CN112520731B - Preparation method and production line of graphene heat-conducting film - Google Patents

Preparation method and production line of graphene heat-conducting film Download PDF

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CN112520731B
CN112520731B CN202011554657.4A CN202011554657A CN112520731B CN 112520731 B CN112520731 B CN 112520731B CN 202011554657 A CN202011554657 A CN 202011554657A CN 112520731 B CN112520731 B CN 112520731B
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CN112520731A (en
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陈云
丁树权
高增光
肖嘉薇
吴然皓
陈新
陈桪
高健
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Guangdong University of Technology
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Abstract

本发明公开了一种石墨烯导热膜的制备方法和生产线,涉及导热器件制备领域。一种石墨烯导热膜的制备方法,包括如下步骤:S1:将碳源和导热增强剂搅拌混合均匀;S2:对混合后的碳源和导热增强剂进行放电加工,得到掺杂石墨烯片;S3:对掺杂石墨烯片进行筛选,得到石墨烯粗片;S4:对石墨烯粗片进行清洗干燥;S5:将清洗干燥后的石墨烯粗片和N‑甲基吡咯烷酮溶液进行调配,得到碳浓浆;S6:将碳浓浆刮涂成石墨烯膜;S7:对石墨烯膜进行放电热压处理,得到石墨烯导热膜。以将广泛碳源进行加工、制备导热薄膜,为解决下一代电子器件的散热问题提供解决方案,满足了易操作、高效率、低成本的产业需求。

Figure 202011554657

The invention discloses a preparation method and production line of a graphene heat-conducting film, and relates to the field of preparation of heat-conducting devices. A method for preparing a graphene thermally conductive film, comprising the following steps: S1: stirring and mixing a carbon source and a thermally conductive enhancer evenly; S2: performing electrical discharge machining on the mixed carbon source and thermally conductive enhancer to obtain a doped graphene sheet; S3: screen the doped graphene sheets to obtain graphene rough sheets; S4: wash and dry the graphene rough sheets; S5: prepare the cleaned and dried graphene rough sheets and N-methylpyrrolidone solution to obtain carbon thick slurry; S6: scrape the carbon thick slurry to form a graphene film; S7: perform discharge hot pressing treatment on the graphene film to obtain a graphene thermally conductive film. To process a wide range of carbon sources and prepare a thermally conductive film, it provides a solution to the heat dissipation problem of the next generation of electronic devices, and meets the industrial needs of easy operation, high efficiency and low cost.

Figure 202011554657

Description

Preparation method and production line of graphene heat-conducting film
Technical Field
The invention relates to the field of preparation of heat-conducting devices, in particular to a preparation method and a production line of a graphene heat-conducting film.
Background
With the problem of large heat generation caused by the increasing functionalization and miniaturization of electronic components, the accumulation of heat has a serious impact on the service life of electronic equipment, and especially with the arrival of the 5G era, higher requirements are put forward on the heat dissipation management performance in communication. Conventional thermal management materials are mainly copper-based, aluminum-based and silver-based metal materials, which have the advantages of good thermal conductivity and easy processing, however, since metal materials have higher density values, non-metallic thermal conductive materials are more suitable in some applications requiring a small weight. In recent years, non-metallic heat conductive materials have been increasingly enriched with intensive research, especially carbon-based materials such as diamond thin films, highly oriented pyrolytic graphene, graphitized polyimide, and the like. Graphene as a typical representative of the carbon material is sp2A dense stack of monolayers of hybridized carbon atoms. The graphene has ultrahigh inherent thermal conductivity of 3500-5300W/m.K and 2630m2The graphene-based material has the advantages of large specific surface area per gram, low atomic mass, flexibility and firm bonding force, so that the graphene-based material can be used for developing a heat conducting film, is expected to meet the heat dissipation requirements of new-generation electronic equipment, and is easy for industrial production.
Chinese patent CN111252759A discloses a method for preparing graphene oxide by peeling graphene/amorphous carbon in liquid phase by light irradiation, and the yield of graphene oxide is affected by the preparation of electrolyte. Chinese patent CN110256981A discloses a preparation and structure of graphene thermal conductive film, which has a complex structure, needs to improve the structural integrity, and is not easy to be produced in mass.
Therefore, the development of the mass production method of the graphene-based heat-conducting film can provide a solution for solving the heat dissipation problem of the next-generation electronic device, and is an application approach for widening graphene materials, and meanwhile, the production cost is reduced.
Disclosure of Invention
In view of the above defects, the present invention provides a method and a production line for manufacturing a graphene thermal conductive film, so as to process a wide range of carbon sources and manufacture a thermal conductive film, to provide a solution for solving the heat dissipation problem of the next generation of electronic devices, and to meet the industrial requirements of easy operation, high efficiency and low cost.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention discloses a preparation method of a graphene heat-conducting film, which comprises the following steps:
s1: uniformly stirring and mixing a carbon source and a heat conduction reinforcing agent;
s2: performing discharge machining on the mixed carbon source and the heat conduction reinforcing agent to obtain a doped graphene sheet;
s3: screening the doped graphene sheets to obtain graphene rough sheets;
s4: cleaning and drying the graphene rough sheet;
s5: mixing the cleaned and dried graphene coarse sheets with an N-methyl pyrrolidone solution to obtain carbon dense slurry;
s6: coating the carbon thick slurry into a graphene film in a blade mode;
s7: and carrying out discharge hot-pressing treatment on the graphene film to obtain the graphene heat-conducting film.
