CN115744884A - Continuous preparation method and system of graphene film with directional heat conduction function - Google Patents
Continuous preparation method and system of graphene film with directional heat conduction function Download PDFInfo
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
A continuous preparation method and a system for a graphene film with a directional heat conduction function comprise a spraying unit, a suction filtration unit, a drying unit, an annealing reduction unit and a winding unit which are sequentially arranged; the spraying unit comprises a graphene oxide storage tank, a metering pump, a gradual shrinkage pipeline and a casting nozzle device which are sequentially arranged; the suction filtration unit comprises a first transmission device, a suction filtration basement membrane, a suction filtration device and an ethanol spraying device; the drying unit comprises a second transmission device, a base film and a heating roller; the annealing reduction unit comprises a third transmission device, a double-roller separation device and a high-temperature furnace; the rolling unit is used for collecting the prepared graphene film. The continuous production system integrates step-by-step shearing, suction filtration film forming, plasticizing-drafting, normal-pressure hot roller drying and annealing reduction treatment, solves the problem of high degree of orientation of graphene sheets, and realizes the oriented heat conduction function and continuous production of graphene films.
Description
Technical Field
The invention relates to the field of nano heat conduction materials, in particular to a continuous preparation method and system of a graphene film with a directional heat conduction function.
Background
With the gradual development of electronic components in the light, small and thin directions, the working temperature of various corresponding electronic components (such as a battery component, a CPU, a GPU, and the like) is greatly increased in a use environment with high power consumption and high transmission rate. And the high-temperature working environment inevitably has adverse effects on the stable reliability and the long service life of the electronic components. Therefore, the preparation method of the graphene film with the efficient and directional heat conduction function has important practical significance for improving the thermal failure problem of the heating electronic component.
The graphene is formed by a single layer of carbon atoms in sp 2 The hybrid six-membered ring planar structure has the length-diameter ratio of generally more than 1000, and is an ideal two-dimensional planar material. The special two-dimensional crystal structure provides a huge channel for phonon transfer, the interface thermal resistance is greatly reduced, the ultrahigh intrinsic in-plane thermal conductivity coefficient is as high as 3500-5300W/(m K), the thermal conductivity is far higher than that of the traditional heat-conducting materials such as boron nitride, aluminum oxide, expanded graphite, heat-dissipating silicon and the like, and the material is the material with the highest known thermal conductivity in the world.
At present, the methods for preparing graphene films mainly include a suction filtration deposition method (example CN113788476 a), a spin coating method (example CN105600775 a), and an interface self-assembly method. However, the conventional technology inevitably introduces a 'stripping-reduction' step, and the conventional chemical reagent reduction process is not only complicated in steps, but also inevitably introduces heteroatoms in the reduction process, so that the application scenario of high-precision electronic devices is difficult to satisfy. In addition, the ordered structure in the highly oriented arrangement can effectively reduce the interface thermal impedance, which is a premise for realizing the excellent thermal conductivity of the graphene film, but the existing film forming technology can not realize the highly oriented orientation of the nanosheet layer and can not realize continuous production.
Therefore, how to solve the problem of high degree of orientation, the method and the system for continuously preparing the graphene film with the directional heat conduction function are provided, and the method and the system have important significance for realizing wide popularization and application of the graphene film in thermal interface materials with high heat dissipation requirements.
Disclosure of Invention
The invention aims to solve the problems in the prior art, provides a continuous preparation method and a continuous preparation system for a graphene film with a directional heat conduction function, and provides a continuous production system integrating step-by-step shearing, suction filtration film forming, plasticizing-drafting, normal-pressure hot roller drying and annealing reduction treatment, so that the problem of high degree of orientation of graphene sheets is solved, and the directional heat conduction function and continuous production of the graphene film are realized.
In order to achieve the purpose, the invention adopts the following technical scheme:
a graphene film continuous preparation system with a directional heat conduction function comprises a spraying unit, a suction filtration unit, a drying unit, an annealing reduction unit and a winding unit which are sequentially arranged;
the spraying unit comprises a graphene oxide storage tank, a metering pump, a gradual shrinkage pipeline and a casting nozzle device which are sequentially arranged; the graphene oxide storage tank is used for placing a graphene oxide solution; two ends of the metering pump are respectively connected with the graphene oxide storage tank and the gradual volume reducing pipeline; the outlet of the gradual reduction pipeline is connected with a casting nozzle device;
the suction filtration unit comprises a first transmission device, a suction filtration basement membrane, a suction filtration device and an ethanol spraying device; the suction filtration basement membrane is attached to the first transmission device, the suction filtration device is located below the suction filtration basement membrane, and the ethanol spraying device is located above the suction filtration basement membrane;
the drying unit comprises a second transmission device, a base film and a heating roller; the second transmission device is arranged close to the first transmission device, the base film is attached to the second transmission device, and the heating roller is clamped at two sides of the base film and the graphene oxide film;
the annealing reduction unit comprises a third transmission device, a double-roller separation device and a high-temperature furnace; the third transmission device is arranged next to the second transmission device; the double-roller separation device is arranged at the joint of the second transmission device and the third transmission device and is used for separating the basement membrane from the graphene oxide film; the high-temperature furnace is used for annealing and reducing the graphene film on the third transmission device;
the winding unit comprises a reel, and the reel is used for collecting the prepared graphene film.
The inner diameter of the inlet of the stepwise reducing pipeline is 40-50 mm, the ratio of the inner diameter of the inlet to the inner diameter of the outlet is 2-6:1, and the length of the pipeline is 1-10 m.
The suction filtration basement membrane adopts a porous nylon membrane, a porous polytetrafluoroethylene membrane or a polyvinylidene fluoride suction filtration membrane, and the pore size is 0.22-0.45 mu m.
