CN115505898A - Copper-based graphene composite material and preparation method thereof - Google Patents
Copper-based graphene composite material and preparation method thereof Download PDFInfo
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Abstract
The embodiment of the application provides a copper-based graphene composite material and a preparation method thereof, and relates to the technical field of composite material preparation. The preparation method of the copper-based graphene composite material comprises the following steps: growing a graphene film on the surface of the copper foil by adopting a chemical vapor deposition method to obtain a copper-based graphene unit layer; stacking at least two copper-based graphene unit layers together to obtain a stacked assembly; and welding the stacked assemblies by adopting an ultrasonic welding technology. The preparation method of the copper-based graphene composite material prepares the composite material with high conductivity through a low-cost, simple and efficient industrial preparation process.
Description
Technical Field
The application relates to the technical field of composite material preparation, in particular to a copper-based graphene composite material and a preparation method thereof.
Background
Copper, copper alloy and copper-based composite materials are widely applied to the industries of aviation, aerospace, electronics, electric power and the like, and along with the rapid development of modern industrial technologies, the materials are required to have high strength and hardness and high conductivity, so that the copper-based composite materials are highly valued in the academic and industrial fields.
The copper-based composite material uses traditional reinforcements, such as carbon fibers, carbon nanotubes, graphite particles and the like, and although the mechanical property can be improved, the electrical conductivity of the copper-based composite material is usually obviously reduced. The graphene is a two-dimensional nano material with a single atomic layer, and the special structure enables the graphene to have excellent mechanical properties (the breaking strength can reach 130 GPa) and electric and heat conduction properties (the mobility of carriers under room temperature can reach 2 x 10) 5 cm 2 V · s, thermal conductivity of about 5000W/(m · K)), is an excellent conductive material under room temperature conditions, and is considered to be an ideal copper-based composite material reinforcement. Due to the unique two-dimensional folded structure of graphene, the graphene-copper composite materials with different configuration designs have great difference in performance, and graphene-copper composite materials with layered and continuous three-dimensional structures can obtain good mechanical and conductive performances, but have certain difficulty in large-scale production.
Chinese patents CN106584976A, CN110079784A and CN108193065B respectively provide a graphene-copper-based layered composite material and a preparation method thereof, which adopt different preparation technologies to obtain graphene-copper-based composite units, and then densify at least two graphene-copper-based composite units by using processes such as hot-pressing sintering, spark plasma sintering, microwave sintering, cold rolling or combination, and obtain the graphene-copper composite material. The method has the following defects in the actual preparation process: on one hand, due to the limitation of sintering equipment, the technological parameters are not easy to control accurately, the production process period is long, the production cost is high, and the industrial application is not easy. On the other hand, due to the fact that sintering temperature is high, energy consumption is high, and the orientation and the structure of the graphene and the copper-based material are easily damaged, the graphene in a final product is not uniformly dispersed and easily forms agglomeration at local parts, the orientation is inconsistent, copper materials are recrystallized at high temperature to become complex polycrystal, and a plurality of non-collinear conductive units are formed, so that adverse effects are generated on the conductivity of the composite material, and the conductivity of the composite material is reduced.
Disclosure of Invention
The embodiment of the application aims to provide a copper-based graphene composite material and a preparation method thereof, and the composite material with high conductivity is prepared through a low-cost, simple and efficient industrial preparation process.
In a first aspect, an embodiment of the present application provides a method for preparing a copper-based graphene composite material, which includes the following steps:
growing a graphene film on the surface of a copper foil by adopting a Chemical Vapor Deposition (CVD) method, wherein the thickness of the copper foil is 1-100 mu m, and obtaining a copper-based graphene unit layer;
stacking at least two copper-based graphene unit layers together to obtain a stacked assembly;
and welding the stacked components by adopting an ultrasonic welding technology, wherein the ultrasonic frequency of ultrasonic welding is 15-100kHz, and the ultrasonic amplitude is 20-60 mu m.
In the technical scheme, a high-quality graphene film is prepared on the surface of a copper foil with an extremely thin thickness, so that a copper-based graphene unit layer is obtained; stacking the layered copper-based graphene unit layers to obtain a stacked assembly, and welding the stacked assembly at a low temperature by utilizing ultrasonic welding with certain frequency and amplitude to obtain the blocky copper-based graphene composite material. The preparation method is low in preparation cost, short in flow, high in efficiency, easy to realize industrialization, capable of overcoming the defects that graphene is easy to agglomerate, the structure is easy to damage, the graphene is not easy to regulate and control and the like, and capable of preparing the copper-based graphene composite material with high conductivity.