Further, the method of performing the electrical discharge machining on the mixed carbon source and the thermal conductivity enhancer in the step S2 is: and (3) loading the mixed carbon source and heat conduction reinforcing agent into a plurality of heat insulation bottles, and sequentially carrying out alternating current electric discharge machining on the plurality of heat insulation bottles to convert the carbon source and the heat conduction reinforcing agent into doped graphene sheets.
Further, the method for cleaning the graphene rough sheet in the step S4 is as follows: firstly, diluted hydrochloric acid with the concentration of 10-20% is used for cleaning, and then N-methyl pyrrolidone is used for cleaning.
Further, the method for blending carbon dense slurry in step S5 is: mixing the graphene crude sheet and the N-methyl pyrrolidone solution in a mass ratio of 5-10: 1, and stirring in a stirrer for 2-5 h.
Further, the graphene film is subjected to the discharge heating and pressing treatment in step S7 by using joule heat to heat, wherein the hot pressing voltage is set to 10V to 100V, the hot pressing capacitance is set to 10mF to 200mF, the hot pressing pressure is set to 20 to 30Mpa, and the processing time is 1h to 3 h.
Further, in the step S1, the resistance of the mixed carbon source and the thermal conductivity enhancer is 1 to 100 Ω.
The invention also discloses a production line of the graphene heat-conducting film, which is applied to the preparation method of the graphene heat-conducting film, and the production line comprises a first conveyor belt, a second conveyor belt, a heat-insulating bottle, a computer, and an electric discharge machining mechanism, a sorting mechanism, a cleaning mechanism, a drying mechanism, a thick slurry blending mechanism, a blade coating mechanism and an electric discharge hot-pressing mechanism which are sequentially arranged; the heat insulation bottle is used for storing the mixed carbon source and the heat conduction reinforcing agent; the first conveyor belt is used for conveying the heat insulation bottles; the electric discharge machining mechanism is used for carrying out electric discharge machining on the heat insulation bottle on the first conveyor belt to obtain doped graphene sheets; the second conveyor belt is used for conveying the doped graphene sheets poured out of the heat insulation bottle; the sorting mechanism is used for screening out graphene rough sheets from the doped graphene sheets on the second conveyor belt; the cleaning mechanism is used for cleaning and drying the graphene rough sheet; the thick slurry preparing mechanism is used for preparing thick carbon slurry; the blade coating mechanism is used for blade coating the carbon dense slurry into a graphene film; the discharge hot-pressing mechanism is used for performing discharge hot-pressing treatment on the graphene film to prepare a graphene heat-conducting film; and the computer is used for carrying out production cycle control on the electric discharge machining mechanism and the electric discharge hot-pressing mechanism.
Furthermore, two ends of the heat insulation bottle are respectively provided with a metal electrode, a first electrical interface and a fixing ring, and the first electrical interfaces at the two ends are respectively electrically connected with the metal electrodes at the same end; the electric discharge machining mechanism comprises a temperature sensing module and a first electric cabinet; the temperature sensing module is used for detecting the temperature of the heat insulation bottle; the first electrical cabinet is provided with a first flourishing discharge capacitor group and a first high-voltage power supply, the first flourishing discharge capacitor group is provided with a second electrical interface, and the first high-voltage power supply is electrically connected with the first flourishing capacitor group; the temperature sensing module and the first high-voltage power supply are respectively in communication connection with the computer; the two first conveyor belts are arranged side by side; the heat insulation bottles are sequentially arranged on the first conveying belt, and fixing rings of the heat insulation bottles are fixedly connected with the first conveying belt on the same side respectively; the plurality of first electrical cabinets are sequentially arranged beside the first conveyor belt, and the second electrical interfaces of the first container groups are electrically connected with the first electrical interfaces of the corresponding heat insulation bottles respectively; the charge-discharge capacitor groups sequentially carry out alternate discharge; and if the computer detects that the temperature peak value of a certain heat insulation bottle is lower than 3000K, the computer controls the first capacitor containing group corresponding to the heat insulation bottle to discharge again until the heat insulation bottle reaches the temperature peak value of 3000K.
Further, the sorting mechanism comprises a blower, an ultrasonic transducer, a distributor and an ultrasonic generator; the blower is arranged on one side of the second conveyor belt, and the plurality of ultrasonic transducers are arranged on the other side of the second conveyor belt opposite to the blower; the air blower is provided with a plurality of air outlets, and the air outlets are arranged towards the opposite side of the second conveyor belt; the ultrasonic generator distributes ultrasonic waves into a plurality of ultrasonic transducers through a distributor.
