Method and system for fusing graphene on copper substrate by using CVD (chemical vapor deposition) method and high-temperature sintering

Abstract

By arranging the copper base material treatment system, the CVD forming system and the hot pressing sintering system, the copper base plate is covered with the graphene layer through the CVD deposition reaction method, the copper base plate is treated through the two-stage annealing system, the copper base plate is softened, the hardness is reduced, and a concave face is conveniently formed in the surface of the copper base plate; according to the method, the copper substrate is arranged in the CVD reaction cavity, a CVD deposition reaction is carried out in the CVD reaction cavity by utilizing the concave surface of the surface of the copper substrate, a copper substrate-graphene layer-copper powder and / or foamy copper-graphene layer composite material is formed, sintering processing is carried out due to the existence of the copper powder layer so as to compactly mix the composite material, and compared with a traditional CVD process, the graphene configuration area can be increased, and the conductivity of the copper substrate is improved. Therefore, the heat conduction effect and the strength effect are enhanced.

Description

Technical Field

[0001] The invention relates to the technical field of graphene composite materials, and in particular to a method and system for fusing graphene on a copper substrate by utilizing a CVD method and high-temperature sintering. Background Art

[0002] High-performance copper materials are key basic materials for the development of high-tech fields in my country. They have important application value in the fields of new energy vehicles, electric drive systems, integrated circuits, power systems, etc. The performance of copper materials can be improved by purification, alloying, and reinforcement composites. Compared with purification and alloying to improve the conductivity of copper, graphene composite materials are more efficient and effective in improving the conductivity of copper. Graphene is essentially a single atomic layer film separated from graphite, and graphene is the material with the best conductivity at room temperature, and its conductivity is about 200 times that of copper. At present, the method of growing graphene on copper foil with copper foil as the substrate is CVD method. CVD method is chemical vapor deposition method, which is a common film manufacturing process. The graphene layer is grown on copper foil as the substrate by CVD method. The copper foil is polished and then placed in a tubular furnace of CVD equipment. Under certain heating temperature conditions, hydrocarbon methane, ethanol and other reaction gases are introduced into the tubular furnace. After a period of reaction, a single layer of graphene can be formed on the copper surface by cooling. The CVD method for preparing copper-graphene composite materials in the prior art is as shown in the attached Figure 1 As shown in the figure, it can be seen that a flat graphene layer is grown on a flat copper substrate layer to form a CVD copper-graphene unit. After generating multiple units, they are hot-pressed at high temperature to form graphene super copper. However, this method of preparing graphene-copper composite materials has the problem of uneven conductivity of the prepared composite materials, that is, in the vertical direction of forming the graphene layer, the copper substrate and the graphene layer have a huge difference in conductivity, so that when the composite material is used, the conductivity will change dramatically in the vertical direction. This is actually caused by the structure of the graphene layer grown on the copper substrate. In order to solve this problem, the graphene layer is made of In order to make graphene and copper combine more tightly, the prior art utilizes graphene to be evenly distributed on the inner surface wall of the pores connected inside the foam copper and on the surface of the foam copper to form a graphene-foam copper material to increase the conductivity and enhance the oxidation resistance of the composite copper; however, since this method does not utilize the CVD method to form a graphene layer on the copper surface, the effect of graphene on the performance of the composite copper is limited; the prior art also adopts a method of crushing copper and mixing it with graphene. Although this method allows the graphene and copper to be fully mixed, it destroys the structure of the copper material itself, and cannot achieve a good composite material effect in the subsequent sintering. Summary of the invention

[0003] In order to solve the above technical problems, the present invention provides a method and system for fusing graphene on a copper substrate by using a CVD method and high-temperature sintering.

[0004] A system for fusing graphene on a copper substrate by using a CVD method and high-temperature sintering, comprising a copper substrate processing system, a CVD molding system, and a hot pressing sintering system; the copper substrate processing system comprises a copper plate surface polishing system and an annealing system; the copper plate enters the annealing system after being polished by the surface polishing system.

[0005] Furthermore, the annealing system comprises an annealing chamber I, an annealing chamber II and an annealing cooling chamber. A temperature control device I is arranged on the top of the annealing chamber I, and a temperature detection device is arranged inside the annealing chamber I.

[0006] Furthermore, annealing chamber II and annealing chamber I are arranged adjacent to each other, and the copper plate enters annealing chamber II after level I annealing in annealing chamber I. A temperature control device II and a winding device are provided in annealing chamber II. The winding device includes a winding shaft and a driving shaft for driving the winding shaft. The temperature of the winding shaft is the same as the temperature in annealing chamber II, and a copper plate surface impact clamping device is provided at the lower end of the winding shaft.

[0007] Furthermore, the copper plate surface impact clamping device includes an impact clamping plate I and an impact clamping plate II on both sides of the copper plate. The impact clamping plate I and the impact clamping plate II are symmetrically arranged on both sides of the copper plate wound around the winding shaft. The side of the impact clamping plate I away from the copper plate is a plane, and the side facing the copper plate is parallel to the side of the impact clamping plate I and has multiple ridges, and the length of the ridges is equal to the side of the impact clamping plate I.

[0008] Furthermore, the side of the impact clamping plate II facing the copper plate and the side away from the steel plate are both flat, and the impact clamping plate I and the impact clamping plate II are both connected to an impact driving device and a moving driving device.

[0009] Furthermore, the annealing cooling chamber and the annealing chamber II are arranged adjacent to each other.

[0010] Furthermore, when the surface of the steel plate is polished, the stains, oil stains and oxide layer on the surface of the copper plate are first removed by polishing equipment, and the removed copper plate is placed in ethanol and 20% hydrochloric acid solution for cleaning for 15 minutes. After cleaning, the copper plate is taken out and then ultrasonically rinsed in an ultrasonic rinser for 10 minutes.