A continuous preparation method of a graphene film with a directional heat conduction function comprises the following steps:
1) Preparing a graphene oxide solution: mixing and stirring graphene oxide, non-oxidized graphene and a composite dispersant with water for 0.5-2 h, and carrying out ultrasonic treatment for 0.5-2 h to prepare a graphene oxide aqueous dispersion, wherein the non-oxidized graphene is used for adjusting the carbonized thickness of a graphene film, and the composite dispersant is used for improving the dispersion uniformity of the graphene oxide aqueous dispersion in a water system; the composite dispersant comprises a component A and a component B which are compounded according to a certain proportion, wherein the component A is an ionic liquid type surfactant and comprises DBA-PF 6 、DBA-Cl、DBA-BF 4 The component B comprises any one of polyvinylpyrrolidone, polyvinyl alcohol, sodium carboxymethylcellulose, hexadecyl ammonium bromide, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, tween, BYK163 and sodium polyacrylate;
2) Step-by-step shear-induced graphene oxide lamellar ordered orientation: placing a graphene oxide solution in a graphene oxide storage tank, passing the solution through a stepwise shrinkage pipeline under the pressure of high-pressure nitrogen through a metering pump, and gradually increasing the shearing force between sheets, and inducing graphene oxide nano sheets to be directionally oriented and arranged along the flow direction of the solution in the high-speed flowing process;
3) Negative pressure film forming and plasticizing thermal stretching of the graphene oxide film: uniformly spraying graphene oxide on the suction filtration base membrane through a casting nozzle device, and slowly enabling the suction filtration base membrane to pass through the suction filtration device to preliminarily form a graphene oxide wet membrane; spraying ethanol on the wet film to induce interlayer plasticization, and inducing inter-lamellar slippage of the graphene oxide film by regulating and controlling the speed ratio of the first transmission device and the second transmission device, wherein the film is directionally oriented and arranged along the long axis direction; finally, carrying out normal-pressure hot-roll drying on the graphene oxide film through a heating roller, removing residual solvent of the film, and reducing the thickness of the film;
4) Film tension heat treatment and winding: through two roller separator, realize that graphite oxide film and basement membrane separate, graphite oxide film carries out annealing reduction processing along with third transmission feeding high temperature furnace under the tension effect in the argon atmosphere, goes out high temperature furnace forced air cooling to room temperature to the rolling.
In the step 1), the concentration of the graphene oxide is 1-10 mg/ml, the thickness of the graphene oxide is 0.55-1.2 nm, and the size of the graphene oxide is 0.5-3 μm; the concentration of the non-oxidized graphene is that the concentration of the composite dispersant is = 0.5; the mass ratio of the component A to the component B is 1:1.
In the step 2), the fluid velocity of the graphene oxide solution conveyed by the pipeline is 0.004-0.05 m 3 S; the pressure of the pipeline is kept between 0.2 and 3MPa.
In the step 3), the concentration of the ethanol in the ethanol spraying device is 80-95%, and the spraying rate is 200ml/s.
The transmission speed ratio V of the first transmission device and the second transmission device 1 :V 2 1.05 to 2.5, V is 1 The rate of (A) is 0.005 to 0.1m/s.
In the step 3), the drying temperature of the heating roller is 60-100 ℃, and the hot-pressing drying time is 0.2-1.5 h.
In the step 4), the annealing reduction temperature is 900-1200 ℃, the annealing reduction time is 0.5-2 h, and the speed ratio V of the winding roller of the winding unit to the third transmission device 4 :V 3 1.05 to 2.55.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
(1) In the system, graphene oxide nanosheets are induced to orient in a pipeline with gradually reduced volume under the action of shearing force and ultra-diffusion, meanwhile, a suction filtration film is formed under the action of a suction filtration device, a suction filtration port is arranged below the suction filtration device, and the graphene oxide nanosheets in a graphene oxide solution are loaded on a suction filtration substrate in a lamellar tiled state, so that a graphene film with uniform graphene lamellar orientation and a directional heat conduction function is obtained;
(2) The system disclosed by the invention adopts the transmission device, and the transmission wheel in the transmission device is utilized to drive the suction filtration substrate to continuously move, so that the batch continuous preparation of the graphene film and the preparation of the large-area graphene film are realized.
Drawings
Fig. 1 is a schematic structural diagram of a graphene film continuous preparation system with a directional heat conduction function;
fig. 2 is a diagram of a graphene film prepared in example 1;
fig. 3 is an SEM image of the graphene thin film prepared in example 1.
Reference numerals: a graphene oxide storage tank 1; a metering pump 2; a pipeline 3 is gradually reduced in volume; a casting head device 4; a buffering slope type slideway 5; carrying out suction filtration on the basement membrane 6; a suction filtration device 7; an ethanol spraying device 8; the roller 9 is heated; a twin roll separation device 10; a high temperature furnace 11; a reel 12; a driving wheel 13-1 and driven wheels 13-2, 13-3 and 13-4 of the first transmission device; a driving wheel 13-5 and driven wheels 13-6, 13-7 and 13-8 of the second transmission device; a driving wheel 13-9 and a driven wheel 13-10 of the third transmission device; and a winding roller 13-11 of the winding unit.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects of the present invention clearer and clearer, the present invention is further described in detail below with reference to the accompanying drawings and embodiments.
As shown in fig. 1, the graphene film continuous preparation system with the directional heat conduction function in the embodiment includes a spraying unit, a suction filtration unit, a drying unit, an annealing reduction unit, and a winding unit, which are sequentially arranged;
the spraying unit comprises a graphene oxide storage tank 1, a metering pump 2, a gradual shrinkage pipeline 3 and a casting nozzle device 4 which are arranged in sequence;
the graphene oxide storage tank 1 is used for placing a graphene oxide solution, the graphene oxide storage tank 1 comprises three pipeline ports, and a nitrogen conveying pipeline is used for maintaining pipeline pressure and providing conveying power; the graphene oxide pipeline is used for supplementing a graphene oxide solution; the graphene oxide solution outlet pipeline is connected with the metering pump 2; the other end of the metering pump 2 is connected with a gradual shrinkage pipeline 3 and used for conveying a graphene oxide solution and regulating and controlling the liquid conveying speed; the outlet of the gradual shrinkage pipeline 3 is connected with a casting nozzle device 4, the gradual shrinkage pipeline 3 is used for realizing gradual shearing orientation and directional assembly of the graphene oxide, the inner diameter of the inlet is 40-50 mm, the ratio of the inner diameter of the inlet to the inner diameter of the outlet is 2-6:1, and the length of the pipeline is 1-10 m; a plurality of pores are arranged in the casting nozzle device 4, and the graphene oxide solution is uniformly sprayed on a buffer slope type slideway 5 of a suction filtration basement membrane 6 with a certain width;
the suction filtration unit comprises a first transmission device, a suction filtration basement membrane 6, a suction filtration device 7 and an ethanol spraying device 8; the suction filtration basement membrane 6 is attached to a first transmission device, and the first transmission device comprises a driving wheel 13-1 and driven wheels 13-2, 13-3 and 13-4; the suction filtration basement membrane 6 adopts a porous nylon membrane, a porous polytetrafluoroethylene membrane or a polyvinylidene fluoride suction filtration membrane, and the pore size is 0.22-0.45 mu m; the suction filtration device 7 is positioned below the suction filtration basement membrane 6 and comprises a suction filtration port, the suction filtration port is provided with a plurality of suction filtration holes, and the suction filtration port can contact the suction filtration basement membrane 6; the ethanol spraying device 8 is positioned above the suction filtration base membrane 6, and the ethanol sprays the plasticized graphene oxide membrane at a spraying rate of 200ml/s;
the drying unit comprises a second transmission device, a base film and a heating roller 9; the second transmission device is arranged close to the first transmission device and comprises a driving wheel 13-5 and driven wheels 13-6, 13-7 and 13-8; the base film is attached to the second transmission device and is made of the same material as the suction filtration base film; the heating roller 9 is clamped on two sides of the base film and the graphene oxide film, and is used for drying the graphene oxide film on one hand and rolling the graphene oxide film on the other hand to further adjust the thickness;
the annealing reduction unit comprises a third transmission device, a double-roller separation device 10 and a high-temperature furnace 11; the third transmission device is arranged close to the second transmission device and comprises a driving wheel 13-9 and a driven wheel 13-10; the double-roller separation device 10 is arranged at the joint of the second transmission device and the third transmission device and is used for separating the basement membrane from the graphene oxide membrane, and the double-roller separation device 10 adopts a shovel-like metal structure and is tightly attached to the basement membrane; the high-temperature furnace 11 is used for annealing and reducing the graphene oxide film on the third transmission device in an argon atmosphere;
the winding unit comprises a winding shaft 12 and winding rollers 13-11 and is used for collecting the prepared graphene film.
