A method and system for fusing graphene on a copper substrate using a CVD process and high temperature sintering

Abstract

The application covers graphene layer on copper substrate by CVD deposition reaction method through setting copper substrate processing system, CVD forming system and hot-pressing sintering system, processes copper substrate by two-stage annealing system to soften and reduce hardness of copper substrate, and facilitates to open concave surface on surface of copper substrate, and performs CVD deposition reaction in CVD reaction cavity by using concave surface on surface of copper substrate to form composite material of copper substrate-graphene layer-copper powder and / or foam copper-graphene layer, and sintering processing is performed due to existence of copper powder layer to densify mixture of composite material, which can increase area of graphene configuration compared with traditional CVD process, thereby strengthening heat conduction effect and strength effect.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of graphene composite materials; in particular, it is a method and system for fusing graphene on a copper substrate using a CVD method and high-temperature sintering. BACKGROUND

[0002] High-performance copper materials are key basic materials for the development of high-tech fields in China. They have important application value in the fields of new energy vehicles, electric drive systems, integrated circuits, and power systems. The performance improvement methods of copper materials include purification, alloying, and reinforcement composite. Compared to purification and alloying to improve the electrical conductivity of copper, graphene composite materials have higher efficiency and better effect. Graphene is essentially a single-atom layer of film separated from graphite, and it is the best material for electrical conductivity at room temperature, with an electrical conductivity of about 200 times that of copper. Currently, the method for growing graphene on copper foil is CVD (Chemical Vapor Deposition). CVD is a common thin film production process that uses copper foil as the substrate to grow a graphene layer. After the copper foil is polished and treated on the surface, it is placed in a CVD device tube furnace. Hydrocarbons such as methane and ethanol are introduced into the tube furnace at a certain heating temperature. After a certain period of reaction, the copper surface is cooled to form a single-layer graphene. Figure 1 As shown in the existing technology, a CVD copper-graphene unit is formed by growing a flat graphene layer on a flat copper substrate layer. After multiple units are generated, they are hot-pressed at high temperature to form a graphene super-copper. However, this method of preparing graphene-copper composite materials has the problem of uneven electrical conductivity of the prepared composite materials. In the vertical direction of the graphene layer, the copper substrate layer and the graphene layer have a large difference in electrical conductivity, which causes the electrical conductivity of the composite material to change dramatically in the vertical direction. This is actually caused by the structure of the graphene layer grown on the copper substrate. To solve this problem and make the graphene and copper combine more closely, the existing technology uses graphene uniformly distributed on the inner surface wall of the interconnected pores of the foam copper and the surface of the foam copper to form a graphene-foam copper material to increase the electrical conductivity and enhance the oxidation resistance of the composite copper. However, this method does not use CVD to form a graphene layer on the copper surface, which limits the influence of graphene on the performance of the composite copper. The existing technology also uses a method of crushing copper and mixing it with graphene. This method allows the graphene and copper to mix thoroughly, but it destroys the structure of the copper material, which cannot achieve good composite material results in subsequent sintering. SUMMARY

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

[0004] A system for fusing graphene on a copper substrate by CVD method and high-temperature sintering, comprising a copper substrate processing system, a CVD forming system, and a hot-press sintering system; the copper substrate processing system comprises a copper plate surface polishing system and an annealing system; the copper plate is polished by the surface polishing system and then enters the annealing system.

[0005] Further, the annealing system comprises an annealing chamber I, an annealing chamber II, and an annealing cooling chamber; the top of the annealing chamber I is provided with a temperature control device I, and the inside of the annealing chamber I is provided with a temperature detection device.

[0006] Further, the annealing chamber II is arranged adjacent to the annealing chamber I, the copper plate enters the annealing chamber II after first-stage annealing in the annealing chamber I, the annealing chamber II is provided with a temperature control device II and a winding device, the winding device comprises a winding shaft and a driving shaft for driving the winding shaft, the temperature of the winding shaft is the same as that in the annealing chamber II, and the lower end of the winding shaft is provided with a copper plate surface impact clamping device.

[0007] Further, the copper plate surface impact clamping device comprises impact clamping plates I and II on both sides of the copper plate, the impact clamping plates I and II are symmetrically arranged on both sides of the copper plate wound by the winding shaft, the side of the impact clamping plate I away from the copper plate is a plane, and the side of the impact clamping plate I toward the copper plate is provided with a plurality of convex edges parallel to the side edge of the impact clamping plate I, and the length of the convex edge is equal to the side edge of the impact clamping plate I.

[0008] Further, the side of the impact clamping plate II toward the copper plate and the side of the impact clamping plate II away from the copper plate are both planes, and the impact clamping plate I and the impact clamping plate II are both connected with an impact driving device and a moving driving device.