Further, the discharge hot-pressing mechanism comprises a hot-pressing upper die, a hot-pressing lower die, a vacuum cavity and a second electrical cabinet; the second electrical cabinet is provided with a second full discharge capacitor group and a second high-voltage power supply; the hot-pressing upper die and the hot-pressing lower die are arranged in the vacuum cavity in an up-down opposite manner; the second container group is electrically connected with the hot pressing upper die and the hot pressing lower die respectively; the second high-voltage power supply is electrically connected with the second holding capacitor group; the second high-voltage power supply is in communication connection with the computer.
According to the preparation method of the graphene heat-conducting film, provided by the invention, an electric field is utilized to carry out a chemical carbonization process and a physical stripping process, the binding force of a graphite layer is overcome, and carbonized graphite carbon is successfully stripped into a sheet layer, so that the preparation method can be applied to almost all carbon-containing carbon sources. Meanwhile, the method utilizes discharge machining and heat conduction enhancer for auxiliary catalysis, so that carbon source carbonization and stripping are controllably completed, the method is suitable for a large part of non-carbonized carbon-containing carbon sources, the high heat conduction of graphene film products is guaranteed, the variety of the carbon sources for machining is expanded, the requirements of environmental protection, low cost, high efficiency, sustainable development and the like are further met, and an effective solution is provided for the large-scale preparation of high-quality high-efficiency graphene. Furthermore, the method has high process feasibility and continuity, can realize automation for most parts, is easy to integrate in the existing production line, greatly saves labor cost and ensures the safety of industrial production.
According to the production line of the graphene heat-conducting film, provided by the invention, the first conveyor belt, the second conveyor belt, the heat-insulating bottle, the computer, the sequential electric discharge machining mechanism, the sorting mechanism, the cleaning mechanism, the drying mechanism, the thick slurry blending mechanism, the blade coating mechanism and the electric discharge hot pressing mechanism are integrated, the automation degree is high, the labor cost is greatly saved, and the industrial production safety is ensured. The production rhythm control is carried out on the electric discharge machining mechanism and the electric discharge hot-pressing mechanism through the computer, voltage control and current control are achieved, the circuit stability of the production line is greatly improved, and the machining quality is optimized.
Drawings
Fig. 1 is a schematic flow chart of a method for preparing a graphene thermal conductive film according to the present invention;
fig. 2 is a schematic structural diagram of a production line of a graphene thermal conductive film according to the present invention;
FIG. 3 is a schematic structural view of an electric discharge machining mechanism in an embodiment of the present invention;
FIG. 4 is a schematic diagram of the configuration of the sorting mechanism in one embodiment of the present invention;
fig. 5 is a schematic structural diagram of an electric discharge hot press mechanism in an embodiment of the present invention.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the accompanying drawings are illustrative only for the purpose of explaining the present invention, and are not to be construed as limiting the present invention.
In the description of the present invention, it is to be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "upper", "lower", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "axial", "radial", "circumferential", and the like, indicate orientations and positional relationships based on those shown in the drawings, and are used merely for convenience of description and for simplicity of description, and do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be considered as limiting the present invention. Furthermore, features defined as "first" and "second" may explicitly or implicitly include one or more of the features for distinguishing between descriptive features, non-sequential, non-trivial and non-trivial.
Referring to fig. 1, the invention discloses a preparation method of a graphene heat-conducting film, which comprises the following steps:
s1: uniformly stirring and mixing a carbon source and a heat conduction reinforcing agent;
s2: performing discharge machining on the mixed carbon source and the heat conduction reinforcing agent to obtain a doped graphene sheet;
s3: screening the doped graphene sheets to obtain graphene rough sheets;
s4: cleaning and drying the graphene rough sheet;
s5: mixing the cleaned and dried graphene coarse sheets with an N-methyl pyrrolidone solution to obtain carbon dense slurry;
s6: coating the carbon thick slurry into a graphene film in a blade mode;
s7: and carrying out discharge hot-pressing treatment on the graphene film to obtain the graphene heat-conducting film.
It should be noted that, in the embodiment of the present invention, the carbon source may be any one or more of biomass carbon material, hydrocarbon material, carbon material refined by processing, and plastic powder. The heat conduction enhancer can be formed by mixing any one or more of metal nitride, inorganic non-metallic material, metal simple substance and metal oxide. Wherein the biomass carbon material is selected from lignin, pine wood powder, straw powder, etc.; hydrocarbon materials such as coke, coal, anthracite, and the like; processed and refined carbon materials such as ketjen black, carbon black, etc.; plastic powders such as polypropylene, polystyrene, etc. Metal nitrides such as boron nitride, silicon nitride, aluminum nitride; inorganic non-metallic materials such as graphite, silicon carbide, carbon fiber, carbon nanotube; simple metal such as copper powder and aluminum powder; metal oxides such as aluminum oxide, zinc oxide.
According to the preparation method of the graphene heat-conducting film, provided by the invention, an electric field is utilized to carry out a chemical carbonization process and a physical stripping process, the binding force of a graphite layer is overcome, and carbonized graphite carbon is successfully stripped into a sheet layer, so that the preparation method can be applied to almost all carbon-containing carbon sources. Meanwhile, the method utilizes discharge machining and heat conduction enhancer for auxiliary catalysis, so that carbon source carbonization and stripping are controllably completed, the method is suitable for a large part of non-carbonized carbon-containing carbon sources, the high heat conduction of graphene film products is guaranteed, the variety of the carbon sources for machining is expanded, the requirements of environmental protection, low cost, high efficiency, sustainable development and the like are further met, and an effective solution is provided for the large-scale preparation of high-quality high-efficiency graphene. Furthermore, the method has high process feasibility and continuity, can realize automation for most parts, is easy to integrate in the existing production line, greatly saves labor cost and ensures the safety of industrial production.