The transmission device in the embodiment comprises a plurality of transmission wheels, wherein the transmission wheels are used for enabling the suction filtration base film 6 and the base film to continuously move at a suction filtration opening and a heating roller 9 respectively; in the moving process, the graphene oxide forms a graphene oxide film under the action of the suction filtration device 7; ethanol spraying and plasticizing, namely plasticizing, drawing and inducing orientation arrangement of the graphene oxide film is realized through the difference of transmission rates of a driving wheel 13-1 and a driving wheel 13-5; and in the annealing reduction treatment process of the high-temperature furnace 11, the conveying belt drives the graphene oxide film to continuously move, the annealing reduction treatment is carried out under the action of argon atmosphere and tension, and the graphene oxide film is reduced at high temperature to form the graphene film.
A continuous preparation method of a graphene film with a directional heat conduction function comprises the following steps:
1) Preparing a graphene oxide solution: mixing and stirring graphene oxide, non-oxidized graphene and a composite dispersant with water for 0.5-2 h, and carrying out ultrasonic treatment for 0.5-2 h to prepare a graphene oxide aqueous dispersion, wherein the non-oxidized graphene is used for adjusting the carbonized thickness of a graphene film, and the composite dispersant is used for improving the dispersion uniformity of a graphene oxide and non-oxidized graphene mixed system in a water system; the compoundThe composite dispersant comprises a component A and a component B which are compounded according to a certain proportion, wherein the component A is an ionic liquid type surfactant and comprises DBA-PF 6 、DBA-Cl、DBA-BF 4 The component B comprises any one of polyvinylpyrrolidone, polyvinyl alcohol, sodium carboxymethylcellulose, hexadecyl ammonium bromide, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, tween, BYK163 and sodium polyacrylate;
2) Step-by-step shear-induced graphene oxide lamellar ordered orientation: placing a graphene oxide solution in a graphene oxide storage tank 1, under the pressure of high-pressure nitrogen through a metering pump 2, gradually increasing the shearing force between the graphene oxide nanosheets through a gradual volume reduction pipeline 3, and inducing the graphene oxide nanosheets to be directionally oriented and arranged along the flow direction of the solution in the high-speed flowing process;
3) Negative pressure film forming and plasticizing thermal stretching of the graphene oxide film: graphene oxide is uniformly sprayed on a suction filtration base film 6 along a buffering slope type slideway 5 through a casting sprayer device 4, and is transmitted through a first transmission device, so that the suction filtration base film coated with the gradually sheared graphene oxide solution slowly passes through a suction filtration device 7, and a graphene oxide wet film is preliminarily formed; spraying ethanol on the wet film to induce interlayer plasticization, and inducing inter-lamellar slippage of the graphene oxide film by regulating and controlling the speed ratio of the first transmission device to the second transmission device, wherein the film is directionally oriented and arranged along the long axis direction; finally, the graphene oxide film is subjected to normal-pressure hot roller drying through a heating roller 9, residual solvent of the film is removed, and the thickness of the film is reduced;
4) Film tension heat treatment and winding: through two roller separator 10, realize that oxidation graphite alkene film and basement membrane separate, graphite alkene film is with third transmission feeding high temperature furnace 11, carries out annealing reduction under the argon atmosphere, tension effect, goes out high temperature furnace 11 forced air cooling to room temperature to the rolling.
In the step 1), the concentration of the graphene oxide is 1-10 mg/ml, the thickness of the graphene oxide is 0.55-1.2 nm, and the size of the graphene oxide is 0.5-3 μm; the concentration of the non-oxidized graphene is that the concentration of the composite dispersant is = 0.5; the mass ratio of the component A to the component B is 1:1.
In the step 2), the fluid velocity of the graphene oxide solution conveyed by the pipeline is 0.004-0.05 m 3 S; the pressure of the pipeline is kept between 0.2 and 3MPa.
In the step 3), the ethanol concentration in the ethanol spraying device 8 is 80-95%, and the spraying rate is 200ml/s.
In the step 3), the drying temperature of the heating roller 9 is 60-100 ℃, and the hot-pressing drying time is 0.2-1.5 h.
In the step 4), the annealing reduction temperature is 900-1200 ℃, and the annealing reduction time is 0.5-2 h.
A transmission speed ratio V of the first transmission and the second transmission 1 :V 2 1.05 to 2.5, V is 1 The rate of (A) is 0.005 to 0.1m/s. (ii) a Third transmission drive wheel 13-9 speed V 3 With the winding roller 13-11 speed V of the winding unit 4 The ratio of (A) to (B) is 1.05-2.55.