Different from the conventional scheme of directly mixing and doping the graphene material in the copper foil in a disordered manner, the method firstly designs a graphene-copper foil unit structure, and adopts a CVD method to directly grow and prepare the integral graphene film on the copper foil, wherein the graphene film has more uniform and consistent orientation, higher quality and lower structural defects; and the graphene film and the copper foil are combined more strongly, a perfect interface can be formed, an effective interface transfer path is provided for charge transfer between different unit layers, and the conductivity of the composite material can be obviously improved theoretically.
Meanwhile, the ultrasonic welding combination method does not need to reach the melting point of the material, the energy-saving effect is remarkable, and the interface between the graphene and the copper foil and the consistent orientation of the respective original materials are kept under the low-temperature condition, so that the high quality and integrity of the original materials are kept, and the structural stability and the high conductivity of the copper foil and the graphene are kept.
In addition, the ultrasonic welding formed composite material can adjust the graphene content by changing the number of layers of the graphene (single-layer or double-layer coating film) and the thickness of the copper foil, and other unit combination modes cannot be successfully carried out under the condition that the copper foil is thin. Under the condition that the copper layer is thick, the content (volume fraction) of graphene in the formed composite material can be almost ignored, and the real electrical property regulation and control cannot be realized; only under the condition that the copper foil is thin enough, graphene with a certain volume fraction can be arranged in the whole composite material, so that the overall resistance is reduced, the combination of all unit materials is realized by adopting ultrasonic waves with certain frequency and amplitude to form a parallel structure, the overall conductivity is improved, and the high-conductivity composite material with strong structural designability is obtained.
In a possible implementation manner, the method further comprises the step of performing stress relief annealing on the welded stack assembly.
In the technical scheme, the residual stress introduced in the ultrasonic welding process is eliminated by stress relief annealing, so that the conductivity and the mechanical property of the copper-based graphene composite material are optimally matched.
In one possible implementation mode, the stress relief annealing is carried out under the protection condition of vacuum or atmosphere, the annealing temperature is 380-440 ℃, and the annealing time is 10-60min.
In one possible implementation, the copper foil is one or a combination of a rolled copper foil, an electrolytic copper foil, and a single crystal copper foil.
In one possible implementation, the copper foil has a thickness of 20-25 μm.
In the above technical solution, the composite material can be formed using a copper foil having a sufficiently thin thickness.
In one possible implementation, the ultrasonic welding is in the form of ultrasonic spot welding or ultrasonic roll welding; and/or, the ultrasonic welding is carried out under vacuum or atmosphere protection conditions.
In one possible implementation, ultrasonic seam welding is performed by rolling the stack with a sonotrode at a pressure of 0.1 to 10kN and a relative linear velocity at the sonotrode of 1 to 100mm/s.
In a second aspect, an embodiment of the present application provides a copper-based graphene composite material, which is prepared by the method for preparing the copper-based graphene composite material provided in the first aspect, the copper-based graphene composite material includes at least two stacked copper-based graphene unit layers, each layer includes a copper foil and a graphene film attached to the surface of the copper foil, and the parts of all the copper-based graphene unit layers are welded together.
In the technical scheme, the graphene and the copper foil in the composite material keep the high quality and integrity of the original material, and have low overall resistance and high overall conductivity.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments of the present application will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and that those skilled in the art can also obtain other related drawings based on the drawings without inventive efforts.
Fig. 1 is a schematic diagram illustrating a principle of preparing a copper-based graphene composite material by ultrasonic welding according to an embodiment of the present application;
FIG. 2 is a cross-sectional microscopic view of a sample of the copper-based graphene composite obtained by ultrasonic welding in example 1;
FIG. 3 is a cross-sectional Raman spectrum of a sample of the copper-based graphene composite obtained by ultrasonic welding in example 1;
fig. 4 is XRD diffraction patterns of copper-based graphene composite samples obtained in example 5 and comparative example 3.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The copper-based graphene composite material and the preparation method thereof according to the embodiments of the present application are specifically described below.
The embodiment of the application provides a preparation method of a copper-based graphene composite material, which comprises the following steps:
(1) The graphene film is formed on the surface of a copper foil by adopting a chemical vapor deposition method, the copper foil can be one or a combination of a rolled copper foil, an electrolytic copper foil and a single crystal copper foil, the thickness of the copper foil is generally 1-100 mu m, optionally 20-100 mu m, further optionally 20-25 mu m, so as to obtain the copper-based graphene unit layer.
