CN115072709B - Graphene heat conduction film and preparation method thereof - Google Patents
Graphene heat conduction film and preparation method thereof Download PDFInfo
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Abstract
The invention aims to provide a graphene heat conduction film and a preparation method thereof, wherein the preparation process of the graphene heat conduction film comprises the following steps: (1) Coating graphene oxide slurry to prepare a graphene oxide film; (2) Carrying out pore-forming treatment and toughening treatment on the graphene oxide film, and then rolling to obtain a porous graphene oxide film coiled material, wherein the pore size of the porous graphene oxide film coiled material is 80-300 mu m; (3) Placing the porous graphene oxide film coiled material into a graphite cylinder for high-temperature heat treatment; (4) And carrying out calendaring treatment on the porous graphene oxide film coiled material subjected to the high-temperature heat treatment to obtain the graphene heat conduction film. The graphene heat-conducting film realizes batch preparation in a coiled material form, so that the whole industrial production efficiency and cost are greatly improved, and the large-scale commercial application of the graphene heat-conducting film is further.
Description
Technical Field
The invention relates to the technical field of graphene heat conduction films, in particular to a coiled graphene heat conduction film and a preparation method thereof.
Background
Graphene (Graphene) is a kind of Graphene which is formed by sp 2 The heat conductivity of the new material with the hybridized connection carbon atoms closely stacked into a single-layer two-dimensional honeycomb lattice structure is as high as 5300W/m.K, and the new material is the highest in the currently known materials. By utilizing the characteristic of graphene, graphene oxide slurry is adopted as a raw material, and is prepared into products such as a graphene heat conducting film, a graphene temperature equalizing plate and the like through processes such as coating, heat treatment, graphitization recrystallization and calendaring, and the products are widely applied to industries such as mobile phones, computers, 5G base stations and military industry to solve the requirements of heat conduction, heat dissipation and the like in the field. At present, the graphene products prepared by the method are all commercially produced on a large scale, and direct economic benefits are generated.
However, because the graphene oxide structure contains a large amount of oxygen-containing functional groups, and the graphene oxide film prepared by the prior art is a microstructure densely stacked layer by layer, in the heat treatment process of the graphene oxide film, a large amount of heat is released or gases such as CO and CO2 are generated due to the rupture of chemical bonds of the oxygen-containing functional groups, so that the graphene film has serious problems of transverse shrinkage and volume expansion, and burst and even direct burning phenomena can occur in the coil preparation process. Therefore, the existing graphene heat-conducting film product is limited to be manufactured into a sheet for production and use, and cannot be produced in a large-scale coiled material form. Obviously, the industrial production efficiency of the product is greatly limited, and the waste of resources is caused, which is contrary to the policies of national green energy conservation and the like; meanwhile, the production cost is too high to be reduced, and large-scale commercial popularization of the products cannot be realized.
Patent CN113480328A provides a large-scale graphene heat-conducting rolled film and a preparation method thereof, which introduces a high-pore fiber fabric and nanocellulose into the graphene heat-conducting film, and establishes an exhaust channel inside the graphene film, so that active substances are discharged in the heat treatment process, and foaming and interfacial delamination of materials are reduced, thereby improving the production yield of the large-scale graphene heat-conducting rolled film, but the method can increase the complexity of the process, and the fiber fabric burns out after high-temperature treatment to laminate the graphene heat-conducting film, so that the heat-conducting performance of the graphene heat-conducting film is reduced.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide a preparation method of a graphene heat conduction film, and the graphene heat conduction film prepared by the method is directly in a coiled material form.