[0011] Furthermore, the rinsed copper plate is placed in a prepared polishing liquid for electrochemical polishing, wherein the components of the polishing liquid are water, phosphoric acid, ethanol, potassium iodate, and hydrogen peroxide; after electrochemical polishing in the polishing liquid, the copper plate is placed in an annealing chamber I for level I annealing.

[0012] Furthermore, the temperature in the annealing chamber I is controlled by the temperature control device I on the top of the annealing chamber I, and the temperature is detected by the temperature detection device inside the annealing chamber I. The temperature in the annealing chamber I is set to 600°C, and the time for the first-level annealing is 3 minutes. After the first-level annealing time is over, the copper substrate is transported to the annealing chamber II and wound onto the winding shaft of the winding device.

[0013] Furthermore, the temperature in the annealing chamber II is controlled by the temperature control device II, and the temperature of the annealing chamber II and the winding shaft is set to 300°C. By adjusting the rotation speed of the driving shaft of the winding shaft, the copper plate can pass through the annealing chamber II at a uniform speed after being flexibly wound on the winding shaft.

[0014] Furthermore, after the copper plate is flexibly wound to the lower end of the winding shaft, the impact driving device drives the impact clamping plate I and the impact clamping plate II to impact both sides of the copper plate, and grooves corresponding to the multiple ridges are pressed out on the side surface of the impact clamping plate I facing the copper plate, while the side surface of the copper plate facing the impact clamping plate II remains flat.

[0015] Furthermore, after the clamping impact, the moving drive device is started so that the impact clamping plate I and the impact clamping plate II clamp the copper plate and enter the annealing cooling chamber for cooling.

[0016] Electrochemical polishing and annealing treatment of the copper substrate can reduce the hardness of the copper substrate and increase the softening degree of the copper substrate. What is different from the general annealing treatment is that annealing chamber I and annealing chamber II are set to perform level I and level II annealing, and the copper substrate is initially softened in the level I annealing at a higher temperature and a shorter time, and then enters the annealing chamber II to soften the copper substrate again under the dual effects of level II annealing and winding on the winding shaft. Different from the copper substrate treated with general annealing, the copper substrate treated with multiple annealing and winding is convenient for processing grooves on the surface.

[0017] Furthermore, the CVD forming system includes a CVD tube furnace, a CVD reaction chamber is arranged in the CVD tube furnace, an observation device is arranged in the chamber, and the CVD reaction chamber is provided with an upper and lower surface as well as front, rear, left and right surfaces; a left support rod and a right support rod are arranged at the front end of the CVD reaction chamber corresponding to the left and right surface positions, and support chambers are arranged inside the left and right support rods, a rotating motor I is arranged on the chamber wall of the left supporting chamber, and a rotating motor II is arranged on the chamber wall of the right supporting chamber, and the rotating motor I and the rotating motor II are both connected to a rotating shaft I, and the other ends of the two rotating shafts I are provided with a copper plate clamping claw I, and the rotating motor I and the rotating motor II are set so that the copper plate clamping claw I clamps the copper plate parallel to the upper and lower surfaces of the CVD reaction chamber.

[0018] Furthermore, a plurality of gas inlet holes and a heating device are arranged on the side surface of the upper surface of the CVD reaction chamber facing the copper plate, and a sliding groove is also arranged on the side surface of the upper surface facing the copper plate, and a copper powder filling device is connected inside the sliding groove.

[0019] Furthermore, the copper powder filling device includes a sliding block, a connecting rod, a copper powder storage box, a nozzle and a control valve; the sliding block is arranged at one end of the connecting rod and slides in a sliding groove on the upper surface, the other end of the connecting rod is connected to the copper powder storage box, and the lower end of the copper powder storage box is connected to multiple nozzles, and each nozzle is controlled to open and close by a control valve.

[0020] Furthermore, the rotary motor I and the rotary motor II are configured so that the copper plate clamping claw I clamps the copper plate with the grooved side facing the multiple nozzles of the copper powder filling device, and the direction of the nozzles is perpendicular to the copper plate.

[0021] Furthermore, multiple gas inlet holes and heating devices are provided on the side faces of the front, back, left and right surfaces of the CVD reaction chamber facing the inner end of the reaction chamber, and multiple heating devices are provided on the side faces of the lower surface of the CVD reaction chamber facing the inner end of the reaction chamber.

[0022] Furthermore, a cylinder is provided on the side surface of the front surface of the CVD reaction chamber facing the inner end of the reaction chamber, and the cylinder is connected to a leveling plate through a piston rod. The lower surface of the leveling plate can contact the upper surface of the copper plate, and the direction of the leveling plate is parallel to the copper plate.

[0023] Furthermore, the annealed and cooled copper plate is placed in the CVD reaction chamber of the CVD tube furnace for CVD reaction, the copper plate clamping claws of the two rotating shafts are driven to clamp the copper plate, and the rotating motors I and II are controlled to drive the rotating shafts to rotate the copper plate to be parallel to the upper surface of the CVD reaction chamber, and the groove side of the copper plate is facing the copper powder filling device.

[0024] Furthermore, after the copper plate is assembled, the CVD tube furnace is closed and the vacuum operation is started. When the vacuum pressure is lower than 1 Pa, the reaction chamber is heated by the heating devices on the walls of the CVD reaction chamber. When the reaction chamber is heated to 700°C, a reaction gas consisting of hydrocarbon methane, ethanol and argon is introduced into the reaction chamber through the gas inlet holes on the walls of the CVD reaction chamber to carry out the CVD deposition reaction of copper-graphene.

[0025] Furthermore, after the reaction time T, the formation of the graphene layer on the copper substrate is observed by an observation device. If the formation is good, the reaction gas is disconnected, and the copper powder filling device is controlled to move on the upper surface of the CVD reaction chamber. After the nozzle is moved to correspond to each groove on the copper plate, the control valve is controlled to open so that the nozzle sprays copper powder into the groove. At this time, a graphene layer is formed on the surface plane side of the copper substrate and in the groove, and the copper powder fills the groove on the graphene layer in the groove.

