CN115073197A - Preparation method of high-thermal-conductivity asphalt-based carbon fiber reinforced porous carbon composite material - Google Patents
Preparation method of high-thermal-conductivity asphalt-based carbon fiber reinforced porous carbon composite material Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 65
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 45
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 45
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 45
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000010426 asphalt Substances 0.000 title claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 51
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 48
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000011302 mesophase pitch Substances 0.000 claims abstract description 38
- 238000009941 weaving Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims description 101
- 239000000835 fiber Substances 0.000 claims description 23
- 239000002243 precursor Substances 0.000 claims description 23
- 238000003763 carbonization Methods 0.000 claims description 21
- 238000010000 carbonizing Methods 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 18
- 230000001590 oxidative effect Effects 0.000 claims description 18
- 238000005187 foaming Methods 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 13
- 238000005087 graphitization Methods 0.000 claims description 12
- 238000005470 impregnation Methods 0.000 claims description 11
- 238000000280 densification Methods 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000007791 liquid phase Substances 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 3
- 239000006260 foam Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 7
- 239000003575 carbonaceous material Substances 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 238000004146 energy storage Methods 0.000 abstract description 2
- 239000011232 storage material Substances 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 239000012299 nitrogen atmosphere Substances 0.000 description 16
- 239000012300 argon atmosphere Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 3
- 239000011295 pitch Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000003041 ligament Anatomy 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Abstract
The invention relates to a preparation method of a high-thermal-conductivity asphalt-based carbon fiber reinforced porous carbon composite material. The carbon-carbon composite material with a large-size special-shaped porous structure can be formed by controlling a weaving process, so that the excellent heat conduction and mechanical properties of the mesophase pitch-based carbon fiber are kept, the porous structure of the material is realized, the heat conduction and mechanical properties of the composite phase-change energy storage material can be improved, and the large-scale production is easy. Compared with the porous foam carbon material obtained by the existing preparation method, the thermal conductivity and the compressive strength of the light porous carbon composite material prepared by the invention are respectively improved by more than 50% and 300%.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a preparation method of a high-thermal-conductivity asphalt-based carbon fiber reinforced porous carbon composite material.
Background
The mesophase pitch-based graphite foam carbon is a light porous material which is formed by mesophase pitch foaming and ultrahigh temperature heat treatment and is composed of pore bubbles and interconnected pore bubble walls and has a three-dimensional reticular structure, besides a plurality of excellent performances of the carbon material, due to the unique ligament-type cross-linked reticular pore bubble structure, a foam carbon framework is microscopically formed into a strip of efficient heat transfer passage by a plurality of graphitized crystal fibers after graphitization high temperature heat treatment, the heat conductivity of the graphite foam along the ligaments and the pore walls can reach 700-1200W/(m.K), the average heat conductivity can also reach 180W/(m.K), and the light porous material has a plurality of excellent physical and chemical performances such as low density, heat resistance, corrosion resistance, impact resistance, wave absorption and noise reduction, low thermal expansion coefficient and the like. However, all the foaming devices adopted at present are high-temperature high-pressure reaction kettles, the industrial continuous production is difficult to realize, the mechanical property of the prepared porous composite material is weak, and the compression strength of the porous composite material obtained by directly foaming asphalt is only 2-3 MPa.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a novel preparation method of a porous carbon-carbon composite material, the porous C/C composite material prepared by the method shows excellent heat conduction and mechanical properties due to the addition of the asphalt-based carbon fiber, and simultaneously realizes the porous structure of the material, and the forming process is simple, low in cost and easy for large-scale production.
In order to solve the technical problems, the invention provides a preparation method of a high-thermal-conductivity asphalt-based carbon fiber reinforced porous carbon composite material, which comprises the following steps:
s1, preparation of a preform: taking the mesophase pitch-based carbonized fiber filament/felt as a raw material, wherein the mesophase pitch-based carbonized fiber filament is woven according to a three-dimensional orthogonal structure, and the mesophase pitch-based carbon fiber felt is needled to prepare a low-density carbon fiber preform;
s2, carrying out liquid phase impregnation densification on the low-density carbon fiber prefabricated body to obtain a porous carbon-carbon composite material precursor, and then carrying out pressurization foaming to obtain a porous carbon-carbon composite material;
s3, carbonization and graphitization: and (4) carbonizing and graphitizing the porous carbon-carbon composite material obtained in the step (S2).