The aim of the invention is achieved by the following technical scheme:
(1) Coating graphene oxide slurry to prepare a graphene oxide film;
preparing graphene oxide film from graphene oxide slurry through continuous coating equipment, wherein the carbon-oxygen ratio of the graphene oxide slurry is 2-6: 1, the prepared graphene oxide film can be directly subjected to the next procedure, or can be rolled and stored firstly. The graphene oxide with the carbon-oxygen ratio in the size range can be selected to effectively ensure that the self-assembled film can be smoothly formed, and meanwhile, the forming and stable heat treatment of the porous graphene oxide film can be reasonably controlled, if the carbon-oxygen ratio is less than 2:1, the reaction in the pore-forming stage or the heat treatment stage is too severe due to the too high oxygen content, and the porous graphene oxide film or the graphene film coiled material cannot be formed completely; if the carbon-oxygen ratio is greater than 6:1, the self-assembly property of the graphene oxide slurry is deteriorated, and the graphene oxide film is not smoothly formed.
Preferably, the graphene oxide sheet diameter in the graphene oxide slurry is 60-230 mu m; and most preferably 120 to 160 μm. The graphene oxide with the sheet diameter range has the following beneficial effects: obtaining the graphene oxide film suitable for reasonable pore diameter control, wherein if the sheet diameter is smaller than 60 mu m, the mechanical strength of the graphene oxide film is too low, and the integrity of the porous graphene film is damaged due to severe bubble generation in the pore-forming stage; if the sheet diameter is larger than 230 mu m, a large number of folds are formed in the graphene oxide film, and then the control of the pore diameter in the pore-forming stage is affected. Typically, but not by way of limitation, the graphene oxide sheets have a diameter of 60 μm, 80 μm, 120 μm, 160 μm, 200 μm, 230 μm.
(2) Carrying out pore-forming treatment and toughening treatment on the graphene oxide film, and then rolling to obtain a porous graphene oxide film coiled material, wherein the pore size of the porous graphene oxide film coiled material is 80-300 mu m;
the pore-forming treatment refers to that a coiled material graphene oxide film passes through a first infiltration tank filled with a pore-forming agent, and a layered microstructure of the graphene oxide film which is densely stacked is opened to form holes which can counteract volume expansion in the high-temperature heat treatment process and facilitate effective discharge of gas (generated by behaviors such as deoxidation in the high-temperature heat treatment process).
The soaking time of the graphene oxide film passing through the first soaking pool is 30-300 s, more preferably 60-120 s. Typical, but non-limiting, soak times are 30s, 60s, 90s, 120s, 150s, 180s, 210s, 240s, 270s, 300s.
The pore diameter of the pore is influenced by factors such as the type and concentration of pore-forming agents, preferably, the pore-forming agents are one or more of hydrazine hydrate, dimethylhydrazine and other hydrazine reagents, and the reagents can be used for changing a layer-by-layer compact graphene oxide film into a microstructure containing a large number of pores; on the other hand, the reagent has stronger reducibility, and can also greatly improve the carbon-oxygen ratio of the graphene oxide film, and the two are very favorable for avoiding bursting or burning out of the coiled material graphene oxide film in the heat treatment process; the concentration of the pore-forming agent is 50-100%. If the concentration of the pore-forming agent is lower than 50%, the graphene oxide film cannot be reduced to a large extent to remarkably improve the carbon-oxygen ratio, and meanwhile, the production rate of bubbles is slow due to the slow reaction rate, and adjacent bubbles are too much aggregated to better control the formation of the target pore diameter.
The size of the pore size determines the integrity of the porous graphene film coiled material after high-temperature heat treatment to a large extent, and preferably, the pore size of the porous graphene oxide film coiled material is 80-300 mu m, more preferably, the pore size is 120-180 mu m. The pore size in this range has the following beneficial effects: the proper pore size can ensure the stable volume expansion of the porous graphene membrane in the heat treatment process to avoid bursting or burning of the graphene coiled material, and if the pore size is smaller than 80 mu m, the pore size is insufficient to counteract the volume expansion caused by excessive gas in a unit area; if the pore diameter is larger than 300 μm, the mechanical strength of the resulting porous graphene oxide coil is significantly reduced due to the excessively large pore diameter, and the coil becomes brittle, and cannot resist the impact of a large amount of gas generated by heat treatment.
