Preparation method of graphene reinforced copper-based composite wire

Abstract

The invention discloses a preparation method of a graphene reinforced copper-based composite wire. According to the graphene silver-plated powder obtained after the surface of graphene is plated with silver through the chemical plating technology, the high-temperature conductivity of the graphene-enhanced copper-based composite wire is effectively improved by controlling the silver content in the graphene silver-plated powder to range from 15.3 wt% to 34.7 wt%, and meanwhile the tensile strength of the copper-based composite wire is kept small in change. The conductivity of the copper-based composite wire prepared by the method is still kept above 70% IACS (International Annealed Copper Standard) under the temperature rise condition of 150 DEG C, and the copper-based composite wire has a wide application prospect in conductor materials of heating equipment.

Description

Technical Field

[0001] The invention belongs to the field of copper-based new materials, and specifically relates to a method for preparing a graphene-reinforced copper-based composite wire. Background Art

[0002] With the development of industry and the emergence of many emerging fields, higher requirements are placed on conductor materials. Pure copper wire has gained wide attention due to its excellent electrical and thermal conductivity. The conductivity of pure copper at room temperature is usually above 100% IACS. However, under elevated temperature conditions, the scattering of free electrons caused by atomic oscillations intensifies, resulting in a significant decrease in the conductivity of pure copper. For example, at 150°C, the conductivity of pure copper drops to about 68% IACS. Therefore, the industry is in urgent need of developing high-quality conductive materials that can serve under elevated temperature conditions. In view of this, the purpose of the present invention is to obtain a conductor material with excellent high-temperature conductivity. Summary of the invention

[0003] The object of the present invention is to provide a method for preparing a graphene-reinforced copper-based composite wire, aiming to obtain a copper-based composite wire with excellent high-temperature electrical conductivity and tensile strength.

[0004] The technical solution of the present invention is as follows:

[0005] A method for preparing a graphene-reinforced copper-based composite wire comprises the following steps:

[0006] Weigh graphene to form a solution system, and stir and disperse it at a speed of 300-350r / min for 30-60min; prepare a 0.3-0.5g / mL silver nitrate solution, mix it with the graphene solution and stir it magnetically for 30-60min, then drop 0.15-0.30g / mL glucose solution as a reducing agent, heat it to about 80-95°C, stir it at a constant temperature to make it fully react, and obtain a silver-containing graphene composite powder, and finally reduce it in a mixed atmosphere of hydrogen / argon to obtain a graphene silver-plated powder, and adjust the amount of graphene so that the proportion of silver in the graphene silver-plated powder is 15.3-34.7wt%;

[0007] The graphene silver-plated powder and copper powder are ground and mixed in a mass ratio of 1:1.82-2.11, and then loaded into an oxygen-free copper tube. The copper tube is rotary forged to an outer diameter of Φ6-8mm using a rotary forging machine, and then multiple drawing deformations are performed on a drawing machine to obtain a wire with a diameter of Φ1-1.2mm. Finally, vacuum annealing is performed at 320-330°C for 2-3h to eliminate stress to obtain a graphene-reinforced copper-based composite wire.

[0008] Preferably, the stirring speed is 350 r / min.

[0009] Preferably, the annealing temperature is 320°C.

[0010] Preferably, the annealing time is 2 h.

[0011] Preferably, the concentration of the silver nitrate solution is 0.5 g / mL.

[0012] Preferably, the concentration of the glucose solution is 0.30 g / mL.

[0013] Preferably, the proportion of silver in the silver-plated graphene powder is 23.4 wt %.

[0014] The graphene silver-plated powder obtained by the present invention after silver is plated on the graphene surface by chemical plating process can significantly improve the high-temperature conductivity of the graphene-enhanced copper-based composite wire. At the same time, the appropriate silver content has little effect on the tensile strength of the graphene-enhanced copper-based composite wire, but too much silver content will have a negative impact on the tensile strength. Therefore, in practice, the silver content in the graphene silver-plated powder should be controlled at 15.3wt%-34.7wt%. DETAILED DESCRIPTION

[0015] The technical effects of the present invention are verified below through specific examples, but the embodiments of the present invention are not limited thereto.

[0016] Example 1

[0017] Weigh graphene to form a solution system, and stir and disperse it at a speed of 300 r / min for 30 minutes; prepare a 0.3 g / mL silver nitrate solution, mix it with the graphene solution and stir it magnetically for 30 minutes, then drop 0.15 g / mL glucose solution as a reducing agent, heat it to 80° C., stir it at a constant temperature to make it fully react, and obtain a silver-containing graphene composite powder, and finally reduce it in a mixed atmosphere of hydrogen / argon to obtain a graphene silver-plated powder, and adjust the amount of graphene so that the proportion of silver in the graphene silver-plated powder is 15.3wt%;

[0018] The graphene silver-plated powder and copper powder were ground and mixed in a mass ratio of 1:1.82, and then loaded into an oxygen-free copper tube. The copper tube was rotary forged to an outer diameter of Φ6 mm using a rotary forging machine, and then multiple drawing deformations were performed on a drawing machine to obtain a wire with a diameter of Φ1 mm. Finally, vacuum annealing was performed at 320°C for 2h to eliminate stress to obtain a graphene-reinforced copper-based composite wire.