Specifically, the method of performing the electrical discharge machining on the mixed carbon source and the thermal conductivity enhancer in the step S2 is: and (3) loading the mixed carbon source and heat conduction reinforcing agent into a plurality of heat insulation bottles A300, and sequentially carrying out alternating current electric discharge machining on the plurality of heat insulation bottles A300 to convert the carbon source and the heat conduction reinforcing agent into doped graphene sheets. In the machining process, the discharge voltage is preferably 100V-300V, and the discharge capacitance is preferably 40 mF-200 mF. In the invention, the mixed carbon source and the heat conduction reinforcing agent are arranged in a plurality of heat insulation bottles A300, so that voltage control and current control can be favorably carried out on the mixed carbon source and the heat conduction reinforcing agent, the circuit stability is improved, and the processing quality is optimized. The mixed carbon source and the heat conduction reinforcing agent are processed by using alternating current, so that the carbon source and the heat conduction reinforcing agent move in two directions, the carbonization effect and the stripping effect are greatly enhanced, and the carbon source is more fully carbonized and converted into graphene sheets.
Further, the method for cleaning the graphene rough sheet in the step S4 is as follows: firstly, diluted hydrochloric acid with the concentration of 10-20% is used for cleaning, and then N-methyl pyrrolidone is used for cleaning. Therefore, metal and inorganic ions in the graphene crude sheet are washed away by dilute hydrochloric acid, the graphene crude sheet is fully dispersed and stripped into small-sheet-layer graphene nanosheets by N-methyl pyrrolidone, the N-methyl pyrrolidone can absorb water among graphene sheet layers, and simultaneously thick slurry with good consistency is conveniently prepared for subsequent coating to prepare a uniform graphene film.
Specifically, the method for blending carbon dense slurry in step S5 includes: mixing the graphene crude sheet and the N-methyl pyrrolidone solution in a mass ratio of 5-10: 1, and stirring in a stirrer for 2-5 h. The graphene crude sheets and the N-methyl pyrrolidone solution are mixed according to the mass ratio of 5-10: 1, so that the concentration of the carbon dense slurry is ensured, and waste caused by excessive amount of the graphene crude sheets is avoided. In addition, the graphene coarse sheets are stirred for 2-5 hours by the stirrer, so that the graphene coarse sheets and the N-methyl pyrrolidone solution are fully mixed and contacted, the dissolution of the graphene coarse sheets in the N-methyl pyrrolidone solution is accelerated, and the efficiency of blending the carbon dense slurry is improved.
Specifically, the method of blade coating the carbon dense slurry to form the film in step S6 is: uniformly coating the carbon thick slurry on a copper foil substrate by using a scraper, and placing the copper foil substrate in a vacuum drying oven for accelerated drying, wherein the drying temperature is set to be 60-90 ℃, and the drying time is 2 h.
Specifically, the graphene film is subjected to the discharge heating and pressing treatment in step S7 by using joule heat to heat, wherein the hot pressing voltage is set to 10V to 100V, the hot pressing capacitance is set to 10mF to 200mF, the hot pressing pressure is set to 20 to 30Mpa, and the processing time is 1h to 3 h. In this manner, the conjugated skeleton in the defective graphene block can be substantially restored in a very short time by joule heat induced by current, and thus the microstructure and the flake arrangement can be finely controlled by voltage and capacitance, and the operation is easy.
Preferably, in the step S1, the resistance of the mixed carbon source and the thermal conductivity enhancer is 1 to 100 Ω. If the carbon source and the thermal conductivity enhancer after mixing are less than 1 ohm, a short circuit effect is caused, the current of the circuit is infinite, and the circuit is damaged. According to the joule heat formula Q ═ U2t/R, under a constant voltage, joule heat is inversely proportional to the square value of resistance, and therefore, if the mixed carbon source and heat conductivity enhancer are higher than 100 ohms, joule heat deficiency occurs, so that the mixed carbon source and heat conductivity enhancer cannot be completely converted into doped graphene sheets, resulting in low production efficiency. Therefore, the embodiment that the resistance of the mixed carbon source and the heat conduction reinforcing agent is 1-100 omega is preferable, the circuit can be protected, the conversion rate of the mixed carbon source and the mixed heat conduction reinforcing agent is high, and the production efficiency is improved.
