CN114029494A - Preparation method of spiral graphene film/copper laminated composite material - Google Patents
Preparation method of spiral graphene film/copper laminated composite material Download PDFInfo
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Abstract
The invention discloses a preparation method of a spiral graphene film/copper laminated composite material, which comprises the following steps: firstly, bonding and curling a highly-oriented graphene film and a hot-melt pressure-sensitive double-sided adhesive, then carrying out heat treatment, and then ultrasonically soaking copper powder ethanol slurry to obtain a highly-oriented graphene film preform; secondly, preparing a zirconium microalloyed copper block; and thirdly, placing the zirconium microalloyed copper block above the graphene film preform, and preparing the graphene film/copper laminated composite material by adopting air pressure infiltration. According to the invention, a micro-alloying copper block melt is immersed into the spiral gap of the high-orientation graphene film preform by adopting an air pressure infiltration method and generates the nano-thick carbide in situ, so that the improvement of the interface bonding strength in the spiral graphene film/copper laminated composite material and the uniform distribution of the graphene film are realized, the mechanical property of the composite material is improved, and the problems of small load of graphene as a copper matrix reinforcement, more graphene/copper interfaces, disordered graphene orientation and limited heat conduction reinforcement effect are solved.
Description
Technical Field
The invention belongs to the technical field of heat management materials, and particularly relates to a preparation method of a spiral graphene film/copper laminated composite material.
Background
With the continuous improvement of the integration of components on a chip, a large amount of heat generated from the integration directly influences the working stability and the safety reliability of an electronic device, so that urgent needs are brought to high-heat-conduction materials. The heat conductivity of the traditional heat conduction materials is lower than 300W/mK, and the higher and higher use requirements cannot be met. At present, carbon material (graphene, carbon nanotube, diamond, etc.) reinforced copper-based composite materials are leading to research and development of hot tide, and become the latest generation of high heat conduction materials. Particularly, graphene is the material with the best heat conduction performance at present, and therefore, the graphene is an excellent potential heat conduction reinforcement. However, none of the graphene reinforced copper-based composites reported so far have high thermal conductivity (<500W/mK) (Powder Technology,2016,301, 601-.
The traditional preparation idea commonly adopted by graphene reinforced composite materials is to uniformly disperse graphene nanosheets in a copper matrix, and the orientation degree of graphene is improved by a certain special process, but the problems of too small graphene loading amount, too much graphene/copper interface and the like cannot be solved at the same time. The load rate of graphene in a metal matrix is generally not more than 5 wt.%, and according to a composite material thermal conductivity formula, the effect of enhancing the thermal conductivity is not obvious when the load capacity of an enhancing body is too small, if the load capacity of graphene is increased, the graphene has a serious agglomeration problem, the disorder is increased, and even if the orientation degree is improved, the high interface thermal resistance caused by introducing a large number of interfaces into a graphene nanosheet cannot be offset, so that the improvement of the thermal conductivity of the composite material is not facilitated. Therefore, although the single-layer graphene has ultrahigh thermal conductivity, the single-layer graphene is not suitable for being directly added to a copper matrix as a thermal conductivity enhancer, and otherwise, the graphene is difficult to get rid of the mutual restriction of factors such as ply orientation, loading amount, interface number and the like, and is difficult to achieve the dilemma.
