0.000 description 7
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical group NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 6
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000001132 ultrasonic dispersion Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 230000017525 heat dissipation Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008093 supporting effect Effects 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
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- C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
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Abstract
The invention discloses an ultra-thick polyimide-based graphite film and a preparation method thereof. The ultra-thick polyimide-based graphite film prepared by the invention has the characteristics of uniform foaming, fine appearance and high thermal conductivity, and the thermal conductivity can reach more than 1350W/m.k, so that the development requirement of the microelectronics field can be met.
Description
Technical Field
The invention relates to the technical field of graphite film preparation, in particular to an ultra-thick polyimide-based graphite film and a preparation method thereof.
Background
Polyimide (PI) film is carbonized at high temperature and graphitized to prepare high-orientation graphite film which is close to a single crystal graphite structure, has excellent performances such as high heat conductivity, convenient processing and forming, and the like, is widely used as a heat dissipation material in the field of microelectronics, and along with the development of miniaturization, high integration and multifunction of electronic products in recent years, higher requirements are put forward on the heat dissipation efficiency of graphite films, and thicker and higher-heat-conductivity PI graphite films are required to be prepared.
Uniformly dispersing a foaming auxiliary agent in the PI film, preparing the PI graphite film by high-temperature carbonization and graphite film forming processes, and uniformly foaming and refining the prepared PI graphite film when the thickness of the PI film is smaller (smaller than 50 mu m); when the thickness of the PI film is larger (more than 75 mu m), the prepared PI graphite film has more apparent defects, such as matt surface wrinkles, uneven foaming, more pit points on the foaming surface and the like, and the problems of difficult processing and forming, reduced heat conductivity and the like of the graphite film and influence the application of the PI graphite film due to the fact that the PI graphite film has serious size shrinkage and unbalanced internal stress in the carbonization and graphitization processes when the thickness of the PI film is larger.
Disclosure of Invention
Based on the technical problems in the background technology, the invention provides an ultra-thick polyimide-based graphite film and a preparation method thereof.
The invention provides a preparation method of an ultra-thick polyimide-based graphite film, which comprises the following steps:
s1, casting a polyamide acid solution containing graphene oxide on a substrate to form a first polymer layer, adhering a layer of porous fabric on the surface of the first polymer layer to form a first fabric layer, casting a polyamide acid solution containing graphene oxide on the surface of the first fabric layer to form a second polymer layer, alternately performing operations of forming the polymer layer and the fabric layer until an N-1 fabric layer and an N polymer layer are formed, and drying, stretching and thermally imidizing the obtained composite film to obtain an ultra-thick polyimide film;
and S2, carbonizing and graphitizing the ultra-thick polyimide film in sequence to obtain the ultra-thick polyimide-based graphite film.
Preferably, in the polyamic acid solution containing graphene oxide, the mass ratio of graphene oxide to polyamic acid is (0.05-2): 100, preferably (0.1-1): 100.
preferably, the preparation method of the polyamic acid solution containing graphene oxide comprises the following steps: and (3) dissolving diamine monomer in aprotic polar solvent, adding graphene oxide dispersion liquid, uniformly mixing, and adding dianhydride monomer for reaction to obtain the polymer.
Preferably, the diamine monomer is p-phenylenediamine, 4' -diaminodiphenyl ether.
Preferably, the dianhydride monomer is 1,2,4, 5-pyromellitic dianhydride.
Preferably, the aprotic polar solvent is DMAc.
Preferably, in S1, n=2-3.
Preferably, in S1, a first polymer layer is formed by casting a film on a substrate with a polyamic acid solution containing graphene oxide, then a layer of porous fabric is stuck on the surface of the first polymer layer to form a first fabric layer, a second polymer layer is formed by casting a film on the surface of the first fabric layer with a polyamic acid solution containing graphene oxide, and then an ultra-thick polyimide film is obtained by drying, stretching and thermal imidization; or casting a polyamide acid solution containing graphene oxide on a substrate to form a first polymer layer, adhering a layer of porous fabric on the surface of the first polymer layer to form a first fabric layer, casting a layer of porous fabric on the surface of the first fabric layer to form a second polymer layer by using the polyamide acid solution containing graphene oxide, adhering a layer of porous fabric on the surface of the second polymer layer to form a second fabric layer, casting a layer of porous fabric on the surface of the second fabric layer by using the polyamide acid solution containing graphene oxide to form a third polymer layer, and drying, stretching and thermal imidization to obtain the ultra-thick polyimide film.
Preferably, the thickness of the ultra-thick polyimide film is 75-150 μm.