Further, the preparation method of the mesophase pitch-based carbonized fiber filament/felt comprises the following steps: pre-oxidizing the mesophase pitch-based fiber filament/felt at the temperature of 180-300 ℃, and then heating to the temperature of 800-1000 ℃ in an inert atmosphere for carbonization treatment.
Further, the weaving method of the mesophase pitch-based carbonized fiber filament specifically comprises the following steps: the XY direction adopts 0 degree/90 degree soft woven layer, the Z direction single strand penetrates in two directions, the structure can not be loose, and the friction force between the fibers is enough to keep the whole shape.
Further, the density of the low-density carbon fiber preform is 0.2 to 0.4g/cm 3 。
Furthermore, the graphite tool in the liquid-phase impregnation densification step adopts a porous structure, the aperture is 5-10mm, so that the pyrolytic carbon and the mesophase pitch can conveniently enter the prefabricated body, and the densification effect is achieved; in addition, the graphite tool is adopted for clamping, so that the deformation of the prefabricated body in the densification and heat treatment processes can be avoided.
The density of the porous carbon-carbon composite material precursor obtained by the liquid phase impregnation step is 0.8-0.9g/cm 3 Keeping the light porous structure of the material;
further, the liquid-phase impregnation densification process comprises the following steps: placing the low-density carbon fiber preform in a graphite tool, placing the graphite tool and the mesophase pitch in a high-pressure kettle, vacuumizing and replacing the atmosphere with inert gas to ensure that the reaction environment is an inert atmosphere, heating to 350 ℃ and vacuumizing in the heating process; after the temperature reaches 300-350 ℃, pressurizing at 4-7MPa, and preserving the heat for 2h to obtain a porous carbon-carbon composite material precursor;
furthermore, in the step of liquid phase impregnation and densification, the impregnation temperature is the temperature corresponding to the viscosity of the mesophase pitch of 1-10Pa.s, the pressure is 4-7Mpa after the temperature reaches 300-350 ℃, and the heat is preserved for 2h, and the experiment shows that the pitch has better impregnation effect under the process.
Further, the pressure foaming process in step S2 is as follows: and (3) putting the porous carbon-carbon composite material precursor into an autoclave, replacing gas with inert gas, filling the inert gas into the autoclave under the pressure of 5-8MPa, heating the autoclave from room temperature to 350 ℃ for heat preservation for 1-3h, continuing heating the autoclave to 500 ℃ for heat preservation for 400 ℃ for heat preservation for 1-3 h.
Further, in the step of pressure foaming, the temperature is increased from room temperature to 320-350 ℃ at the temperature increase rate of 4-6 ℃/min; the temperature is raised from 350 ℃ to 500 ℃ at the temperature raising rate of 0.3-0.8 ℃/min from 320 ℃ to 400 ℃ and experiments show that the foaming rate is strictly controlled according to the conditions, so that the excellent foaming effect can be realized.
Further, the method is characterized in that the carbonization treatment temperature is 1000-1500 ℃.
Further, the graphitization treatment temperature is 2800-3000 ℃, and the temperature rise rate is 5-10 ℃/min.
The invention also provides a high-thermal-conductivity asphalt-based carbon fiber reinforced porous carbon composite material which is prepared by the preparation method and has the density of only 0.5-0.6g/cm 3 The size of the micropores is controlled to be 200-500 mu m, the thermal conductivity is 250-450W/m.K, and the compressive strength is 25-60 MPa.
Compared with the prior art, the invention takes the mesophase pitch-based carbonized fiber filament/felt which is easy to weave and form as the raw material to prepare the low-density prefabricated body, and adopts pitch liquid-phase impregnation and pressurized foaming to prepare the light porous carbon-carbon composite material. The carbon-carbon composite material with a large-size special-shaped porous structure can be formed by controlling a weaving process, so that the excellent heat conduction and mechanical properties of the mesophase pitch-based carbon fiber are kept, the porous structure of the material is realized, the heat conduction and mechanical properties of the composite phase-change energy storage material can be improved, and the large-scale production is easy. Compared with the porous foam carbon material obtained by the existing preparation method, the thermal conductivity and the compressive strength of the light porous carbon composite material prepared by the invention are respectively improved by more than 50% and 300%.