[0026] Furthermore, after filling the groove, the cylinder on the front surface is controlled to move to drive the piston rod to push the leveling plate toward the copper plate to level the copper powder in the filled groove. After leveling, the reaction gas is continued to be controlled to be introduced through the gas inlet holes on each wall of the CVD reaction chamber to perform a CVD deposition reaction, thereby forming a second graphene layer on the first graphene layer at the flat surface of the copper substrate and the copper powder layer at the groove, thereby forming a copper-graphene composite material.

[0027] For the annealing system; in other embodiments, it can be known that the annealing system includes an annealing chamber I, an annealing chamber II and an annealing cooling chamber; the copper plate surface impact clamping device in the annealing chamber II includes an impact clamping plate I and an impact clamping plate II on both sides of the copper plate, and the impact clamping plate I and the impact clamping plate II are symmetrically arranged on both sides of the copper plate wound around the winding shaft, and the impact clamping plate II is lower than the impact clamping plate I in the vertical direction, and the side of the impact clamping plate I away from the copper plate is a plane, and the side facing the copper plate is parallel to the side of the impact clamping plate I and is provided with a plurality of convex ridges, and the length of the convex ridges is equal to the side of the impact clamping plate I; the side of the impact clamping plate II away from the copper plate is a plane, and the side facing the copper plate is parallel to the side of the impact clamping plate II and is provided with a plurality of convex ridges.

[0028] Furthermore, the ridges on the surfaces of the impact clamping plate I and the impact clamping plate II facing the copper plate include two side surfaces and a top surface, and the two side surfaces and the top surface form the ridges into a trapezoid.

[0029] Furthermore, after the copper plate is flexibly wound to the lower end of the winding shaft, the impact driving device drives the impact clamping plate I and the impact clamping plate II to impact both sides of the copper plate, and grooves are impacted on both sides of the copper plate facing the impact clamping plate.

[0030] As for the CVD molding system, it can be known in other embodiments; the CVD molding system includes a CVD tube furnace, a CVD reaction chamber is arranged in the CVD tube furnace, an observation device is arranged in the chamber, and the CVD reaction chamber is provided with upper and lower surfaces and front, back, left and right surfaces; each surface of the CVD reaction chamber is provided with a plurality of gas inlet holes and a heating device facing the interior of the chamber.

[0031] Furthermore, rotating motors are arranged on the left and right surfaces of the CVD reaction chamber, and both rotating motors are connected to a rotating shaft II. The other end of the rotating shaft II is connected to a copper plate clamping claw II, and the two copper plate clamping claws II clamp the copper plate.

[0032] Furthermore, two rotating motors are arranged to rotate the copper plate to form an angle α with the horizontal plane through the copper plate clamping claw II.

[0033] Furthermore, the angle of α can be 30 degrees, 45 degrees, or 60 degrees.

[0034] Furthermore, copper powder filling devices are provided above the upper surface and below the lower surface of the copper plate, and the copper powder filling devices include a sliding block, a connecting rod, a cross bar, a copper powder storage box, a nozzle and a control valve; the sliding block is provided at one end of the connecting rod and moves in the slide groove on the cross bar, and the other end of the connecting rod is connected to the copper powder storage box, and the lower end of the copper powder storage box is connected to a plurality of nozzles, and each nozzle is controlled to open and close by a control valve.

[0035] Furthermore, the positions of the copper powder filling devices corresponding to the upper and lower surfaces of the copper plate are set so that each nozzle is perpendicular to the upper and lower surfaces of the copper plate.

[0036] Furthermore, when the CVD reaction is carried out, after the reaction time T, the formation of the graphene layer on the copper substrate is observed through an observation device. If the formation is good, the reaction gas is controlled to be disconnected, and the copper powder filling device corresponding to the upper and lower surfaces of the copper plate is controlled to move on the cross bar inside the CVD reaction chamber. After the nozzle is moved to correspond to each groove on the copper plate, the control valve is controlled to open so that the nozzle sprays copper powder into the groove. At this time, graphene layers are formed on the upper and lower surface plane sides of the copper substrate and in the grooves, and the copper powder fills the grooves on the graphene layer in the grooves.

[0037] Furthermore, after filling, the reaction gas is continuously controlled to be introduced through the gas inlet holes on each wall of the CVD reaction chamber to perform a CVD deposition reaction, thereby forming a second graphene layer on the first graphene layer at the flat upper and lower surfaces of the copper substrate and the copper powder layer at the groove, thereby forming a copper-graphene composite material.

[0038] Furthermore, the hot pressing and sintering system includes a hot pressing and sintering box body, the hot pressing and sintering box body includes a hot pressing and sintering box, and the hot pressing and sintering box includes a preheating chamber, a hot pressing and sintering chamber, and a cooling chamber; the three chambers are arranged in sequence, and the preheating chamber and the hot pressing and sintering chamber are both provided with a heating device and a temperature control device; a hot pressing head is also provided in the hot pressing and sintering chamber, and the preheating chamber, the hot pressing and sintering chamber, and the cooling chamber are transmitted through a conveyor belt.

[0039] Furthermore, after the CVD deposition reaction, the copper-graphene composite material is placed in a preheating chamber for preheating, and the temperature in the preheating chamber is controlled to be preheated at 150° C. for 5 minutes. After preheating, the copper-graphene composite material is transported to the hot pressing sintering chamber by a conveyor belt.

