Composite conductor material and preparation method thereof

Abstract

The present application discloses a composite conductor material and a preparation method thereof, wherein the composite conductor material comprises a graphene-three-dimensional copper skeleton composite of at least two particle sizes; the graphene-three-dimensional copper skeleton composite comprises a three-dimensional porous copper skeleton, the three-dimensional porous skeleton having a plurality of first pores, the surface of which is attached with a graphene layer; the graphene-three-dimensional copper skeleton composite has a plurality of second pores, and at least a portion of the graphene-three-dimensional copper skeleton composites of the at least two particle sizes are accommodated in the second pores of the graphene-three-dimensional copper skeleton composites of the larger particle size. The composite conductor material provided by the present application increases the contact area between copper and graphene, thereby increasing the graphene content, and improves the uniform and orderly distribution of graphene, effectively preventing its agglomeration, thereby improving the conductivity and wear resistance of the composite conductor material.

Description

Technical Field

[0001] The present application relates to the technical field of conductor materials, and in particular to a composite conductor material and a method for preparing the composite conductor material. Background Art

[0002] Graphene is a sp 2 Graphene is a new material in which hybrid-connected carbon atoms are tightly stacked into a single-layer two-dimensional honeycomb lattice structure. This structure gives graphene many properties, such as a nearly zero band gap, very high carrier mobility, large specific surface area, excellent electrical and thermal conductivity, excellent mechanical properties, and indices such as Young's modulus and fracture strength comparable to those of carbon nanotubes. These properties make graphene have great application prospects in many aspects.

[0003] In the field of conductors, graphene is often mixed with metals such as copper and silver to enhance the metal's electrical conductivity, wear resistance, and corrosion resistance. Taking copper as an example, copper is prepared into powder and then mixed with graphene. There are usually two mixing methods: one is to deposit a layer of graphene on the surface of the copper powder through CVD (Chemical Vapor Deposition), and the other is to mix metal powder with graphene sheets and then process the copper powder into the desired products such as wires and cables, electrical contact conductors, etc. through methods such as pressing. Currently, both methods of mixing graphene with metals only contact the surface of the copper particles with graphene, but do not contain graphene inside the particles. During the subsequent processing, the surface of the metal particles deforms, which makes it difficult for the graphene to form a uniform, orderly, and stable distribution in the conductor. Graphene is mixed into metal powder through the metal surface, and the proportion of graphene mixed is limited. When the graphene content on the surface of metal particles is high, the graphene on the surfaces of different metal particles is easy to agglomerate to form graphite during subsequent processing, resulting in a decrease in the overall conductivity, hardness and other properties of the metal mixture material. When the graphene content on the metal surface is low, due to the small content of graphene in the metal mixture, the excellent performance of graphene has limited effect on improving the overall performance of the metal mixture.

[0004] Therefore, how to control the high content ratio and uniform and orderly distribution of graphene in the metal-graphene mixture becomes the key to influencing the properties such as conductivity and wear resistance of the metal-graphene hybrid material. Summary of the Invention

[0005] In view of this, the present application provides a composite conductor material and a preparation method thereof, aiming to improve the problem that graphene is difficult to distribute uniformly and orderly in a metal-graphene mixture.

[0006] An embodiment of the present application is implemented as follows: a composite conductor material includes a graphene-three-dimensional copper skeleton complex of at least two particle sizes; the graphene-three-dimensional copper skeleton complex includes a three-dimensional porous copper skeleton, the three-dimensional porous skeleton has a plurality of first pores, and a graphene layer is attached to the surface of the first pores; the graphene-three-dimensional copper skeleton complex has a plurality of second pores, and among the graphene-three-dimensional copper skeleton complexes of at least two particle sizes, at least a portion of the graphene-three-dimensional copper skeleton complexes with small particle size is accommodated in the second pores of the graphene-three-dimensional copper skeleton complex with large particle size.

[0007] Optionally, in some embodiments of the present application, the material of the three-dimensional porous copper skeleton includes copper or a first copper alloy; and / or

[0008] The number of graphene layers is 3 to 6; and / or

[0009] The composite conductor material includes a first graphene-three-dimensional copper skeleton complex, a second graphene-three-dimensional copper skeleton complex,..., and an Nth graphene-three-dimensional copper skeleton complex, wherein N is an integer greater than or equal to 2, and the particle size of the first graphene-three-dimensional copper skeleton complex>the particle size of the second graphene-three-dimensional copper skeleton complex>...>the Nth graphene-three-dimensional copper skeleton complex.

