Electrochemical deposition device and deposition method of graphene-enhanced copper-based composite material

Abstract

The present invention relates to the field of electrochemical deposition, and discloses an electrochemical deposition device for graphene-enhanced copper-based composite materials, comprising an electrolytic cell, a wire rack, and an ultrasonic vibrating rod, wherein the electrolytic cell comprises an outer tank shell, an inner tank shell, and a tank bottom plate, wherein a plurality of vertical partitions are fixedly connected between the outer tank shell and the inner tank shell, and the plurality of vertical partitions divide the space between the outer tank shell and the inner tank shell into a plurality of cooling chambers, a water storage tank is arranged above the middle of the tank bottom plate, a vertical partition is fixed in the water storage tank and divided into cooling chambers, each cooling chamber is connected with a water inlet pipe and a water outlet pipe, wire racks are placed on both sides of the water storage tank, an ultrasonic vibrating rod is placed in each wire rack, a plurality of temperature sensors are placed in the electrolyte, and a controller controls the switches of the water inlet pipe and the water outlet pipe of each cooling chamber respectively according to the data of each temperature sensor. The present invention realizes zoned cooling, the tank body is divided into a plurality of cooling areas, and the temperature is controlled respectively to ensure uniform temperature of the electrolyte.

Description

Technical Field

[0001] The invention relates to the field of electrochemical deposition, and in particular to an electrochemical deposition device and a deposition method for a graphene-enhanced copper-based composite material. Background Art

[0002] Copper-based wire is a common conductive wire. Graphene-reinforced copper-based composite conductive wire is a wire that adds graphene as a reinforcing phase to the copper matrix to improve the conductive properties. This material combines the high conductivity of copper and the advantages of graphene. It has excellent properties such as high conductivity, high strength and high thermal conductivity. It is suitable for electronics, electricity, communications, new energy vehicles and other fields.

[0003] Among them, the electrochemical deposition method is a common preparation method for conductive wires of graphene-enhanced copper-based composite materials. In this method, the dispersion form of graphene in the electrolyte is uniformly dispersed in the form of nanosheets. This is because if the graphene powder is directly added to the electrolyte, it will be difficult to disperse evenly due to agglomeration, thereby affecting the performance of the composite material. In order to achieve uniform dispersion of graphene in the electrolyte during the chemical deposition process, the electrolyte will be stirred to maintain uniform dispersion of graphene and copper ions, prevent sedimentation or agglomeration, and thus ensure the uniformity of the deposited layer and the performance of the composite material.

[0004] However, in the process of implementing relevant technical solutions, it was found that at least the following technical problems exist: For materials such as graphene dispersed in the form of nanosheets, ultrasonic stirring is usually used. Ultrasonic stirring does not require mechanical contact and avoids contamination, but ultrasonic stirring will cause the electrolyte temperature to rise. This is because ultrasonic energy is converted into heat energy in the liquid. The increase in temperature may affect the stability of the electrolyte, the control of the deposition process and the performance of the final material. Summary of the invention

[0005] The present invention provides an electrochemical deposition device and a deposition method for graphene-enhanced copper-based composite materials, thereby solving the technical problem in the prior art that ultrasonic stirring causes the temperature of the graphene electrolyte to rise, thereby affecting the stability of the electrolyte, the control of the deposition process and the performance of the final material. The present invention realizes zoned cooling, and the tank body is divided into multiple cooling zones, and the temperatures are controlled separately to ensure uniform electrolyte temperature.

[0006] The present invention provides an electrochemical deposition device for graphene-enhanced copper-based composite materials, comprising an electrolytic cell, a wire rack and an ultrasonic vibrating rod, wherein the electrolytic cell comprises an outer cell shell, an inner cell shell and a cell bottom plate, wherein the outer cell shell and the inner cell shell are spaced apart and both are vertically fixed to the cell bottom plate, wherein a plurality of vertical partitions are fixedly connected between the outer cell shell and the inner cell shell, wherein the plurality of vertical partitions are equidistantly arranged around a circle of the electrolytic cell, and wherein the plurality of vertical partitions divide the space between the outer cell shell and the inner cell shell into a plurality of cooling chambers. A water storage tank is arranged above the middle of the tank bottom plate, and there is a gap between the outer wall of the water storage tank and the upper surface of the tank bottom plate and the inner wall of the inner tank shell. Vertical partitions are fixed in the water storage tank and divided into cooling chambers. Each cooling chamber is connected to a water inlet pipe and a water outlet pipe. The wire racks are placed on both sides of the water storage tank, and the ultrasonic vibrating rod is placed in each of the wire racks. Multiple temperature sensors are placed in the electrolyte, and the controller controls the switches of the water inlet pipe and the water outlet pipe of each cooling chamber according to the data of each temperature sensor.