In the invention, DBA-PF shown as component A 6 、DBA-Cl、DBA-BF 4 The structure of (1) is as follows:
example 1
Preparing a graphene oxide solution: mixing and stirring the graphene oxide, the non-oxidized graphene, the composite dispersant and water for 0.5h, and carrying out ultrasonic treatment for 0.5h, wherein the concentration of the graphene oxide is 1mg/ml; the concentration ratio of graphene oxide to non-oxidized graphene to composite dispersant =1: 0.5; the component A is DBA-PF 6 The component B is sodium dodecyl benzene sulfonate, and the mass ratio of the sodium dodecyl benzene sulfonate is 1:1; the graphene oxide solution is conveyed to a graphene oxide storage tank 1 through a pipeline, the graphene oxide solution is conveyed under the dual action of 0.2MPa nitrogen and a metering pump 2, and the fluid speed V =0.004m 3 And/s, leading the graphene to pass through a pipeline with gradual shrinkage, inducing the orientation of the nanosheets step by step through ultra-diffusion shearing, realizing the directional assembly of the graphene lamellar layer, and gradually shrinking the volumeThe inlet inner diameter of the pipe 3 is 50mm, and the inlet inner diameter: the ratio of the inner diameter of the outlet to the inner diameter of the outlet is 3:1, the length of the pipeline is 5m, then graphene oxide sheets which are cut step by step and assembled in an oriented mode are uniformly sprayed on a suction filtration basement membrane 6 through a casting nozzle device 4 along a buffer slope type slide way 5, the suction filtration basement membrane 6 is a porous nylon membrane, the aperture size of the basement is 0.22 mu m, the graphene oxide sheets are conveyed through a first transmission device at the speed of 0.005m/s, the suction filtration basement coated with the graphene oxide solution which is cut step by step slowly passes through a suction filtration device 7, in the moving process, graphene oxide in the graphene oxide solution initially forms a graphene oxide wet membrane under the action of the suction filtration device 7, the graphene oxide membrane is plasticized by ethanol, the spraying rate is 200ml/s, the graphene oxide membrane is conveyed through a second transmission device at the speed V 2 :V 1 1, drying the graphene oxide wet film by a hot roller at normal pressure, and performing film-forming drying treatment on the graphene oxide wet film at 60 ℃ for 0.5 hour while rolling the graphene oxide film to adjust the thickness; the graphene oxide film is separated from the basement membrane by a double-roller separation device 10, moved to a high-temperature furnace 11 along with a conveyor belt, and subjected to annealing reduction treatment under the action of argon atmosphere and tension, wherein V 4 :V 3 1, annealing and reducing at 900 ℃ for 0.5h to obtain a graphene film, and finally collecting the graphene film by using a reel 12. The transverse thermal conductivity coefficient of the graphene film is 1132W/(m.K), and the film thickness is 5 mu m.
Fig. 2 is a diagram of a graphene film prepared in this embodiment. Fig. 3 is an SEM image of the graphene thin film prepared in the present example, wherein fig. 3 (a) is an SEM image of a surface of the graphene thin film, and fig. 3 (b) is a SEM image of a cross-section of the graphene thin film; as can be seen from the transverse SEM image of fig. 3 (a), the graphene film has a flat surface and the graphene sheet layers are stacked transversely and densely; as can be seen from the longitudinal SEM image of FIG. 3 (b), the thickness is about 5 μm, the structure is dense, and the sheet is shaped.
Example 2
Preparing a graphene oxide solution, mixing and stirring graphene oxide, non-oxidized graphene, a composite dispersant and water for 2h, performing ultrasonic treatment for 2h, wherein the concentration of the graphene oxide is 10mg/ml, the concentration ratio of the graphene oxide to the non-oxidized graphene to the composite dispersant is =1:0.5,the composite dispersing agent comprises a component A and a component B, wherein the component A is DBA-Cl, the component B is BYK163, the mass ratio of the component A to the component B is 1:1, graphene oxide solution is conveyed into a graphene oxide storage tank 1 through a pipeline, the graphene oxide solution is conveyed under the double action of nitrogen gas 1MPa and a metering pump 2, and the fluid speed V =0.02m 3 And/s, enabling the graphene to pass through a pipeline with gradually reduced volume, and inducing orientation of the nanosheets step by step through ultra-diffusion shearing to realize oriented assembly of graphene lamella, wherein the inner diameter of an inlet of the pipeline 3 with gradually reduced volume is 50mm, and the inner diameter of the inlet is as follows: the inner diameter ratio of the outlet is 3:1, the length of the pipeline is 10m, then graphene oxide sheets which are cut and directionally assembled step by step are uniformly sprayed on a suction filtration basement membrane 6 along a buffer slope type slideway 5 through a casting nozzle device 4, a polyvinylidene fluoride suction filtration membrane is adopted as a suction filtration base, the aperture size of the basement is 0.45 mu m, the graphene oxide sheets are conveyed through a first transmission device at the speed of 0.005m/s, the suction filtration base sprayed with the graphene oxide solution which is cut step by step slowly passes through a suction filtration device 7, in the moving process, graphene oxide in the graphene oxide solution initially forms a graphene oxide wet film under the action of the suction filtration device 7, the graphene oxide film is plasticized by spraying ethanol, the spraying rate is 200ml/s, the graphene oxide film is conveyed through a second transmission device at the speed V 2 :V 1 1, drying the graphene oxide wet film by a hot roller at normal pressure, and performing film-forming drying treatment on the graphene oxide wet film for 1h at 60 ℃ while rolling the graphene oxide film to adjust the thickness; the graphene oxide film is separated from the basement membrane by a double-roller separation device 10, moved to a high-temperature furnace 11 along with a conveyor belt, and subjected to annealing reduction treatment under the action of argon atmosphere and tension, wherein V 4 :V 3 And 1, annealing and reducing at 900 ℃ to obtain the graphene film, and finally collecting the graphene film by a reel 12. The graphene film has a transverse thermal conductivity 1413W/(m.K) and a thickness of 52 μm.
Example 3
Preparing a graphene oxide solution, mixing and stirring graphene oxide, non-oxidized graphene, a composite dispersant and water for 2 hours and carrying out ultrasonic treatment for 2 hours, wherein the concentration of the graphene oxide is 5mg/ml, the concentration ratio is that the graphene oxide: non-oxidized state graphene: 1, composite dispersant =1, composite dispersant, component a being DBA-BF 4 The component B is hexadecylammonium bromide with the mass ratio of 1:1, graphene oxide solution is conveyed into a graphene oxide storage tank 1 through a pipeline, the graphene oxide solution is conveyed under the dual action of nitrogen gas 1MPa and a metering pump 2, and the fluid speed V =0.01m 3 And/s, enabling the graphene to pass through a pipeline with gradually reduced volume, and inducing orientation of the nanosheets step by step through ultra-diffusion shearing to realize oriented assembly of graphene lamella, wherein the inner diameter of an inlet of the pipeline 3 with gradually reduced volume is 40mm, and the inner diameter of the inlet is as follows: the ratio of the inner diameter of the outlet to the inner diameter of the outlet is 4:1, the length of the pipeline is 10m, then graphene oxide sheets which are cut step by step and assembled in an oriented mode are uniformly sprayed on a suction filtration basement membrane 6 through a casting nozzle device 4 along a buffer slope type slide way 5, the suction filtration basement membrane 6 is a porous nylon membrane, the pore size of the basement membrane is 0.22 mu m, the graphene oxide sheets are conveyed through a first transmission device at the speed of 0.005m/s, the suction filtration basement coated with the graphene oxide solution which is cut step by step slowly passes through a suction filtration device 7, in the moving process, graphene oxide in the graphene oxide solution initially forms a graphene oxide wet membrane under the action of the suction filtration device 7, the graphene oxide wet graphene oxide membrane is plasticized by ethanol and sprayed, the spraying rate is 200ml/s, the graphene oxide membrane is conveyed through a second transmission device at the speed V 2 :V 1 1, drying the graphene oxide wet film by a hot roller at normal pressure, and performing film-forming drying treatment on the graphene oxide wet film for 1h at 100 ℃ while rolling the graphene oxide film to adjust the thickness; the graphene oxide film is separated from the basement membrane by a double-roller separation device 10, moved to a high-temperature furnace 11 along with a conveyor belt, and subjected to annealing reduction treatment under the action of argon atmosphere and tension, wherein V 3 :V 4 And =2:1, the annealing reduction temperature is 1200 ℃, the annealing time is 2 hours, the graphene film is obtained, and finally the graphene film is collected by a reel 12. The graphene film has a transverse thermal conductivity of 1317W/(m.K) and a thickness of 27 μm.
