Preparation method of graphene superconducting copper wire, graphene superconducting copper wire and stripping device

Abstract

This invention relates to a method for preparing graphene superconducting copper wire, the graphene superconducting copper wire, and a peeling device. The method employs a swing-and-scrape technique. Oxygen-free copper spheres coated with adhesive are added to an upper frame containing artificial graphite. The frame is vibrated and swings to adhere the adhesive to the artificial graphite on the surface of the oxygen-free copper spheres. The oxygen-free copper spheres with adhered artificial graphite are then transferred to a frame coated with adhesive. The frame is vibrated and swings again to repeatedly peel and bond the artificial graphite and adhesive on the surface of the oxygen-free copper spheres, resulting in a few-layer graphene and thus a graphene composite copper material. This method enables the continuous preparation of defect-free graphene. In the swing-and-scrape device, the oxygen-free copper spheres are subjected to high-speed swinging vibrations in all directions, causing them to roll back and forth. This results in the adhesion of artificial graphite microsheets to the surface of the oxygen-free copper spheres, which is then repeatedly peeled and bonded, thereby obtaining graphene with a low layer count and no structural defects.

Description

Technical Field

[0001] This invention relates to the field of wire and cable technology, and in particular to a method for preparing graphene superconducting copper wire, the graphene superconducting copper wire and stripping device. Background Technology

[0002] The copper wire and cable industry in China has an annual output value exceeding 1.4 trillion yuan. The cable industry extensively uses polymer materials, composite materials, and metallic materials, with an estimated annual usage of trillions of yuan. Therefore, improvements in material performance are crucial to the advancement of the cable industry. Copper or copper alloys are the most commonly used materials in wires and cables, due to their low price, excellent electrical and thermal conductivity, and good plasticity and corrosion resistance. However, pure copper conductors have low strength, are prone to breakage, and have a high rate of power grid failures.

[0003] Graphene, known as the "king of new materials" due to its excellent thermal, electrical, mechanical, and optical properties, has great application potential in fields such as wire and cable, aerospace, energy conservation and environmental protection, electronic information, and transportation. It has already shown promising application prospects in both traditional and emerging fields such as composite materials, energy conservation and environmental protection, thermal management, new energy, electronic information, and aerospace. Because of its ultra-high carrier transport speed and thermal conductivity, graphene experiences lower signal loss during propagation compared to ordinary materials; therefore, graphene-coated copper wires have excellent applications in high-quality signal transmission, liquid crystals, and flexible displays. Liquid-phase organic molecules have relatively simple molecular structures, resulting in lower pyrolysis temperatures and fewer defects in the grown graphene. Compared to gases such as methane, it offers advantages such as higher efficiency, lower growth temperatures, lower cost, and greater safety and reliability.

[0004] Patent CN113481406A discloses a method for preparing graphene copper wire. This method mainly involves: ball milling a mixture of few-layer graphene oxide powder and oxygen-free copper powder, followed by low-temperature hot-pressing sintering and vacuum melting to prepare a graphene copper alloy, which is then used to fabricate graphene copper wire. The main problems with this method are: first, the graphene oxide prepared by the Hunmers method has lattice defects and a high carbon-to-oxygen ratio, resulting in poor thermal and electrical conductivity, and subsequent processes struggle to control the degree of graphene oxide reduction; second, while mechanical ball milling is used to mix the graphene oxide and oxygen-free copper powder, the poor wettability between graphene and copper leads to unsatisfactory interfacial bonding; and third, the agglomeration of graphene during the composite process. Therefore, solving these problems to obtain high-performance graphene copper wire is a major challenge that needs to be addressed. Summary of the Invention

[0005] To overcome the problems mentioned above, this invention provides a method for preparing graphene superconducting copper wire, the graphene superconducting copper wire, and a peeling device. The method employs a swing peeling technique, which enables the continuous preparation of defect-free graphene. In the swing peeling device, oxygen-free copper balls are subjected to high-speed swinging vibrations in all directions and roll back and forth, causing artificial graphite microsheets to adhere to the surface of the oxygen-free copper balls. The process is further repeated by peeling and bonding, thereby obtaining graphene with a low number of layers and no structural defects.