[0009] Further, the annealing cooling chamber is arranged adjacent to the annealing chamber II.

[0010] Further, when polishing the surface of the steel plate, first, use a polishing device to remove stains, oil stains, and oxide layers on the surface of the copper plate, put the removed copper plate into an ethanol and 20% hydrochloric acid solution for cleaning for 15 minutes, take out the copper plate after cleaning, and then perform ultrasonic washing in an ultrasonic washing device for 10 minutes.

[0011] Further, the washed copper plate is placed in a prepared polishing liquid for electrochemical polishing, the composition of the polishing liquid is water, phosphoric acid, ethanol, potassium iodate, and hydrogen peroxide; after electrochemical polishing in the polishing liquid, the copper plate is placed in the annealing chamber I for first-stage annealing.

[0012] Further, 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℃, and the time of the first-stage annealing is 3 minutes; after the first-stage annealing is completed, the copper substrate is transported to the annealing chamber II and wound on the winding shaft of the winding device.

[0013] Further, the temperature in the annealing chamber II is controlled by the temperature control device II, the temperature in the annealing chamber II and the winding shaft is set to 300℃, and the rotation speed of the driving shaft driving the winding shaft is adjusted so that the copper plate can pass through the annealing chamber II at a uniform speed after being flexibly wound on the winding shaft.

[0014] Further, after the copper plate is flexibly wound to the lower end of the winding shaft, the two sides of the copper plate are impacted by the impact clamping plate I and the impact clamping plate II driven by the impact driving device, and a plurality of grooves corresponding to the convex edges are pressed on the side surface of the copper plate facing the impact clamping plate I, and the side surface of the copper plate facing the impact clamping plate II is still a plane.

[0015] Further, after the clamping impact, the moving driving device is started to make the impact clamping plate I and the impact clamping plate II clamp the copper plate into the annealing cooling chamber for cooling.

[0016] The 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. Different from the general annealing treatment, the first-stage and second-stage annealing are performed by setting the annealing chamber I and the annealing chamber II, the copper substrate is initially softened at a high temperature for a short time in the first-stage annealing, and then is re-softened in the second-stage annealing and the winding of the winding shaft, which is different from the copper substrate treated by the general annealing treatment. The copper substrate treated by the multiple annealing and winding softening treatment is convenient for processing grooves on the surface.

[0017] Further, the CVD forming system comprises a CVD tube furnace, a CVD reaction cavity is arranged in the CVD tube furnace, an observation device is arranged in the cavity, and upper and lower surfaces and front and rear and left and right surfaces are arranged inside the CVD reaction cavity; a left support rod and a right support rod are arranged at the front end of the CVD reaction cavity corresponding to the positions of the left and right surfaces, support cavities are arranged inside the left and right support rods, a rotary motor I is arranged on the chamber wall of the left support cavity, a rotary motor II is arranged on the chamber wall of the right support cavity, the rotary motor I and the rotary motor II are connected with rotating shafts I, copper plate clamping jaws I are arranged at the other ends of the two rotating shafts I, and the rotary motor I and the rotary motor II are set to clamp the copper plate by the copper plate clamping jaws I parallel to the upper and lower surfaces of the CVD reaction cavity.

[0018] Further, the upper surface of the CVD reaction cavity is provided with a plurality of gas inlets and heating devices on the side surface facing the copper plate, and a sliding groove is further provided on the side surface of the upper surface facing the copper plate, and a copper powder filling device is connected in the sliding groove.

[0019] Further, the copper powder filling device comprises 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 the sliding groove of the upper surface, the other end of the connecting rod is connected with the copper powder storage box, a plurality of nozzles are communicated at the lower end of the copper powder storage box, and each nozzle is controlled to open and close by the control valve.

[0020] Further, the rotary motor I and the rotary motor II are set to make the copper plate clamping jaw I clamp the side of the copper plate with the groove facing the plurality of nozzles of the copper powder filling device, and the direction of the nozzle is perpendicular to the copper plate.

[0021] Further, the front, rear, left and right surfaces of the CVD reaction cavity are provided with a plurality of gas inlets and heating devices on the side surface facing the inner end of the reaction cavity, and the lower surface of the CVD reaction cavity is provided with a plurality of heating devices on the side surface facing the inner end of the reaction cavity.

[0022] Further, a gas cylinder is further provided on the front surface of the CVD reaction cavity on the side surface facing the inner end of the reaction cavity, the gas cylinder is connected with a leveling plate through a piston rod, the lower surface of the leveling plate can be in contact with the upper surface of the copper plate, and the direction of the leveling plate is parallel to the copper plate.