[0019] Example 2

[0020] Weigh graphene to form a solution system, and stir and disperse it at a speed of 300 r / min for 30 minutes; prepare a 0.3 g / mL silver nitrate solution, mix it with the graphene solution and stir it magnetically for 30 minutes, then drop 0.15 g / mL glucose solution as a reducing agent, heat it to 80° C., stir it at a constant temperature to make it fully react, and obtain a silver-containing graphene composite powder, and finally reduce it in a mixed atmosphere of hydrogen / argon to obtain a graphene silver-plated powder, and adjust the amount of graphene so that the proportion of silver in the graphene silver-plated powder is 18.5wt%;

[0021] The graphene silver-plated powder and copper powder were ground and mixed in a mass ratio of 1:1.82, and then loaded into an oxygen-free copper tube. The copper tube was rotary forged to an outer diameter of Φ6 mm using a rotary forging machine, and then multiple drawing deformations were performed on a drawing machine to obtain a wire with a diameter of Φ1 mm. Finally, vacuum annealing was performed at 320°C for 2h to eliminate stress to obtain a graphene-reinforced copper-based composite wire.

[0022] Example 3

[0023] Weigh graphene to form a solution system, and stir and disperse it at a speed of 300 r / min for 30 minutes; prepare a 0.3 g / mL silver nitrate solution, mix it with the graphene solution and stir it magnetically for 30 minutes, then drop 0.15 g / mL glucose solution as a reducing agent, heat it to 80° C., stir it at a constant temperature to make it fully react, and obtain a silver-containing graphene composite powder, and finally reduce it in a mixed atmosphere of hydrogen / argon to obtain a graphene silver-plated powder, and adjust the amount of graphene so that the proportion of silver in the graphene silver-plated powder is 23.4wt%;

[0024] The graphene silver-plated powder and copper powder were ground and mixed in a mass ratio of 1:1.82, and then loaded into an oxygen-free copper tube. The copper tube was rotary forged to an outer diameter of Φ6 mm using a rotary forging machine, and then multiple drawing deformations were performed on a drawing machine to obtain a wire with a diameter of Φ1 mm. Finally, vacuum annealing was performed at 320°C for 2h to eliminate stress to obtain a graphene-reinforced copper-based composite wire.

[0025] Example 4

[0026] Weigh graphene to form a solution system, and stir and disperse it at a speed of 300 r / min for 30 minutes; prepare a 0.3 g / mL silver nitrate solution, mix it with the graphene solution and stir it magnetically for 30 minutes, then drop 0.15 g / mL glucose solution as a reducing agent, heat it to 80° C., stir it at a constant temperature to make it fully react, and obtain a silver-containing graphene composite powder, and finally reduce it in a mixed atmosphere of hydrogen / argon to obtain a graphene silver-plated powder, and adjust the amount of graphene so that the proportion of silver in the graphene silver-plated powder is 29.6wt%;

[0027] The graphene silver-plated powder and copper powder were ground and mixed in a mass ratio of 1:1.82, and then loaded into an oxygen-free copper tube. The copper tube was rotary forged to an outer diameter of Φ6 mm using a rotary forging machine, and then multiple drawing deformations were performed on a drawing machine to obtain a wire with a diameter of Φ1 mm. Finally, vacuum annealing was performed at 320°C for 2h to eliminate stress to obtain a graphene-reinforced copper-based composite wire.

[0028] Example 5

[0029] Weigh graphene to form a solution system, and stir and disperse it at a speed of 300 r / min for 30 minutes; prepare a 0.3 g / mL silver nitrate solution, mix it with the graphene solution and stir it magnetically for 30 minutes, then drop 0.15 g / mL glucose solution as a reducing agent, heat it to 80° C., stir it at a constant temperature to make it fully react, and obtain a silver-containing graphene composite powder, and finally reduce it in a mixed atmosphere of hydrogen / argon to obtain a graphene silver-plated powder, and adjust the amount of graphene so that the proportion of silver in the graphene silver-plated powder is 34.7wt%;

[0030] The graphene silver-plated powder and copper powder were ground and mixed in a mass ratio of 1:1.82, and then loaded into an oxygen-free copper tube. The copper tube was rotary forged to an outer diameter of Φ6 mm using a rotary forging machine, and then multiple drawing deformations were performed on a drawing machine to obtain a wire with a diameter of Φ1 mm. Finally, vacuum annealing was performed at 320°C for 2h to eliminate stress to obtain a graphene-reinforced copper-based composite wire.