[0006] The technical solution adopted by this invention to solve its technical problem is: a method for preparing graphene superconducting copper wire, the preparation method comprising the following steps:

[0007] Step 1: Pretreatment of oxygen-free copper balls: Soak the oxygen-free copper balls in adhesive water, take them out and let them dry to obtain oxygen-free copper balls with adhesive coating on the surface.

[0008] Step 2: Preparation of graphene composite copper material: The oxygen-free copper balls with adhesive coating are added into the upper frame containing artificial graphite. The adhesive coating on the surface of the oxygen-free copper balls adheres to the artificial graphite by vibrating and swaying the frame. The oxygen-free copper balls with the artificial graphite adhered to their surface are transferred to the frame with adhesive coating. The artificial graphite and adhesive coating on the surface of the oxygen-free copper balls are repeatedly peeled off and bonded by vibrating and swaying the frame. The peeling process yields a few layers of graphene, thus obtaining the graphene composite copper material.

[0009] Step 3: Preparation of graphene superconducting copper preform: The graphene composite copper material is hot-pressed and sintered to combine graphene and copper, thus obtaining the graphene superconducting copper preform.

[0010] Step 4: Preparation of graphene-modified oxygen-free copper rod: The graphene superconducting copper blank is placed in a melting furnace and cerium-rich mixed rare earth is added. The furnace is then melted under nitrogen protection and the graphene oxygen-free copper rod is obtained by directional solidification.

[0011] Step 5: Preparation of graphene superconducting copper busbar: After removing the oxide layer, oil and burrs from the surface of the graphene oxygen-free copper rod, it is fed into a continuous extruder for continuous extrusion to obtain the graphene superconducting copper busbar.

[0012] Step 6: Preparation of graphene superconducting copper wire: The graphene superconducting copper busbar is added to a drawing machine for drawing and annealing under nitrogen protection to obtain the graphene superconducting copper wire.

[0013] Preferably, the oxygen-free copper spheres have an oxygen volume content of less than 20 PPM and a diameter of 0.5 mm to 2 mm.

[0014] Preferably, the self-adhesive is an oil-soluble self-adhesive with a solid content of 10% to 20% and a viscosity of 100-200 mP.s, or a water-soluble self-adhesive with a solid content of 15% to 25% and a viscosity of 100-250 mP.s.

[0015] Preferably, in step two, a swinging peeling device is used to prepare graphene composite copper material. The swinging peeling device includes an upper frame, a middle frame and a bottom frame. Artificial graphite is placed in the upper frame, and the middle frame and the bottom frame are coated with an adhesive layer. The rotation speed of the swinging peeling device is 900 rpm / min to 1800 rpm / min, and the double amplitude is 2 mm to 6 mm.

[0016] Preferably, the hot pressing sintering is carried out at a sintering temperature of 830-880℃, a pressure of 30-40 MPa, and a sintering time of 2-4 hours.

[0017] Preferably, the melting temperature of the smelting furnace is 1200-1300℃.

[0018] Preferably, the amount of cerium-rich mixed rare earth added is 0.02wt% to 0.20wt% of the graphene superconducting copper preform.

[0019] Preferably, the mass fraction of each element in the cerium-rich mixed rare earth is 50-56% cerium, 24-30% lanthanum, 10-15% neodymium, and 1-5% praseodymium.

[0020] Preferably, the continuous online annealing method of the annealing heat treatment is used, with an annealing temperature of 300℃~450℃.

[0021] The present invention also provides a graphene superconducting copper wire, comprising the graphene superconducting copper wire prepared by the above preparation method.