[0040] Furthermore, the temperature in the hot pressing sintering chamber is set to three nodes, namely 650°C, 800°C, and 850°C, by a temperature control device; after the copper-graphene composite material is fed into the hot pressing sintering chamber, the temperature is controlled at T 0 After the temperature in the hot pressing sintering chamber reaches 650°C, the temperature is then controlled at 3T. 0 After reaching 800℃, stop heating and keep at 800℃T 0 time, control the hot pressing head to hot press the copper-graphene composite material at this temperature, and then continue to control the temperature at T 0 The temperature rises to 850℃ within a certain time to complete hot pressing sintering.

[0041] Furthermore, after the hot pressing and sintering is completed, the composite material is placed in a cooling chamber for cooling.

[0042] From the sintering principle of copper-graphene composite materials, it can be known that sintering for too long in the low temperature area or in the high temperature area will cause the performance of the composite material after sintering to decrease, and will affect the conductivity and strength properties of the composite material. As can be seen from the figure, the material density of the copper-graphene composite material increases most rapidly between 650℃-800℃, and tends to be flat after 850℃, and the conductivity and strength properties of the composite material also increase rapidly in this temperature range. Therefore, when sintering, the temperature is quickly raised to pass through the low temperature area below 650℃, so that the composite material is sintered for a long time between 650℃-800℃ and hot pressed at the same time, and then sintered for a short time in the high temperature area above 800℃ to prevent excessive sintering.

[0043] The beneficial effects of the present invention are as follows: a copper substrate processing system, a CVD molding system, and a hot pressing sintering system are provided to cover a graphene layer on a copper substrate by a CVD deposition reaction method, and the copper substrate is processed by a two-stage annealing system so that the copper substrate is softened to reduce the hardness and a concave surface is conveniently opened on the surface of the copper substrate, and a CVD deposition reaction is performed in a CVD reaction chamber by utilizing the concave surface of the copper substrate to form a composite material of a copper substrate-graphene layer-copper powder layer, and due to the presence of the copper powder layer, a sintering process is performed to densely mix the composite material, and compared with the traditional CVD process, the area of ​​graphene configuration can be increased, thereby enhancing its thermal conductivity and strength effects; on the other hand, by configuring the copper powder and foam copper on this basis, in addition to having excellent thermal and electrical conductivity The result is that it has high ductility and a certain degree of looseness compared to substrate processing. It has a large margin of adjustment during mechanical processing, which can adapt to various processing needs to the maximum extent, and can better combine with substrates and graphene, which can not only meet the coordination of graphene and copper materials, but also meet the needs of processing; in addition, for a single substrate, in the length direction, the corresponding grooves and convex ridges on the two surfaces and the setting of the composite material in the grooves, compared to a single copper substrate, solve the singleness of thermal conductivity, electrical conductivity, and mechanical properties of a single copper material, especially when horizontal plate-like materials are used in superimposed processing, the performance difference between different layers will be reduced, and the overall performance of the product will be improved. Even if it is not superimposed processing, it has better performance than existing substrate processing products. In addition, by preparing graphene by CVD outside of foam copper and copper powder, the composite properties of the copper substrate will be maximized, and its thermal conductivity and strength effects will be improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] Attached Figure 1 This is a diagram of the copper-graphene CVD deposition reaction in the prior art.

[0045] Attached Figure 2 Schematic diagram of the annealing system in Example 1.

[0046] Attached Figure 3 This is a schematic diagram of the annealing system in Example 2.

[0047] Attached Figure 4A-4B Schematic diagram of the CVD reaction chamber in Example 1.

[0048] Attached Figure 5A-5B This is a schematic diagram of the CVD reaction chamber in Example 2.

[0049] Attached Figure 6 Schematic diagram of the copper substrate in Example 1.

[0050] Attached Figure 7 Schematic diagram of the copper substrate in Example 2.

[0051] Attached Figure 8 Schematic diagram of the composite material in Example 1.

[0052] Attached Fig. 9 Schematic diagram of the composite material in Example 2.

[0053] Attached Fig.10 Schematic diagram of the hot pressing sintering chamber.

[0054] Attached Fig.11 This is the relationship between the density of the composite material and the sintering temperature.

[0055] Figure markings: 1-annealing chamber I, 2-copper plate, 3-winding shaft, 4-impact clamping plate I, 5-impact clamping plate II, 6-convex ridge, 7-right support rod, 8-upper surface, 9-CVD reaction chamber heating device, 10-gas inlet hole, 11-rear surface, 12-front surface, 13-lower surface, 14-left support rod, 15-rotating shaft I, 16-copper plate clamping claw I, 17-connecting rod, 18-copper powder storage box, 19-nozzle, 20-CVD reaction chamber, 21-cylinder, 22-smoothing plate, 23-left surface, 24-right surface, 25-rotating shaft II, 26-cross bar, 27-copper plate clamping claw II, 28-preheating chamber, 29-hot pressing sintering chamber, 30-cooling chamber, 31-hot pressing head, 32-groove, 33-protrusion. DETAILED DESCRIPTION