[0023] Further, the copper plate cooled after annealing is placed in the CVD reaction cavity of the CVD tube furnace for CVD reaction, the copper plate clamping jaw of the two rotating shafts clamps the copper plate, and the rotary motor I and the rotary motor II are controlled to drive the rotating shafts to rotate to rotate the copper plate to be parallel to the upper surface of the CVD reaction cavity, and the side of the groove of the copper plate faces the copper powder filling device.

[0024] Further, after the copper plate is assembled, the CVD tube furnace is closed and vacuumizing operation is started, when the pressure is lower than 1Pa, the reaction cavity is heated by the heating devices on the walls of the CVD reaction cavity, when the temperature is heated to 700℃, the reaction gas composed of hydrocarbon methane and ethanol and argon is introduced into the reaction cavity through the gas inlets on the walls of the CVD reaction cavity to carry out CVD deposition reaction of copper-graphene.

[0025] Further, after the reaction time T, the formation of the graphene layer on the copper substrate is observed by the observation device, if the formation is good, the control valve is opened to control the copper powder filling device to move on the upper surface of the CVD reaction cavity, and the nozzle is controlled to spray copper powder into the groove. At this time, the graphene layer is formed on the surface plane side of the copper substrate and in the groove, and the copper powder fills the groove.

[0026] Further, after the groove is filled, the gas cylinder on the front surface is controlled to move the piston rod to push the leveling plate to move towards the copper plate to level the copper powder in the filled groove. After leveling, the reaction gas is continuously introduced into the gas inlet hole on each wall of the CVD reaction cavity to perform CVD deposition reaction, thereby forming a second layer of graphene on the first layer of graphene on the flat surface of the copper substrate and the copper powder layer in the groove, thereby forming a copper-graphene composite material.

[0027] For the annealing system, in other embodiments, the annealing system includes annealing chamber I, annealing chamber II and annealing cooling chamber; the copper plate surface impact clamping device in the annealing chamber II includes impact clamping plate I and impact clamping plate II on both sides of the copper plate, which are symmetrically arranged on both sides of the copper plate wound by the winding shaft, the impact clamping plate II is lower than the impact clamping plate I in the vertical direction, the side away from the copper plate of the impact clamping plate I is a plane, and the side towards the copper plate is provided with a plurality of convex edges parallel to the side edge of the impact clamping plate I, and the length of the convex edge is equal to the side edge of the impact clamping plate I; the side away from the copper plate of the impact clamping plate II is a plane, and the side towards the copper plate is provided with a plurality of convex edges parallel to the side edge of the impact clamping plate II.

[0028] Further, the convex edges on the side surface towards the copper plate of the impact clamping plate I and the impact clamping plate II include two side surfaces and a top surface, which form a trapezoidal shape.

[0029] Further, after the flexible winding of the copper plate 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, and grooves are formed on both sides of the copper plate towards the impact clamping plate.

[0030] For the CVD forming system, in other embodiments, the CVD forming system includes a CVD tube furnace, a CVD reaction cavity is arranged in the CVD tube furnace, an observation device is arranged in the cavity, and the CVD reaction cavity is internally provided with upper and lower surfaces and front and rear and left and right surfaces; each surface of the CVD reaction cavity is provided with a plurality of gas inlet holes and heating devices towards the cavity.

[0031] Further, the left and right surfaces of the CVD reaction cavity are provided with rotating motors, both of which are connected with rotating shaft II, the other end of the rotating shaft II is connected with copper plate clamping jaw II, and the two copper plate clamping jaws II clamp the copper plate.

[0032] Further, the two rotating motors are arranged to rotate the copper plate to an angle of alpha with the horizontal plane through the copper plate clamping jaw II.

[0033] Further, the angle alpha can be 30 degrees, 45 degrees or 60 degrees.

[0034] Further, the upper surface of the copper plate is provided with a copper powder filling device above and below the lower surface, which includes a sliding block, a connecting rod, a crossbar, a copper powder storage box, a nozzle and a control valve; the sliding block is arranged at one end of the connecting rod and moves in the sliding groove on the crossbar, the other end of the connecting rod is connected with the copper powder storage box, the lower end of the copper powder storage box is communicated with a plurality of nozzles, and each nozzle is controlled to open and close by the control valve.

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

[0036] Further, during the CVD reaction, after the reaction time T, the formation of the graphene layer on the copper substrate is observed by the observation device, if the formation is good, the control valve is controlled to open to make the nozzles spray copper powder into the grooves, at this time, the graphene layer is formed on the upper and lower surface plane sides of the copper substrate and the grooves, and the copper powder fills the grooves on the graphene layer in the grooves.