[0022] Preferably, the graphene superconducting copper wire has a diameter of 0.1–1.8 mm.

[0023] The present invention also provides a swing peeling device, comprising multiple frames arranged from top to bottom and a vibrating body. The bottom frame has a material collection port on its side wall, and the other frames have discharge pipes on their inner edges. The discharge port of the discharge pipe corresponds to the center position of the frame below. The top frame has a layer of artificial graphite film on its upper surface, and the other frames have an adhesive layer on their upper surfaces.

[0024] The beneficial effects of this invention are:

[0025] 1. The method for preparing graphene superconducting copper wire according to the present invention has no environmental pollution in the graphene preparation process and no impurity elements are introduced in the subsequent preparation process. The resulting graphene superconducting copper is used to produce materials, thereby improving the conductivity and thermal conductivity of copper wire.

[0026] 2. The method for preparing graphene superconducting copper wire described in this invention uses a swinging peeling device to achieve high-speed swinging and rolling of oxygen-free copper balls to repeatedly bond and peel them mechanically. The resulting graphene has no structural defects and the lattice is free of non-carbon atom doping, maximizing the preservation of the original electron mobility and thermal conductivity of graphene. Furthermore, by coating the surface of oxygen-free copper with graphene, the problem of graphene and copper dispersion is indirectly solved.

[0027] 3. The graphene superconducting copper wire prepared by the method of the present invention has a tensile strength of 300 MPa to 350 MPa, a yield strength of 150 MPa to 260 MPa, a conductivity of 103% to 107%, and a thermal conductivity of 550 W / m·K to 600 W / m·K. Attached Figure Description

[0028] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0029] Figure 1 This is a schematic diagram of the structure of a swing-type peeling device for graphene superconducting copper according to an embodiment of the present invention.

[0030] Figure 2 This is a schematic diagram of the structure of a swing-type peeling device for graphene superconducting copper according to an embodiment of the present invention.

[0031] Figure 3 This is a schematic diagram of the upper frame structure of a swing-type peeling device for graphene superconducting copper according to an embodiment of the present invention.

[0032] Figure 4 This is a schematic diagram of the middle frame structure of a swing-type peeling device for graphene superconducting copper according to an embodiment of the present invention.

[0033] Figure 5 This is a schematic diagram of the bottom frame structure of a swing-type peeling device for graphene superconducting copper according to an embodiment of the present invention.

[0034] Legend:

[0035] 1. Top frame; 2. Middle frame; 3. Bottom frame; 4. Discharge pipe; 5. Collection port; 6. Vibrating body; 7. Drive motor; 8. Artificial graphite layer; 9. Adhesive layer Detailed Implementation

[0036] The present invention will now be described in further detail with reference to the accompanying drawings. These drawings are simplified schematic diagrams, illustrating only the basic structure of the invention, and therefore only show the components relevant to the invention.

[0037] Example 1

[0038] This embodiment describes a method for preparing graphene superconducting copper wire, such as... Figure 1 As shown, it includes the following steps:

[0039] Step 1: Pretreatment of oxygen-free copper balls: Soak the oxygen-free copper balls in adhesive water, take them out and let them dry to obtain oxygen-free copper balls with adhesive coating on the surface.

[0040] Step 2: Preparation of graphene composite copper material: The oxygen-free copper balls with adhesive coating are added into the upper frame containing artificial graphite. The adhesive coating on the surface of the oxygen-free copper balls adheres to the artificial graphite by vibrating and swaying the frame. The oxygen-free copper balls with the artificial graphite adhered to their surface are transferred to the frame with adhesive coating. The artificial graphite and adhesive coating on the surface of the oxygen-free copper balls are repeatedly peeled off and bonded by vibrating and swaying the frame. The peeling process yields a few layers of graphene, thus obtaining the graphene composite copper material.