Preferably, the porous fabric has an average pore size of 0.01 to 0.2mm, preferably 0.05 to 0.1mm.
Preferably, in S1, the step of subjecting the obtained composite film to drying, stretching and thermal imidization includes: drying the obtained composite film at 150-200 ℃, longitudinally stretching and transversely stretching to obtain a longitudinal stretching multiplying power of 1.0-1.05 and a transverse stretching multiplying power of 1.0-1.2, and finally heating to 400 ℃ in a gradient manner to carry out thermal imidization.
Preferably, in S2, the specific step of carbonizing includes: under vacuum state, heating to 500-650deg.C at 3-5deg.C/min, maintaining for 30-60min, heating to 700-850deg.C at 3-5deg.C/min, maintaining for 30-60min, heating to 900-1000deg.C at 3-5deg.C/min, and maintaining for 30-60min.
Preferably, in S2, the specific step of graphitizing comprises: under the protection of inert gas, the temperature is firstly increased to 1800-2200 ℃ at the heating rate of 20-30 ℃/min, the temperature is kept for 60-90min, then the temperature is increased to 2400-2600 ℃ at the heating rate of 20-30 ℃/min, the temperature is kept for 60-90min, and finally the temperature is increased to 2850-3000 ℃ at the heating rate of 20-30 ℃/min, and the temperature is kept for 90-120min.
An ultra-thick polyimide-based graphite film, which is prepared by the preparation method.
The beneficial effects of the invention are as follows:
the preparation method comprises the steps of preparing an ultra-thick polyimide film by compounding a polyamide acid solution containing graphene oxide with a porous fabric in a multi-layer manner, and preparing a graphite film by carbonization and graphitization; on the one hand, graphene oxide is uniformly dispersed in an ultra-thick polyimide film through an in-situ polymerization method, when the ultra-thick polyimide film is treated through high-temperature carbonization and graphitization processes, non-carbon atoms in a PI film molecular chain are removed, residual carbon atoms are recrystallized and arranged to form a graphite film with a graphene crystal structure, and the graphene oxide and the graphite film have the same carbon skeleton structure, so that structural defects after the non-carbon atoms are removed can be made up in the high-temperature recrystallization process, a denser and more uniform PI graphite film is formed, and the graphitization degree of the PI graphite film can be further improved by adding the graphene oxide, so that the thermal conductivity of the PI graphite film is improved; on the other hand, after the porous fabric structure is compounded with the polyamic acid solution, the uniform and compact microporous structure can be used for the vertical permeation of the polyamic acid solution, and after drying, stretching and thermal imidization, the tight connection between the fabric and polyimide molecular chains is realized, and the fabric structure has a framework supporting effect in the carbonization and graphitization processes, so that the problems of serious size shrinkage and unbalanced internal stress in the carbonization and graphitization processes of the ultra-thick polyimide film are solved, and the foaming uniformity and the appearance fineness of the PI graphite film are promoted.
In conclusion, the ultra-thick polyimide-based graphite film prepared by the invention has the characteristics of uniform foaming, fine appearance and high thermal conductivity, and the thermal conductivity can reach more than 1350W/m.k, so that the development requirement of the microelectronics field can be met.
Drawings
Fig. 1 is a photograph of the surface of a polyimide-based ink film of example 1 of the present invention.
Fig. 2 is a photograph of the surface of a polyimide-based ink film of comparative example 1 of the present invention.
Detailed Description
The technical scheme of the invention is described in detail through specific embodiments.
Example 1
Preparing a polyamic acid solution containing graphene oxide:
adding 0.047g of graphene oxide into DMAc, and performing ultrasonic dispersion to obtain graphene oxide dispersion liquid; 3.93g of p-phenylenediamine and 17.00g of 4,4' -diaminodiphenyl ether are dissolved in DMAc solution, then uniformly mixed with the graphene oxide dispersion liquid obtained above, and then 25.9g of 1,2,4, 5-pyromellitic dianhydride is added for reaction, so that a polyamide acid solution containing graphene oxide with the solid content of 18% is obtained.