[0010] Optionally, in some embodiments of the present application, the first copper alloy includes copper and a doping element, and the doping element includes one or more of nickel, bismuth, antimony, tellurium, zirconium, silicon, and molybdenum; and / or

[0011] The composite conductor material includes a first graphene-three-dimensional copper skeleton complex, a second graphene-three-dimensional copper skeleton complex, a third graphene-three-dimensional copper skeleton complex and a fourth graphene-three-dimensional copper skeleton complex; and / or

[0012] The composite conductor material further includes copper powder, and the copper powder is filled in the graphene-three-dimensional copper skeleton composite.

[0013] Optionally, in some embodiments of the present application, in the first copper alloy, the mass ratio of the copper to the anti-doping element is (50-68): (1-1.5); and / or

[0014] The particle size of the first graphene-three-dimensional copper skeleton complex is 10 5 ~5ⅹ10 5 nm, and the particle size of the second graphene-three-dimensional copper skeleton complex is 10 4 ~5ⅹ10 4 nm, the particle size of the third graphene-three-dimensional copper skeleton complex is 100-300 nm, and the particle size of the fourth graphene-three-dimensional copper skeleton complex is 50-80 nm; and / or

[0015] In the composite conductor material, the content of the first graphene-three-dimensional copper skeleton complex is 1 part, the content of the second graphene-three-dimensional copper skeleton complex is 1.2-2 parts, the content of the third graphene-three-dimensional copper skeleton complex is 2.6-3 parts, and the content of the fourth graphene-three-dimensional copper skeleton complex is 4 parts, by volume; and / or

[0016] The mass ratio of the copper powder to the three-dimensional porous copper skeleton is (0.01-0.5):100; and / or

[0017] The particle size of the copper powder is 10 to 30 nm.

[0018] Accordingly, the present application also provides a method for preparing a composite conductor material, comprising the following steps:

[0019] providing a second copper alloy of at least two particle sizes, wherein the second copper alloy comprises copper and an active metal doped in the copper;

[0020] Placing the second copper alloy of at least two particle sizes in an acidic solution for an acidic chemical bath to remove active metals in the second copper alloy, thereby obtaining a three-dimensional porous copper skeleton of at least two particle sizes, wherein the three-dimensional porous copper skeleton has a plurality of first pores;

[0021] Depositing graphene on the surface of the first pores of the three-dimensional porous copper skeleton with different particle sizes to form a graphene layer bonded to the pore walls of the first pores, thereby obtaining graphene-three-dimensional copper skeleton complexes with at least two particle sizes, wherein the graphene-three-dimensional copper skeleton complexes have second pores, and the pore walls of the second pores are the graphene layers;

[0022] The graphene-three-dimensional copper skeleton complexes of different particle sizes are mixed, and the graphene-three-dimensional copper skeleton complexes of small particle size are filled into the second pores of the graphene-three-dimensional copper skeleton complexes of large particle size to obtain a composite conductor material.

[0023] The composite conductor material includes a first graphene-three-dimensional copper skeleton complex, a second graphene-three-dimensional copper skeleton complex,..., an Nth graphene-three-dimensional copper skeleton complex, wherein N is an integer greater than or equal to 2, and the particle size of the first graphene-three-dimensional copper skeleton complex>the particle size of the second graphene-three-dimensional copper skeleton complex>...>the Nth graphene-three-dimensional copper skeleton complex; and / or

[0024] The active metal includes one or more of aluminum, iron, zinc and magnesium; and / or

[0025] The acidic solution includes one or more of hydrochloric acid and nitric acid.

[0026] Optionally, in some embodiments of the present application, the composite conductor material includes a first graphene-three-dimensional copper skeleton complex, a second graphene-three-dimensional copper skeleton complex, a third graphene-three-dimensional copper skeleton complex and a fourth graphene-three-dimensional copper skeleton complex.

[0027] Optionally, in some embodiments of the present application, the particle size of the first graphene-three-dimensional copper skeleton complex is 10 5 ~5ⅹ10 5 nm, and the particle size of the second graphene-three-dimensional copper skeleton complex is 10 4 ~5ⅹ10 4 nm, the particle size of the third graphene-three-dimensional copper skeleton complex is 100-300 nm, and the particle size of the fourth graphene-three-dimensional copper skeleton complex is 50-80 nm.

[0028] Optionally, in some embodiments of the present application, in the graphene-three-dimensional copper skeleton complex, the number of graphene layers is 3 to 6; and / or

[0029] In the second copper alloy, the mass ratio of the copper to the active metal is (50-68): (27-45); and / or

[0030] The mass fraction of the acidic solution is 20% to 40%.