Disclosure of Invention
The present invention is directed to provide a method for preparing a spiral graphene film/copper layered composite material, which overcomes the above-mentioned shortcomings of the prior art. According to the method, a microalloyed copper block melt is immersed into a spiral gap of a high-orientation graphene film preform by using an air pressure infiltration method, and a nano-scale thick carbide is generated in situ on the surface of a graphene film, so that the interface bonding strength in a spiral graphene film/copper laminated composite material is improved, the graphene film is uniformly distributed, the mechanical property of the composite material is improved, and the problems of small load capacity, multiple graphene/copper interfaces, disordered graphene orientation and limited heat conduction enhancement effect of graphene serving as a copper matrix reinforcement are solved.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a method for preparing a helical graphene film/copper layered composite material, the method comprising the steps of:
step one, preparing a high-orientation graphene film preform:
101, bonding a highly-oriented graphene film with a hot-melt pressure-sensitive double-sided adhesive, and then curling to form a graphene film spirally-distributed cylinder;
102, putting the graphene film spiral distribution cylinder formed in the step 101 into a graphite mold, then heating the graphene film spiral distribution cylinder in an air atmosphere, and ultrasonically cleaning the graphene film spiral distribution cylinder by using ethanol to obtain a graphene film spiral body;
103, putting the graphene film spiral body obtained in the step 102 and a graphite mold into copper powder ethanol slurry together for ultrasonic soaking, so that copper powder enters gaps of the graphene spiral body, and obtaining a high-orientation graphene film prefabricated body;
step two, preparing the zirconium microalloyed copper block: smelting the raw material for preparing the zirconium microalloyed copper alloy by a vacuum induction smelting method for more than three times to obtain a zirconium microalloyed copper block; the mass content of the zirconium element in the zirconium microalloyed copper block is 0.1-0.7%;
step three, preparing the graphene film/copper laminated composite material by air pressure infiltration:
301, putting the high-orientation graphene film preform obtained in the step 103 and a graphite mold into a quartz crucible, and putting the zirconium microalloyed copper block prepared in the step two above the graphite mold;
step 302, transferring the graphite mold with the zirconium microalloyed copper block in the step 301 to a heating area of gas pressure permeation equipment, vacuumizing a furnace chamber of the gas pressure permeation equipment until the vacuum degree is lower than 0.1Pa, performing electromagnetic induction heating and preserving heat;
and 303, after the heat preservation in the step 302 is finished, immediately filling high-purity argon into a furnace chamber of the gas pressure permeation device, preserving heat and pressure, and then cooling to room temperature along with the furnace to obtain the spiral graphene film/copper laminated composite material.
The method comprises the steps of bonding a highly-oriented graphene film with a hot-melt pressure-sensitive double-sided adhesive, then curling to form a graphene film spirally-distributed cylinder, heating, wherein the hot-melt pressure-sensitive double-sided adhesive comprises C, H, O main chemical components, heating the hot-melt pressure-sensitive double-sided adhesive to completely convert the hot-melt pressure-sensitive double-sided adhesive into water, carbon dioxide and a small amount of residual amorphous carbon, performing ultrasonic cleaning by using ethanol to completely remove the hot-melt pressure-sensitive double-sided adhesive to obtain a graphene film spiral body with gaps between adjacent spirals, placing the graphene film spiral body into ethanol slurry of copper powder to perform ultrasonic soaking, and enabling the copper powder to enter the gaps of the graphene spiral body to obtain a highly-oriented graphene film prefabricated body with uniformly-distributed graphene films, uniform inter-film intervals and copper powder attached to the inter-film gaps, so that the mutual adhesion of the graphene films is reduced, and the uniform distribution of the graphene films is facilitated; placing a zirconium microalloyed copper block above a graphite mould provided with a high-orientation graphene film preform, carrying out electromagnetic induction heating and heat preservation under vacuum, melting copper powder, completely melting the zirconium microalloyed copper block to form a melt, then filling high-purity argon gas for heat preservation and pressure preservation to promote the zirconium microalloyed copper block melt to be fully immersed into and fill in gaps of the graphene film, and leading microalloyed zirconium elements to have full interface reaction with the graphene film, so that nano-scale thick carbide is generated on the surface of the graphene film in situ, and the wetting angle between the carbide and the copper is far smaller than that between the graphene film and the copper, namely the wettability between the copper and the graphene film is improved through the generation of the carbide, thereby reducing the resistance of pore capillary action on the copper melt impregnation, improving the fluidity of the melt, and improving the interface combination and the distribution state of the graphene film, the method has the advantages that the interface bonding strength in the spiral graphene film/copper-layered composite material is improved, the graphene film is uniformly distributed, the characteristics of high orientation, high heat conduction and micron-sized thickness of the highly oriented graphene film are utilized, the problems of small load capacity, multiple graphene/copper interfaces, disordered graphene orientation and limited heat conduction enhancing effect of graphene serving as a copper matrix reinforcement are solved, and the heat conduction performance of the composite material is greatly enhanced.