Example 4
Preparing a graphene oxide solution, mixing and stirring graphene oxide, non-oxidized graphene, a composite dispersant and water for 2 hours, and performing ultrasonic treatment for 1 hour, wherein the concentration of the graphene oxide is 3mg/ml, the concentration ratio of the graphene oxide to the non-oxidized graphene to the composite dispersant is =1 and 0.5 6 Component BThe graphene oxide solution is polyvinylpyrrolidone, the mass ratio of the polyvinylpyrrolidone to the polyvinylpyrrolidone is 1:1, the graphene oxide solution is conveyed into a graphene oxide storage tank 1 through a pipeline, the graphene oxide solution is conveyed under the dual action of 0.4MPa nitrogen and a metering pump 2, and the fluid speed V =0.04m 3 And/s, leading the graphene to pass through a pipeline with gradually reduced volume, and gradually inducing nanosheet orientation through ultra-diffusion shearing to realize directional assembly of graphene lamella, wherein the inner diameter of an inlet of the pipeline 3 with gradually reduced volume is 50mm, and the inner diameter of the inlet is as follows: the ratio of the inner diameter of the outlet to the inner diameter of the outlet is 2.5; the graphene oxide sheets which are cut step by step and assembled in an oriented mode are evenly sprayed on a suction filtration basement membrane 6 through a curtain coating sprayer device 4 along a buffering slope type slide way 5, the filter membrane basement is a porous nylon membrane, the aperture size of the basement is 0.22 mu m, the graphene oxide sheets are conveyed through a first transmission device at the speed of 0.005m/s, the suction filtration basement coated with the graphene oxide solution which is cut step by step slowly passes through a suction filtration device 7, in the moving process, graphene oxide in the graphene oxide solution initially forms a graphene oxide wet film under the action of the suction filtration device 7, ethanol sprays and plasticizes the graphene oxide membrane, the spraying rate is 200ml/s, the graphene oxide film is conveyed through a second transmission device at the speed V 2 :V 1 1, drying the graphene oxide wet film by a normal-pressure hot roller, and performing film-forming drying treatment on the graphene oxide wet film for 0.5h at 60 ℃ while rolling the graphene oxide film to adjust the thickness; the graphene oxide film is separated from the basement membrane by a double-roller separation device 10, moved to a high-temperature furnace 11 along with a conveyor belt, and subjected to annealing reduction treatment under the action of argon atmosphere and tension, wherein V 4 :V 3 1, annealing and reducing at 900 ℃ for 2h to obtain a graphene film, and finally collecting the graphene film by a reel 12. The transverse thermal conductivity coefficient of the graphene film is 1274W/(m.K), and the thickness of the graphene film is 17 mu m.
Example 5
Preparing a graphene oxide solution, mixing and stirring graphene oxide, non-oxidized graphene, a composite dispersant and water for 2 hours, and performing ultrasonic treatment for 0.5 hour, wherein the concentration of the graphene oxide is 4mg/ml, the concentration ratio of the graphene oxide to the non-oxidized graphene to the composite dispersant is 1 4 The component B is polyethyleneEnol with the mass ratio of 1:1, conveying the graphene oxide solution into a graphene oxide storage tank 1 through a pipeline, conveying the graphene oxide solution under the dual effects of 2MPa nitrogen and a metering pump 2, and controlling the fluid speed V =0.02m 3 And/s, enabling the graphene to pass through a pipeline with gradually reduced volume, and inducing orientation of the nanosheets step by step through ultra-diffusion shearing to realize oriented assembly of graphene lamella, wherein the inner diameter of an inlet of the pipeline 3 with gradually reduced volume is 50mm, and the inner diameter of the inlet is as follows: the ratio of the inner diameter of the outlet is 3:1, and the length of the pipeline is 5m; the graphene oxide sheets which are cut step by step and directionally assembled are uniformly sprayed on a suction filtration substrate along a buffering slope type slideway 5 through a casting nozzle device 4, the filter membrane substrate is a porous polytetrafluoroethylene membrane, the aperture size of the substrate is 0.22 mu m, the graphene oxide sheets are conveyed through a first transmission device at the speed of 0.1m/s, the suction filtration substrate sprayed with the graphene oxide solution which is cut step by step slowly passes through a suction filtration device 7, in the moving process, graphene oxide in the graphene oxide solution initially forms a graphene oxide wet film under the action of the suction filtration device 7, ethanol sprays and plasticizes the graphene oxide membrane, the spraying rate is 200ml/s, the graphene oxide sheets are conveyed through a second transmission device at the speed of V 2 :V 1 1, drying the graphene oxide wet film by a hot roller at normal pressure, and performing film-forming drying treatment on the graphene oxide wet film for 1h at 100 ℃ while rolling the graphene oxide film to adjust the thickness; the graphene oxide film is separated from the basement membrane by a double-roller separation device 10, moved to a high-temperature furnace 11 along with a conveyor belt, and subjected to annealing reduction treatment under the action of argon atmosphere and tension, wherein V 4 :V 3 1, annealing and reducing at 1200 ℃ for 2h to obtain a graphene film, and finally collecting the graphene film on a reel 12. The graphene film has a transverse thermal conductivity coefficient of 1245W/(m.K) and a thickness of 24 μm.