Referring to fig. 2 to 5, the invention further provides a production line of the graphene thermal conductive film, which is applied to the preparation method of the graphene thermal conductive film. The production line comprises a first conveyor belt A100, a second conveyor belt A200, a heat insulation bottle A300, a computer A400, and an electric discharge machining mechanism B100, a sorting mechanism B200, a cleaning mechanism B300, a drying mechanism B400, a thick slurry blending mechanism B500, a blade coating mechanism B600 and an electric discharge hot-pressing mechanism B700 which are sequentially arranged. The heat insulation bottle A300 is used for storing the mixed carbon source and the heat conduction reinforcing agent. The first conveyor a100 is used to convey the heat-insulated bottle a 300. The electric discharge machining mechanism B100 is used for carrying out electric discharge machining on the heat insulation bottle A300 on the first conveyor belt A100 to obtain doped graphene sheets. The second conveyor belt a200 is used to convey the doped graphene sheets poured out of the insulated bottle a 300. The sorting mechanism B200 is used for screening out graphene rough sheets from the doped graphene sheets on the second conveyor belt A200. The cleaning mechanism B300 is used for cleaning and drying the graphene rough sheets. The thick slurry preparing mechanism B500 is used for preparing the carbon thick slurry. The blade coating mechanism B600 is used for blade coating the carbon concentrated slurry into a graphene film. The discharge hot-pressing mechanism B700 is used for performing discharge hot-pressing treatment on the graphene film to prepare the graphene heat-conducting film. The computer a400 is configured to perform tact control on the electric discharge machining mechanism B100 and the electric discharge hot press mechanism B700.
According to the production line of the graphene heat-conducting film, the first conveyor belt A100, the second conveyor belt A200, the heat-insulating bottle A300, the computer A400, the discharge machining mechanism B100, the sorting mechanism B200, the cleaning mechanism B300, the drying mechanism B400, the thick slurry blending mechanism B500, the blade coating mechanism B600 and the discharge hot-pressing mechanism B700 are integrated in sequence, the degree of automation is high, the labor cost is greatly saved, and the industrial production safety is guaranteed. The computer A400 is used for controlling the production rhythm of the discharge machining mechanism B100 and the discharge hot-pressing mechanism B700, so that voltage control and current control are realized, the circuit stability of the production line is greatly improved, and the machining quality is optimized.
It should be noted that, two ends of the heat-insulating bottle a300 are respectively provided with a metal electrode a310, a first electrical interface a320 and a fixing ring (not shown in the figure), and the first electrical interfaces a320 at the two ends are respectively electrically connected with the metal electrode a310 at the same end; the metal electrodes A310 at the two ends are used for conducting current, so that the current is mixed with the carbon source and the heat conduction reinforcing agent, and the carbon source and the heat conduction reinforcing agent are converted into the doped graphene sheet. The electric discharge machining mechanism B100 includes a temperature sensing module B110 and a first electrical cabinet B120. The temperature sensing module B110 is used for detecting the temperature of the heat insulation bottle A300. Specifically, the temperature sensing module B110 may be a high-resolution spectrometer equipped with a filter, and the real-time temperature peak is obtained by fitting the collected light wave intensity to a black body radiation equation and performing back-stepping; the maximum light intensity of a sample area can be obtained by combining image processing of a high-speed camera provided with a filter, and then a real-time temperature peak value is obtained by Planck distribution reverse-deduction.
The first electrical cabinet B120 has a first holding capacitor group B121 and a first high-voltage power supply B122, the first holding capacitor group B121 has a second electrical interface B123, and the first high-voltage power supply B122 is electrically connected with the first holding capacitor group B121; so as to charge the first capacitor bank by the first high-voltage power supply B122. The temperature sensing module B110 and the first high-voltage power supply B122 are respectively in communication connection with the computer A400; the temperature peak value of the heat insulation bottle A300 in the machining process is obtained by the computer A400, the first capacitor containing group B121 in the first electrical cabinet B120 is controlled to be charged and discharged, and the production rhythm control of the electric discharge machining mechanism B100 is further realized.
The two first conveyor belts a100 are arranged side by side; the heat insulation bottles A300 are sequentially arranged on the first conveyor belt A100, and fixing rings of the heat insulation bottles A300 are fixedly connected with the first conveyor belt on the same side respectively; the plurality of first electrical cabinets B120 are sequentially arranged beside the first conveyor belt a100, and the second electrical interfaces B123 of the first capacitor holding groups B121 are electrically connected to the first electrical interfaces a320 of the corresponding heat-insulating bottles a300 respectively; the charge-discharge capacitor groups sequentially carry out alternate discharge; if the computer a400 detects that the temperature peak of a certain heat-insulating bottle a300 is lower than 3000K, the computer a400 controls the first capacitor bank B121 corresponding to the heat-insulating bottle a300 to discharge again until the heat-insulating bottle a300 reaches the temperature peak of 3000K.