[0037] Further, after filling, the reaction gas is continuously introduced into the CVD reaction cavity through the gas inlet holes on the walls to carry out CVD deposition reaction, so as to form a second layer of graphene on the first layer of graphene on the flat upper and lower surfaces of the copper substrate and the copper powder layer in the grooves, thereby forming a copper-graphene composite material.

[0038] Further, the hot-pressing sintering system includes a hot-pressing sintering box, which includes a hot-pressing sintering chamber, a preheating cavity, a hot-pressing sintering cavity and a cooling cavity inside the hot-pressing sintering chamber; the three cavities are arranged in sequence, and heating devices and temperature control devices are arranged inside the preheating cavity and the hot-pressing sintering cavity; a hot-pressing head is further arranged in the hot-pressing sintering cavity, and the preheating cavity, the hot-pressing sintering cavity and the cooling cavity are transmitted by a transmission belt.

[0039] Further, 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 at 150℃ for 5 minutes. After preheating, the copper-graphene composite material is transported to the hot-pressing sintering chamber by a conveying belt.

[0040] Further, the temperature in the hot-pressing sintering chamber is set to three points, i.e., 650℃, 800℃, and 850℃, by the temperature control device. After the copper-graphene composite material is sent into the hot-pressing sintering chamber, the temperature is controlled to rise to 650℃ within T0 time. After the temperature in the hot-pressing sintering chamber reaches 650℃, the temperature is controlled to rise to 800℃ within 3T0 time. After reaching 800℃, the temperature is stopped from rising and maintained at 800℃ for T0 time. The hot-pressing head is controlled to hot-press the copper-graphene composite material at this temperature. Then, the temperature is controlled to rise to 850℃ within T0 time to complete the hot-pressing sintering.

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

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

[0043] The beneficial effects of this invention are as follows: By setting up a copper substrate processing system, a CVD molding system, and a hot-pressing sintering system, a graphene layer is deposited on a copper substrate using a CVD deposition reaction method. A two-stage annealing system is used to treat the copper substrate, softening it, reducing its hardness, and facilitating the creation of concave surfaces on its surface. The concave surfaces of the copper substrate are then used for CVD deposition within the CVD reaction chamber, forming a composite material of copper substrate-graphene layer-copper powder layer. The presence of the copper powder layer allows for sintering to achieve a dense mixture of the composite material. Compared to traditional CVD processes, this increases the area of ​​graphene deposition, thereby enhancing its thermal conductivity and strength. Furthermore, the copper powder and copper foam incorporated on this basis not only possess excellent thermal and electrical conductivity... The resulting material exhibits high ductility and a degree of looseness compared to substrate processing, allowing for greater adjustment margins during machining and maximizing adaptability to various processing requirements. It also integrates better with substrates and graphene, satisfying both the compatibility of graphene and copper materials and the processing needs. Furthermore, for a single substrate, the corresponding grooves and ridges on both sides along the length, along with the composite material within the grooves, overcome the limitations of single copper substrates in terms of thermal conductivity, electrical conductivity, and mechanical properties. This is particularly beneficial when using horizontal plate-like materials in stacked processing, reducing performance differences between layers and improving overall product performance. Even without stacked processing, it offers superior performance compared to existing substrate-processed products. Additionally, CVD preparation of graphene on copper foam and copper powder maximizes the composite properties of the copper substrate, enhancing its thermal conductivity and strength. Attached Figure Description

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

[0045] Appendix Figure 2 This is a schematic diagram of the annealing system in Example 1.

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

[0047] Appendix Figures 4A-4B This is a schematic diagram of the CVD reaction chamber in Example 1.

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

[0049] Appendix Figure 6 This is a schematic diagram of the copper substrate in Example 1.

[0050] Appendix Figure 7 This is a schematic diagram of the copper substrate in Example 2.

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

[0052] Figure 1 is a schematic diagram of the composite material in Example 1. Figure 9 Schematic diagram of the composite material in Example 2.

[0053] Figure 2 is a schematic diagram of the composite material in Example 2. Figure 10 Schematic diagram of the hot-pressing sintering cavity.

[0054] Figure 3 is a schematic diagram of the hot-pressing sintering cavity. Figure 11 Figure 4 is a graph of the relationship between the density of the composite material and the sintering temperature.

[0055] Figure 1 is a schematic diagram of the composite material in Example 1. Figure 2 is a schematic diagram of the composite material in Example 2. Figure 3 is a schematic diagram of the hot-pressing sintering cavity. Figure 4 is a graph of the relationship between the density of the composite material and the sintering temperature. DETAILED DESCRIPTION

[0056] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments in the present application, all the other embodiments obtained by those of ordinary skill in the art without creative work fall within the protection scope of the present application.