[0041] Step 3: Preparation of graphene superconducting copper preform: The graphene composite copper material is hot-pressed and sintered to combine graphene and copper, thus obtaining the graphene superconducting copper preform.

[0042] Step 4: Preparation of graphene-modified oxygen-free copper rod: The graphene superconducting copper blank is placed in a melting furnace and cerium-rich mixed rare earth is added. The furnace is then melted under nitrogen protection and the graphene oxygen-free copper rod is obtained by directional solidification.

[0043] Step 5: Preparation of graphene superconducting copper busbar: After removing the oxide layer, oil and burrs from the surface of the graphene oxygen-free copper rod, it is fed into a continuous extruder for continuous extrusion to obtain the graphene superconducting copper busbar.

[0044] Step 6: Preparation of graphene superconducting copper wire: The graphene superconducting copper busbar is added to a drawing machine for drawing and annealing under nitrogen protection to obtain the graphene superconducting copper wire.

[0045] In step one, as an example, the selected oxygen-free copper spheres have an oxygen volume content of less than 20 PPM and a diameter of 0.5 mm to 2 mm. Specifically, the oxygen volume content of the oxygen-free copper can be 15 PPM, 10 PPM, etc., and the diameter of the oxygen-free copper spheres can be 0.5 mm, 1 mm, 1.2 mm, 1.5 mm, 1.8 mm, 2 mm, etc.

[0046] In this embodiment, an artificial graphite film made of polyimide (PI) film is used as the graphene raw material, and oxygen-free copper balls and self-adhesive are used as the release medium.

[0047] In step one, either oil-soluble or water-soluble self-adhesive is used. When using oil-soluble self-adhesive, its solid content can be 10% to 20% and its viscosity can be 100-200 mP.s. When using water-soluble self-adhesive, its solid content can be 15% to 25% and its viscosity can be 100-250 mP.s.

[0048] In step two, a swing exfoliation device is used to prepare graphene composite copper material, which can realize the continuous preparation of defect-free graphene. In the swing exfoliation device, oxygen-free copper balls are subjected to high-speed swing vibration in all directions and roll back and forth, so that artificial graphite micro flakes are attached to the surface of the oxygen-free copper balls. The process is further repeated to peel and bond, thereby obtaining graphene with low layer count and no structural defects.

[0049] Specifically, the swing-type exfoliation device includes an upper frame, a middle frame, and a bottom frame. Artificial graphite is placed inside the upper frame, while the middle and bottom frames are coated with an adhesive layer. By vibrating the swing frame, the adhesive layer on the surface of the oxygen-free copper spheres adheres to the artificial graphite within the upper frame. Subsequently, the oxygen-free copper spheres with the adhered artificial graphite fall into the middle frame. Vibration of the swing frame causes repeated peeling and bonding of the artificial graphite and adhesive layer on the surface of the oxygen-free copper spheres. This process is repeated once more in the bottom frame, resulting in the extraction of few-layer graphene, thus obtaining a graphene-copper composite material without structural defects, solving the problem of graphene and copper dispersion. The swing-type exfoliation device in this method enables the controllable, continuous, and green preparation of graphene-superconducting copper composite materials.

[0050] In this embodiment, the rotation speed of the swing peeling device is 900 rpm / min to 1800 rpm / min. After passing through the transmission device, the double amplitude of the swing peeling device is between 2 mm and 6 mm.

[0051] In step three, the hot pressing sintering temperature is 830℃~880℃, the pressure is 30~40MPa, and the sintering time is 2~4 hours. Specifically, in this embodiment, the sintering temperature can be 830℃, 850℃, 880℃, etc., and the pressure can be 30MPa or 40MPa.

[0052] Next, step four is carried out: preparation of graphene-modified oxygen-free copper rods: graphene superconducting copper blanks are placed in a melting furnace, and cerium-rich mixed rare earths are added. The mixture is melted under nitrogen protection and then solidified in a directional manner to obtain graphene oxygen-free copper rods.