Typically, the high purity argon in step 303 is 99.999% by mass purity argon.
The preparation method of the spiral graphene film/copper laminated composite material is characterized in that in step 101, the thickness of the high-orientation graphene film is 25-100 micrometers, and the thickness of the hot-melt pressure-sensitive double-sided adhesive tape is 80 micrometers. The preferred thickness of the highly oriented graphene film and the hot melt pressure sensitive double sided adhesive tape facilitates implementation of the curling process and maintains the high thermal conductivity of the highly oriented graphene film.
The preparation method of the spiral graphene film/copper laminated composite material is characterized in that the temperature of the heating treatment in the step 102 is 400-600 ℃. The temperature of the heating treatment ensures that the hot-melt pressure-sensitive double-sided adhesive is fully converted into water, carbon dioxide and a small amount of residual amorphous carbon, and is thoroughly removed by subsequent ultrasonic cleaning, thereby avoiding the generation of undesirable residues.
The preparation method of the spiral graphene film/copper laminated composite material is characterized in that the particle size of copper powder in the copper powder ethanol slurry in the step 103 is 5-20 microns. The optimized particle size of the copper powder ensures that the copper powder particles can easily enter gaps of the curled high-orientation graphene film in the graphene film spiral body, and the copper powder particles play a supporting role among the high-orientation graphene films, thereby being beneficial to the impregnation of the subsequent zirconium microalloyed copper melt.
The preparation method of the spiral graphene film/copper laminated composite material is characterized in that the electromagnetic induction heating temperature in the step 302 is 1100-1200 ℃, and the heat preservation time is 20-40 min. The optimized temperature and the heat preservation time of the electromagnetic induction heating ensure that the copper powder and the zirconium microalloyed copper block are completely melted by heating to form a melt, thereby ensuring the smooth proceeding of the subsequent air pressure infiltration.
The preparation method of the spiral graphene film/copper laminated composite material is characterized in that in the step 303, high-purity argon is filled until the pressure is 1 MPa-1.5 MPa, and the heat preservation and pressure maintaining time is 20 min-40 min. The charging pressure and the heat preservation and pressure maintaining time promote the microalloyed copper block to be melted and fully immersed into and fill in the gap of the graphene film, so that the microalloyed zirconium element and the graphene film have full interfacial reaction, and the interfacial bonding and the distribution state of the graphene film are further improved.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, a zirconium microalloyed copper block melt is introduced into the spiral gap of the high-orientation graphene film preform by adopting an air pressure infiltration method, so that the nano-scale thick carbide is generated in situ on the surface of the graphene film, the wettability between copper and the graphene film is improved, the interface bonding strength in the spiral graphene film/copper laminated composite material is improved, the graphene film is uniformly distributed, and the mechanical property and the heat conductivity of the composite material are improved.
2. According to the invention, the highly-oriented graphene film with high thermal conductivity is directly used as the thermal conductivity enhancer, the high thermal conductivity of the highly-oriented graphene film in the plane of the layered structure and the zero barrier effect of the interface on heat flow are exerted, so that the thermal conductivity of the spiral graphene film/copper layered composite material is greatly improved, and compared with graphene nanosheets, the highly-oriented graphene film is used for avoiding the problems of more graphene/copper interfaces, small graphene load and disordered graphene orientation when the graphene is used for enhancing the copper by thermal conductivity.