Preparation of an ultra-thick polyimide-based graphite film:
s1, casting a polyamide acid solution containing graphene oxide on a glass substrate to form a first polymer layer, adhering a layer of porous fabric with an average pore diameter of 0.05mm on the surface of the first polymer layer to form a first fabric layer, casting the polyamide acid solution containing graphene oxide on the surface of the first fabric layer to form a second polymer layer, drying the obtained composite film at 180 ℃, longitudinally stretching, transversely stretching, wherein the multiplying power of the longitudinal stretching is 1.01, the multiplying power of the transverse stretching is 1.1, and finally heating in a gradient manner, and sequentially carrying out heat preservation at 100 ℃ for 30min, 150 ℃ for 30min, 200 ℃ for 30min, 250 ℃ for 30min, 300 ℃ for 30min, 350 ℃ for 30min and thermal imidization at 400 ℃ to obtain an ultra-thick polyimide film with the thickness of 75 mu m;
s2, heating the ultra-thick polyimide film to 600 ℃ at a heating rate of 5 ℃/min under a vacuum state, preserving heat for 30min, heating to 800 ℃ at a heating rate of 5 ℃/min, preserving heat for 30min, heating to 1000 ℃ at a heating rate of 5 ℃/min, preserving heat for 60min for carbonization, heating to 2200 ℃ at a heating rate of 20 ℃/min under the protection of argon, preserving heat for 60min, heating to 2600 ℃ at a heating rate of 20 ℃/min, preserving heat for 60min, heating to 2850 ℃ at a heating rate of 20 ℃/min, preserving heat for 120min for graphitization, and naturally cooling to obtain the ultra-thick polyimide-based graphite film.
Example 2
Preparing a polyamic acid solution containing graphene oxide:
adding 0.235g of graphene oxide into DMAc, and performing ultrasonic dispersion to obtain graphene oxide dispersion liquid; 3.93g of p-phenylenediamine and 17.00g of 4,4' -diaminodiphenyl ether are dissolved in DMAc solution, then uniformly mixed with the graphene oxide dispersion liquid obtained above, and then 25.9g of 1,2,4, 5-pyromellitic dianhydride is added for reaction, so that a polyamide acid solution containing graphene oxide with the solid content of 18% is obtained.
Preparation of an ultra-thick polyimide-based graphite film:
s1, casting a polyamide acid solution containing graphene oxide on a glass substrate to form a first polymer layer, adhering a layer of porous fabric with an average pore diameter of 0.05mm on the surface of the first polymer layer to form a first fabric layer, casting the polyamide acid solution containing graphene oxide on the surface of the first fabric layer to form a second polymer layer, drying the obtained composite film at 180 ℃, longitudinally stretching, transversely stretching, wherein the multiplying power of the longitudinal stretching is 1.02, the multiplying power of the transverse stretching is 1.12, and finally heating in a gradient manner, and sequentially carrying out heat preservation at 100 ℃ for 30min, 150 ℃ for 30min, 200 ℃ for 30min, 250 ℃ for 30min, 300 ℃ for 30min, 350 ℃ for 30min and thermal imidization to obtain an ultra-thick polyimide film with the thickness of 100 mu m;
s2, heating the ultra-thick polyimide film to 600 ℃ at a heating rate of 5 ℃/min under a vacuum state, preserving heat for 30min, heating to 800 ℃ at a heating rate of 5 ℃/min, preserving heat for 30min, heating to 1000 ℃ at a heating rate of 5 ℃/min, preserving heat for 60min for carbonization, heating to 2200 ℃ at a heating rate of 20 ℃/min under the protection of argon, preserving heat for 60min, heating to 2600 ℃ at a heating rate of 20 ℃/min, preserving heat for 60min, heating to 2850 ℃ at a heating rate of 20 ℃/min, preserving heat for 120min for graphitization, and naturally cooling to obtain the ultra-thick polyimide-based graphite film.
Example 3
Preparing a polyamic acid solution containing graphene oxide:
adding 0.470g of graphene oxide into DMAc, and performing ultrasonic dispersion to obtain graphene oxide dispersion liquid; 3.93g of p-phenylenediamine and 17.00g of 4,4' -diaminodiphenyl ether are dissolved in DMAc solution, then uniformly mixed with the graphene oxide dispersion liquid obtained above, and then 25.9g of 1,2,4, 5-pyromellitic dianhydride is added for reaction, so that a polyamide acid solution containing graphene oxide with the solid content of 18% is obtained.