[0057] Embodiment 1: a system for fusing graphene on a copper substrate using a CVD method and high-temperature sintering, comprising a copper substrate processing system, a CVD forming system, and a hot-press sintering system; the copper substrate processing system comprises a copper plate surface polishing system and an annealing system; the copper plate is polished by the surface polishing system and then enters the annealing 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, and the inside of the annealing chamber I 1 is provided with a temperature detection device; the annealing chamber II is arranged adjacent to the annealing chamber I; the copper plate 2 enters the annealing chamber II after being annealed in the annealing chamber I 1; 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 temperature of the winding shaft 3 is the same as that in the annealing chamber II; the lower end of the winding shaft 3 is provided with a copper plate surface impact clamping device; the copper plate surface impact clamping device comprises impact clamping plates I 4 and II 5 on both sides of the copper plate; the impact clamping plates I 4 and II 5 are symmetrically arranged on both sides of the copper plate wound by the winding shaft; the side of the impact clamping plate I 4 away from the copper plate 2 is a plane; the side of the impact clamping plate I 4 facing the copper plate 2 is provided with a plurality of convex edges 6 parallel to the side edge of the impact clamping plate I 4; the length of the convex edge 6 is equal to the side edge 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 planes; the impact clamping plates I 4 and II 5 are both connected with impact driving devices and movement driving devices; and the annealing cooling chamber is arranged adjacent to the annealing chamber II.

[0058] The CVD forming system comprises a CVD tube furnace, a CVD reaction cavity 20 is arranged in the CVD tube furnace, an observation device is arranged in the cavity, the CVD reaction cavity 20 is internally provided with upper and lower surfaces and front, rear, left and right surfaces; the front end of the CVD reaction cavity 20 is provided with a left supporting rod 14 and a right supporting rod 7 corresponding to the positions of the left and right surfaces, the inside of the left and right supporting rods is provided with a supporting cavity, a rotary motor I is arranged on the cavity wall of the left supporting cavity, a rotary motor II is arranged on the cavity wall of the right supporting cavity, the rotary motor I and the rotary motor II are both connected with a rotating shaft I 15, the other end of the two rotating shafts I 15 is provided with a copper plate clamping jaw I 16, the rotary motor I and the rotary motor II are set to clamp the copper plate parallel to the upper and lower surfaces of the CVD reaction cavity by the copper plate clamping jaw I 16, a plurality of gas inlet holes 10 and heating devices 9 are arranged on the side surface of the upper surface of the CVD reaction cavity 20 towards the copper plate, a sliding groove is further arranged on the side surface of the upper surface towards the copper plate, a copper powder filling device is connected in 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 with the copper powder storage box 18, a plurality of nozzles 19 are communicated at the lower end of the copper powder storage box 18, each nozzle 19 is controlled to open and close by the control valve, the rotary motor I and the rotary motor II are set to clamp the copper plate by the copper plate clamping jaw I 16, the side of the copper plate with a groove faces the plurality of nozzles 19 of the copper powder filling device, the direction of the nozzle 19 is perpendicular to the copper plate 2, a plurality of gas inlet holes 10 and heating devices 9 are arranged on the side surface of the front, rear, left and right surfaces of the CVD reaction cavity 20 towards the inner end of the reaction cavity, a plurality of heating devices 9 are arranged on the side surface of the lower surface 13 of the CVD reaction cavity 20 towards the inner end of the reaction cavity 20, a gas cylinder 21 is further arranged on the side surface of the front surface of the CVD reaction cavity 20 towards the inner end of the reaction cavity, the gas cylinder 21 is connected with a leveling plate 22 through a piston rod, the lower surface of the leveling plate 22 can be in contact with the upper surface of the copper plate 2, and the direction of the leveling plate 22 is parallel to the copper plate 2.

[0059] The hot-pressing sintering system comprises a hot-pressing sintering box body, a hot-pressing sintering box is arranged in the hot-pressing sintering box body, the hot-pressing sintering box comprises a preheating cavity 28, a hot-pressing sintering cavity 29 and a cooling cavity 30; the three cavities are arranged in sequence, heating devices and temperature control devices are arranged in the preheating cavity 28 and the hot-pressing sintering cavity 29; a hot-pressing head 31 is further arranged in the hot-pressing sintering cavity, and the preheating cavity 28, the hot-pressing sintering cavity 29 and the cooling cavity 30 are transmitted through a transmission belt.

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

[0061] Step one: 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 the ethanol and 20% concentration hydrochloric acid solution for cleaning for 15 minutes, take out the copper plate after cleaning, and then ultrasonic washing in the ultrasonic washing device for 10 minutes.

[0062] Step two: put the washed copper plate into the prepared polishing solution for electrochemical polishing, the composition of the polishing solution is water, phosphoric acid, ethanol, potassium iodate and hydrogen peroxide; after electrochemical polishing in the polishing solution, put the copper plate into annealing chamber I for I annealing.