3. According to the invention, the layered composite material is prepared in a spiral distribution mode, so that graphene in the composite material is curled to form a spiral structure, the stress state of a graphene film is changed, namely, the uniaxial stress state of the graphene film distributed perpendicular to a curved surface does not exist, and a copper matrix formed by a copper powder melt and an impregnated zirconium microalloyed copper block melt exists in a spiral continuous whole, so that the mechanical strength of the composite material is improved, and the defect of poor mechanical property of the whole composite material caused by weak van der Waals force between graphene sheets in the graphene film/copper layered composite material prepared by conventional layer-by-layer stacking is overcome.
4. According to the invention, the zirconium microalloyed copper is introduced into the spiral gap through an air pressure infiltration method, and the microalloyed elements in the zirconium microalloyed copper are basically partially gathered at the interface due to the interface reaction with the graphene film, so that the heat-conducting property of the copper matrix is not reduced, and the heat-conducting property of the spiral graphene film/copper laminated composite material is further ensured.
The technical solution of the present invention is further described in detail by the accompanying drawings and examples.
Drawings
Fig. 1 is a schematic diagram of a process for preparing a helical graphene film/copper layered composite material according to the present invention.
Fig. 2 is a cross-sectional SEM image of the helical graphene film/copper layered composite prepared in example 1 of the present invention.
Fig. 3 is a cross-sectional SEM image of the helical graphene film/copper layered composite prepared in comparative example 1 of the present invention.
Detailed Description
Example 1
As shown in fig. 1, the present embodiment includes the following steps:
step one, preparing a high-orientation graphene film preform:
101, bonding a highly-oriented graphene film with the thickness of 100 microns with a hot-melt pressure-sensitive double-sided adhesive with the thickness of 80 microns, and then curling to form a graphene film spirally-distributed cylinder;
102, putting the graphene film spiral distribution cylinder formed in the step 101 into a graphite mold, then heating the graphene film spiral distribution cylinder in an air atmosphere at 600 ℃, and ultrasonically cleaning the graphene film spiral distribution cylinder by using ethanol to obtain a graphene film spiral body;
103, putting the graphene film spiral body obtained in the step 102 and a graphite mold into copper powder ethanol slurry together for ultrasonic soaking, so that copper powder enters gaps of the graphene spiral body, and obtaining a high-orientation graphene film prefabricated body; the particle size of copper powder in the copper powder ethanol slurry is 5-20 microns;
step two, preparing the zirconium microalloyed copper block: smelting high-purity copper with the mass purity of 99.99 percent and high-purity zirconium with the mass purity of 99.99 percent for more than three times by adopting a vacuum induction smelting method to obtain a zirconium microalloyed copper block; the mass content of the zirconium element in the zirconium microalloyed copper block is 0.4 percent;
step three, preparing the graphene film/copper laminated composite material by air pressure infiltration:
301, putting the high-orientation graphene film preform obtained in the step 103 and a graphite mold into a quartz crucible, and putting the zirconium microalloyed copper block prepared in the step two above the graphite mold;
step 302, transferring the graphite mold with the zirconium microalloyed copper block in the step 301 to a heating area of gas pressure permeation equipment, vacuumizing a furnace chamber of the gas pressure permeation equipment until the vacuum degree is lower than 0.1Pa, performing electromagnetic induction to 1150 ℃, and preserving heat for 30 min;
and step 303, after the heat preservation in the step 302 is finished, immediately filling argon with the mass purity of 99.999% into a furnace chamber of the gas pressure permeation equipment until the pressure is 1.2MPa, preserving heat and maintaining pressure for 30min, then immediately closing a heating power supply, and cooling to room temperature along with the furnace to obtain the spiral graphene film/copper layered composite material.