[0031] Comparative Example 1

[0032] Graphene powder and copper powder are ground and mixed in a mass ratio of 1:1.82, and then loaded into an oxygen-free copper tube. The copper tube is rotary forged to an outer diameter of Φ6 mm using a rotary forging machine, and then multiple drawing deformations are performed on a drawing machine to obtain a wire with a diameter of Φ1 mm. Finally, vacuum annealing is performed at 320°C for 2h to eliminate stress to obtain a graphene-reinforced copper-based composite wire.

[0033] Comparative Example 2

[0034] Weigh graphene to form a solution system, and stir and disperse it at a speed of 300 r / min for 30 minutes; prepare a 0.3 g / mL silver nitrate solution, mix it with the graphene solution and stir it magnetically for 30 minutes, then drop 0.15 g / mL glucose solution as a reducing agent, heat it to 80° C., stir it at a constant temperature to make it fully react, and obtain a silver-containing graphene composite powder, and finally reduce it in a mixed atmosphere of hydrogen / argon to obtain a graphene silver-plated powder, and adjust the amount of graphene so that the proportion of silver in the graphene silver-plated powder is 60wt%;

[0035] The graphene silver-plated powder and copper powder were ground and mixed in a mass ratio of 1:1.82, and then loaded into an oxygen-free copper tube. The copper tube was rotary forged to an outer diameter of Φ6 mm using a rotary forging machine, and then multiple drawing deformations were performed on a drawing machine to obtain a wire with a diameter of Φ1 mm. Finally, vacuum annealing was performed at 320°C for 2h to eliminate stress to obtain a graphene-reinforced copper-based composite wire.

[0036] Next, we evaluated the high temperature (150°C) conductivity and room temperature tensile strength of the graphene-enhanced copper-based composite wires in Examples 1-5 and Comparative Examples 1-2. In order to ensure the comparability of each group of samples, the other process conditions except the different silver content in the graphene silver-plated powder must be exactly the same during the experiment. The experimental results are shown in Table 1.

[0037] Table 1 Experimental data of each sample

[0038] serial number 150℃ electrical conductivity / IACS% Room temperature tensile strength / MPa Example 1 71.31 272 Example 2 73.60 269 Example 3 75.63 277 Example 4 74.17 273 Example 5 73.19 275 Comparative Example 1 68.55 268 Comparative Example 2 70.44 251 Stress-relief annealed pure copper wire 68％ 273

[0039] As can be seen from Table 1, the graphene silver-plated powder obtained by silver plating on the graphene surface by chemical plating process can significantly improve the high-temperature conductivity of the graphene-enhanced copper-based composite wire. At the same time, the appropriate silver content has little effect on the tensile strength of the graphene-enhanced copper-based composite wire, but too much silver content will have a negative impact on the tensile strength. Therefore, in practice, the silver content in the graphene silver-plated powder should be controlled at 15.3wt%-34.7wt%.

[0040] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the technical principles of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A method for preparing a graphene-reinforced copper-based composite wire, characterized in that: The preparation method comprises the following steps: Weigh graphene to form a solution system, and stir and disperse it at a speed of 300-350r / min for 30-60min; prepare a 0.3-0.5g / mL silver nitrate solution, mix it with the graphene solution and stir it magnetically for 30-60min, then drop 0.15-0.30g / mL glucose solution as a reducing agent, heat it to about 80-95°C, stir it at a constant temperature to make it fully react, and obtain a silver-containing graphene composite powder, and finally reduce it in a mixed atmosphere of hydrogen / argon to obtain a graphene silver-plated powder, and adjust the amount of graphene so that the proportion of silver in the graphene silver-plated powder is 15.3-34.7wt%; The graphene silver-plated powder and copper powder are ground and mixed in a mass ratio of 1:1.82-2.11, and then loaded into an oxygen-free copper tube. The copper tube is rotary forged to an outer diameter of Φ6-8mm using a rotary forging machine, and then multiple drawing deformations are performed on a drawing machine to obtain a wire with a diameter of Φ1-1.2mm. Finally, vacuum annealing is performed at 320-330°C for 2-3h to eliminate stress to obtain a graphene-reinforced copper-based composite wire.

2. A preparation method according to claim 1, characterized in that: The stirring speed is 350 r / min.

3. A preparation method according to claim 1, characterized in that: The annealing temperature is 320°C.

4. A preparation method according to claim 1, characterized in that: The annealing time is 2h.

5. A preparation method according to claim 1, characterized in that: The concentration of the silver nitrate solution was 0.5 g / mL.

6. A preparation method according to claim 1, characterized in that: The concentration of glucose solution was 0.30 g / mL.

7. A preparation method according to claim 1, characterized in that: The proportion of silver in the silver-coated graphene powder is 23.4wt%.