After being reduced by hydrazine pore-forming agents, the carbon-oxygen ratio of the porous graphene oxide membrane coiled material is 20-70: 1, a step of; this means that the film will suffer less breakage of oxygen containing functional groups during the heat treatment stage, i.e. the gas yield is reduced and the risk of bursting or burning out the coil graphene is reduced.
The toughening treatment means that the graphene oxide film subjected to pore-forming treatment continuously passes through a second infiltration tank containing a toughening agent to improve the toughness of the film material so as to better resist shrinkage or expansion phenomenon in the heat treatment process of the graphene oxide film, and the continuously infiltrated graphene oxide film is introduced into a tunnel at the temperature of 40-80 ℃ through a roller to be dried and shaped and then wound, so that the porous graphene oxide film coiled material is obtained.
The soaking time of the graphene oxide film passing through the second soaking pool is 10-120 s, more preferably 60-90 s. Typical, but non-limiting, soak times are 10s, 30s, 60s, 90s, 120s.
The toughening agent is an aqueous solution with high content of metal cations, and further, the metal ions are Fe 2+ 、Fe 3+ 、Co 2+ 、Ni + 、Cu 2+ 、Ca 2+ And the like, which can be crosslinked with graphene oxide to improve the tensile strength of the whole membrane material.
(3) Placing the porous graphene oxide film coiled material into a graphite cylinder for high-temperature heat treatment;
the diameter of the graphite cylinder is 1-3 mm larger than that of the porous graphene oxide film coiled material, and the graphite cylinder can inhibit further expansion of the graphene film in the sintering graphitization process.
The high-temperature heat treatment is sectional heat treatment under the protection of inert gas; specifically, the temperature of the first section is firstly increased to 600-1200 ℃ from room temperature, the heating rate is 1-3 ℃/min, and the temperature is kept for 3-8 hours; the temperature of the second stage is increased to 1200-2000 ℃, the temperature rising rate is 3-8 ℃/min, and the temperature is kept for 3-8 h; and the temperature of the third section is increased to 2000-3200 ℃, the temperature rising rate is 5-10 ℃/min, and the temperature is kept for 1-3 h. The sectional heat treatment can effectively control the gas release speed in the porous graphene oxide coiled material to finally obtain the graphene coiled material with a complete structure, and meanwhile, the heat treatment mode solves the efficiency problem of a multistage heat treatment process requiring oven pretreatment, carbonization furnace treatment and graphitization furnace treatment in the prior art.
Further, the inert gas is one or more of argon, nitrogen, helium and the like.
(4) And carrying out rolling treatment on the porous graphene oxide film coiled material subjected to the high-temperature heat treatment to obtain the graphene heat conduction film, wherein the rolling mode is vacuum rolling, the vacuum condition is 1-5 Pa, and the rolling pressure is 100-300 MPa.
By adopting the preparation method, the continuous production of the large-sheet-diameter graphene heat conduction film can be realized, and the prepared graphene heat conduction film is in the form of coiled material, and has the density of 1.6-2.2 g/cm 3 The thermal conductivity is 800-2000W/m.K.
The invention has the beneficial effects that:
(1) According to the invention, through a unique pore-forming process before the graphene heat-conducting film heat treatment, hole spaces capable of counteracting volume expansion are manufactured in the internal structure of the graphene oxide film, and meanwhile, the holes are beneficial to effectively discharging gas in the graphene oxide film heat treatment process, so that the situation that the graphene heat-conducting film coiled material bursts or burns out in the existing preparation process is fundamentally solved.
(2) Compared with the existing graphene heat-conducting film heat treatment process, the method introduces unique holes in the graphene oxide film structure which is densely stacked layer by layer to offset the problems of volume expansion and the like in the heat treatment (particularly in the low-temperature severe deoxidation stage), and the graphene oxide film coiled material manufactured by the method does not need to be subjected to pretreatment in a low-temperature section (the heat treatment temperature is less than 200 ℃) to ensure the integrity of the material. Therefore, the method reduces the energy consumption in the production process of the graphene heat-conducting film and improves the production efficiency.