[0056] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0057] Embodiment 1: A system for fusing graphene on a copper substrate by using a CVD method and high-temperature sintering, comprising a copper substrate processing system, a CVD molding system, and a hot pressing sintering system; the copper substrate processing system comprises a copper plate surface polishing system and an annealing system; the copper plate enters the annealing system after being polished by the surface polishing system, the annealing system comprises an annealing chamber Ⅰ1, an annealing chamber Ⅱ and an annealing cooling chamber, a temperature control device Ⅰ is arranged on the top of the annealing chamber Ⅰ1, a temperature detection device is arranged inside the annealing chamber Ⅰ1, the annealing chamber Ⅱ and the annealing chamber Ⅰ1 are arranged adjacent to each other, the copper plate 2 enters the annealing chamber Ⅱ after undergoing level I annealing in the annealing chamber Ⅰ1, the annealing chamber Ⅱ is provided with a temperature control device Ⅱ and a winding device, the winding device comprises a winding shaft 3 and a driving shaft for driving the winding shaft, the winding shaft 3 The temperature of the copper plate is the same as the temperature in the annealing chamber II. A copper plate surface impact clamping device is provided at the lower end of the winding shaft 3. The copper plate surface impact clamping device includes an impact clamping plate Ⅰ4 and an impact clamping plate Ⅱ5 on both sides of the copper plate. The impact clamping plate Ⅰ4 and the impact clamping plate Ⅱ5 are symmetrically arranged on both sides of the copper plate wound around the winding shaft. The side of the impact clamping plate Ⅰ4 away from the copper plate 2 is a plane, and the side facing the copper plate 2 is parallel to the side of the impact clamping plate Ⅰ4. A plurality of convex ridges 6 are provided, and the length of the convex ridges 6 is equal to the side of the impact clamping plate Ⅰ4. The side of the impact clamping plate Ⅱ5 facing the copper plate and the side away from the steel plate are both planes. The impact clamping plate Ⅰ4 and the impact clamping plate Ⅱ5 are both connected with an impact driving device and a moving driving device. The annealing cooling chamber and the annealing chamber II are adjacently arranged.

[0058] The CVD molding system includes a CVD tube furnace, a CVD reaction chamber 20 is arranged in the CVD tube furnace, an observation device is arranged in the chamber, and the CVD reaction chamber 20 is provided with an upper and lower surface and a front, rear, left and right surface; a left support rod 14 and a right support rod 7 are arranged at the front end corresponding to the left and right surface positions in the CVD reaction chamber 20, and support chambers are arranged inside the left and right support rods, and a rotating motor I is arranged on the chamber wall of the left supporting chamber, and a rotating motor II is arranged on the chamber wall of the right supporting chamber, and the rotating motor I and the rotating motor II The rotating motors Ⅰ and Ⅱ are connected to the rotating shaft Ⅰ15, and the other ends of the two rotating shafts Ⅰ15 are provided with copper plate clamping claws Ⅰ16. The rotating motors Ⅰ and Ⅱ are set so that the copper plate clamping claws Ⅰ16 clamp the copper plate parallel to the upper and lower surfaces of the CVD reaction chamber. A plurality of gas inlet holes 10 and a heating device 9 are provided on the side of the upper surface of the CVD reaction chamber 20 facing the copper plate. A sliding groove is also provided on the side of the upper surface facing the copper plate. A copper powder filling device is connected inside the sliding groove. The copper powder filling device includes a sliding block, a connecting rod 17 , a copper powder storage box 18, a nozzle 19 and a control valve; a sliding block is arranged at one end of the connecting rod 17 and slides in the sliding groove on the upper surface, the other end of the connecting rod 17 is connected to the copper powder storage box 18, the lower end of the copper powder storage box 18 is connected to a plurality of nozzles 19, each nozzle 19 is controlled to open and close by a control valve, the rotating motor Ⅰ and the rotating motor Ⅱ are set to the copper plate clamping claw Ⅰ16 clamping the copper plate with the groove side facing the plurality of nozzles 19 of the copper powder filling device, the direction of the nozzle 19 is perpendicular to the copper plate 2, the CVD reaction chamber 2 A plurality of gas inlet holes 10 and a heating device 9 are provided on the side surface of the front, rear, left and right surfaces of the CVD reaction chamber 20 facing the inner end of the reaction chamber, a plurality of heating devices 9 are provided on the side surface of the lower surface 13 of the CVD reaction chamber 20 facing the inner end of the reaction chamber 20, and a cylinder 21 is also provided on the side surface of the front surface of the CVD reaction chamber 20 facing the inner end of the reaction chamber, and the cylinder 21 is connected to a screed plate 22 through a piston rod, and the lower surface of the screed plate 22 can contact the upper surface of the copper plate 2, and the direction of the screed plate 22 is parallel to the copper plate 2.

[0059] The hot pressing and sintering system includes a hot pressing and sintering box body, which includes a hot pressing and sintering box. The hot pressing and sintering box includes a preheating chamber 28, a hot pressing and sintering chamber 29, and a cooling chamber 30. The three chambers are arranged in sequence, and a heating device and a temperature control device are provided inside the preheating chamber 28 and the hot pressing and sintering chamber 29. A hot pressing head 31 is also provided in the hot pressing and sintering chamber. The preheating chamber 28, the hot pressing and sintering chamber 29, and the cooling chamber 30 are transported among the three chambers through a conveyor belt.

[0060] A method for fusing graphene on a copper substrate using the CVD method of Example 1 and a system for fusing graphene on a copper substrate by high temperature sintering, comprising the following steps:

[0061] Step 1: When polishing the surface of the steel plate, first use the polishing equipment to remove the stains, oil stains and oxide layer on the surface of the copper plate, put the removed copper plate into ethanol and 20% hydrochloric acid solution for cleaning for 15 minutes, take out the copper plate after cleaning, and then ultrasonically rinse it in an ultrasonic cleaning device for 10 minutes.

[0062] Step 2: Place the rinsed copper plate into a prepared polishing solution for electrochemical polishing, wherein the components of the polishing solution are water, phosphoric acid, ethanol, potassium iodate, and hydrogen peroxide; after electrochemical polishing in the polishing solution, place the copper plate into an annealing chamber I for level I annealing.

[0063] Step 3: Control the temperature in annealing chamber I through the temperature control device I on the top of annealing chamber I, and detect the temperature through the temperature detection device inside annealing chamber I, set the temperature in annealing chamber I to 600°C, and the time of level I annealing to 3 minutes; after the level I annealing time is over, transport the copper substrate to annealing chamber II and wind it onto the winding shaft of the winding device.