Drawings
FIG. 1 is a structure view of the intermediate phase pitch-based carbonized fiber filament according to the present invention.
Detailed Description
The invention is further described with reference to specific embodiments. The example data of the present invention should not be construed as limitations of the invention, and reasonable variations are intended to be within the scope of the invention.
In the following examples and comparative examples, the mesophase pitch-based carbonized fiber filaments were woven in the following manners: the XY direction adopts 0 degree/90 degree soft woven layer, the Z direction single strand is through in two directions, the concrete structure is shown in figure 1.
Example 1
S1, pre-oxidizing and carbonizing the continuous mesophase pitch-based carbon fiber filament, wherein the pre-oxidizing process comprises the following steps: heating from room temperature to 180 ℃ at the speed of 2 ℃/min in the air atmosphere, and then heating to 280 ℃ at the speed of 0.5 ℃/min; the carbonization procedure is as follows: heating from room temperature to 400 deg.C at 0.5 deg.C/min under nitrogen atmosphere, heating to 1000 deg.C at 1 deg.C/min, and maintaining for 20 min. Weaving the obtained carbonized fiber filaments in a three-dimensional orthogonal structure according to a certain volume fraction and arrangement mode to obtain the carbonized fiber filaments with the density of 0.2g/cm 3 、0.4g/cm 3 、0.6g/cm 3 The braided body of (1).
S2, placing the braided body and the mesophase pitch into a high-pressure kettle, replacing gas in the high-pressure kettle twice with nitrogen, heating from room temperature to 350 ℃ at a heating rate of 4 ℃/min after replacement, and vacuumizing in the heating process; and after the temperature is raised to 350 ℃, pressurizing to 7MPa, and preserving heat for 2h to obtain a precursor of the porous carbon-carbon composite material. And (3) putting the precursor into an autoclave, replacing the gas in the autoclave twice with nitrogen, filling the autoclave with 8MPa of pressure, heating the autoclave from room temperature to 350 ℃ at the heating rate of 4 ℃/min, preserving the heat for 3 hours, continuing heating the autoclave to 500 ℃ at the heating rate of 0.3 ℃/min, and preserving the heat for 3 hours to obtain the carbon-carbon composite material.
And S3, carbonizing and graphitizing the obtained carbon-carbon composite material. The carbonization procedure is as follows: the temperature was raised from room temperature to 400 ℃ at 0.5 ℃/min under nitrogen atmosphere and then to 1500 ℃ at 1 ℃/min. The graphitization procedure is as follows: the final sample properties are shown in table 1, with a temperature rise from room temperature to 3000 ℃ at 5 ℃/min under argon atmosphere:
TABLE 1
Example 2
S1, pre-oxidizing and carbonizing the mesophase pitch-based carbon fiber felt, wherein the pre-oxidizing process comprises the following steps: heating from room temperature to 180 ℃ at the speed of 2 ℃/min in the air atmosphere, and then heating to 280 ℃ at the speed of 0.5 ℃/min; the carbonization procedure is as follows: heating from room temperature to 400 deg.C at 0.5 deg.C/min under nitrogen atmosphere, heating to 1000 deg.C at 1 deg.C/min, and maintaining for 30 min. The obtained carbon fiber felt was subjected to needling to obtain a carbon fiber felt having a density of 0.2g/cm, respectively 3 、 0.4g/cm 3 、0.6g/cm 3 The preform of (4).
S2, placing the woven body and the mesophase pitch into an autoclave, replacing the gas in the autoclave twice with nitrogen, heating from room temperature to 350 ℃ at a heating rate of 4 ℃/min after replacement, and vacuumizing in the heating process; and after the temperature is raised to 350 ℃, pressurizing to 7MPa, and preserving heat for 2h to obtain a precursor of the porous carbon-carbon composite material. And (3) putting the precursor into an autoclave, replacing the gas in the autoclave twice with nitrogen, filling the autoclave with 8MPa of pressure, heating the autoclave from room temperature to 350 ℃ at the heating rate of 4 ℃/min, preserving the heat for 3h, continuing heating the autoclave to 500 ℃ at the heating rate of 0.3 ℃/min, and preserving the heat for 3h to obtain the carbon-carbon composite material.