Preparation of an ultra-thick polyimide-based graphite film:
s1, casting a polyamide acid solution containing graphene oxide on a glass substrate to form a first polymer layer, adhering a layer of porous fabric with an average pore diameter of 0.1mm on the surface of the first polymer layer to form a first fabric layer, casting the polyamide acid solution containing graphene oxide on the surface of the first fabric layer to form a second polymer layer, drying the obtained composite film at 180 ℃, longitudinally stretching, transversely stretching, wherein the multiplying power of the longitudinally stretching is 1.04, the multiplying power of the transversely stretching is 1.15, and finally heating in a gradient manner, and sequentially carrying out heat preservation at 100 ℃ for 30min, 150 ℃ for 30min, 200 ℃ for 30min, 250 ℃ for 30min, 300 ℃ for 30min, 350 ℃ for 30min and thermal imidization to obtain an ultra-thick polyimide film with the thickness of 150 mu m;
s2, heating the ultra-thick polyimide film to 600 ℃ at a heating rate of 5 ℃/min under a vacuum state, preserving heat for 30min, heating to 800 ℃ at a heating rate of 5 ℃/min, preserving heat for 30min, heating to 1000 ℃ at a heating rate of 5 ℃/min, preserving heat for 60min for carbonization, heating to 2200 ℃ at a heating rate of 20 ℃/min under the protection of argon, preserving heat for 60min, heating to 2600 ℃ at a heating rate of 20 ℃/min, preserving heat for 60min, heating to 2850 ℃ at a heating rate of 20 ℃/min, preserving heat for 120min for graphitization, and naturally cooling to obtain the ultra-thick polyimide-based graphite film.
Example 4
Preparing a polyamic acid solution containing graphene oxide:
adding 0.047g of graphene oxide into DMAc, and performing ultrasonic dispersion to obtain graphene oxide dispersion liquid; 3.93g of p-phenylenediamine and 17.00g of 4,4' -diaminodiphenyl ether are dissolved in DMAc solution, then uniformly mixed with the graphene oxide dispersion liquid obtained above, and then 25.9g of 1,2,4, 5-pyromellitic dianhydride is added for reaction, so that a polyamide acid solution containing graphene oxide with the solid content of 18% is obtained.
Preparation of an ultra-thick polyimide-based graphite film:
s1, casting a polyamide acid solution containing graphene oxide on a glass substrate to form a first polymer layer, adhering a layer of porous fabric with an average pore diameter of 0.1mm on the surface of the first polymer layer to form a first fabric layer, casting a polyamide acid solution containing graphene oxide on the surface of the first fabric layer to form a second polymer layer, adhering a layer of porous fabric on the surface of the second polymer layer to form a second fabric layer, casting a polyamide acid solution containing graphene oxide on the surface of the second fabric layer to form a third polymer layer, drying the obtained composite film at 180 ℃, longitudinally stretching and transversely stretching the composite film, wherein the longitudinal stretching multiplying power is 1.04, the transverse stretching multiplying power is 1.15, and finally gradient heating, sequentially carrying out heat preservation at 100 ℃ for 30min, at 150 ℃ for 30min, at 250 ℃ for 30min, at 300 ℃ for 30min, at 350 ℃ for 30min, and carrying out thermal imidization at 400 ℃ for 30min to obtain a polyimide film with a thickness of 150 mu m;
s2, heating the ultra-thick polyimide film to 600 ℃ at a heating rate of 5 ℃/min under a vacuum state, preserving heat for 30min, heating to 800 ℃ at a heating rate of 5 ℃/min, preserving heat for 30min, heating to 1000 ℃ at a heating rate of 5 ℃/min, preserving heat for 60min for carbonization, heating to 2200 ℃ at a heating rate of 20 ℃/min under the protection of argon, preserving heat for 60min, heating to 2600 ℃ at a heating rate of 20 ℃/min, preserving heat for 60min, heating to 2850 ℃ at a heating rate of 20 ℃/min, preserving heat for 120min for graphitization, and naturally cooling to obtain the ultra-thick polyimide-based graphite film.
Comparative example 1
Preparing a polyamic acid solution containing graphene oxide:
adding 0.047g of graphene oxide into DMAc, and performing ultrasonic dispersion to obtain graphene oxide dispersion liquid; 3.93g of p-phenylenediamine and 17.00g of 4,4' -diaminodiphenyl ether are dissolved in DMAc solution, then uniformly mixed with the graphene oxide dispersion liquid obtained above, and then 25.9g of 1,2,4, 5-pyromellitic dianhydride is added for reaction, so that a polyamide acid solution containing graphene oxide with the solid content of 18% is obtained.