[0007] Furthermore, a plurality of equally spaced conical columns are provided on the upper surface of the trough bottom plate, and the tips of the conical columns are vertically upward.

[0008] Furthermore, an upper bottom plate is horizontally arranged above the groove bottom plate, and the edge of the upper bottom plate is fixedly connected to the inner wall of the inner groove shell and sealed. A deposition chamber is formed between the upper bottom plate and the groove bottom plate. A plurality of through holes are opened on the upper bottom plate for the conical column to pass through. When the conical column is placed on the groove bottom plate, there is a gap between the conical column and the through hole. When the conical column is lifted up, the conical column and the through hole are sealed.

[0009] Furthermore, the bottoms of the conical columns are connected to each other through connecting rods to form a whole, and a pull ring is fixedly connected to one of the conical columns on both sides of the water storage tank, and the pull ring is used for pulling up with an electric hoist.

[0010] Furthermore, a water outlet slot is provided on the outer tank shell, the water outlet slot is connected to the sedimentation chamber, and the cooling chamber between the outer tank shell and the inner tank shell is isolated from the water outlet slot, and a sealing plate for sealing the water outlet slot is slidably provided on the outer wall of the outer tank shell.

[0011] Furthermore, a water receiving trough is provided below the water outlet, and a water spray head is installed on the water receiving trough, and the water spray head is used to spray clean water into the sedimentation chamber.

[0012] Furthermore, a short tube is provided in the water storage tank, and the short tube passes through the water storage tank. The short tube is used for the electrolytes on both sides of the water storage tank to circulate with each other.

[0013] Furthermore, there is a spacing between the slot bottom plate and the bottom edge of the outer slot shell, and heat dissipation fins are fixed to the lower surface of the slot bottom plate.

[0014] The present invention also discloses an electrochemical deposition method of graphene-enhanced copper-based composite materials. The electrochemical deposition device of the graphene-enhanced copper-based composite materials as described above is used. The electrochemical deposition method comprises: winding a copper-based wire on a wire rack; lowering the wire rack into an electrolytic cell; introducing a configured electrolyte containing a graphene suspension into the electrolytic cell; lowering an ultrasonic vibration rod into the electrolytic cell; starting the ultrasonic vibration rod; using the copper-based wire as a working electrode and connecting a power supply for deposition; and controlling the temperature of each cooling chamber respectively so that the electrolyte in the electrolytic cell maintains a preset temperature.

[0015] One or more technical solutions provided in the present invention have at least the following technical effects or advantages: Since the periphery of the electrolytic cell is divided into multiple cooling chambers, multiple temperature sensors can monitor the temperature of the electrolyte in the corresponding area of ​​the cooling chamber. When the temperature of a certain area is higher than the preset temperature, the controller can automatically control the switch of the water inlet pipe and the water outlet pipe of the corresponding cooling chamber to cool down the high-temperature area, thereby realizing zoned temperature control and ensuring uniform electrolyte temperature. This solves the technical problem in the prior art that ultrasonic stirring will cause the temperature of the graphene electrolyte to rise, affecting the performance of the final material. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 It is an overall schematic diagram of an electrolytic cell in an electrochemical deposition device in Example 1 of the present invention; Figure 2 This is a schematic diagram of the wire rack and the ultrasonic vibration rod after being lifted up in the first embodiment of the present invention; Figure 3 A top view of the electrolytic cell in Embodiment 1 of the present invention; Figure 4 It is a cross-sectional schematic diagram of a partial structure of an electrolytic cell in Embodiment 1 of the present invention; Figure 5 This is a schematic diagram of the structure of the water storage tank in the first embodiment of the present invention; Figure 6 A bottom view of the electrolytic cell in Embodiment 1 of the present invention; Figure 7 This is a schematic diagram of the structure between the upper base plate and the conical column in the first embodiment of the present invention in an unsealed state; Figure 8 for Figure 7 Another perspective of the picture; In the figure: 1. electrolytic cell; 11. outer tank shell; 111. water outlet slot; 12. inner tank shell; 13. tank bottom plate; 14. vertical partition; 15. water storage tank; 151. short tube; 16. conical column; 17. upper bottom plate; 171. perforation; 18. sealing plate; 19. cooling fin; 101. cooling chamber; 102. water inlet pipe; 103. water outlet pipe; 104. sedimentation chamber; 105. connecting rod; 106. pull ring; 201. water receiving trough; 202. sprinkler head; 2. wire rack; 3. ultrasonic vibrator. DETAILED DESCRIPTION