[0064] Step 4: Control the temperature in the annealing chamber II by the temperature control device II, set the temperature of the annealing chamber II and the winding shaft to 300°C, and adjust the rotation speed of the driving shaft of the winding shaft so that the copper plate can pass through the annealing chamber II at a uniform speed after being flexibly wound on the winding shaft. After the copper plate is flexibly wound to the lower end of the winding shaft, drive the impact clamping plate I and the impact clamping plate II through the impact driving device to impact both sides of the copper plate, and press out grooves corresponding to the multiple ridges on the side surface of the impact clamping plate I facing the copper plate, while the side surface of the copper plate facing the impact clamping plate II is still flat. After clamping and impacting, start the moving driving device so that the impact clamping plate I and the impact clamping plate II clamp the copper plate and enter the annealing cooling chamber for cooling.

[0065] Step 5: Place the annealed and cooled copper plate into the CVD reaction chamber of the CVD tube furnace for CVD reaction, drive the copper plate clamping claws of the two rotating shafts to clamp the copper plate, and control the rotating motors I and II to drive the rotating shafts to rotate the copper plate until it is parallel to the upper surface of the CVD reaction chamber, and face the groove side of the copper plate toward the copper powder filling device.

[0066] Step 6: After assembling the copper plate, close the CVD tube furnace and start the vacuum operation. When the vacuum pressure is lower than 1Pa, the reaction chamber is heated by the heating devices on the walls of the CVD reaction chamber. When heated to 700°C, a reaction gas consisting of hydrocarbon methane, ethanol and argon is introduced into the reaction chamber through the gas inlet holes on the walls of the CVD reaction chamber to carry out the CVD deposition reaction of graphene-copper.

[0067] Step seven: After the reaction time T, the formation of the graphene layer on the copper substrate is observed by an observation device. If the formation is good, the reaction gas is disconnected, and the copper powder filling device is controlled to move on the upper surface of the CVD reaction chamber. After the nozzle is moved to correspond to each groove on the copper plate, the control valve is controlled to open so that the nozzle sprays copper powder into the groove. At this time, a graphene layer is formed on the surface plane side of the copper substrate and in the groove, and the copper powder fills the groove on the graphene layer in the groove.

[0068] Step 8: After filling the groove, the cylinder on the front surface is controlled to move to drive the piston rod to push the leveling plate toward the copper plate to level the copper powder in the filled groove. After leveling, the reaction gas is continued to be controlled to be introduced through the gas inlet holes on each wall of the CVD reaction chamber to perform a CVD deposition reaction, thereby forming a second graphene layer on the first graphene layer at the flat surface of the copper substrate and the copper powder layer at the groove, thereby forming a copper-graphene composite material.

[0069] Step nine: After the CVD deposition reaction, the copper-graphene composite material is placed in a preheating chamber for preheating, and the temperature in the preheating chamber is controlled to be preheated at 150° C. for 5 minutes. After preheating, the copper-graphene composite material is transported to the hot pressing sintering chamber by a conveyor belt.

[0070] Step 10: The temperature in the hot pressing sintering chamber is set to three nodes, namely 650°C, 800°C, and 850°C, by using a temperature control device; after the copper-graphene composite material is fed into the hot pressing sintering chamber, the temperature is controlled at T 0 After the temperature in the hot pressing sintering chamber reaches 650°C, the temperature is then controlled at 3T. 0 After reaching 800℃, stop heating and keep at 800℃T 0 time, control the hot pressing head to hot press the copper-graphene composite material at this temperature, and then continue to control the temperature at T 0 The temperature is raised to 850°C within a certain time to complete hot pressing sintering; after hot pressing sintering, the composite material is placed in a cooling chamber for cooling.

[0071] The copper plate in Example 1 is a copper substrate with a flat surface on one side and a plurality of grooves on the other side.

[0072] Embodiment 2: A system for fusing graphene on a copper substrate by using a CVD method and high-temperature sintering, the annealing system comprising an annealing chamber Ⅰ1, an annealing chamber Ⅱ and an annealing cooling chamber; the copper plate surface impact clamping device in the annealing chamber Ⅱ comprises an impact clamping plate Ⅰ4 and an impact clamping plate Ⅱ5 on both sides of the copper plate, the impact clamping plate Ⅰ4 and the impact clamping plate Ⅱ5 are symmetrically arranged on both sides of the copper plate 2 wound by the winding shaft 3, the impact clamping plate Ⅱ5 is located lower than the impact clamping plate Ⅰ4 in the vertical direction, and the impact clamping plate Ⅰ4 is away from the impact clamping plate Ⅰ4. One side of the copper plate is a plane, and the side facing the copper plate 2 is parallel to the side of the impact clamping plate I4 and is provided with a plurality of ridges 6, and the length of the ridges 6 is equal to the side of the impact clamping plate I4; the side of the impact clamping plate II5 away from the copper plate is a plane, and the side facing the copper plate is parallel to the side of the impact clamping plate II5 and is provided with a plurality of ridges 6; the ridges 6 on the surface of the impact clamping plate I4 and the impact clamping plate II5 facing the copper plate include two side surfaces and one top surface, and the two side surfaces and one top surface form the ridges into a trapezoid.

[0073] The CVD forming system includes a CVD tube furnace, in which a CVD reaction chamber 20 is arranged, in which an observation device is arranged, and the interior of the CVD reaction chamber 20 is provided with an upper and lower surface and a front, rear, left and right surface; each surface of the CVD reaction chamber 20 is provided with a plurality of gas inlet holes 10 and a heating device 9 facing the interior of the chamber, and a rotating motor is arranged on the left surface 23 and the right surface 24 of the CVD reaction chamber 20, and the two rotating motors are connected to a rotating shaft II 25, and the other end of the rotating shaft II 25 is connected to a copper plate clamping claw II 27, and the two copper plate clamping claws II 27 clamp the copper plate, and the two rotating motors are arranged to rotate the copper plate 2 to be aligned with the copper plate clamping claw II 27. The horizontal plane is at an angle of α, and the angle α can be 30 degrees, 45 degrees, or 60 degrees. Copper powder filling devices are provided above the upper surface and below the lower surface of the copper plate 2, and the copper powder filling device includes a sliding block, a connecting rod 17, a cross bar 26, a copper powder storage box 18, a nozzle 19, and a control valve; the sliding block is provided at one end of the connecting rod 17 and moves in the slide groove on the cross bar 26, and the other end of the connecting rod is connected to the copper powder storage box 18, and the lower end of the copper powder storage box 18 is connected to a plurality of nozzles 19, each of which is controlled to open and close by a control valve, and the positions of the copper powder filling devices corresponding to the upper and lower surfaces of the copper plate 2 are set so that each nozzle 19 is perpendicular to the upper and lower surfaces of the copper plate 2.