As an embodiment, the copper foil is a single crystal copper foil, and the corresponding copper-based graphene unit layer is prepared as follows:
placing the polycrystalline copper foil doped with metal elements on a high-temperature resistant substrate horizontally, placing the substrate into chemical vapor deposition equipment, and introducing inert gas, wherein the inert gas is N 2 Or Ar, thenThen heating to 800-1100 deg.C, introducing H 2 Gas, H 2 The flow rate is 2-500sccm, and the annealing process is carried out;
after the annealing is finished, CH starts to be introduced 4 And Ar at a flow rate of 0.2 to 50sccm 4 The content of the mixed gas is 200-20000ppm by volume, and H is adjusted 2 The flow rate of the growth medium is 0.2-50sccm, and the growth time is 10min-20h;
and after the growth is finished, cooling to room temperature to obtain the single crystal copper foil attached with the oversized single crystal graphene film, namely the copper-based graphene unit layer.
It should be noted that in the embodiment of the application, the graphene film may be formed by deposition on a single side or two sides of the copper foil, so as to achieve the purpose of adjusting the graphene content in the copper-based graphene unit layer, and further adjusting the graphene content in the copper-based graphene composite material.
(2) Stacking at least two copper-based graphene unit layers together from bottom to top to obtain a stacked assembly.
(3) And (3) welding the stacked components by adopting an ultrasonic welding technology, wherein the ultrasonic frequency of the ultrasonic welding is usually 15-100kHz, optionally 20-100kHz, further optionally 20-25kHz, and the ultrasonic amplitude is usually 20-60 mu m, optionally 20-40 mu m, so as to prepare the bulk copper-based graphene composite material.
The ultrasonic welding can be carried out by an ultrasonic welding machine, the ultrasonic frequency of the conventional ultrasonic welding machine is fixed, and the commonly used frequencies are 15kHz, 20kHz, 28kHz, 30kHz, 35kHz, 40kHz and the like.
In the embodiments of the present application, the ultrasonic welding is in the form of ultrasonic spot welding or ultrasonic roll welding, typically in the form of roll welding. Ultrasonic welding is performed under vacuum or atmosphere protection, typically under vacuum.
Referring to fig. 1, ultrasonic seam welding is to roll a stack assembly by using a cylindrical sonotrode, wherein adjacent copper foils in the stack assembly are locally heated and metallurgically bonded under the combined action of ultrasonic vibration and positive pressure generated by the sonotrode, the pressure is usually 0.1-10kN, optionally 1-7.5kN, and the relative linear velocity at the sonotrode is usually 1-100mm/s, optionally 10-40mm/s. Specifically, a stacked assembly formed by copper-based graphene unit layers is placed below a sonotrode of ultrasonic welding equipment for ultrasonic seam welding, the welding equipment is started after welding parameters are set, and adjacent copper foils in the stacked assembly are locally heated and metallurgically bonded under the combined action of ultrasonic vibration and positive pressure, so that the blocky copper-based graphene composite material is formed.
In addition, the copper-based graphene composite material obtained by welding can be used as a target product according to actual requirements, or the copper-based graphene composite material obtained by performing stress relief annealing on the welded stacked assembly can be used as a target product. As an embodiment, the stress relief annealing is performed by placing the bulk copper-based graphene composite material into an annealing furnace, and performing the stress relief annealing under vacuum or atmosphere protection conditions, typically under vacuum conditions, with a vacuum degree of 10 -2 The annealing temperature is 380-440 ℃, the annealing time is 10-60min, and after stress is removed, the strength of the composite material is reduced and the conductivity is increased.
The embodiment of the application further provides a copper-based graphene composite material, which is prepared by adopting the preparation method of the copper-based graphene composite material. Structurally, the copper-based graphene composite material comprises at least two copper-based graphene unit layers which are stacked together, wherein each layer comprises a copper foil and a graphene film attached to the surface of the copper foil, and parts of all the copper-based graphene unit layers are welded together.
The features and properties of the present application are described in further detail below with reference to examples.