[0017] In order to better understand the technical solution of the present application, the above technical solution will be described in detail below in conjunction with the accompanying drawings and specific implementation methods.

[0018] Example 1: Electrochemical deposition device for graphene-enhanced copper-based composite materials, referring to Figure 1 and Figure 2 As shown, the electrochemical deposition device includes an electrolytic cell 1, a wire rack 2, and an ultrasonic vibrating rod 3. A copper-based wire is wound on the wire rack 2 as a working electrode, and the ultrasonic vibrating rod 3 is placed in the middle of the wire rack 2. The wire rack 2 and the ultrasonic vibrating rod 3 can be lifted and lowered by an electric hoist. The ultrasonic vibrating rod 3 will cause the electrolyte to fluctuate to prevent the electrolyte from settling. The electrolyte is pre-configured and passed into the electrolytic cell 1, and the electrolyte contains a graphene suspension. The electrochemical deposition device also includes a reference electrode and a counter electrode. A saturated calomel electrode or a silver / silver chloride electrode can be used as a reference electrode, and a graphite rod can be used as a counter electrode.

[0019] Reference Figure 2 , Figure 3 as well as Figure 4The electrolytic cell 1 comprises an outer tank shell 11, an inner tank shell 12, a tank bottom plate 13, a vertical partition 14, and a water storage tank 15. The tank bottom plate 13 is arranged horizontally; the outer tank shell 11 and the inner tank shell 12 are both vertically fixed to the tank bottom plate 13, the outer tank shell 11 is located outside the inner tank shell 12, and there is a spacing between the outer tank shell 11 and the inner tank shell 12. A plurality of vertical partitions 14 are arranged equidistantly around a circle of the electrolytic cell 1, and a plurality of vertical partitions 14 divide the space between the outer tank shell 11 and the inner tank shell 12 into a plurality of cooling chambers 101. Each cooling chamber 101 is connected to a water inlet pipe 102 and a water outlet pipe 103. The water inlet pipe 102 is connected to a cooling water source, and cooling water can be introduced into the cooling chamber 101, and The cooling water in the cooling chamber 101 is circulated by the water outlet pipe 103; the water tank 15 is flat, and is located in the middle of the inner cavity of the electrolytic cell 1, and the width of the inner cavity is consistent with the width between the outer tank shell 11 and the inner tank shell 12. The water tank 15 is perpendicular to the length direction of the electrolytic cell 1, and there is a gap between the outer wall of the water tank 15 and the tank bottom plate 13 and the inner tank shell 12, so that the electrolyte on both sides of the water tank 15 can communicate with each other. A vertical partition 14 is also fixed in the middle of the water tank 15 and divides the water tank 15 into two cooling chambers 101, each cooling chamber 101 is connected to a water inlet pipe 102 and a water outlet pipe 103, and a short pipe 151 is arranged in the water tank 15, and the short pipe 151 passes through the cooling chamber 101 of the water tank 15, and the electrolyte on both sides of the water tank 15 can circulate with each other through the short pipe 151. Two wire racks 2 can be provided and located at two sides of the water storage tank 15 respectively. Two ultrasonic vibration rods 3 can also be provided and placed in the two wire racks 2 respectively. A plurality of temperature sensors are placed in the electrolyte.

[0020] Reference Figure 4 and Figure 6 There is a gap between the bottom plate 13 and the bottom edge of the outer tank shell 11, so that there is space below the bottom plate 13, and the heat dissipation fins 19 can be fixed on the lower surface of the bottom plate 13. The heat dissipation fins 19 can be used as a basic heat dissipation to dissipate the heat in the electrochemical deposition.