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

[0064] Step four: control the temperature in the annealing chamber II through the temperature control device II, set the temperature in the annealing chamber II and the winding shaft to 300℃, adjust the rotating speed of the driving shaft driving the winding shaft so that the copper plate can pass through the annealing chamber II at a uniform speed after flexible winding on the winding shaft, after flexible winding the copper plate to the lower end of the winding shaft, drive the impact clamping plate I and the impact clamping plate II to impact the two sides of the copper plate through the impact driving device, and press a plurality of grooves corresponding to the convex edges on the side surface of the impact clamping plate I facing the copper plate, the side surface of the copper plate facing the impact clamping plate II is still a plane, after clamping and impacting, start the moving driving device to make the impact clamping plate I and the impact clamping plate II clamp the copper plate into the annealing cooling chamber for cooling.

[0065] Step five: put the annealed and cooled copper plate into the CVD reaction cavity of the CVD tube furnace for CVD reaction, drive the copper plate clamping jaws of the two rotating shafts to clamp the copper plate, and control the rotary motor I and the rotary motor II to drive the rotating shafts to rotate the copper plate to be parallel to the upper surface of the CVD reaction cavity, and the groove side of the copper plate faces the copper powder filling device.

[0066] Step six: after assembling the copper plate, close the CVD tube furnace and start the vacuum pumping operation, when the pressure is lower than 1Pa, heat the reaction cavity through the heating devices on the walls of the CVD reaction cavity, when the temperature reaches 700℃, introduce the reaction gas composed of hydrocarbon methane and ethanol and argon into the reaction cavity through the gas inlet holes on the walls of the CVD reaction cavity to carry out the CVD deposition reaction of graphene-copper.

[0067] Step seven: after the reaction time T, the formation of graphene layer on the copper substrate is observed by the observation device, if the formation is good, the control valve is opened to control the copper powder filling device to move on the upper surface of the CVD reaction chamber, and the nozzle is controlled to spray copper powder into the groove. At this time, the 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 eight: after filling the groove, the gas cylinder on the front surface is controlled to move the piston rod to push the leveling plate to move towards the copper plate to level the copper powder in the filled groove. After leveling, the reaction gas is continuously introduced into the gas inlet hole on each wall of the CVD reaction chamber to carry out CVD deposition reaction, so as to form a second layer of graphene on the first layer of graphene on the flat surface of the copper substrate and the copper powder layer in 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 the preheating chamber for preheating, and the temperature in the preheating chamber is controlled at 150℃ for 5min. After preheating, the copper-graphene composite material is transported to the hot pressing sintering chamber by the conveying belt.

[0070] Step ten: the temperature in the hot pressing sintering chamber is set to three nodes, i.e. 650℃, 800℃ and 850℃, by the temperature control device. After the copper-graphene composite material is sent into the hot pressing sintering chamber, the temperature is controlled to rise to 650℃ within T0 time. After the temperature in the hot pressing sintering chamber reaches 650℃, the temperature is controlled to rise to 800℃ within 3T0 time. After reaching 800℃, the temperature is stopped to keep 800℃ for T0 time. The hot pressing head is controlled to hot press the copper-graphene composite material at this temperature, and then the temperature is controlled to rise to 850℃ within T0 time to complete the hot pressing sintering. After the hot pressing sintering is completed, the composite material is placed in the 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] The embodiment 2 is a system for fusing graphene on a copper substrate by using CVD method and high-temperature sintering. The annealing system comprises an annealing chamber I 1, an annealing chamber II and an annealing cooling chamber. The copper plate surface impact clamping device in the annealing chamber II comprises impact clamping plates I 4 and II 5 on both sides of the copper plate. The impact clamping plates I 4 and II 5 are symmetrically arranged on both sides of the copper plate 2 wound around the winding shaft 3. The impact clamping plate II 5 is lower than the impact clamping plate I 4 in the vertical direction. The side of the impact clamping plate I 4 away from the copper plate is a plane. The side of the impact clamping plate I 4 towards the copper plate is provided with a plurality of convex edges 6 parallel to the side of the impact clamping plate I 4. The length of the convex edge 6 is equal to the side of the impact clamping plate I 4. The side of the impact clamping plate II 5 away from the copper plate is a plane. The side of the impact clamping plate II 5 towards the copper plate is provided with a plurality of convex edges 6 parallel to the side of the impact clamping plate II 5. The convex edges 6 on the side surface of the impact clamping plates I 4 and II 5 towards the copper plate comprise two side surfaces and a top surface, which form a trapezoidal shape.