Specifically, in an embodiment of the present invention, referring to fig. 3, the first electrical cabinet B120 is set to 3 groups, and when the first conveyor a100 conveys three thermal insulation bottles a300, the first group of the first holding capacitor group B121 performs electric discharge machining on the first thermal insulation bottle a300, and the first group of the first holding capacitor group B121 performs charging immediately after the machining is completed. After the first group is discharged, the second group of the first capacitor bank B121 is discharged to the second heat insulation bottle a300, and the second group of the first capacitor bank B121 is charged immediately after being processed. After the second group finishes discharging, the first capacitor group B121 in the first electrical cabinet B120 of the third group discharges the third thermal insulation bottle a300, and the first capacitor group B121 of the third group immediately charges after finishing discharging. Because the discharge processing temperature is directly related to the quality of graphene, generally, it is considered that high-quality few-layer graphene can be obtained only when the temperature reaches more than 3000K, therefore, after the third heat-insulating bottle a300 is processed, the computer a400 detects and judges whether the temperature peak value in the heating process of the 3 heat-insulating bottles a300 is lower than 3000K, if the temperature peak value of a certain heat-insulating bottle a300 is detected to be lower than 3000K, the computer a400 controls the first containing capacitor group B121 corresponding to the heat-insulating bottle a300 to discharge again until the heat-insulating bottle a300 is detected to reach the temperature peak value of 3000K; if the temperature peak values of the 3 heat-insulating bottles a300 reach 3000K, the first conveyor belt a100 sends out the three heat-insulating bottles a300 which are processed, and transports the three heat-insulating bottles a300 to be processed to corresponding positions, and the first holding capacitors of the 3 groups of first electrical cabinets B120 discharge in turn again according to the sequence. In this embodiment, the computer a400 controls the first holding capacitor groups B121 in each group of the first electrical cabinets B120 to alternately charge and discharge, so as to fully utilize the efficiency of the electric wires, reduce the idle time of the equipment, improve the production efficiency of the graphene to the maximum, and ensure the quality of the graphene.
It is further worth noting that, referring to fig. 4, the sorting mechanism B200 includes a blower B210, an ultrasonic transducer B220, a distributor B230, and an ultrasonic generator B240; the blower B210 is disposed at one side of the second conveyor belt a200, and a plurality of the ultrasonic transducers B220 are disposed at the other side of the second conveyor belt a200 opposite to the blower B210; the air blower B210 is provided with a plurality of air outlets B211, and the air outlets B211 are arranged towards the opposite side of the second conveyor belt a 200; the ultrasonic generator B240 distributes the ultrasonic waves into the several ultrasonic transducers B220 through the distributor B230. Therefore, when the doped graphene sheets are conveyed to the sorting mechanism B200 by the second conveyor belt A200, under the combined action of the ultrasonic field and the wind field, the doped graphene sheets realize that the graphene coarse sheets are sorted at the upper air inlet, and the graphene fine sheets are sorted at the lower air inlet, so that the graphene coarse sheets are sorted.
Specifically, the discharge hot-pressing mechanism B700 includes an upper hot-pressing mold B710, a lower hot-pressing mold B720, a vacuum chamber B730, and a second electrical cabinet B740; the second electrical cabinet B740 has a second holding capacitor bank B741 and a second high-voltage power supply B742; the hot pressing upper die B710 and the hot pressing lower die B720 are disposed in the vacuum chamber B730 in an up-down opposite manner; effectively avoiding the oxidation of the graphene film in the discharge hot-pressing process so as to ensure the quality of the graphene heat-conducting film. The second capacitor containing group B741 is electrically connected to the hot-pressing upper die B710 and the hot-pressing lower die B720, respectively; so as to realize the power supply and heating of the hot-pressing upper die B710 and the hot-pressing lower die B720. The second high-voltage power supply B742 is electrically connected to the second holding capacitor group B741; to enable the second high voltage power supply B742 to charge the second hold capacitor. The second high voltage power supply B742 is communicatively connected to the computer a 400. So that the computer A400 controls the second holding capacitor group B741 to discharge and charge, and further realizes the production cycle control of the discharge hot-pressing mechanism B700. In this way, the conjugated skeleton in the defective graphene block can be substantially restored within a very short time by joule heat induced by current, and thus voltage and capacitance are finely controlled by the computer a400, thereby realizing control of microstructure and sheet arrangement, and handling is easy.
Specifically, the washing mechanism B300 includes a washing tank (not shown) for washing away impurities attached to the graphene platelets.
Specifically, the drying mechanism includes a drying box (not shown), and the drying box is used for drying the graphene rough sheets.
Specifically, the thick slurry preparing mechanism B500 includes a preparing tank (not shown) for mixing the graphene crude sheets with the N-methylpyrrolidone solution, and a stirrer (not shown) for stirring the mixed graphene crude sheets with the N-methylpyrrolidone solution.
Specifically, the blade coating mechanism B600 includes a scraper (not shown in the figure), a copper foil substrate (not shown in the figure), and a vacuum drying oven (not shown in the figure), wherein the blade coating mechanism B600 uniformly coats the carbon dense slurry on the copper foil substrate through the scraper, and the vacuum drying oven is used for drying the prepared graphene film.
The technical principle of the present invention is described above in connection with specific embodiments. The description is made for the purpose of illustrating the principles of the invention and should not be construed in any way as limiting the scope of the invention. Based on the explanations herein, those skilled in the art will be able to conceive of other embodiments of the present invention without inventive effort, which would fall within the scope of the present invention.