Fig. 2 is a cross-sectional SEM image of the helical graphene film/copper layered composite material prepared in this example, and it can be seen from fig. 2 that the graphene film and copper in the helical graphene film/copper layered composite material are alternately and uniformly distributed, and the interface bonding between the graphene film and the copper is good, which indicates that the present invention uses an air pressure infiltration method to immerse the zirconium microalloyed copper block melt into the spiral gap of the highly oriented graphene film preform for modification, and the wettability between copper and the graphene film is improved by the interface reaction, the flow resistance of molten copper is reduced, the uniform distribution of the graphene film is promoted, and the interface bonding strength and the thermal conductivity of the composite material are improved.
Comparative example 1
This comparative example comprises the following steps:
step one, preparing a high-orientation graphene film preform:
101, bonding a highly-oriented graphene film with the thickness of 100 microns with a hot-melt pressure-sensitive double-sided adhesive with the thickness of 80 microns, and then curling to form a graphene film spirally-distributed cylinder;
102, putting the graphene film spiral distribution cylinder formed in the step 101 into a graphite mold, then heating the graphene film spiral distribution cylinder in an air atmosphere at 600 ℃, and ultrasonically cleaning the graphene film spiral distribution cylinder by using ethanol to obtain a graphene film spiral body;
103, placing the graphene film spiral body obtained in the step 102 into copper powder ethanol slurry for ultrasonic soaking, so that copper powder enters gaps of the graphene spiral body, and obtaining a high-orientation graphene film prefabricated body; the particle size of copper powder in the copper powder ethanol slurry is 5-20 microns;
step two, preparing the graphene film/copper laminated composite material by air pressure infiltration:
step 201, placing the highly-oriented graphene film preform obtained in step 103 and a graphite mold into a quartz crucible, and placing a copper block with the mass purity of 99.99% above the graphite mold;
step 202, transferring the graphite mold with the copper block placed in the step 201 to a heating area of gas pressure permeation equipment, then vacuumizing a furnace chamber of the gas pressure permeation equipment until the vacuum degree is lower than 0.1Pa, performing electromagnetic induction heating to 1150 ℃, and preserving heat for 30 min;
and 203, after the heat preservation in the step 202 is finished, immediately filling argon with the mass purity of 99.999% into a furnace chamber of the gas pressure permeation equipment until the pressure is 1.2MPa, preserving heat and maintaining pressure for 30min, then immediately closing a heating power supply, and cooling to room temperature along with the furnace to obtain the spiral graphene film/copper layered composite material.
Fig. 3 is a cross-sectional SEM image of the helical graphene film/copper layered composite material prepared in the present comparative example, and it can be seen from fig. 3 that the graphene film and copper in the helical graphene film/copper layered composite material are not uniformly distributed, the interface bonding is not good, and a gap exists at the interface, indicating that the wettability between copper and the graphene film is poor, the interface bonding and the distribution state of the graphene film are deteriorated, and the interface bonding strength and the thermal conductivity of the composite material are not improved.
Comparing fig. 2 and fig. 3, it can be seen that the method of the present invention adds the microalloying element zirconium to the copper matrix by using the air pressure infiltration method, which is beneficial to the uniform distribution of the graphene film and improves the interface bonding of the spiral graphene film/copper laminated composite material.