[0074] A method for fusing graphene on a copper substrate by utilizing the CVD method of Example 2 and the system for fusing graphene on a copper substrate by high-temperature sintering, replacing step 4 of the method of Example 1: after the copper plate is flexibly wound to the lower end of the winding shaft, the impact driving device drives the impact clamping plate I and the impact clamping plate II to impact both sides of the copper plate, and grooves are impacted on both sides of the copper plate facing the impact clamping plate.

[0075] Steps seven and eight of the method of alternative embodiment 1: when performing a CVD reaction, after the reaction time T, the formation of the graphene layer on the copper substrate is observed by an observation device. If the formation is good, the reaction gas is controlled to be disconnected, and the copper powder filling device corresponding to the upper and lower surfaces of the copper plate is controlled to move on the cross bar inside the CVD reaction chamber. After the nozzle is moved to correspond to each groove on the copper plate, the control valve is controlled to open so that the nozzle sprays copper powder into the groove. At this time, graphene layers are formed on the upper and lower surface plane sides of the copper substrate and in the grooves, and the copper powder fills the grooves on the graphene layer in the grooves; after filling, the reaction gas is continued to be controlled to be introduced through the gas inlet holes on each wall of the CVD reaction chamber for CVD deposition reaction, thereby forming a second graphene layer on the first graphene layer at the flat upper and lower surfaces of the copper substrate and the copper powder layer at the grooves, thereby forming a copper-graphene composite material.

[0076] The copper plate substrate in Example 2 is constructed as follows: a portion of the material of the copper plate is removed on the first side of the copper plate to form alternating grooves and protrusions, and a portion of the material of the copper plate is removed on the second side of the copper plate to form alternating grooves and protrusions; the grooves on the first side correspond to the protrusions on the second side, and the protrusions on the first side correspond to the grooves on the second side; or the grooves on the first side correspond to the grooves on the second side, and the protrusions on the first side correspond to the protrusions on the second side; wherein the shapes of the protrusions and grooves include: the grooves or protrusions are trapezoidal or square.

[0077] In the above embodiment, the copper powder used to fill the groove can be replaced with a combination of foam copper and copper powder. The processing method can include depositing a graphene layer in the groove, evenly spreading a layer of copper powder in the groove, filling the foam copper material, compacting, filling the compacted foam copper with copper powder material, and performing secondary compaction; the result can be sintered and then subjected to a second CVD step.

[0078] As a further improvement, the plate may be circular, the grooves or protrusions on the first surface may be fan-shaped, and the corresponding protrusions or grooves on the second surface may be radial strips (not shown in the figure).

[0079] As a further improvement, the plate may be circular, the groove on the first surface may be annular, and the groove on the second surface may be in the shape of radial strips extending along the radius of the circle (not shown in the figure).

[0080] As a further improvement, in the second embodiment, the grooves on the first side and the grooves on the second side of the copper plate are vertically arranged, the grooves on the first side are filled with copper powder, and the grooves on the second side are filled with foamed copper, or the grooves on the first side are filled with copper powder and foamed copper, and the grooves on the second side are filled with copper powder or foamed copper.

Claims

1. A system for fusing graphene on a copper substrate by using a CVD method and high-temperature sintering, comprising a copper substrate processing system, a CVD molding system, and a hot pressing sintering system; the copper substrate processing system comprises a copper plate surface polishing system and an annealing system; the copper plate enters the annealing system after being polished by the surface polishing system, the annealing system comprises an annealing chamber I (1), an annealing chamber II, and an annealing cooling chamber, the top of the annealing chamber I (1) is provided with a temperature control device I, the interior of the annealing chamber I (1) is provided with a temperature detection device, the annealing chamber II and the annealing chamber I are arranged adjacent to each other, the copper plate (2) enters the annealing chamber II after undergoing level I annealing in the annealing chamber I (1), and the annealing chamber II is provided with a temperature control device I The invention comprises a temperature control device II and a winding device, wherein the winding device comprises a winding shaft (3) and a driving shaft for driving the winding shaft, and the temperature of the winding shaft (3) is the same as the temperature in the annealing chamber II; a copper plate surface impact clamping device is arranged at the lower end of the winding shaft (3), and the copper plate surface impact clamping device comprises an impact clamping plate I (4) and an impact clamping plate II (5) on both sides of the copper plate, and the impact clamping plate I (4) and the impact clamping plate II (5) are symmetrically arranged on both sides of the copper plate wound by the winding shaft, and the side of the impact clamping plate I (4) away from the copper plate (2) is a plane, and the side facing the copper plate (2) is provided with a plurality of convex edges (6) parallel to the side of the impact clamping plate I (4).

2. The system for fusing graphene on a copper substrate using a CVD method and high temperature sintering according to claim 1, characterized in that: The length of the convex ridge (6) is equal to the side of the impact clamping plate I (4); the side of the impact clamping plate II (5) facing the copper plate and the side away from the steel plate are both flat; the impact clamping plate I (4) and the impact clamping plate II (5) are both connected to an impact driving device and a moving driving device; the annealing cooling chamber and the annealing chamber II are adjacently arranged.