[0053] In step four, the melting temperature in the smelting furnace is 1200–1300°C. Specifically, in this embodiment, the melting temperature in the smelting furnace can be 1200°C, 1250°C, 1300°C, etc.

[0054] As an example, in step four, the amount of cerium-rich mixed rare earth added is 0.02wt% to 0.20wt% of the graphene superconducting copper preform, and the mass fraction of each element in the cerium-rich mixed rare earth is 50-56% cerium, 24-30% lanthanum, 10-15% neodymium, and 1-5% praseodymium.

[0055] Specifically, the amount of cerium mixed rare earth added is 0.02wt%, 0.05wt%, 0.10wt%, and 0.20wt% of the graphene superconducting copper preform, and the mass fraction of each element in the cerium-rich mixed rare earth can be 50%, 52%, 54%, and 56% cerium, 24%, 26%, 28%, and 30% lanthanum, 10%, 12.5%, and 15% neodymium, and 1%, 2%, 3%, 4%, and 5% praseodymium.

[0056] Step 5, preparation of graphene superconducting copper busbar: After removing the oxide layer, oil and burrs from the surface of the graphene oxygen-free copper rod, it is fed into a continuous extruder for continuous extrusion to obtain the graphene superconducting copper busbar.

[0057] Step six, preparation of graphene superconducting copper wire: The graphene superconducting copper busbar is added to a stretching machine for drawing and annealing under nitrogen protection to obtain the graphene superconducting copper wire.

[0058] In step six, the continuous online annealing heat treatment is performed, with the annealing temperature selected as 300℃~450℃. Specifically, the continuous online annealing heat treatment can be performed at temperatures such as 300℃, 350℃, 400℃, and 450℃.

[0059] Example 2

[0060] A graphene superconducting copper wire, prepared by the method described in Example 1, has a diameter of 0.1–1.8 mm.

[0061] Example 3

[0062] like Figure 2-5 The swing stripping device shown includes multiple frames arranged from top to bottom and a vibrator 6. The vibrator 6 can provide a rotation speed of 900 rpm / min to 1800 rpm / min. After passing through the transmission mechanism, the vibrator 6 enables the frames to vibrate with a double amplitude between 2 mm and 6 mm.

[0063] The frames are stacked, and the bottom frame has a material collection port 5 on its side wall. Except for the bottom frame, the other frames have discharge pipes 4 on their inner edges. The discharge port of the discharge pipe 4 corresponds to the center of the frame below.

[0064] Among them, the uppermost frame has a layer of artificial graphite film 8 on its upper surface, and the upper surfaces of the other frames have an adhesive layer 9.

[0065] During operation, the oxygen-free copper balls are sequentially vibrated and peeled off from the upper frame, pushed to the bottom frame, and enter the collection port 5. This causes the artificial graphite and adhesive on the surface of the oxygen-free copper balls to be repeatedly peeled off and bonded. The peeling process yields a few layers of graphene, thus obtaining graphene composite copper material.

[0066] For details, see Figure 2 The vibrating body 6 is located below the bottom frame 3; see also Figure 3 , 4 5. The frame includes an upper frame 1 at the top, a middle frame 2 below the upper frame 1, and a bottom frame 3; the upper surface of the upper frame 1 is provided with a layer of artificial graphite film 8, and the upper surfaces of the middle frame 2 and the bottom frame 3 are provided with an adhesive layer 9.

[0067] Based on the above-described preferred embodiments of the present invention, and through the foregoing description, those skilled in the art can make various changes and modifications without departing from the inventive concept. The technical scope of this invention is not limited to the contents of the specification, but must be determined according to the scope of the claims.