[0021] As an electrochemical deposition process of graphene-enhanced copper-based composite materials, using an ultrasonic vibrator 3 to stir the electrolyte is suitable for uniform dispersion of graphene. Ultrasonic energy is converted into heat energy in the liquid, namely cavitation effect and frictional heat generation. The temperature increase may affect the stability of the electrolyte, the control of the deposition process and the performance of the final material. The present invention divides the periphery of the electrolytic cell 1 into multiple cooling chambers 101. Multiple temperature sensors can monitor the temperature of the electrolyte in the corresponding areas of the cooling chambers 101. When the temperature of a certain area is higher than the preset temperature, the controller can automatically control the switch of the water inlet pipe 102 and the water outlet pipe 103 of the corresponding cooling chamber 101 to cool down the high-temperature area, thereby realizing zoned temperature control and ensuring uniform electrolyte temperature.

[0022] Reference Figure 4 , Figure 7 as well as Figure 8 A plurality of equidistantly arranged conical columns 16 are provided on the upper surface of the bottom plate 13 of the trough, and the tips of the conical columns 16 are vertically upward. The bottoms of the conical columns 16 are interconnected by connecting rods 105 to form a whole. A pull ring 106 is fixed to one of the conical columns 16 on both sides of the water storage tank 15, and the wire rope on the electric hoist can be tied to the pull ring 106 to move the conical column 16 upward as a whole. An upper bottom plate 17 is horizontally arranged above the trough bottom plate 13. The edge of the upper bottom plate 17 is fixedly connected to the inner wall of the inner trough shell 12 and is sealed. The upper bottom plate 17 is provided with a plurality of through holes 171 for the conical column 16 to pass through. A deposition chamber 104 is formed between the upper bottom plate 17 and the trough bottom plate 13. When the conical column 16 is placed on the trough bottom plate 13, there is a gap between the conical column 16 and the through hole 171. After the conical column 16 is lifted by the electric hoist, the surface of the conical column 16 will fit on the hole wall of the through hole 171. The conical column 16 and the through hole 171 are in a sealed state, and the electrolyte on the upper bottom plate 17 will not flow into the deposition chamber 104.

[0023] The cone column can act as a spoiler to destroy the laminar flow state of the electrolyte and promote the formation of turbulence. The turbulence can enhance the mixing effect of the electrolyte, reduce dead zones, and ensure uniform circulation of the electrolyte in the tank. In addition, after contacting the cone column, metal debris or undissolved salts in the electrolyte will flow downward along the surface of the cone column under the action of gravity and eventually flow into the deposition chamber 104. Therefore, the cone column can not only enhance the mixing effect of the electrolyte, but also facilitate the sedimentation of the precipitate in the electrolyte.

[0024] Reference Figure 1 , Figure 2 and Figure 4 Water outlet slots 111 are provided on both side walls in the length direction of the outer tank shell 11, and the water outlet slots 111 are connected to the sedimentation chamber 104, and the cooling chamber 101 between the outer tank shell 11 and the inner tank shell 12 is isolated from the water outlet slots 111, and the cooling water in the cooling chamber 101 will not enter the sedimentation chamber 104. A sealing plate 18 for sealing the water outlet slot 111 is slidably provided on the outer wall of the outer tank shell 11, and the sealing plate 18 can move downward to seal the water outlet slot 111, so that the sedimentation chamber 104 is in a sealed state, and a water receiving trough 201 is provided below the water outlet slot 111, and the water receiving trough 201 is connected with the water outlet slot 111, and a water spray head 202 is installed on the water receiving trough 201, and the water spray head 202 is used to spray clean water into the sedimentation chamber 104.

[0025] When the sediment in the deposition chamber 104 needs to be cleaned, the conical column 16 is moved upward as a whole by an electric hoist, so that the conical column 16 and the through hole 171 are sealed, and the electrolyte on the upper bottom plate 17 does not flow into the deposition chamber 104, and then the water outlet 111 is opened, and the sediment in the deposition chamber 104 flows into the water receiving trough 201, and the water spray head 202 can be used to spray and clean the deposition chamber 104. Therefore, the conical column can be used as a spoiler, which can enhance the mixing effect of the electrolyte and is also conducive to the sedimentation of the sediment in the electrolyte. When the deposition chamber 104 is cleaned, the conical column can also play a role in sealing the deposition chamber 104, preventing the electrolyte above from flowing into the deposition chamber 104.