And S3, carbonizing and graphitizing the obtained carbon-carbon composite material. The carbonization procedure is as follows: the temperature was raised from room temperature to 400 ℃ at 0.5 ℃/min under nitrogen atmosphere and then to 1500 ℃ at 1 ℃/min. The graphitization procedure is as follows: the final sample properties are shown in table 2, with a temperature rise from room temperature to 3000 ℃ at 5 ℃/min under argon atmosphere:
TABLE 2
Example 3
S1, pre-oxidizing and carbonizing the continuous mesophase pitch-based carbon fiber filament, wherein the pre-oxidizing process comprises the following steps: heating from room temperature to 180 ℃ at the speed of 2 ℃/min in the air atmosphere, and then heating to 280 ℃ at the speed of 0.5 ℃/min; the carbonization procedure is as follows: heating from room temperature to 400 deg.C at 0.5 deg.C/min under nitrogen atmosphere, heating to 1000 deg.C at 1 deg.C/min, and maintaining for 20 min. Weaving the obtained carbonized fiber filaments in a three-dimensional orthogonal structure according to a certain volume fraction and arrangement mode to obtain the carbonized fiber filaments with the density of 0.4g/cm 3 The braided body of (1).
S2, placing the braided body and the mesophase pitch into a high-pressure kettle, replacing gas in the high-pressure kettle twice with nitrogen, heating from room temperature to 350 ℃ at a heating rate of 4 ℃/min after replacement, and vacuumizing in the heating process; and after the temperature is raised to 350 ℃, pressurizing at 7MPa, and preserving heat for 2 hours to obtain a precursor of the porous carbon-carbon composite material. And (3) putting the precursor into an autoclave, replacing the gas in the autoclave twice with nitrogen, filling the autoclave with 5MPa of pressure, heating the autoclave from room temperature to 350 ℃ at the heating rate of 4 ℃/min, preserving the heat for 3h, continuing heating the autoclave to 500 ℃ at the heating rate of 0.3 ℃/min, and preserving the heat for 3h to obtain the carbon-carbon composite material.
And S3, carbonizing and graphitizing the obtained carbon-carbon composite material. The carbonization procedure is as follows: the temperature was raised from room temperature to 400 ℃ at 0.5 ℃/min under nitrogen atmosphere and then to 1500 ℃ at 1 ℃/min. The graphitization procedure is as follows: the final sample properties are shown in table 3, with a temperature rise from room temperature to 3000 ℃ at 5 ℃/min under argon atmosphere:
TABLE 3
Example 4
S1, pre-oxidizing and carbonizing the mesophase pitch-based carbon fiber felt, wherein the pre-oxidizing process comprises the following steps: heating from room temperature to 180 ℃ at a speed of 2 ℃/min in air atmosphere, and then heating to 280 ℃ at a speed of 0.5 ℃/min; the carbonization procedure is as follows: heating from room temperature to 400 deg.C at 0.5 deg.C/min under nitrogen atmosphere, heating to 1000 deg.C at 1 deg.C/min, and maintaining for 30 min. HandleThe obtained carbon fiber felt is needled to obtain the carbon fiber felt with the density of 0.4g/cm 3 The preform of (4).
S2, placing the braided body and the mesophase pitch into a high-pressure kettle, replacing gas in the high-pressure kettle twice with nitrogen, heating from room temperature to 350 ℃ at a heating rate of 4 ℃/min after replacement, and vacuumizing in the heating process; and after the temperature is raised to 350 ℃, pressurizing at 7MPa, and preserving heat for 2 hours to obtain a precursor of the porous carbon-carbon composite material. And (3) putting the precursor into an autoclave, replacing the gas in the autoclave twice with nitrogen, filling the autoclave with 5MPa of pressure, heating the autoclave from room temperature to 350 ℃ at the heating rate of 4 ℃/min, preserving the heat for 3h, continuing heating the autoclave to 500 ℃ at the heating rate of 0.3 ℃/min, and preserving the heat for 3h to obtain the carbon-carbon composite material.