Example 6
Preparing a graphene oxide solution, mixing and stirring graphene oxide, non-oxidized graphene, a composite dispersant and water for 2h, and performing ultrasonic treatment for 2h, wherein the concentration of the graphene oxide is 10mg/ml, the concentration ratio of the graphene oxide to the non-oxidized graphene to the composite dispersant is 0.5The graphene solution is conveyed to a graphene oxide storage tank 1 through a pipeline, the graphene oxide solution is conveyed under the double effects of 2MPa nitrogen and a metering pump 2, and the fluid speed V =0.015m 3 And/s, enabling the graphene to pass through a pipeline with gradually reduced volume, and inducing orientation of the nanosheets step by step through ultra-diffusion shearing to realize oriented assembly of graphene lamella, wherein the inner diameter of an inlet of the pipeline 3 with gradually reduced volume is 50mm, and the inner diameter of the inlet is as follows: the ratio of the inner diameter of the outlet to the outer diameter of the outlet is 2.5, and the length of the pipeline is 10m; the graphene oxide sheets which are cut step by step and assembled in an oriented mode are uniformly sprayed on a suction filtration basement membrane 6 through a curtain coating sprayer device 4 along a buffering slope type slide way 5, the filter membrane basement membrane is a porous polytetrafluoroethylene membrane, the pore size of the basement is 0.3 mu m, the graphene oxide sheets are conveyed through a first transmission device at the speed of 0.1m/s, the suction filtration basement coated with the graphene oxide solution which is cut step by step slowly passes through a suction filtration device 7, in the moving process, graphene oxide in the graphene oxide solution initially forms a graphene oxide wet film under the action of the suction filtration device 7, the graphene oxide film is plasticized by ethanol spraying, the spraying rate is 200ml/s, the graphene oxide film is conveyed through a second transmission device at the speed V 2 :V 1 1, drying the graphene oxide wet film by a normal-pressure hot roller, and performing film-forming drying treatment on the graphene oxide wet film for 0.2h at 60 ℃, and rolling the graphene oxide film to adjust the thickness; the graphene oxide film is separated from the basement membrane by a double-roller separation device 10, moved to a high-temperature furnace 11 along with a conveyor belt, and subjected to annealing reduction treatment under the action of argon atmosphere and tension, wherein V 3 :V 4 1, annealing and reducing at 1100 ℃ for 1h to obtain a graphene film, and finally collecting the graphene film by using a reel 12. The transverse thermal conductivity coefficient of the graphene film is 1390W/(m.K), and the thickness of the graphene film is 51 mu m.
Example 7
Preparing a graphene oxide solution, mixing and stirring graphene oxide, non-oxidized graphene, a composite dispersing agent and water for 2 hours, and performing ultrasonic treatment for 2 hours, wherein the concentration of the graphene oxide is 6mg/ml, the concentration ratio of the graphene oxide to the non-oxidized graphene to the composite dispersing agent =1, the component A is DBA-PF 6 The component B is sodium carboxymethyl cellulose with the mass ratio of 1:1, and the graphite oxide is prepared by mixingThe graphene solution is conveyed to a graphene oxide storage tank 1 through a pipeline, the graphene oxide solution is conveyed under the double effects of 0.5MPa of nitrogen and a metering pump 2, and the fluid speed V =0.02m 3 And/s, enabling the graphene to pass through a pipeline with gradually reduced volume, and inducing orientation of the nanosheets step by step through ultra-diffusion shearing to realize oriented assembly of graphene lamella, wherein the inner diameter of an inlet of the pipeline 3 with gradually reduced volume is 50mm, and the inner diameter of the inlet is as follows: the inner diameter ratio of the outlet is 2.5, the length of the pipeline is 5m, graphene oxide sheets which are cut step by step and assembled in a directional mode are uniformly sprayed on a suction filtration basement membrane 6 along a buffer slope type slide way 5 through a casting nozzle device 4, the filter membrane basement membrane is a polyvinylidene fluoride suction filtration membrane, the aperture size of the basement is 0.45 mu m, the graphene oxide sheets are conveyed through a first transmission device, the speed of the graphene oxide sheets is 0.03m/s, the suction filtration basement coated with the graphene oxide solution which is cut step by step is enabled to slowly pass through a suction filtration device 7, in the moving process, graphene oxide in the graphene oxide solution initially forms a graphene oxide wet film under the action of the suction filtration device 7, the graphene oxide film is sprayed through ethanol, the spraying rate is 200ml/s, the graphene oxide film is conveyed through a second transmission device, and the speed V is higher than the speed of the graphene oxide film 2 :V 1 1, drying the graphene oxide wet film by a hot roller at normal pressure, and performing film-forming drying treatment on the graphene oxide wet film for 1h at 100 ℃ while rolling the graphene oxide film to adjust the thickness; the graphene oxide film is separated from the basement membrane by a double-roller separation device 10, moved to a high-temperature furnace 11 along with a conveyor belt, and subjected to annealing reduction treatment under the action of argon atmosphere and tension, wherein V 4 :V 3 1, the annealing reduction temperature is 1200 ℃, the annealing reduction time is 0.5h, a graphene film is obtained, and finally, the graphene film is collected by a reel 12. The transverse thermal conductivity coefficient of the graphene film is 1284W/(m.K), and the thickness of the graphene film is 29 mu m.
Example 8
Preparing a graphene oxide solution, mixing and stirring graphene oxide, non-oxidized graphene, a composite dispersant and water for 1h, and performing ultrasonic treatment for 1h, wherein the concentration of the graphene oxide is 8mg/ml, the concentration ratio of the graphene oxide to the non-oxidized graphene to the composite dispersant is 0.5Liquid is conveyed into a graphene oxide storage tank 1 through a pipeline, liquid conveying is carried out under the double actions of 0.5MPa of nitrogen and a metering pump 2, and the fluid speed V =0.008m is controlled 3 The/s, make it through the pipeline of reducing the appearance step by step, through superdiffusion shearing induction nanometer piece orientation step by step, realize the directional equipment of graphite alkene lamina layer, constantly stir in transportation process, the entry internal diameter of reducing the appearance pipeline 3 step by step is 50mm, entry internal diameter: the ratio of the inner diameter of the outlet to the outer diameter of the outlet is 2.5, and the length of the pipeline is 5m; the graphene oxide lamella which is cut step by step and directionally assembled is evenly sprayed on a suction filtration basement membrane 6 through a tape casting sprayer device 4 along a buffering slope type slide way 5, the filter membrane basement membrane is a porous polytetrafluoroethylene membrane, the aperture size of the basement is 0.3 mu m, the graphene oxide lamella is conveyed through a first transmission device at the speed of 0.07m/s, the suction filtration basement coated with the graphene oxide solution which is cut step by step slowly passes through a suction filtration device 7, in the moving process, graphene oxide in the graphene oxide solution initially forms a graphene oxide wet film under the action of the suction filtration device 7, the graphene oxide lamella is plasticized through ethanol spraying, the spraying speed is 200ml/s, the graphene oxide lamella is conveyed through a second transmission device at the speed V 2 :V 1 1, drying the graphene oxide wet film by a hot roller at normal pressure, and performing film-forming drying treatment on the graphene oxide wet film for 1h at 80 ℃ while rolling the graphene oxide film to adjust the thickness; the graphene oxide film is separated from the basement membrane by a double-roller separation device 10, moved to a high-temperature furnace 11 along with a conveyor belt, and subjected to annealing reduction treatment under the action of argon atmosphere and tension, wherein V 4 :V 3 1, annealing and reducing at 1100 ℃ for 2h to obtain the graphene film, and finally collecting the graphene film by using a reel 12. The graphene film has a lateral thermal conductivity of 1401W/(m.K) and a thickness of 39 μm.