3. The system for fusing graphene on a copper substrate using a CVD method and high temperature sintering according to claim 2; characterized in that The CVD molding system comprises a CVD tube furnace, wherein a CVD reaction chamber (20) is arranged in the CVD tube furnace, an observation device is arranged in the chamber, and the CVD reaction chamber (20) is provided with an upper and lower surface and a front, rear, left and right surface; a left support rod (14) and a right support rod (7) are arranged at the front end corresponding to the left and right surface positions in the CVD reaction chamber (20), and a support chamber is arranged inside the left and right support rods, and a rotating motor I is arranged on the chamber wall of the left supporting chamber, and a rotating motor II is arranged on the chamber wall of the right supporting chamber, and the rotating motors I and II are both connected to a rotating shaft I (15), and the other ends of the two rotating shafts I (15) are both provided with a copper plate clamping claw I (16), and the rotating motors I and II are set so that the copper plate clamping claw I (16) clamps the copper plate parallel to the upper and lower surfaces of the CVD reaction chamber.

4. The system for fusing graphene on a copper substrate using a CVD method and high temperature sintering according to claim 3; characterized in that: A plurality of gas inlet holes (10) and a heating device (9) are arranged on the side surface of the upper surface of the CVD reaction chamber (20) facing the copper plate, and a sliding groove is also arranged on the side surface of the upper surface facing the copper plate. A copper powder filling device is connected inside the sliding groove. The copper powder filling device comprises a sliding block, a connecting rod (17), a copper powder storage box (18), a nozzle (19) and a control valve. The sliding block is arranged at one end of the connecting rod (17) and slides in the sliding groove on the upper surface. The other end of the connecting rod (17) is connected to the copper powder storage box (18). The lower end of the copper powder storage box (18) is connected to a plurality of nozzles (19), and each nozzle (19) is controlled to open and close by a control valve.

5. The system for fusing graphene on a copper substrate using a CVD method and high temperature sintering according to claim 4, characterized in that: The rotating motor I and the rotating motor II are configured such that the copper plate clamping claw I (16) clamps the copper plate with the grooved side facing the multiple nozzles (19) of the copper powder filling device, and the direction of the nozzles (19) is perpendicular to the copper plate (2).

6. The system for fusing graphene on a copper substrate using a CVD method and high temperature sintering according to claim 5, characterized in that: The hot pressing sintering system comprises a hot pressing sintering box body, the hot pressing sintering box body comprises a hot pressing sintering box, the hot pressing sintering box comprises a preheating chamber (28), a hot pressing sintering chamber (29), and a cooling chamber (30); the three chambers are arranged in sequence, and a heating device and a temperature control device are arranged inside the preheating chamber (28) and the hot pressing sintering chamber (29); a hot pressing head (31) is also arranged in the hot pressing sintering chamber, and the preheating chamber (28), the hot pressing sintering chamber (29), and the cooling chamber (30) are transported between the three chambers via a conveyor belt.

7. A method for fusing graphene on a copper substrate using the CVD method of claims 1-6 and a system for fusing graphene on a copper substrate by high temperature sintering, comprising the following steps: Step 1: Polish the surface of the steel plate. Step 2: Place the rinsed copper plate into the prepared polishing solution for electrochemical polishing. Step 3: The temperature in the annealing chamber I is controlled by the temperature control device I on the top of the annealing chamber I; after the stage I annealing time is over, the copper substrate is transported to the annealing chamber II and wound onto the winding shaft of the winding device; Step 4: After the copper plate is flexibly wound to the lower end of the winding shaft, the impact clamping plate I and the impact clamping plate II are driven by the impact driving device to impact the two sides of the copper plate; Step 5: placing the annealed and cooled copper plate into a CVD reaction chamber of a CVD tube furnace for CVD reaction; Step 6: After assembling the copper plate, close the CVD tube furnace and start the vacuum operation. When the vacuum pressure is lower than 1Pa, the reaction chamber is heated by the heating devices on the walls of the CVD reaction chamber. When heated to 700°C, a reaction gas composed of hydrocarbon methane, ethanol and argon is introduced into the reaction chamber through the gas inlet holes on the walls of the CVD reaction chamber to carry out the CVD deposition reaction of copper-graphene.

8. The method according to claim 7, characterized in that: Step 7: After the CVD deposition reaction, the copper-graphene composite material is placed in the preheating chamber of the hot pressing sintering system for preheating, and the temperature in the preheating chamber is controlled to be preheated at 150°C for 5 minutes. After preheating, the copper-graphene composite material is transported to the hot pressing sintering chamber by a conveyor belt. Step eight: lowering the temperature in the hot pressing sintering chamber by means of a temperature control device to three nodes, namely 650°C, 800°C and 850°C; after feeding the copper-graphene composite material into the hot pressing sintering chamber, controlling the temperature to rise to 650°C within T0, and after the temperature in the hot pressing sintering chamber reaches 650°C, controlling the temperature to rise to 800°C within 3T0, and after reaching 800°C, stopping the temperature rise and maintaining 800°C for T0, at which temperature the hot pressing head is controlled to hot press the copper-graphene composite material, and then continuing to control the temperature to rise to 850°C within T0 to complete the hot pressing sintering; after completing the hot pressing sintering, placing the composite material into a cooling chamber for cooling.

9. The copper-graphene composite material obtained by the method according to claim 7, characterized in that: Alternating grooves and protrusions are formed on the copper plate; wherein the grooves and protrusions are in the form of: the grooves on the first surface correspond to the protrusions on the second surface, and the protrusions on the first surface correspond to the grooves on the second surface; wherein the shapes of the protrusions and grooves include trapezoids and squares.

10. The composite material according to claim 9, characterized in that: The first surface groove and the second surface groove are filled with the same or different filling materials, and the filling materials are any one or more of copper powder and foam copper.

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