Preparation of polyimide-based graphite film:
s1, carrying out tape casting film formation on a glass substrate by using a polyamic acid solution containing graphene oxide, drying the obtained composite film at 180 ℃, carrying out longitudinal stretching and transverse stretching, wherein the longitudinal stretching multiplying power is 1.01, the transverse stretching multiplying power is 1.1, and finally carrying out gradient heating, and carrying out thermal imidization at 100 ℃ for 30min, 150 ℃ for 30min, 200 ℃ for 30min, 250 ℃ for 30min, 300 ℃ for 30min, 350 ℃ for 30min and 400 ℃ for 30min in sequence to obtain a polyimide film with the thickness of 75 mu m;
s2, heating the polyimide film to 600 ℃ at a heating rate of 5 ℃/min under a vacuum state, preserving heat for 30min, heating to 800 ℃ at a heating rate of 5 ℃/min, preserving heat for 30min, heating to 1000 ℃ at a heating rate of 5 ℃/min, preserving heat for 60min for carbonization, heating to 2200 ℃ at a heating rate of 20 ℃/min under the protection of argon, preserving heat for 60min, heating to 2600 ℃ at a heating rate of 20 ℃/min, preserving heat for 60min, heating to 2850 ℃ at a heating rate of 20 ℃/min, preserving heat for 120min for graphitization, and naturally cooling to obtain the polyimide-based graphite film.
Test examples
Polyimide-based graphite films prepared in examples 1 to 3 of the present invention and comparative example 1 were evaluated, and specific evaluation properties and indexes are as follows:
(a) Evaluation of apparent defect Properties: the surface of the polyimide-based graphite film was visually observed, and the number of surface pits in an area of 10cm×10cm was measured based on this;
and (3) evaluating the heat conducting property of the graphite film: the thermal conductivity was used to characterize the thermal conductivity of polyimide-based graphite films, and tested according to GB/T22588-2008.
The evaluation results are shown in Table 1.
Table 1 evaluation of properties of polyimide-based graphite films prepared in examples 1 to 3 and comparative example 1
| Surface defect grade | Thermal conductivity (W/m.k) | |
| Example 1 | S | 1352 |
| Example 2 | S | 1383 |
| Example 3 | A | 1410 |
| Comparative example 1 | C | 1057 |
Note that: in table 1, stage S: 0 surface defects; class a: 5 or fewer surface defects; b level: 10 or fewer surface defects; c level: more than 10 surface defects.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (9)
1. A method for preparing an ultra-thick polyimide-based graphite film, comprising:
s1, casting a polyamide acid solution containing graphene oxide on a substrate to form a first polymer layer, adhering a layer of porous fabric on the surface of the first polymer layer to form a first fabric layer, casting a polyamide acid solution containing graphene oxide on the surface of the first fabric layer to form a second polymer layer, alternately performing operations of forming the polymer layer and the fabric layer until an N-1 fabric layer and an N polymer layer are formed, and then drying, stretching and thermally imidizing the obtained composite film to obtain an ultra-thick polyimide film;
and S2, carbonizing and graphitizing the ultra-thick polyimide film in sequence to obtain the ultra-thick polyimide-based graphite film.
2. The ultra-thick polyimide-based graphite film as claimed in claim 1, wherein in the polyamic acid solution containing graphene oxide, a mass ratio of graphene oxide to polyamic acid is (0.05-2): 100, preferably (0.1-1): 100.
3. the ultra-thick polyimide-based graphite film of claim 1, wherein the preparation method of the graphene oxide-containing polyamic acid solution comprises the steps of: and (3) dissolving diamine monomer in aprotic polar solvent, adding graphene oxide dispersion liquid, uniformly mixing, and adding dianhydride monomer for reaction to obtain the polymer.
4. The ultra-thick polyimide-based graphite film as claimed in claim 1, wherein n=2 to 3 in S1.
5. The ultra-thick polyimide-based ink film according to claim 1, wherein the thickness of the ultra-thick polyimide film is 75-150 μm.
6. The ultra thick polyimide-based graphite film as claimed in claim 1, wherein the porous fabric has an average pore diameter of 0.01 to 0.2mm, preferably 0.05 to 0.1mm.
7. The ultra-thick polyimide-based graphite film as claimed in claim 1, wherein in S2, the carbonization step comprises: under vacuum state, heating to 500-650deg.C at 3-5deg.C/min, maintaining for 30-60min, heating to 700-850deg.C at 3-5deg.C/min, maintaining for 30-60min, heating to 900-1000deg.C at 3-5deg.C/min, and maintaining for 30-60min.
8. The ultra-thick polyimide-based graphite film as claimed in claim 1, wherein in S2, the graphitizing step comprises: under the protection of inert gas, the temperature is firstly increased to 1800-2200 ℃ at the heating rate of 20-30 ℃/min, the temperature is kept for 60-90min, then the temperature is increased to 2400-2600 ℃ at the heating rate of 20-30 ℃/min, the temperature is kept for 60-90min, and finally the temperature is increased to 2850-3000 ℃ at the heating rate of 20-30 ℃/min, and the temperature is kept for 90-120min.
9. An ultra-thick polyimide-based graphite film, characterized by being produced by the production method according to any one of claims 1 to 8.
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