Example 2
As shown in fig. 1, the present embodiment includes the following steps:
step one, preparing a high-orientation graphene film preform:
101, bonding a highly-oriented graphene film with the thickness of 70 microns with a hot-melt pressure-sensitive double-sided adhesive with the thickness of 80 microns, and then curling to form a graphene film spirally-distributed cylinder;
102, putting the graphene film spiral distribution cylinder formed in the step 101 into a graphite mold, then heating the graphene film spiral distribution cylinder in an air atmosphere at 500 ℃, and ultrasonically cleaning the graphene film spiral distribution cylinder by using ethanol to obtain a graphene film spiral body;
103, putting the graphene film spiral body obtained in the step 102 and a graphite mold into copper powder ethanol slurry together for ultrasonic soaking, so that copper powder enters gaps of the graphene spiral body, and obtaining a high-orientation graphene film prefabricated body; the particle size of copper powder in the copper powder ethanol slurry is 5-20 microns;
step two, preparing the zirconium microalloyed copper block: smelting high-purity copper with the mass purity of 99.99 percent and high-purity zirconium with the mass purity of 99.99 percent for more than three times by adopting a vacuum induction smelting method to obtain a zirconium microalloyed copper block; the mass content of the zirconium element in the zirconium microalloyed copper block is 0.7 percent;
step three, preparing the graphene film/copper laminated composite material by air pressure infiltration:
301, putting the high-orientation graphene film preform obtained in the step 103 and a graphite mold into a quartz crucible, and putting the zirconium microalloyed copper block prepared in the step two above the graphite mold;
step 302, transferring the graphite mold with the zirconium microalloyed copper block in the step 301 to a heating area of gas pressure permeation equipment, vacuumizing a furnace chamber of the gas pressure permeation equipment until the vacuum degree is lower than 0.1Pa, performing electromagnetic induction to 1200 ℃, and preserving heat for 20 min;
and step 303, after the heat preservation in the step 302 is finished, immediately filling argon with the mass purity of 99.999% into a furnace chamber of the gas pressure permeation equipment until the pressure is 1.5MPa, preserving heat and maintaining pressure for 20min, then immediately closing a heating power supply, and cooling to room temperature along with the furnace to obtain the spiral graphene film/copper layered composite material.
Example 3
As shown in fig. 1, the present embodiment includes the following steps:
step one, preparing a high-orientation graphene film preform:
101, bonding a highly-oriented graphene film with the thickness of 25 microns with a hot-melt pressure-sensitive double-sided adhesive with the thickness of 80 microns, and then curling to form a graphene film spirally-distributed cylinder;
102, putting the graphene film spiral distribution cylinder formed in the step 101 into a graphite mold, then heating the graphene film spiral distribution cylinder in an air atmosphere at 400 ℃, and ultrasonically cleaning the graphene film spiral distribution cylinder by using ethanol to obtain a graphene film spiral body;
103, putting the graphene film spiral body obtained in the step 102 and a graphite mold into copper powder ethanol slurry together for ultrasonic soaking, so that copper powder enters gaps of the graphene spiral body, and obtaining a high-orientation graphene film prefabricated body; the particle size of copper powder in the copper powder ethanol slurry is 5-20 microns;
step two, preparing the zirconium microalloyed copper block: smelting high-purity copper with the mass purity of 99.99 percent and high-purity zirconium with the mass purity of 99.99 percent for more than three times by adopting a vacuum induction smelting method to obtain a zirconium microalloyed copper block; the mass content of the zirconium element in the zirconium microalloyed copper block is 0.1 percent;
step three, preparing the graphene film/copper laminated composite material by air pressure infiltration:
301, putting the high-orientation graphene film preform obtained in the step 103 and a graphite mold into a quartz crucible, and putting the zirconium microalloyed copper block prepared in the step two above the graphite mold;
step 302, transferring the graphite mold with the zirconium microalloyed copper block in the step 301 to a heating area of gas pressure permeation equipment, vacuumizing a furnace chamber of the gas pressure permeation equipment until the vacuum degree is lower than 0.1Pa, performing electromagnetic induction to 1100 ℃ and preserving heat for 40 min;
and step 303, after the heat preservation in the step 302 is finished, immediately filling argon with the mass purity of 99.999% into a furnace chamber of the gas pressure permeation equipment until the pressure is 1MPa, preserving heat and maintaining pressure for 40min, then immediately turning off a heating power supply, and cooling to room temperature along with the furnace to obtain the spiral graphene film/copper laminated composite material.