(3) The method disclosed by the invention is tightly carried out around the graphene material, does not involve the assistance of any polymer fiber fabric, nanocellulose and polyimide film (PI), and avoids the influence of the materials on the heat conduction performance of the graphene heat conduction film finished product and reduces the complexity of the production process.
(4) The graphene heat-conducting film provided by the invention can be subjected to continuous die cutting and forming to form the required shape by a conventional cutting means, has no obvious difference in performance from the graphene heat-conducting film produced in the prior art, realizes batch preparation in a coiled material form, greatly improves the whole industrial production efficiency and cost, and can be further applied to large-scale commercialization.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, and that other drawings can be obtained according to these drawings without inventive faculty for a person skilled in the art.
Fig. 1 is a schematic diagram of the principle of counteracting volume expansion and exhausting gas by the micro-porous structure of the coiled graphene heat-conducting film.
Fig. 2 is a microstructure of a cross section of a non-porous graphene oxide film in comparative example 4 of the present invention.
Detailed Description
The present invention is further described below with reference to examples and fig. 1 for the understanding of those skilled in the art, and the description of the embodiments is not intended to limit the present invention.
The following are the specific examples section:
example 1
(1) Large-size graphene oxide (purchased from Kunming cloud Sibori technology Co., ltd.) with the particle size distribution D50 of 133.4 μm is selected to prepare coating slurry, and a dense graphene oxide film is prepared through continuous coating equipment coating, drying, stripping, rolling and other processes, and the carbon-oxygen ratio is measured to be 4.6:1.
(2) Placing the compact graphene oxide film into a first infiltration tank filled with 60wt% of hydrazine hydrate through a simple winding and unwinding device, and infiltrating for 60s, wherein the compact graphene oxide film is gradually thickened, and a large number of holes are formed in a microstructure; continue to pass through the Fe 2+ And (3) soaking the solution in a second soaking tank for 60 seconds, and then, completely drying in a drying tunnel with the constant temperature of 50 ℃ and rolling for standby. The SEM test results show that the average pore diameter of the porous graphene oxide film obtained in this stage is 140.3 μm, and the carbon-oxygen ratio is 56:1.
(3) Placing the porous graphene oxide film coiled material into a graphite cylinder with the coiling diameter of 1mm, placing the graphite cylinder and the graphite cylinder into a high-temperature furnace continuously protected by argon, and setting a heating program: in the first stage, the temperature is raised to 800 ℃ from room temperature, the heating rate is 1 ℃/min, and the temperature is kept for 5 hours; in the second stage, the temperature is increased from 800 ℃ to 1500 ℃, the heating rate is 2 ℃/min, and the temperature is kept for 6 hours; in the third stage, the temperature is raised from 1500 ℃ to 3200 ℃, the heating rate is 5 ℃/min, and the temperature is kept for 1h. Obtaining the porous graphene film coiled material with complete structure and bubble-free surface, wherein the average density is0.26 g/cm 3 The heat conductivity coefficient is more than 250W/mK.
(4) And further calendaring the porous graphene film coiled material under the vacuum degree of 1Pa and the pressure of 180MPa to obtain the graphene heat-conducting film in the coiled material form.
The density of the graphene heat conduction film finished product is measured to be 2.0g/cm by a conventional density detection means and a relaxation-resistant 467 heat conduction coefficient meter 3 The heat conductivity coefficient is more than 1900W/mK.
Example 2
(1) Large-size graphene oxide (purchased from Kunming cloud Sibori technology Co., ltd.) with the particle size distribution D50 of 172.3 μm is selected to prepare coating slurry, and a dense graphene oxide film is prepared through continuous coating equipment coating, drying, stripping, rolling and other processes, and the carbon-oxygen ratio is measured to be 4.8:1.
(2) The same pore-forming treatment and toughening treatment as in example 1 were carried out, and the average pore diameter of the porous graphene oxide film was 149.2 μm and the carbon-oxygen ratio was 61:1.