And S3, carbonizing and graphitizing the obtained carbon-carbon composite material. The carbonization procedure is as follows: the temperature was raised from room temperature to 400 ℃ at 0.5 ℃/min under nitrogen atmosphere and then to 1500 ℃ at 1 ℃/min. The graphitization procedure is as follows: the final sample was heated from room temperature to 3000 c at 5 c/min under argon atmosphere and the properties of the final sample are shown in table 4:
TABLE 4
Comparative example 1
S1, pre-oxidizing and carbonizing the continuous mesophase pitch-based carbon fiber filament, wherein the pre-oxidizing process comprises the following steps: heating from room temperature to 180 ℃ at the speed of 2 ℃/min in the air atmosphere, and then heating to 280 ℃ at the speed of 0.5 ℃/min; the carbonization procedure is as follows: heating from room temperature to 400 deg.C at 0.5 deg.C/min under nitrogen atmosphere, heating to 1000 deg.C at 1 deg.C/min, and maintaining for 20 min. Weaving the obtained carbonized fiber filaments in a three-dimensional orthogonal structure according to a certain volume fraction and arrangement mode to obtain the carbonized fiber filaments with the density of 0.2g/cm 3 、0.4g/cm 3 、0.6g/cm 3 The braided body of (1).
S2, placing the braided body and the mesophase pitch into a high-pressure kettle, replacing gas in the high-pressure kettle twice with nitrogen, heating from room temperature to 350 ℃ at a heating rate of 4 ℃/min after replacement, and vacuumizing in the heating process; and after the temperature is raised to 350 ℃, pressurizing to 7MPa, and preserving heat for 2h to obtain a precursor of the porous carbon-carbon composite material. And (3) putting the precursor into an autoclave, replacing the gas in the autoclave twice with nitrogen, heating the temperature to 350 ℃ from room temperature at the heating rate of 4 ℃/min under the normal pressure environment, preserving the heat for 3h, continuously heating the temperature to 500 ℃ at the heating rate of 0.3 ℃/min, and preserving the heat for 3h to obtain the carbon-carbon composite material.
And S3, carbonizing and graphitizing the obtained carbon-carbon composite material. The carbonization procedure is as follows: the temperature was raised from room temperature to 400 ℃ at 0.5 ℃/min under nitrogen atmosphere and then to 1500 ℃ at 1 ℃/min. The graphitization procedure is as follows: the final sample properties are shown in table 5, with a temperature rise from room temperature to 3000 ℃ at 5 ℃/min under argon atmosphere:
TABLE 5
Comparative example 2
S1, pre-oxidizing and carbonizing the mesophase pitch-based carbon fiber felt, wherein the pre-oxidizing process comprises the following steps: heating from room temperature to 180 ℃ at the speed of 2 ℃/min in the air atmosphere, and then heating to 280 ℃ at the speed of 0.5 ℃/min; the carbonization procedure is as follows: heating from room temperature to 400 deg.C at 0.5 deg.C/min under nitrogen atmosphere, heating to 1000 deg.C at 1 deg.C/min, and maintaining for 30 min. The obtained carbon fiber felt was subjected to needling to obtain a carbon fiber felt having a density of 0.2g/cm, respectively 3 、 0.4g/cm 3 、0.6g/cm 3 The preform of (4).
S2, placing the braided body and the mesophase pitch into a high-pressure kettle, replacing gas in the high-pressure kettle twice with nitrogen, heating from room temperature to 350 ℃ at a heating rate of 4 ℃/min after replacement, and vacuumizing in the heating process; and after the temperature is raised to 350 ℃, pressurizing to 7MPa, and preserving heat for 2h to obtain a precursor of the porous carbon-carbon composite material. And (3) putting the precursor into an autoclave, replacing the gas in the autoclave twice with nitrogen, heating the temperature to 350 ℃ from room temperature at the heating rate of 4 ℃/min under the normal pressure environment, preserving the heat for 3h, continuously heating the temperature to 500 ℃ at the heating rate of 0.3 ℃/min, and preserving the heat for 3h to obtain the carbon-carbon composite material.