Example 1
The embodiment provides a copper-based graphene composite material, which is prepared according to the following preparation method:
cutting a rolled copper foil with the thickness of 25 mu m and the purity of more than 99.9 percent into a proper size, placing the rolled copper foil into a tube furnace, strictly controlling the temperature and the atmosphere conditions in the tube furnace by adopting a CVD (chemical vapor deposition) technology (referring to the process of the first test in the specific implementation mode of CN 105603514B), and depositing and growing graphene films on the upper surface and the lower surface of the copper foil substrate to obtain the copper-based graphene unit layer.
After 40 layers of the obtained copper-based graphene unit layers are stacked in order, the copper-based graphene unit layers are placed in ultrasonic welding equipment, and the following welding parameters are adopted: and carrying out ultrasonic welding under the atmospheric condition, with the frequency of 20KHz, the amplitude of 30 mu m, the pressure of 4.6kN and the rolling speed of 30mm/s to obtain the three-dimensional bulk copper-based graphene composite material with the thickness of about 1 mm.
And (3) carrying out stress relief annealing on the prepared copper-based graphene composite material at 400 ℃ for 30min under a vacuum condition so as to further improve the conductivity of the product.
The electric conductivity of the copper-based graphene composite material before and after stress relief annealing is respectively as follows: 97.8% IACS,102.6% IACS; the breaking strength is: 358Mpa and 274Mpa.
Example 2
The embodiment provides a copper-based graphene composite material, which is prepared according to the following preparation method:
cutting a rolled copper foil with the thickness of 25 mu m and the purity of more than 99.9 percent into proper sizes, placing the rolled copper foil into a tube furnace, adopting a CVD technology, strictly controlling the temperature and the atmosphere conditions in the tube furnace, and depositing and growing graphene films on the upper surface and the lower surface of the copper foil substrate to obtain the copper-based graphene unit layer.
After 40 layers of the obtained copper-based graphene unit layers are stacked in order, the copper-based graphene unit layers are placed into ultrasonic welding equipment, and the following welding parameters are adopted: and carrying out ultrasonic welding under the vacuum condition, wherein the frequency is 20KHz, the amplitude is 30 mu m, the pressure is 4.6kN, and the rolling speed is 30mm/s, so as to obtain the three-dimensional bulk copper-based graphene composite material with the thickness of about 1 mm.
And (3) carrying out stress relief annealing on the prepared copper-based graphene composite material at 400 ℃ for 40min under a vacuum condition so as to further improve the conductivity of the product.
The conductivity of the copper-based graphene composite material before and after stress relief annealing is respectively as follows: 98.6% IACS,103.5% IACS; the breaking strength is: 366Mpa and 269Mpa.
Example 3
The embodiment provides a copper-based graphene composite material, which is prepared according to the following preparation method:
cutting a rolled copper foil with the thickness of 60 mu m and the purity of more than 99.9 percent into proper size, placing the copper foil into a tube furnace, adopting a CVD technology, strictly controlling the temperature and atmosphere conditions in the tube furnace, and depositing and growing graphene films on the upper surface and the lower surface of the copper foil substrate to obtain the copper-based graphene unit layer.
After 20 layers of the obtained copper-based graphene unit layers are stacked in order, the copper-based graphene unit layers are placed into ultrasonic welding equipment, and the following welding parameters are adopted: and carrying out ultrasonic welding under the atmospheric condition, the frequency of 20KHz, the amplitude of 30 microns, the pressure of 4.6kN and the rolling speed of 30mm/s to obtain the three-dimensional bulk copper-based graphene composite material with the thickness of about 1.2 mm.
And (3) carrying out stress relief annealing on the prepared copper-based graphene composite material at 400 ℃ for 20min under the condition of argon protection so as to further improve the conductivity of the product.
The electric conductivity of the copper-based graphene composite material before and after stress relief annealing is respectively as follows: 97.1% by weight of IACS,101.8% by weight of IACS; the breaking strength is: 355MPa,262MPa.
Example 4
The embodiment provides a copper-based graphene composite material, which is prepared according to the following preparation method:
cutting an electrolytic copper foil with the thickness of 20 mu m and the purity of more than 99.9 percent into proper size, placing the electrolytic copper foil into a tube furnace, adopting a CVD technology, strictly controlling the temperature and the atmosphere conditions in the tube furnace, and depositing and growing graphene films on the upper surface and the lower surface of the copper foil substrate to obtain the copper-based graphene unit layer.