(3) The same high temperature heat treatment as in example 1 was conducted to obtain a porous graphene film roll material having a complete structure and no bubbles on the surface, and the average density was 0.31g/cm 3 The heat conductivity coefficient is more than 280W/mK.
(4) The same calendaring treatment as in example 1 was carried out, and the measured density of the graphene heat-conducting film finished product was 1.8 g/cm 3 The heat conductivity coefficient is more than 1700W/mK.
Example 3
(1) The same as in example 1.
(2) Placing the compact graphene oxide film into a first infiltration tank filled with 60wt% of dimethylhydrazine through a simple winding and unwinding device, and infiltrating for 60s, wherein the compact graphene oxide film is gradually thickened, and a large number of holes are formed in a microstructure; continue to pass through the Fe 2+ And (3) soaking the solution in a second soaking tank for 60 seconds, and then, completely drying in a drying tunnel with the constant temperature of 50 ℃ and rolling for standby. The SEM and XPS tests were conducted to obtain the microstructure and carbon-oxygen ratio of the porous graphene oxide film at this stage, and the SEM test results revealed that the average pore diameter of the porous graphene oxide film obtained at this stage was 113.2 μm and the carbon-oxygen ratio was 44:1。
(3) The same high temperature heat treatment as in example 1 was conducted to obtain a porous graphene film roll material with a complete structure and no bubbles on the surface, and the average density was 0.22 g/cm 3 The heat conductivity coefficient is more than 230W/mK.
(4) The same calendaring treatment as in example 1 was carried out, and the measured density of the graphene heat-conducting film finished product was 1.9g/cm 3 The heat conductivity coefficient is more than 1500W/mK.
Example 4
(1) The same as in example 1.
(2) Placing the compact graphene oxide film into a first infiltration tank filled with 80wt% of hydrazine hydrate through a simple winding and unwinding device, and infiltrating for 60s, wherein the compact graphene oxide film is gradually thickened, and a large number of holes are formed in a microstructure; continue to pass through the Fe 2+ And (3) soaking the solution in a second soaking tank for 60 seconds, and then, completely drying in a drying tunnel with the constant temperature of 50 ℃ and rolling for standby. The SEM test results show that the average pore diameter of the porous graphene oxide film obtained in this stage of this example is 126.6 μm, and the carbon-oxygen ratio is 68:1.
(3) The same high temperature heat treatment as in example 1 was conducted to obtain a porous graphene film roll material having a complete structure and no bubbles on the surface, and the average density was 0.48g/cm 3 The heat conductivity coefficient is more than 300/mK.
(4) The same rolling treatment as in example 1 was carried out, and the measured density of the graphene heat-conducting film finished product was 2.0g/cm 3 The heat conductivity coefficient is more than 1200W/mK.
Example 5
(1) The same as in example 1.
(2) Placing the compact graphene oxide film into a first infiltration tank filled with 60wt% of hydrazine hydrate through a simple winding and unwinding device, and infiltrating for 120s, wherein the compact graphene oxide film becomes thicker gradually, and a large number of holes are formed in a microstructure; continue to pass through the Fe 2+ And (3) soaking the solution in a second soaking tank for 120 seconds, and then, completely drying in a drying tunnel with constant temperature of 50 ℃ and rolling for standby. Cutting test for SEM and XPS to obtain porous oxidation at this stageThe microstructure and carbon-oxygen ratio of the graphene film, and the SEM test result show that the average pore diameter of the porous graphene oxide film obtained in this stage of this example is 170.8 μm, and the carbon-oxygen ratio is 63:1.
(3) The same high temperature heat treatment as in example 1 was conducted to obtain a porous graphene film roll material having a complete structure and no bubbles on the surface, and the average density was 0.32g/cm 3 The heat conductivity coefficient is more than 200/mK.
(4) The same rolling treatment as in example 1 was carried out, and the measured density of the graphene heat-conducting film finished product was 2.0g/cm 3 The heat conductivity coefficient is more than 1300W/mK.