And S3, carbonizing and graphitizing the obtained carbon-carbon composite material. The carbonization procedure is as follows: the temperature was raised from room temperature to 400 ℃ at 0.5 ℃/min under nitrogen atmosphere and then to 1500 ℃ at 1 ℃/min. The graphitization procedure is as follows: the final sample properties are shown in table 6, with a temperature rise from room temperature to 3000 ℃ at 5 ℃/min under argon atmosphere:
TABLE 6
Comparative example 3
S1, pre-oxidizing and carbonizing the continuous mesophase pitch-based carbon fiber filament, wherein the pre-oxidizing process comprises the following steps: heating from room temperature to 180 ℃ at the speed of 2 ℃/min in the air atmosphere, and then heating to 280 ℃ at the speed of 0.5 ℃/min; the carbonization procedure is as follows: heating from room temperature to 400 deg.C at 0.5 deg.C/min under nitrogen atmosphere, heating to 1000 deg.C at 1 deg.C/min, and maintaining for 20 min. Weaving the obtained carbonized fiber filaments in a three-dimensional orthogonal structure according to a certain volume fraction and arrangement mode to obtain the carbonized fiber filaments with the density of 0.4g/cm 3 The braided body of (1).
S2, placing the braided body and the mesophase pitch into a high-pressure kettle, replacing gas in the high-pressure kettle twice with nitrogen, heating from room temperature to 350 ℃ at a heating rate of 4 ℃/min after replacement, and vacuumizing in the heating process; and after the temperature is raised to 350 ℃, pressurizing to 7MPa, and preserving heat for 2h to obtain a precursor of the porous carbon-carbon composite material. And (3) putting the precursor into an autoclave, replacing the gas in the autoclave twice with nitrogen, filling the autoclave with 10MPa of pressure, heating the autoclave from room temperature to 350 ℃ at the heating rate of 4 ℃/min, preserving the heat for 3h, continuing heating the autoclave to 500 ℃ at the heating rate of 0.3 ℃/min, and preserving the heat for 3h to obtain the carbon-carbon composite material.
And S3, carbonizing and graphitizing the obtained carbon-carbon composite material. The carbonization procedure is as follows: the temperature was raised from room temperature to 400 ℃ at 0.5 ℃/min under nitrogen atmosphere and then to 1500 ℃ at 1 ℃/min. The graphitization procedure is as follows: the final sample properties are shown in table 7, with a temperature rise from room temperature to 3000 ℃ at 5 ℃/min under argon atmosphere:
TABLE 7
Comparative example 4
S1, pre-oxidizing and carbonizing the mesophase pitch-based carbon fiber felt, wherein the pre-oxidizing process comprises the following steps: heating from room temperature to 180 ℃ at the speed of 2 ℃/min in the air atmosphere, and then heating to 280 ℃ at the speed of 0.5 ℃/min; the carbonization procedure is as follows: heating from room temperature to 400 deg.C at 0.5 deg.C/min under nitrogen atmosphere, heating to 1000 deg.C at 1 deg.C/min, and maintaining for 30 min. The obtained carbon fiber felt was subjected to needling to obtain a carbon fiber felt having a density of 0.4g/cm, respectively 3 The preform of (4).
S2, placing the braided body and the mesophase pitch into a high-pressure kettle, replacing gas in the high-pressure kettle twice with nitrogen, heating from room temperature to 350 ℃ at a heating rate of 4 ℃/min after replacement, and vacuumizing in the heating process; and after the temperature is raised to 350 ℃, pressurizing to 7MPa, and preserving heat for 2h to obtain a precursor of the porous carbon-carbon composite material. And (3) putting the precursor into an autoclave, replacing the gas in the autoclave twice with nitrogen, filling the autoclave with 10MPa of pressure, heating the autoclave from room temperature to 350 ℃ at the heating rate of 4 ℃/min, preserving the heat for 3h, continuing heating the autoclave to 500 ℃ at the heating rate of 0.3 ℃/min, and preserving the heat for 3h to obtain the carbon-carbon composite material.
And S3, carbonizing and graphitizing the obtained carbon-carbon composite material. The carbonization procedure is as follows: the temperature was raised from room temperature to 400 ℃ at 0.5 ℃/min under nitrogen atmosphere and then to 1500 ℃ at 1 ℃/min. The graphitization procedure is as follows: the final sample properties are shown in table 8, with a temperature rise from room temperature to 3000 ℃ at 5 ℃/min under argon atmosphere:
TABLE 8
According to the embodiment and the comparative example, the material prepared by the foaming process adopted in the embodiment of the invention has larger micropore size and lower density, while the density and the micropore size of the material prepared by the foaming process in the comparative example can not meet the requirements of the required porous material, and the comprehensive performance of the porous carbon-carbon composite material product prepared by the method of the invention is obviously better.