After 50 layers of the obtained copper-based graphene unit layers are stacked in order, the copper-based graphene unit layers are placed into ultrasonic welding equipment, and the following welding parameters are adopted: ultrasonic welding under atmospheric conditions at a frequency of 20KHz, an amplitude of 36 μm, a pressure of 6.6kN and a rolling speed of 40mm/s to obtain a three-dimensional bulk copper-based graphene composite material having a thickness of about 1mm, the electrical conductivity and the breaking strength of which were 98.2% IACS and 345MPa, respectively.
Example 5
The embodiment provides a copper-based graphene composite material, which is prepared according to the following preparation method:
cutting a single crystal copper foil with the thickness of 25 mu m and the purity of more than 99.9 percent into a proper size, placing the single crystal copper foil into a tube furnace, adopting a CVD (chemical vapor deposition) technology, strictly controlling the temperature and atmosphere conditions in the tube furnace, and depositing and growing graphene films on the upper surface and the lower surface of the copper foil substrate to obtain the copper-based graphene unit layer.
After 40 layers of the obtained copper-based graphene unit layers are stacked in order, the copper-based graphene unit layers are placed in ultrasonic welding equipment, and the following welding parameters are adopted: and carrying out ultrasonic welding under the vacuum condition, the frequency of 20KHz, the amplitude of 36 mu m, the pressure of 6.6kN and the rolling speed of 30mm/s to obtain the three-dimensional bulk copper-based graphene composite material with the thickness of about 1 mm.
And (3) carrying out stress relief annealing on the prepared copper-based graphene composite material at the temperature of 420 ℃ for 30min under a vacuum condition so as to further improve the conductivity of the product.
The conductivity of the copper-based graphene composite material before and after stress relief annealing is respectively as follows: 99.6% IACS, 104.6%; the breaking strength is: 335Mpa and 264Mpa.
Comparative example 1
The comparative example provides a copper-based graphene composite material, which is prepared according to the following preparation method:
cutting a rolled copper foil with the thickness of 25 mu m and the purity of more than 99.9 percent into proper sizes, placing the rolled copper foil into a tube furnace, adopting a CVD technology, strictly controlling the temperature and the atmosphere conditions in the tube furnace, and depositing and growing graphene films on the upper surface and the lower surface of the copper foil substrate to obtain the copper-based graphene unit layer.
After 40 layers of the obtained copper-based graphene unit layers are stacked in order, the copper-based graphene unit layers are placed in ultrasonic welding equipment, and the following welding parameters are adopted: and carrying out ultrasonic welding under the atmospheric condition, the frequency of 20KHz, the amplitude of 15 microns, the pressure of 0.5kN and the rolling speed of 30mm/s to obtain the three-dimensional bulk copper-based graphene composite material with the thickness of about 1 mm.
After the copper-based graphene composite material is welded, part of copper foils are not welded, the binding force is weak, and the welding fails possibly due to the welding performed in the atmosphere and the welding fails due to the excessively small amplitude.
Comparative example 2
The comparative example provides a copper-based graphene composite material, which is prepared according to the following preparation method:
cutting an electrolytic copper foil with the thickness of 20 mu m and the purity of more than 99.9% into a proper size, uniformly coating the prepared graphene suspension (obtained by adding single-layer graphene into ethanol and performing ultrasonic dispersion treatment, wherein the mass content of the graphene is 0.1%) on the surface of the copper foil, and drying to obtain the copper-based graphene unit layer.
After 50 layers of the obtained copper-based graphene unit layers are stacked in order, placing the copper-based graphene unit layers into ultrasonic welding equipment, and adopting the following welding parameters: and carrying out ultrasonic welding under the atmospheric condition, with the frequency of 35KHz, the amplitude of 25 mu m, the pressure of 4.8kN and the rolling speed of 20mm/s to obtain the three-dimensional blocky copper-based graphene composite material with the thickness of about 1 mm.
The copper-based graphene composite material has poor welding effect, has a phenomenon of partial non-welding, and has electrical conductivity and breaking strength of 89.2% IACS,308Mpa respectively.
Comparative example 3
The comparative example provides a copper-based graphene composite material, which is prepared according to the following preparation method:
cutting a single crystal copper foil with the thickness of 25 mu m and the purity of more than 99.9 percent into proper sizes, placing the single crystal copper foil into a vacuum tube furnace, adopting a CVD technology, strictly controlling the physical and atmosphere conditions in the tube furnace, and depositing and growing graphene films on the upper surface and the lower surface of the copper foil substrate to obtain the copper-based graphene unit layer.