Claims

1. A method for preparing graphene superconducting copper wire, characterized in that, The preparation method includes the following steps: Step 1, pretreatment of oxygen-free copper balls: Immerse oxygen-free copper balls in adhesive water, remove and dry them to obtain oxygen-free copper balls with adhesive coating on the surface; Step 2, preparation of graphene composite copper material: Add the above-mentioned oxygen-free copper balls with adhesive coating to an upper frame containing artificial graphite, and use vibration and swaying of the frame to make the adhesive on the surface of the oxygen-free copper balls adhere to the artificial graphite; Transfer the oxygen-free copper balls with adhesive on the surface to a frame with adhesive coating, and use vibration and swaying of the frame to repeatedly peel off and adhere the artificial graphite and adhesive on the surface of the oxygen-free copper balls, peeling off to obtain a few layers of graphene, thereby obtaining graphene composite copper material. The uppermost frame has a layer of bare artificial graphite film on its upper surface. The graphene composite copper material is prepared using a swaying peeling device, which includes an upper frame, a middle frame and a bottom frame. Artificial graphite is placed in the upper frame, and the middle and bottom frames are coated with... The adhesive layer is peeled off at a speed of 900 rpm / min to 1800 rpm / min with a double amplitude of 2 mm to 6 mm. Step 3: Preparation of graphene superconducting copper preform: The graphene composite copper material is hot-pressed and sintered to combine graphene and copper, resulting in a graphene superconducting copper preform. Step 4: Preparation of graphene-modified oxygen-free copper rod: The graphene superconducting copper preform is placed in a melting furnace, and cerium-rich mixed rare earth elements are added. Melting is carried out under nitrogen protection, and the graphene oxygen-free copper rod is obtained through directional solidification. Step 5: Preparation of graphene superconducting copper busbar: After removing the oxide layer, oil, and burrs from the surface of the graphene oxygen-free copper rod, it is fed into a continuous extruder for continuous extrusion to obtain the graphene superconducting copper busbar. Step 6: Preparation of graphene superconducting copper wire: The graphene superconducting copper busbar is added to a stretching machine for drawing and annealing under nitrogen protection to obtain the graphene superconducting copper wire.

2. The method for preparing graphene superconducting copper wire according to claim 1, characterized in that: The oxygen-free copper spheres have an oxygen volume content of less than 20 PPM and a diameter of 0.5 mm to 2 mm.

3. The method for preparing graphene superconducting copper wire according to claim 1, characterized in that: The self-adhesive is an oil-soluble self-adhesive with a solid content of 10% to 20% and a viscosity of 100-200 mP.s, or a water-soluble self-adhesive with a solid content of 15% to 25% and a viscosity of 100-250 mP.s.

4. The method for preparing graphene superconducting copper wire according to claim 1, characterized in that: The hot pressing sintering is carried out at a sintering temperature of 830-880℃, a pressure of 30-40 MPa, and a sintering time of 2-4 hours.

5. The method for preparing graphene superconducting copper wire according to claim 1, characterized in that: The amount of cerium-rich mixed rare earth added is 0.02wt% to 0.20wt% of the graphene superconducting copper preform.

6. The method for preparing graphene superconducting copper wire according to claim 5, characterized in that: The mass fraction of each element in the cerium-rich mixed rare earth is 50-56% cerium, 24-30% lanthanum, 10-15% neodymium, and 1-5% praseodymium.

7. The method for preparing graphene superconducting copper wire according to claim 1, characterized in that: The continuous online annealing method for the annealing heat treatment selects an annealing temperature of 300℃~450℃.

8. A graphene superconducting copper wire, characterized in that: Including graphene superconducting copper wire prepared by the preparation method according to any one of claims 1-7.

9. A swing-type peeling device, characterized in that: It includes multiple frames arranged from top to bottom and a vibrator (6). The bottom frame has a material collection port (5) on its side wall, and the other frames have discharge pipes (4) on their inner edges. The discharge port of the discharge pipe (4) corresponds to the center of the frame below. The top frame has a layer of artificial graphite film (8) on its upper surface, and the other frames have an adhesive layer (9) on their upper surface.

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