Claims (2)

1.一种石墨烯导热膜的制备方法,其特征在于,包括如下步骤:1. a preparation method of graphene thermal conductive film, is characterized in that, comprises the steps: S1:将碳源和导热增强剂搅拌混合均匀,混合后的碳源和导热增强剂的电阻为1~100Ω;S1: Stir and mix the carbon source and the thermal conductivity enhancer evenly, and the resistance of the mixed carbon source and thermal conductivity enhancer is 1-100Ω; S2:对混合后的碳源和导热增强剂装在隔热瓶中进行放电加工,得到掺杂石墨烯;其中,在所述步骤S2中对混合后的碳源和导热增强剂进行放电加工的方法是:将混合后的碳源和导热增强剂装在多个隔热瓶中,对多个隔热瓶依次进行交流电放电加工,放电电压为100V~300V,放电电容为40mF~200mF,使碳源和导热增强剂转化为掺杂石墨烯片;S2: the mixed carbon source and thermal conductivity enhancer are placed in a thermal insulation bottle for electrical discharge machining to obtain doped graphene; wherein in the step S2, the mixed carbon source and thermal conductivity enhancer are subjected to electrical discharge machining. The method is as follows: the mixed carbon source and thermal conductivity enhancer are placed in a plurality of heat-insulating bottles, and alternating current electric discharge processing is performed on the plurality of heat-insulating bottles in turn, the discharge voltage is 100V-300V, and the discharge capacitance is 40mF-200mF, so that the carbon The source and thermal conductivity enhancer are converted into doped graphene sheets; S3:对掺杂石墨烯片进行筛选,得到石墨烯粗片;S3: Screening the doped graphene sheets to obtain rough graphene sheets; S4:对石墨烯粗片进行清洗干燥;其中,在所述步骤S4中对石墨烯粗片进行清洗的方法是:先使用浓度为10%~20%的稀盐酸进行清洗,再使用N-甲基吡咯烷酮进行清洗;S4: cleaning and drying the graphene rough sheet; wherein, in the step S4, the method for cleaning the graphene rough sheet is: firstly use dilute hydrochloric acid with a concentration of 10% to 20% for cleaning, and then use N-methyl pyrrolidone for cleaning; S5:将清洗干燥后的石墨烯粗片和N-甲基吡咯烷酮溶液进行调配,得到碳浓浆;其中,所述步骤S5中调配碳浓浆的方法是:将石墨烯粗片和N-甲基吡咯烷酮溶液以质量比为5~10:1的质量比混合,并置于搅拌器中搅拌2~5h;S5: prepare the cleaned and dried graphene flakes and the N-methylpyrrolidone solution to obtain a carbon thick slurry; wherein, the method for preparing the carbon thick slurry in the step S5 is: combine the graphene rough flakes and the N-methyl pyrrolidone solution The pyrrolidone solution is mixed in a mass ratio of 5 to 10:1, and placed in a stirrer to stir for 2 to 5 hours; S6:将碳浓浆刮涂成石墨烯膜;S6: Scratch the carbon thick slurry into a graphene film; S7:对石墨烯膜进行放电热压处理,得到石墨烯导热膜;其中,所述步骤S7中对石墨烯膜进行放电热压处理的方法是,采用焦耳热进行加热,热压电压设定为10V~100V,热压电容设定为10mF~200mF,热压压强设定为20~30Mpa,加工时间为1h~3h。S7: performing discharge hot-pressing treatment on the graphene film to obtain a graphene thermally conductive film; wherein, the method for performing discharge hot-pressing treatment on the graphene film in the step S7 is to use Joule heat for heating, and the hot-pressing voltage is set to 10V ~ 100V, the hot pressing capacitor is set to 10mF ~ 200mF, the hot pressing pressure is set to 20 ~ 30Mpa, and the processing time is 1h ~ 3h. 2.一种石墨烯导热膜的生产线,应用在如权利要求1所述的一种石墨烯导热膜的制备方法,其特征在于:所述生产线包括第一传送带、第二传送带、隔热瓶、计算机以及依次设置的放电加工机构、分选机构、清洗机构、干燥机构、调配浓浆机构、刮涂机构和放电热压机构;2. a production line of graphene thermal conductive film, applied in the preparation method of a kind of graphene thermal conductive film as claimed in claim 1, it is characterized in that: described production line comprises the first conveyor belt, the second conveyor belt, thermal insulation bottle, A computer and an electrical discharge machining mechanism, a sorting mechanism, a cleaning mechanism, a drying mechanism, a thick slurry preparation mechanism, a scraping coating mechanism and a discharge hot pressing mechanism arranged in sequence; 所述隔热瓶用于装存混合后的碳源和导热增强剂;The heat-insulating bottle is used for storing the mixed carbon source and thermal conductivity enhancer; 所述第一传送带用于传送用于输送所述隔热瓶;the first conveyor belt is used for conveying the heat-insulating bottles; 所述放电加工机构用于对所述第一传送带上的所述隔热瓶放电加工,制得掺杂石墨烯片;The electrical discharge machining mechanism is used for electrical discharge machining of the heat insulating bottle on the first conveyor belt to obtain a doped graphene sheet; 所述第二传送带用于输送从所述隔热瓶倒出的掺杂石墨烯片;The second conveyor belt is used for conveying the doped graphene sheets poured out from the thermal insulation bottle; 所述分选机构用于对所述第二传送带上的掺杂石墨烯片筛选出石墨烯粗片;The sorting mechanism is used to screen out the graphene coarse flakes from the doped graphene flakes on the second conveyor belt; 所述清洗机构用于对石墨烯粗片进行清洗和干燥;The cleaning mechanism is used for cleaning and drying the graphene rough sheet; 所述调配浓浆机构用于调配出碳浓浆;The