And (3) orderly stacking 40 layers of the obtained copper-based graphene unit layers, and performing hot-pressing sintering at 950 ℃ and 30Mpa under the protection of inert gas to obtain the copper-based graphene composite material.
The bulk copper-based graphene composite material prepared above was subjected to stress relief annealing under the same conditions as in example 5 (under vacuum conditions, heat preservation at 420 ℃ for 30 min).
The conductivity of the copper-based graphene composite material after stress relief annealing is as follows: 101.4% iacs; the breaking strength is: 267Mpa.
Comparative example 4
The present comparative example provides a copper-based graphene composite material, which is different from example 1 in that: the thickness of the copper foil was 15 μm.
The copper-based graphene composite material is cracked in the process after welding.
FIG. 2 is a cross-sectional microstructure diagram (OM) of a sample of the copper-based graphene composite obtained by ultrasonic welding in example 1; FIG. 3 is a cross-sectional Raman spectrum of a copper-based graphene composite material sample obtained by ultrasonic welding in example 1, and from the analysis result in FIG. 3, the single-layer graphene has two typical Raman characteristics, respectively at 1582cm -1 Near G peak and at 2700cm -1 Left and right G 'peaks, and for the graphene sample containing defects or at the edge of the graphene, a G' peak at 1350cm may also occur -1 Defect D peaks on the left and right, and located 1620cm -1 The nearby D' peak indicates that the graphene structure is well preserved by the preparation method, and can be used as a fast channel of electrons during conduction, so that the conductivity of the graphene/copper laminated composite material can be effectively improved.
Fig. 4 is XRD diffraction patterns of copper-based graphene composite samples obtained in example 5 and comparative example 3, wherein curve a is a sample prepared in comparative example 3 by using hot press molding, and curve b is a sample prepared in example 5 by using ultrasonic welding. From fig. 4, it is found that the single crystal structure of the copper foil is not significantly damaged in the sample prepared by ultrasonic welding in example 5, while the diffraction pattern of the sample prepared by hot press molding in comparative example 3 shows other crystal diffraction peaks of the Cu material, indicating that the single crystal copper foil is recrystallized during the preparation process, which reduces the electrical conductivity thereof.
In summary, the copper-based graphene composite material and the preparation method thereof provided by the embodiment of the application prepare the composite material with high conductivity through a low-cost, simple and efficient industrial preparation process.
The above description is only an example of the present application and is not intended to limit the scope of the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (8)
1. The preparation method of the copper-based graphene composite material is characterized by comprising the following steps of:
growing a graphene film on the surface of a copper foil by adopting a chemical vapor deposition method, wherein the thickness of the copper foil is 1-100 mu m, and obtaining a copper-based graphene unit layer;
stacking at least two copper-based graphene unit layers together to obtain a stacked assembly;
and welding the stacked assembly by adopting an ultrasonic welding technology, wherein the ultrasonic frequency of ultrasonic welding is 15-100kHz, and the ultrasonic amplitude is 20-60 mu m.
2. The method for preparing the copper-based graphene composite material according to claim 1, further comprising a step of stress-relief annealing the welded stacked assembly.
3. The preparation method of the copper-based graphene composite material according to claim 2, wherein the stress relief annealing is performed under a vacuum or atmosphere protection condition, the annealing temperature is 380-440 ℃, and the annealing time is 10-60min.
4. The preparation method of the copper-based graphene composite material according to claim 1, wherein the copper foil is one or a combination of a rolled copper foil, an electrolytic copper foil and a single crystal copper foil.
5. The method for preparing the copper-based graphene composite material according to claim 1, wherein the copper foil has a thickness of 20 to 25 μm.
6. The preparation method of the copper-based graphene composite material according to claim 1, wherein the ultrasonic welding is in the form of ultrasonic spot welding or ultrasonic roll welding; and/or, the ultrasonic welding is carried out under vacuum or atmosphere protection conditions.
7. The preparation method of the copper-based graphene composite material according to claim 6, wherein the ultrasonic roll welding is to roll the stacked assembly by using a sonotrode, the pressure is 0.1-10kN, and the relative linear velocity at the sonotrode is 1-100mm/s.
8. A copper-based graphene composite material, which is prepared by the method for preparing the copper-based graphene composite material according to any one of claims 1 to 7, wherein the copper-based graphene composite material comprises at least two copper-based graphene unit layers stacked together, each layer comprises a copper foil and a graphene film attached to the surface of the copper foil, and the parts of all the copper-based graphene unit layers are welded together.
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