[0073] The CVD forming system comprises a CVD tube furnace. A CVD reaction cavity 20 is arranged in the CVD tube furnace. An observation device is arranged in the cavity. The CVD reaction cavity 20 is internally provided with upper and lower surfaces and front, rear, left and right surfaces. Each surface of the CVD reaction cavity 20 is provided with a plurality of gas inlet holes 10 and heating devices 9 towards the inside of the chamber. A rotating motor is arranged on the left surface 23 and the right surface 24 of the CVD reaction cavity 20. The two rotating motors are connected with rotating shafts II 25. The other ends of the rotating shafts II 25 are connected with copper plate clamping jaws II 27. The two copper plate clamping jaws II 27 clamp the copper plate. The two rotating motors rotate the copper plate 2 to an angle of α with the horizontal plane through the copper plate clamping jaws II 27. The angle α can be 30 degrees, 45 degrees or 60 degrees. Copper powder filling devices are arranged above the upper surface and below the lower surface of the copper plate 2. The copper powder filling devices comprise sliding blocks, connecting rods 17, cross bars 26, copper powder storage boxes 18, nozzles 19 and control valves. The sliding blocks are arranged at one end of the connecting rods 17 and move in the sliding grooves on the cross bars 26. The other ends of the connecting rods are connected with the copper powder storage boxes 18. The lower ends of the copper powder storage boxes 18 are communicated with a plurality of nozzles 19. Each nozzle is controlled to open and close by a control valve. The positions of the copper powder filling devices corresponding to the upper and lower surfaces of the copper plate 2 are arranged. Each nozzle 19 is perpendicular to the upper and lower surfaces of the copper plate 2.

[0074] The method for fusing graphene on a copper substrate by using the system for fusing graphene on a copper substrate by using CVD method and high-temperature sintering in the embodiment 2 replaces the fourth step in the method of the embodiment 1. 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, and grooves are formed on both sides of the copper plate towards the impact clamping plates.

[0075] In step seven to eight of the method of the first embodiment, when the CVD reaction is performed, after the reaction time T, the formation of the graphene layer on the copper substrate is observed by the observation device, and if the formation is good, the supply of the reaction gas is controlled to be stopped, the corresponding copper powder filling device on the upper and lower surfaces of the copper plate is controlled to move on the horizontal rod inside the CVD reaction chamber, and after the nozzles correspond to each groove on the copper plate, the control valve is controlled to be opened to allow the nozzles to spray copper powder into the grooves. At this time, the graphene layer is formed on the upper and lower surface planes 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 continuously supplied through the gas supply holes on the walls of the CVD reaction chamber to perform CVD deposition reaction, thereby forming a second layer of graphene on the first layer of graphene on the flat upper and lower surfaces of the copper substrate and the copper powder layer in the grooves, thereby forming a copper-graphene composite material.

[0076] In the second embodiment, the copper plate substrate is configured as follows: a portion of the material of the copper plate is removed on the first surface 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 surface of the copper plate to form alternating grooves and protrusions; 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; or the grooves on the first surface correspond to the grooves on the second surface, and the protrusions on the first surface correspond to the protrusions on the second surface; wherein the shapes of the protrusions and grooves include: the grooves or protrusions are trapezoidal or square.

[0077] In the above embodiments, the copper powder used to fill the grooves can be replaced by a combination of copper foam and copper powder. In the processing method, after the graphene layer is deposited in the grooves, a layer of copper powder can be uniformly laid on the grooves, and foam copper material can be filled and compacted. After compaction, copper powder material can be filled on the compacted foam copper and subjected to secondary compaction. The resulting product can be sintered and then subjected to a second CVD step.

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

[0079] As a further improvement, the plate can be circular, and the grooves on the first surface are circular rings, and the grooves on the second surface are 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 surface and the grooves on the second surface are arranged vertically, the grooves on the first surface are filled with copper powder, the second surface is filled with foam copper, or the grooves on the first surface are filled with copper powder and foam copper, and the second surface is filled with copper powder or foam copper.

Claims

1. A system for fusing graphene on a copper substrate using CVD and high-temperature sintering, comprising a copper substrate processing system, a CVD forming system, and a hot pressing sintering system; the copper substrate processing system includes 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 including annealing chamber I (1), annealing chamber II and annealing cooling chamber, a temperature control device I is provided on the top of annealing chamber I (1), a temperature detection device is provided inside annealing chamber I (1), annealing chamber II and annealing chamber I are arranged adjacent to each other, the copper plate (2) enters annealing chamber II after undergoing first-stage annealing in annealing chamber I (1), and annealing chamber II is provided with... There is a temperature control device II and a winding device. The winding device includes a winding shaft (3) and a drive shaft for driving the winding shaft. 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 provided at the lower end of the winding shaft (3). The copper plate surface impact clamping device includes impact clamping plates I (4) and impact clamping plates II (5) on both sides of the copper plate. The impact clamping plates I (4) and impact clamping plates II (5) are symmetrically arranged on both sides of the copper plate wound by the winding shaft. 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 parallel to the side of the impact clamping plate I (4) with multiple protruding ridges (6).