Example 6
(1) Large-size graphene oxide (purchased from Kunming cloud Sichuan Rui technology Co., ltd.) with the sheet diameter particle size distribution D50 of 60.6 μm is selected to prepare coating slurry, and the coating slurry is coated, dried, peeled off, rolled and other processes are carried out by continuous coating equipment to prepare a compact graphene oxide coiled material, and the carbon-oxygen ratio is measured to be 5.8:1.
(2) Placing the compact graphene oxide film into a first infiltration tank filled with 60wt% of hydrazine hydrate through a simple winding and unwinding device, and infiltrating for 120s, wherein the compact graphene oxide film becomes thicker gradually, and a large number of holes are formed in a microstructure; continue to pass through the Fe 2+ And (3) soaking the solution in a second soaking tank for 120 seconds, and then, completely drying in a drying tunnel with constant temperature of 50 ℃ and rolling for standby. The SEM test results show that the average pore diameter of the porous graphene oxide film obtained in this stage is 125.3 μm, and the carbon-oxygen ratio is 67:1.
(3) The same high temperature heat treatment as in example 1 was conducted to obtain a porous graphene film roll material having a complete structure and no bubbles on the surface, and the average density was 0.56g/cm 3 The heat conductivity coefficient is more than 230/mK.
(4) The same rolling treatment as in example 1 was carried out, and the measured density of the graphene heat-conducting film finished product was 2.0g/cm 3 The heat conductivity coefficient is more than 800W/mK.
Comparative example 1
(1) Graphene oxide with the sheet diameter distribution D50 of 40.2 mu m (purchased from Kunming Yuntian Rui technology Co., ltd.) is selected to prepare coating slurry, and the coating slurry is coated, dried, peeled and rolled by continuous coating equipment to prepare a compact graphene oxide coiled material, and the carbon-oxygen ratio is measured to be 3.8:1.
(2) The simple winding and unwinding device is used for winding and soaking the graphene oxide film in a first soaking pool containing 80% of hydrazine hydrate for 10s, so that the graphene oxide film is seriously crushed and cannot be dried and wound, and the subsequent process section treatment is finished.
Comparative example 2
(1) The same as in example 1.
(2) Placing the compact graphene oxide film into a first infiltration tank filled with 30wt% of hydrazine hydrate through a simple winding and unwinding device, and infiltrating for 5s, wherein the compact graphene oxide film is gradually thickened, and a certain hole is formed in a microstructure; continue to pass through the Fe 2+ And (3) soaking the solution in a second soaking tank for 60 seconds, and then, completely drying in a drying tunnel with the constant temperature of 50 ℃ and rolling for standby. The test for SEM and XPS was performed to obtain the microstructure and carbon-oxygen ratio of the porous graphene oxide film at this stage, and the SEM test result shows that the average pore diameter of the porous graphene oxide film obtained at this stage in this example is 56.3 μm, and the carbon-oxygen ratio is 19.6:1.
(3) The same high-temperature heat treatment as in example 1 was performed, and the graphene coiled material was broken into several pieces, and a complete and continuous graphene heat-conducting film coiled material could not be formed.
Comparative example 3
(1) The same as in example 1.
(2) Placing the coiled material into a first infiltration tank filled with 60wt% of sodium bicarbonate through a simple coiling and uncoiling device, and infiltrating for 5s, wherein the dense graphene oxide film is gradually thickened, and a certain hole is formed in a microstructure; continue to pass through the Fe 2+ And (3) soaking the solution in a second soaking tank for 60 seconds, and then, completely drying in a drying tunnel with the constant temperature of 50 ℃ and rolling for standby. The test for SEM and XPS was performed to obtain the microstructure and carbon-oxygen ratio of the porous graphene oxide film at this stage, and the SEM test result shows that the average pore diameter of the porous graphene oxide film obtained at this stage in this example is 90.2 μm, and the carbon-oxygen ratio is 5.9:1.
the same high-temperature heat treatment as in example 1 was performed, and the high-temperature heat treatment furnace was a frying furnace, and the graphene film coil was burned seriously.