[0026] The functional principle of the first embodiment can be explained through the following operation mode: The periphery of the electrolytic cell 1 is divided into a plurality of cooling chambers 101, and a plurality of temperature sensors can monitor the temperature of the electrolyte in the corresponding area of ​​the cooling chamber 101. When the temperature of a certain area is higher than the preset temperature, the controller can automatically control the switch of the water inlet pipe 102 and the water outlet pipe 103 of the corresponding cooling chamber 101 to cool down the high-temperature area, thereby realizing zoned temperature control and ensuring uniform electrolyte temperature. The cone column can be used as a spoiler to enhance the mixing effect of the electrolyte and also provide assistance for the stability of the electrolyte, thereby solving the technical problem in the prior art that ultrasonic stirring will cause the temperature of the graphene electrolyte to rise and affect the performance of the final material.

[0027] Embodiment 2: An electrochemical deposition method for graphene-enhanced copper-based composite material, using the electrochemical deposition device in Embodiment 1, the electrochemical deposition method comprises the following steps: S1, winding the copper wire wire on the wire rack 2.

[0028] In a specific implementation, there are gaps between the copper wires wound on the wire rack 2 .

[0029] S2, lowering the wire rack 2 into the electrolytic cell 1.

[0030] In a specific implementation, the wire rack 2 can be lowered and moved upward by an electric hoist.

[0031] S3, introducing the prepared electrolyte containing the graphene suspension into the electrolytic cell 1.

[0032] In a specific implementation, the electrolyte can be prepared by dissolving copper salt in deionized water, adding an appropriate amount of acid to adjust the pH value of the electrolyte to 1-3, adding the dispersed graphene suspension to the electrolyte, and stirring the electrolyte with a magnetic stirrer or a mechanical stirrer to ensure that the graphene is evenly dispersed.

[0033] In a specific implementation, the preparation process of the graphene suspension can be to add graphene oxide or reduced graphene oxide into deionized water, use an ultrasonic disperser to disperse the graphene until a uniform suspension is formed, and add a dispersant (such as PVP) as needed to improve the dispersion stability of the graphene.

[0034] S4, lowering the ultrasonic vibration rod 3 into the electrolytic cell 1.

[0035] In a specific implementation, the ultrasonic vibration rod 3 can be lowered and moved upward by an electric hoist.

[0036] S5, start the ultrasonic vibration rod 3.

[0037] In specific implementations, ultrasonic stirring is usually used for materials such as graphene that are dispersed in the form of nanosheets. Ultrasonic stirring does not require mechanical contact and avoids contamination.

[0038] S6, using the copper-based substrate as the working electrode and turning on the power supply for deposition.

[0039] In a specific implementation, the copper-based wire is used as the working electrode, the counter electrode can be a graphite rod, and the reference electrode can be a saturated calomel electrode or a silver / silver chloride electrode.

[0040] S7, controlling the temperature of each cooling chamber 101 respectively so that the electrolyte in the electrolytic cell 1 maintains a preset temperature.

[0041] In a specific implementation, multiple temperature sensors can monitor the temperature of the electrolyte in the corresponding area of ​​the cooling chamber 101. When the temperature of a certain area is higher than the preset temperature, the controller can automatically control the switch of the water inlet pipe 102 and the water outlet pipe 103 of the corresponding cooling chamber 101 to cool down the high-temperature area, thereby realizing zoned temperature control.

[0042] Obviously, those skilled in the art can make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if these modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include these modifications and variations.

[0043] What has been described above are only preferred specific implementations of the embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field, within the technical scope disclosed by the present invention, can make equivalent replacements or changes based on the technical solutions and concepts of the present invention, which should be covered by the protection scope of the present invention.