2. The system for fusing graphene on a copper substrate using CVD and high-temperature sintering according to claim 1, characterized in that: The length of the protruding 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 arranged adjacent to each other.

3. The system for fusing graphene on a copper substrate using CVD and high-temperature sintering according to claim 2; characterized in that... The CVD forming system includes a CVD tube furnace, which is equipped with a CVD reaction chamber (20). An observation device is installed inside the chamber. The CVD reaction chamber (20) has upper and lower surfaces, as well as front, back, left and right surfaces. A left support rod (14) and a right support rod (7) are installed at the front end of the CVD reaction chamber (20) corresponding to the positions of the left and right surfaces. A support cavity is installed inside the left and right support rods. A rotary motor I is installed on the cavity wall of the left support cavity, and a rotary motor II is installed on the cavity wall of the right support cavity. Rotary motor I and rotary motor II are connected to a rotating shaft I (15). A copper plate clamping claw I (16) is installed at the other end of the two rotating shafts I (15). The rotary motors I and II are configured to clamp the copper plate parallel to the upper and lower surfaces of the CVD reaction chamber using the copper plate clamping claw I (16).

4. The system for fusing graphene on a copper substrate using CVD and high-temperature sintering according to claim 3; characterized in that: The upper surface of the CVD reaction chamber (20) facing the copper plate has multiple gas inlet holes (10) and heating devices (9). The upper surface facing the copper plate also has a sliding groove. 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. The sliding block is set 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 multiple nozzles (19). Each nozzle (19) is controlled to open and close by a control valve.

5. The system for fusing graphene on a copper substrate using CVD and high-temperature sintering according to claim 4; characterized in that: Rotary motor I and rotary motor II are configured such that 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 CVD and high-temperature sintering according to claim 5; characterized in that: The hot-press sintering system includes a hot-press sintering box, which contains a hot-press sintering chamber. The hot-press sintering chamber contains a preheating chamber (28), a hot-press sintering chamber (29), and a cooling chamber (30). The three chambers are arranged in sequence. The preheating chamber (28) and the hot-press sintering chamber (29) are equipped with heating devices and temperature control devices. The hot-press sintering chamber is also equipped with a hot-pressing head (31). The three chambers, namely the preheating chamber (28), the hot-press sintering chamber (29), and the cooling chamber (30), are connected by a conveyor belt.

7. A method for fusing graphene on a copper substrate using the CVD method and high-temperature sintering system described in claims 1-6, 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 inside annealing chamber I is controlled by the temperature control device I at the top of annealing chamber I; after the first-stage annealing time is completed, the copper substrate is transported to 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 both sides of the copper plate. Step 5: Place the annealed and cooled copper plate into the CVD reaction chamber of the CVD tube furnace for CVD reaction; Step Six: After assembling the copper plates, shut down the CVD tube furnace and begin the vacuuming process. When the vacuum pressure is below 1 Pa, heat the reaction chamber through the heating devices on each wall of the CVD reaction chamber. When the temperature reaches 700°C, introduce a reaction gas composed of hydrocarbons, methane, ethanol, and argon into the reaction chamber through the gas inlet holes on each wall 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. The temperature in the preheating chamber is controlled at 150℃ for 5 minutes. After preheating, the copper-graphene composite material is transported to the hot pressing sintering chamber by a conveyor belt. Step 8: Set the temperature in the hot-pressing sintering chamber to three points using a temperature control device: 650℃, 800℃, and 850℃. After the copper-graphene composite material is fed into the hot-pressing sintering chamber, control the temperature to rise to 650℃ within time T0. After the temperature in the hot-pressing sintering chamber reaches 650℃, control the temperature to rise to 800℃ within time 3T0. After reaching 800℃, stop the temperature rise and maintain 800℃ for time T0. At this temperature, control the hot press head to hot-press the copper-graphene composite material, and then continue to control the temperature to rise to 850℃ within time T0 to complete the hot-pressing sintering. After the hot-pressing sintering is completed, place the composite material into the 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 side correspond to the protrusions on the second side, and the protrusions on the first side correspond to the grooves on the second side; wherein the shapes of the protrusions and grooves include trapezoidal and square.

10. The composite material according to claim 9, characterized in that: The first and second grooves may be filled with the same or different materials, and the materials may be copper powder or copper foam, or any one or more of them.

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