The data show that the preparation method provided by the invention not only keeps the excellent heat conduction and mechanical properties of the mesophase pitch-based carbon fiber, but also realizes the porous structure of the material, and the porous carbon composite material prepared by the method can replace the traditional mesophase pitch-based graphite foam carbon, has more excellent properties compared with the foam carbon, and has great utilization value.
Claims (10)
1. A preparation method of a high-thermal-conductivity asphalt-based carbon fiber reinforced porous carbon-carbon composite material is characterized by comprising the following steps:
s1, taking the mesophase pitch-based carbonized fiber filament/felt as a raw material, weaving the mesophase pitch-based carbonized fiber filament according to a three-dimensional orthogonal structure, and needling the mesophase pitch-based carbonized fiber felt to prepare a low-density carbon fiber preform;
s2, carrying out liquid phase impregnation densification on the low-density carbon fiber prefabricated body to obtain a porous carbon-carbon composite material precursor, and then carrying out pressurization foaming to obtain a porous carbon-carbon composite material;
s3, carbonizing and graphitizing the porous carbon-carbon composite material obtained in the step S2.
2. The preparation method of the high-thermal-conductivity asphalt-based carbon fiber reinforced porous carbon-carbon composite material according to claim 1, wherein the preparation method of the mesophase asphalt-based carbonized fiber filament/felt comprises the following steps: pre-oxidizing the mesophase pitch-based fiber filament/felt at the temperature of 180-300 ℃, and then heating to the temperature of 800-1000 ℃ in an inert atmosphere for carbonization treatment.
3. The preparation method of the high-thermal-conductivity asphalt-based carbon fiber reinforced porous carbon composite material according to claim 1, wherein the low-density carbon fiber is prefabricatedThe density of the body is 0.2-0.4g/cm 3 。
4. The preparation method of the high thermal conductivity asphalt-based carbon fiber reinforced porous carbon composite material according to claim 1, wherein the liquid phase impregnation densification process in step S2 is as follows: placing the low-density carbon fiber preform in a graphite tool, placing the graphite tool and the mesophase pitch in a high-pressure kettle, vacuumizing, replacing the atmosphere with inert gas, heating to 300-350 ℃, and vacuumizing in the heating process; after the temperature reaches 300-350 ℃, pressurizing and preserving heat to obtain the porous carbon-carbon composite material precursor.
5. The preparation method of the high thermal conductivity asphalt-based carbon fiber reinforced porous carbon composite material according to claim 1, wherein the pressure foaming process in step S2 is as follows: and (3) putting the porous carbon-carbon composite material precursor into an autoclave, replacing gas with inert gas, filling the inert gas into the autoclave under the pressure of 5-8MPa, heating the autoclave from room temperature to 350 ℃ for heat preservation for 1-3h, continuing heating the autoclave to 500 ℃ for heat preservation for 400 ℃ for heat preservation for 1-3 h.
6. The preparation method of the highly heat-conductive asphalt-based carbon fiber reinforced porous carbon-carbon composite material as claimed in claim 4, wherein in the liquid phase impregnation and densification step, after the temperature reaches 300-350 ℃, the pressure is increased by 4-7MPa, and the temperature is maintained for 2 h.
7. The method for preparing the highly heat-conductive asphalt-based carbon fiber reinforced porous carbon-carbon composite material as claimed in claim 5, wherein in the pressure foaming process, the temperature is raised from room temperature to 320-350 ℃ at a temperature raising rate of 4-6 ℃/min; raising the temperature from 350 ℃ to 500 ℃ at a temperature raising rate of 0.3-0.8 ℃/min.
8. The preparation method of the high thermal conductivity asphalt-based carbon fiber reinforced porous carbon-carbon composite material as claimed in claim 1, wherein the carbonization temperature is 1000-1500 ℃.
9. The method for preparing the highly heat-conductive asphalt-based carbon fiber reinforced porous carbon-carbon composite material as claimed in claim 1, wherein the graphitization treatment temperature is 2800-3000 ℃, and the temperature increase rate is 5-10 ℃/min.
10. A high thermal conductivity asphalt-based carbon fiber reinforced porous carbon-carbon composite material, characterized by being prepared by the preparation method of any one of claims 1 to 9.
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