Claims

1. An electrochemical deposition device for graphene-enhanced copper-based composite materials, comprising an electrolytic cell (1), a wire rack (2) and an ultrasonic vibrating rod (3), characterized in that: The electrolytic cell (1) comprises an outer cell shell (11), an inner cell shell (12), and a cell bottom plate (13); the outer cell shell (11) and the inner cell shell (12) are spaced apart from each other and are both vertically fixed to the cell bottom plate (13); a plurality of vertical partitions (14) are fixed between the outer cell shell (11) and the inner cell shell (12); the plurality of vertical partitions (14) are equidistantly arranged around a circumference of the electrolytic cell (1); the plurality of vertical partitions (14) divide the space between the outer cell shell (11) and the inner cell shell (12) into a plurality of cooling chambers (101); a water storage tank (15) is arranged above the middle of the cell bottom plate (13); the water storage tank (15) is provided at a position adjacent to the outer cell shell (11) and the inner cell shell (12); There is a gap between the outer wall of the tank (15) and the upper surface of the tank bottom plate (13) and the inner wall of the inner tank shell (12). A vertical partition (14) is fixed in the water storage tank (15) and is divided into cooling chambers (101). Each cooling chamber (101) is connected to a water inlet pipe (102) and a water outlet pipe (103). The wire racks (2) are placed on both sides of the water storage tank (15). The ultrasonic vibration rod (3) is placed in each wire rack (2). A plurality of temperature sensors are placed in the electrolyte. The controller controls the switch of the water inlet pipe (102) and the water outlet pipe (103) of each cooling chamber (101) according to data from each temperature sensor.

2. The electrochemical deposition device of graphene-enhanced copper-based composite material according to claim 1, characterized in that: The upper surface of the trough bottom plate (13) is provided with a plurality of equally spaced conical columns (16), with the tips of the conical columns (16) pointing vertically upwards.

3. The electrochemical deposition device of graphene-enhanced copper-based composite material according to claim 2, characterized in that: An upper bottom plate (17) is horizontally arranged above the groove bottom plate (13), and the edge of the upper bottom plate (17) is fixedly connected to the inner wall of the inner groove shell (12) and is sealed. A deposition chamber (104) is formed between the upper bottom plate (17) and the groove bottom plate (13). The upper bottom plate (17) is provided with a plurality of through holes (171) for the conical column (16) to pass through. When the conical column (16) is placed on the groove bottom plate (13), there is a gap between the conical column (16) and the through hole (171). When the conical column (16) is lifted up, the conical column (16) and the through hole (171) are sealed.

4. The electrochemical deposition device of graphene-enhanced copper-based composite material according to claim 3, characterized in that: The bottoms of the conical columns (16) are connected to each other via a connecting rod (105) to form a whole. A pull ring (106) is fixedly connected to one of the conical columns (16) on both sides of the water storage tank (15). The pull ring (106) is used for pulling up with an electric hoist.

5. The electrochemical deposition device of graphene-enhanced copper-based composite material according to claim 3, characterized in that: The outer tank shell (11) is provided with a water outlet slot (111), the water outlet slot (111) is communicated with the sedimentation chamber (104), and the cooling chamber (101) between the outer tank shell (11) and the inner tank shell (12) is isolated from the water outlet slot (111), and a sealing plate (18) for sealing the water outlet slot (111) is slidably provided on the outer wall of the outer tank shell (11).

6. The electrochemical deposition device of graphene-enhanced copper-based composite material according to claim 5, characterized in that: A water receiving trough (201) is provided below the water outlet trough (111), and a water spray head (202) is installed on the water receiving trough (201), and the water spray head (202) is used to spray clean water into the sedimentation chamber (104).

7. The electrochemical deposition device of graphene-enhanced copper-based composite material according to claim 1, characterized in that: A short tube (151) is provided in the water storage tank (15), the short tube (151) passes through the water storage tank (15), and the short tube (151) is used for the electrolyte on both sides of the water storage tank (15) to circulate with each other.

8. The electrochemical deposition device of graphene-enhanced copper-based composite material according to claim 1, characterized in that: There is a distance between the slot bottom plate (13) and the bottom edge of the outer slot shell (11), and heat dissipation fins (19) are fixed to the lower surface of the slot bottom plate (13).

9. A method for electrochemical deposition of graphene-enhanced copper-based composite materials, characterized in that: Using the electrochemical deposition device of the graphene-enhanced copper-based composite material according to any one of claims 1 to 8, the electrochemical deposition method comprises: Winding the copper wire base on the wire rack 2; Lower the wire rack 2 into the electrolytic cell 1; The prepared electrolyte containing the graphene suspension is introduced into the electrolytic cell 1; Lower the ultrasonic vibration rod 3 into the electrolytic cell 1; Start the ultrasonic vibrator 3; Use a copper-based substrate as the working electrode and connect it to a power source for deposition; The temperature of each cooling chamber 101 is controlled separately so that the electrolyte in the electrolytic cell 1 is kept at a preset temperature.

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