The thermal conductivity of the helical graphene film/copper layered composite materials prepared in examples 1 to 3 of the present invention and comparative example 1 was compared with that of the graphene/copper layered composite material in the prior art, and the results are shown in table 1.
TABLE 1
In Table 1, vol% represents a volume percentage, and wt% represents a mass percentage.
Document 1, Xin Gao, et al, Mechanical properties and thermal conductivity of graphene re-expressed co-coater matrix composites [ J ]. Powder Technology,2016,301: 601-.
Document 2 Huaijie Cao, et al, Thermal properties of in situ grown graphene re-expressed coppermatrix expressed compositions [ J ]. Journal of Alloys and compositions 2019,771: 228-.
As can be seen from table 1, the graphene loading and the thermal conductivity of the helical graphene film/copper layered composite material prepared in examples 1 to 3 of the present invention are far higher than those of the prior art, and the thermal conductivity of the helical graphene film/copper layered composite material prepared in example 1 is also far higher than that of comparative example 1 under the same graphene loading, which indicates that the micro-alloying element is added to the copper matrix by using the air pressure infiltration method, so that the uniform distribution of the graphene film is facilitated, and the thermal conductivity of the composite material is greatly improved.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (6)
1. A method for preparing a helical graphene film/copper layered composite material, the method comprising the steps of:
step one, preparing a high-orientation graphene film preform:
101, bonding a highly-oriented graphene film with a hot-melt pressure-sensitive double-sided adhesive, and then curling to form a graphene film spirally-distributed cylinder;
102, putting the graphene film spiral distribution cylinder formed in the step 101 into a graphite mold, then heating the graphene film spiral distribution cylinder in an air atmosphere, and ultrasonically cleaning the graphene film spiral distribution cylinder by using ethanol to obtain a graphene film spiral body;
103, putting the graphene film spiral body obtained in the step 102 and a graphite mold into copper powder ethanol slurry together for ultrasonic soaking, so that copper powder enters gaps of the graphene spiral body, and obtaining a high-orientation graphene film prefabricated body;
step two, preparing the zirconium microalloyed copper block: smelting the raw material for preparing the zirconium microalloyed copper alloy by a vacuum induction smelting method for more than three times to obtain a zirconium microalloyed copper block; the mass content of the zirconium element in the zirconium microalloyed copper block is 0.1-0.7%;
step three, preparing the graphene film/copper laminated composite material by air pressure infiltration:
301, putting the high-orientation graphene film preform obtained in the step 103 and a graphite mold into a quartz crucible, and putting the zirconium microalloyed copper block prepared in the step two above the graphite mold;
step 302, transferring the graphite mold with the zirconium microalloyed copper block in the step 301 to a heating area of gas pressure permeation equipment, vacuumizing a furnace chamber of the gas pressure permeation equipment until the vacuum degree is lower than 0.1Pa, performing electromagnetic induction heating and preserving heat;
and 303, after the heat preservation in the step 302 is finished, immediately filling high-purity argon into a furnace chamber of the gas pressure permeation device, preserving heat and pressure, and then cooling to room temperature along with the furnace to obtain the spiral graphene film/copper laminated composite material.
2. The method of claim 1, wherein the thickness of the highly oriented graphene film in step 101 is 25 μm to 100 μm, and the thickness of the hot melt pressure sensitive double sided tape is 80 μm.
3. The method of claim 1, wherein the temperature of the heating step 102 is 400 ℃ to 600 ℃.
4. The method of claim 1, wherein the particle size of the copper powder in the copper powder ethanol slurry in step 103 is 5 μm to 20 μm.
5. The method for preparing the helical graphene film/copper laminated composite material according to claim 1, wherein the electromagnetic induction heating temperature in step 302 is 1100-1200 ℃, and the heat preservation time is 20-40 min.
6. The method of claim 1, wherein in step 303, the high-purity argon is introduced to a pressure of 1MPa to 1.5MPa, and the holding time is 20min to 40 min.
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