Example 9
Preparing a graphene oxide solution, mixing and stirring graphene oxide, non-oxidized graphene, a composite dispersant and water for 1.5h, and performing ultrasonic treatment for 1h, wherein the concentration of the graphene oxide is 9mg/ml, the concentration ratio of the graphene oxide to the non-oxidized graphene to the composite dispersant is 1 4 The component B is hexadecyl ammonium bromide with the mass ratio of 1:1,the graphene oxide solution is conveyed to a graphene oxide storage tank 1 through a pipeline, the graphene oxide solution is conveyed under the double effects of nitrogen gas 1MPa and a metering pump 2, and the fluid speed V =0.004m 3 And/s, enabling the graphene to pass through a pipeline with gradually reduced volume, and inducing orientation of the nanosheets step by step through ultra-diffusion shearing to realize oriented assembly of graphene lamella, wherein the inner diameter of an inlet of the pipeline 3 with gradually reduced volume is 50mm, and the inner diameter of the inlet is as follows: the ratio of the inner diameter of the outlet to the outer diameter of the outlet is 2.5, and the length of the pipeline is 5m; cut directional assembled's oxidation graphite alkene lamella step by step and evenly spray on suction filtration basement membrane 6 along buffering slope type slide 5 through curtain coating shower nozzle device 4, the filter membrane basement membrane is porous nylon membrane, basement aperture size is 0.4 mu m, convey through first transmission, its speed is 0.05m/s, make the suction filtration basement that the spraying has the oxidation graphite alkene solution after cutting step by step slowly pass through suction filtration device 7, in the removal process, oxidation graphite alkene in the oxidation graphite alkene solution is under suction filtration device 7's effect, preliminarily form the wet film of oxidation graphite alkene, ethanol sprays plastify oxidation graphite alkene membrane, spray rate is 200ml/s, convey through second transmission, speed V 2 :V 1 =2:1, drying the graphene oxide wet film by a hot roller under normal pressure, performing film-forming drying treatment on the graphene oxide wet film for 1h at 90 ℃, rolling the graphene oxide film at the same time, and adjusting the thickness; the graphene oxide film is separated from the base film by the double-roller separation device 10, the graphene oxide film is moved to a high-temperature furnace 11 along with a conveying belt, annealing reduction treatment is carried out under the action of argon atmosphere and tension, the annealing reduction temperature is 1100 ℃, the annealing reduction time is 1h, the graphene film is obtained, and finally a reel 12 is used for collection. The graphene film has a transverse thermal conductivity of 1405W/(m.K) and a thickness of 47 μm.
Example 10
Preparing a graphene oxide solution, mixing and stirring graphene oxide, non-oxidized graphene, a composite dispersant and water for 1h, and performing ultrasonic treatment for 2h, wherein the concentration of the graphene oxide is 10mg/ml, the concentration ratio of the graphene oxide to the non-oxidized graphene to the composite dispersant is =1, the A component is DBA-BF 4 The component B is sodium polyacrylate with the mass ratio of 1:1, and graphene oxide solution is conveyed to graphene oxide through a pipelineIn the storage tank 1, graphene oxide solution is conveyed under the dual action of nitrogen gas 1MPa and a metering pump 2, and the fluid speed V =0.01m 3 And/s, enabling the graphene to pass through a pipeline with gradually reduced volume, and inducing orientation of the nanosheets step by step through ultra-diffusion shearing to realize oriented assembly of graphene lamella, wherein the inner diameter of an inlet of the pipeline 3 with gradually reduced volume is 50mm, and the inner diameter of the inlet is as follows: the ratio of the inner diameter of the outlet to the outer diameter of the outlet is 2.5, and the length of the pipeline is 10m; the graphene oxide sheets which are cut step by step and assembled in an oriented mode are uniformly sprayed on a suction filtration basement membrane 6 through a curtain coating sprayer device 4 along a buffering slope type slide way 5, the filter membrane basement membrane is a porous polytetrafluoroethylene membrane, the pore size of the basement is 0.45 mu m, the graphene oxide sheets are conveyed through a first transmission device at the speed of 0.05m/s, the suction filtration basement coated with the graphene oxide solution which is cut step by step slowly passes through a suction filtration device 7, in the moving process, graphene oxide in the graphene oxide solution initially forms a graphene oxide wet film under the action of the suction filtration device 7, the graphene oxide film is plasticized by ethanol spraying, the spraying rate is 200ml/s, the graphene oxide film is conveyed through a second transmission device at the speed V 2 :V 1 1, drying the graphene oxide wet thin film by a hot roller at normal pressure, and performing film-forming drying treatment on the graphene oxide wet thin film at 100 ℃ while rolling the graphene oxide film to adjust the thickness; the graphene oxide film and the base film are separated through a double-roller separation device 10, the graphene oxide film and the base film move to a high-temperature furnace 11 along with a conveying belt, annealing reduction treatment is carried out under the action of argon atmosphere and tension, the annealing reduction temperature is 1200 ℃, the annealing reduction time is 2 hours, the graphene film is obtained, and finally a reel 12 is used for collection. The transverse thermal conductivity of the graphene film is 1421W/(m.K), and the thickness of the graphene film is 53 μm.