thick stock preparation mechanism is used for preparing carbon thick stock; 所述刮涂机构用于将碳浓浆刮涂成石墨烯膜;The scraping mechanism is used for scraping the carbon thick slurry into a graphene film; 所述放电热压机构用于对石墨烯膜进行放电热压处理,制成石墨烯导热膜;The discharge hot-pressing mechanism is used for discharging and hot-pressing the graphene film to make a graphene thermally conductive film; 所述计算机用于对所述放电加工机构和所述放电热压机构进行生产节拍控制;The computer is used to control the production cycle of the electric discharge machining mechanism and the electric discharge hot pressing mechanism; 所述隔热瓶的两端分别设有金属电极、第一电接口和固定环,两端的第一电接口分别与同端的金属电极电连接;Both ends of the heat-insulating bottle are respectively provided with metal electrodes, a first electrical interface and a fixing ring, and the first electrical interfaces at both ends are respectively electrically connected to the metal electrodes at the same end; 所述放电加工机构包括温度传感模块和第一电气柜;The electrical discharge machining mechanism includes a temperature sensing module and a first electrical cabinet; 所述温度传感模块用于检测隔热瓶的温度;The temperature sensing module is used to detect the temperature of the thermal insulation bottle; 所述第一电气柜具有第一盛放电容器组和第一高压电源,所述第一盛放电容器组具有第二电接口,所述第一高压电源与所述第一盛放电容器组电连接;The first electrical cabinet has a first storage capacitor bank and a first high-voltage power supply, the first storage capacitor bank has a second electrical interface, and the first high-voltage power supply is electrically connected to the first storage capacitor bank ; 所述温度传感模块和所述第一高压电源分别与所述计算机通信连接;The temperature sensing module and the first high-voltage power supply are respectively connected in communication with the computer; 两个所述第一传送带并排设置;two of the first conveyor belts are arranged side by side; 若干个隔热瓶依次排列地设置在所述第一传送带上,各个隔热瓶的固定环分别与同侧的第一传动带固定连接;Several heat-insulating bottles are arranged in sequence on the first conveyor belt, and the fixing rings of each heat-insulating bottle are respectively fixedly connected with the first drive belt on the same side; 若干个第一电气柜依次排列的设置在所述第一传送带的旁侧,各个第一盛放电容器组的第二电接口分别于对应的隔热瓶的第一电接口电连接;各个所述盛放电容器组依次地进行轮流放电;A plurality of first electrical cabinets are arranged in sequence on the side of the first conveyor belt, and the second electrical interfaces of each first storage capacitor bank are respectively electrically connected to the first electrical interfaces of the corresponding thermal insulation bottles; The discharge capacitor banks are discharged in turn in turn; 若计算机检测出某一隔热瓶的温度峰值低于3000K,则计算机控制与该隔热瓶对应的第一盛放电容器组再次放电,直到检测到该隔热瓶达到3000K的温度峰值;If the computer detects that the temperature peak value of a thermal insulation bottle is lower than 3000K, the computer controls the first storage capacitor bank corresponding to the thermal insulation bottle to discharge again until it is detected that the thermal insulation bottle reaches a temperature peak value of 3000K; 所述分选机构包括鼓风机、超声换能器、分配器和超声发生器;The sorting mechanism includes a blower, an ultrasonic transducer, a distributor and an ultrasonic generator; 所述鼓风机设置在所述第二传送带的一侧,若干个所述超声换能器与所述鼓风机相对地设置在所述第二传送带的另一侧;The blower is arranged on one side of the second conveyor belt, and a plurality of the ultrasonic transducers are arranged on the other side of the second conveyor belt opposite to the blower; 所述鼓风机具有若干个出风口,所述出风口朝第二传送带的对侧设置;The blower has several air outlets, and the air outlets are arranged toward the opposite side of the second conveyor belt; 所述超声发生器通过分配器将超声波分配至若干个超声换能器中;The ultrasonic generator distributes ultrasonic waves to several ultrasonic transducers through a distributor; 所述放电热压机构包括热压上模、热压下模、真空腔和第二电气柜;The discharge hot pressing mechanism includes a hot pressing upper die, a hot pressing lower die, a vacuum cavity and a second electrical cabinet; 所述第二电气柜具有第二盛放电容器组和第二高压电源;The second electrical cabinet has a second storage capacitor bank and a second high-voltage power supply; 所述热压上模和热压下模上下相对地设置在所述真空腔内;The hot-pressing upper die and the hot-pressing lower die are arranged in the vacuum chamber oppositely up and down; 所述第二盛放电容器组分别与热压上模和热压下模电连接;The second storage capacitor group is electrically connected with the hot pressing upper mold and the hot pressing lower mold respectively; 所述第二高压电源与所述第二盛放电容器组电连接;the second high-voltage power supply is electrically connected to the second storage capacitor bank; 所述第二高压电源与所述计算机通信连接。The second high voltage power supply is communicatively connected to the computer.
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