Comparative example 4
(1) The same as in example 1.
(2) Placing the materials into a graphite cylinder with the diameter of 1mm larger than the self-rolling diameter, placing the materials into a high-temperature furnace continuously protected by argon, and setting a temperature-raising program: in the first stage, the temperature is raised to 800 ℃ from room temperature, the heating rate is 1 ℃/min, and the temperature is kept for 5 hours; in the second stage, the temperature is increased from 800 ℃ to 1500 ℃, the heating rate is 2 ℃/min, and the temperature is kept for 6 hours; in the third stage, the temperature is raised from 1500 ℃ to 3200 ℃, the heating rate is 5 ℃/min, and the temperature is kept for 1h.
The high-temperature heat treatment furnace is used for frying, and the graphene film coiled material is seriously burnt.
Comparative example 5
(1) The same as in example 1.
(2) The same as in example 1.
(3) And (3) placing the graphene coiled material into a graphite cylinder with the diameter of 1mm larger than that of the self-coil, and placing the graphite cylinder and the graphite cylinder into a high-temperature furnace with continuous protection of argon, wherein the set temperature is directly increased to 3000 ℃ from room temperature, the heating rate is 0.5 ℃/min, and the graphene coiled material is seriously burnt.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above embodiments are preferred embodiments of the present invention, and besides, the present invention may be implemented in other ways, and any obvious substitution is within the scope of the present invention without departing from the concept of the present invention.
Claims (6)
1. The preparation method of the graphene heat conduction film is characterized by comprising the following steps of:
(1) Coating graphene oxide slurry to prepare a graphene oxide film, wherein the size of graphene oxide sheets in the graphene oxide slurry is 60-230 mu m;
(2) The graphene oxide film is subjected to pore-forming treatment and toughening treatment and then rolled to obtain a porous graphene oxide film coiled material, wherein the pore size of the porous graphene oxide film coiled material is 80-300 mu m, the pore-forming treatment is to pass the graphene oxide film through a first infiltration tank containing a pore-forming agent, the pore-forming agent is one or more of hydrazine reagents, the concentration of the pore-forming agent is 50-100%, the toughening treatment is to pass the graphene oxide film through a second infiltration tank containing a toughening agent, and the toughening agent is an aqueous solution with high content of metal cations;
(3) Placing the porous graphene oxide film coiled material into a graphite cylinder, and performing high-temperature heat treatment, wherein the high-temperature heat treatment is sectional heat treatment under the protection of inert gas, specifically, the temperature of the first section is firstly increased to 600-1200 ℃ from room temperature, the heating rate is 1-3 ℃/min, and the temperature is kept for 3-8 hours; the temperature of the second stage is increased to 1200-2000 ℃, the temperature rising rate is 3-8 ℃/min, and the temperature is kept for 3-8 h; the temperature of the third section is increased to 2000-3200 ℃, the temperature rising rate is 5-10 ℃/min, and the temperature is kept for 1-3 h;
(4) And carrying out calendaring treatment on the porous graphene oxide film coiled material subjected to the high-temperature heat treatment to obtain the graphene heat conduction film.
2. The method for preparing the graphene heat conducting film according to claim 1, wherein the method comprises the following steps: the pore size of the porous graphene oxide membrane coiled material is 120-180 mu m.
3. The method for preparing the graphene heat conducting film according to claim 1, wherein the method comprises the following steps: the time for passing through the first infiltration tank is 30-300 s.
4. The method for preparing the graphene heat conducting film according to claim 1, wherein the method comprises the following steps: the time for passing through the second infiltration tank is 10-120 s.
5. The method for preparing the graphene heat conducting film according to claim 1, wherein the method comprises the following steps: the diameter of the graphite cylinder is 1-3 mm larger than that of the porous graphene oxide film coiled material.
6. A graphene thermal conductive film prepared according to any one of claims 1-5, characterized in that: the density of the graphene heat conduction film is 1.6-2.2 g/cm 3 The thermal conductivity is 800-2000W/m.K.
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