Claims (10)
1. The utility model provides a graphite alkene film serialization preparation system with directional heat conduction function which characterized in that: the device comprises a spraying unit, a suction filtration unit, a drying unit, an annealing reduction unit and a winding unit which are arranged in sequence;
the spraying unit comprises a graphene oxide storage tank, a metering pump, a gradual shrinkage pipeline and a casting nozzle device which are sequentially arranged; the graphene oxide storage tank is used for placing a graphene oxide solution; two ends of the metering pump are respectively connected with the graphene oxide storage tank and the gradual shrinkage pipeline; the outlet of the gradual reduction pipeline is connected with a casting nozzle device;
the suction filtration unit comprises a first transmission device, a suction filtration basement membrane, a suction filtration device and an ethanol spraying device; the suction filtration basement membrane is attached to the first transmission device, the suction filtration device is located below the suction filtration basement membrane, and the ethanol spraying device is located above the suction filtration basement membrane;
the drying unit comprises a second transmission device, a base film and a heating roller; the second transmission device is arranged close to the first transmission device, the base film is attached to the second transmission device, and the heating roller is clamped at two sides of the base film and the graphene oxide film;
the annealing reduction unit comprises a third transmission device, a double-roller separation device and a high-temperature furnace; the third transmission device is arranged next to the second transmission device; the double-roller separation device is arranged at the joint of the second transmission device and the third transmission device and is used for separating the basement membrane from the graphene oxide film; the high-temperature furnace is used for annealing and reducing the graphene oxide film on the third transmission device;
the winding unit comprises a reel, and the reel is used for collecting the prepared graphene film.
2. The system for continuously preparing the graphene film with the directional heat conduction function according to claim 1, wherein: the inner diameter of the inlet of the stepwise reducing pipeline is 40-50 mm, the ratio of the inner diameter of the inlet to the inner diameter of the outlet is 2-6:1, and the length of the pipeline is 1-10 m.
3. The system for continuously preparing the graphene film with the directional heat conduction function according to claim 1, wherein: the suction filtration basement membrane adopts a porous nylon membrane, a porous polytetrafluoroethylene membrane or a polyvinylidene fluoride suction filtration membrane, and the pore size is 0.22-0.45 mu m.
4. A continuous preparation method of a graphene film with a directional heat conduction function is characterized in that the system of any one of claims 1 to 3 is adopted, and the method comprises the following steps:
1) Preparing a graphene oxide solution: mixing and stirring graphene oxide, non-oxidized graphene and a composite dispersant with water for 0.5-2 h, and carrying out ultrasonic treatment for 0.5-2 h to prepare a graphene oxide aqueous dispersion, wherein the non-oxidized graphene is used for adjusting the carbonized thickness of a graphene film, and the composite dispersant is used for improving the dispersion uniformity of the graphene oxide aqueous dispersion in a water system; the composite dispersant comprises a component A and a component B which are compounded according to a certain proportion, wherein the component A is an ionic liquid type surfactant and comprises DBA-PF 6 、DBA-Cl、DBA-BF 4 The component B comprises any one of polyvinylpyrrolidone, polyvinyl alcohol, sodium carboxymethylcellulose, hexadecyl ammonium bromide, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, tween, BYK163 and sodium polyacrylate;
2) Step-by-step shear-induced graphene lamellar ordered orientation: placing a graphene oxide solution in a graphene oxide storage tank, passing the solution through a stepwise shrinkage pipeline under the pressure of high-pressure nitrogen through a metering pump, and gradually increasing the shearing force between sheets, and inducing graphene oxide nano sheets to be directionally oriented and arranged along the flow direction of the solution in the high-speed flowing process;
3) Negative pressure film forming and plasticizing thermal stretching of the graphene oxide film: uniformly spraying graphene oxide on the suction filtration base membrane through a casting nozzle device, and slowly enabling the suction filtration base membrane to pass through the suction filtration device to preliminarily form a graphene oxide wet membrane; spraying ethanol on the wet film to induce interlayer plasticization, and inducing inter-lamellar slippage of the graphene oxide film by regulating and controlling the speed ratio of the first transmission device to the second transmission device, wherein the film is directionally oriented and arranged along the long axis direction; finally, carrying out normal-pressure hot roller drying on the graphene oxide film through a heating roller to remove residual solvent of the film and reduce the thickness of the film;
4) Film tension heat treatment and winding: through two roller separator, realize the separation of oxidation graphite alkene film and basement membrane, oxidation graphite alkene film is along with third transmission feeding high temperature furnace, carries out annealing reduction under the argon atmosphere, tension effect, goes out high temperature furnace forced air cooling to room temperature to the rolling.
5. The method of claim 4, wherein: in the step 1), the concentration of the graphene oxide is 1-10 mg/ml, the thickness of the graphene oxide is 0.55-1.2 nm, and the size of the graphene oxide is 0.5-3 μm; the concentration of the non-oxidized graphene is that the concentration of the composite dispersant is = 0.5; the mass ratio of the component A to the component B is 1:1.
6. The method of claim 4, wherein: in the step 2), the fluid velocity of the graphene oxide solution conveyed by the pipeline is 0.004-0.05 m 3 S; the pressure of the pipeline is kept between 0.2 and 3MPa.
7. The method of claim 4, wherein: in the step 3), the concentration of the ethanol in the ethanol spraying device is 80-95%, and the spraying rate is 200ml/s.
8. The method of claim 4, wherein: in step 3), the transmission speed ratio V of the first transmission device and the second transmission device 1 :V 2 1.05 to 2.5, V is 1 The rate of (A) is 0.005 to 0.1m/s.
9. The method of claim 4, wherein: in the step 3), the drying temperature of the heating roller is 60-100 ℃, and the hot-pressing drying time is 0.2-1.5 h.
10. The method of claim 4, wherein: in the step 4), the annealing reduction temperature is 900-1200 ℃, the annealing reduction time is 0.5-2 h, and the speed ratio V of the winding roller of the winding unit to the third transmission device 4 :V 3 1.05 to 2.55.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105271209A (en) * | 2015-11-05 | 2016-01-27 | 北京旭碳新材料科技有限公司 | Graphene film and method and device for continuously producing graphene film |
| CN107140619A (en) * | 2017-05-27 | 2017-09-08 | 杭州高烯科技有限公司 | A kind of graphene thick film of high heat conduction and preparation method thereof |
| CN208216054U (en) * | 2018-04-04 | 2018-12-11 | 中山松德新材料装备有限公司 | A kind of annealing shaping equipment of the tape casting electronic protective film |
| CN113788476A (en) * | 2021-09-13 | 2021-12-14 | 中钢集团南京新材料研究院有限公司 | System and method for continuously preparing graphene film |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105271209A (en) * | 2015-11-05 | 2016-01-27 | 北京旭碳新材料科技有限公司 | Graphene film and method and device for continuously producing graphene film |
| CN107140619A (en) * | 2017-05-27 | 2017-09-08 | 杭州高烯科技有限公司 | A kind of graphene thick film of high heat conduction and preparation method thereof |
| CN208216054U (en) * | 2018-04-04 | 2018-12-11 | 中山松德新材料装备有限公司 | A kind of annealing shaping equipment of the tape casting electronic protective film |
| CN113788476A (en) * | 2021-09-13 | 2021-12-14 | 中钢集团南京新材料研究院有限公司 | System and method for continuously preparing graphene film |
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