[0031] Optionally, in some embodiments of the present application, the method of depositing graphene includes a vapor deposition method; and / or

[0032] The second copper alloy further comprises a doping element; the doping element comprises one or more of nickel, bismuth, antimony, tellurium, zirconium, silicon, and molybdenum; the mass ratio of the copper to the doping element is (50-68): (1-1.5); and / or

[0033] After obtaining the composite conductor material, the method further includes performing ball milling treatment, wherein the ball milling treatment time is 0.5 to 1 hour, the ball-to-material ratio is (4 to 6):1, and the rotation speed is 210 to 240 r / min.

[0034] The composite conductor material described in the present application includes graphene-three-dimensional copper skeleton complexes of at least two particle sizes, and the second pores of the large-particle-size graphene-three-dimensional copper skeleton complex accommodate a small-particle-size graphene-three-dimensional copper skeleton complex. The surfaces of several first pores of the three-dimensional porous skeleton are attached with a graphene layer. Compared with the prior art in which a graphene deposition layer is formed on the outer surface of the copper body or graphene is deposited in porous copper of only one particle size, the small-particle-size graphene-three-dimensional porous copper skeleton described in the present application is filled in the second pores of the large-particle-size graphene-three-dimensional porous copper skeleton, which can further increase the contact area with graphene, thereby increasing the content of graphene in the composite conductor material, improving the uniform and orderly distribution of graphene in copper, effectively preventing the problems of graphene agglomeration and disordered distribution, and thereby improving the conductivity and wear resistance of the composite conductor material. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the following briefly introduces the drawings required for use in the description of the embodiments. Obviously, the drawings described below are only some embodiments of the present application. For those skilled in the art, other drawings can be obtained based on these drawings without creative work.

[0036] Figure 1 This is a flow chart of a method for preparing a composite conductor material provided in an embodiment of the present application. DETAILED DESCRIPTION

[0037] The following will be combined with the drawings in the embodiments of the present application to clearly and completely describe the technical solutions in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without making creative work are within the scope of protection of this application. In addition, it should be understood that the specific embodiments described herein are only used to illustrate and explain the present application and are not used to limit the present application.

[0038] In this application, unless otherwise indicated, directional terms such as "upper" and "lower" generally refer to the upper and lower positions of a device in actual use or operation, specifically in the drawing directions of the accompanying drawings; whereas "inner" and "outer" refer to the outline of the device. Furthermore, in the description of this application, the term "including" means "including but not limited to." Terms such as first, second, and third are used merely as designations and do not impose numerical requirements or establish a sequential order.

[0039] In this application, "and / or" describes the association relationship between associated objects, indicating that three relationships can exist. For example, A and / or B can mean: A exists alone, A and B exist at the same time, and B exists alone. A and B can be singular or plural.

[0040] In this application, "at least one" means one or more, and "plurality" means two or more. "One or several", "at least one of the following" or similar expressions refer to any combination of these items, including any combination of single items or plural items. For example, "at least one of a, b, or c", or "at least one of a, b, and c" can all mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be single or multiple.

[0041] Various embodiments of the present application may be presented in the form of a range; it should be understood that the description in the form of a range is only for convenience and brevity and should not be understood as a hard limitation on the scope of the present application; therefore, the range description should be considered to have specifically disclosed all possible sub-ranges and single numbers within the range. For example, the description of a range from 1 to 6 should be considered to have specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5 and 6, which applies regardless of the range. In addition, whenever a numerical range is indicated herein, it is meant to include any cited number (fractional or integer) within the indicated range.

[0042] The technical solution of this application is as follows:

[0043] In a first aspect, embodiments of the present application provide a composite conductor material comprising a graphene-three-dimensional copper skeleton composite of at least two particle sizes. The graphene-three-dimensional copper skeleton composite comprises a three-dimensional porous copper skeleton having a plurality of first pores, with a graphene layer attached to the surface of the first pores. The graphene-three-dimensional copper skeleton composite has a plurality of second pores, and among the at least two particle sizes of graphene-three-dimensional copper skeleton composites, at least a portion of the small-sized graphene-three-dimensional copper skeleton composites is accommodated in the second pores of the large-sized graphene-three-dimensional copper skeleton composite. In other words, the small-sized graphene-three-dimensional copper skeleton composite is accommodated in the second pores of the large-sized graphene-three-dimensional copper skeleton composite.

[0044] The composite conductor material described in the present application includes graphene-three-dimensional copper skeleton complexes of at least two particle sizes, and the second pores of the large-particle-size graphene-three-dimensional copper skeleton complex accommodate a small-particle-size graphene-three-dimensional copper skeleton complex. The surfaces of several first pores of the three-dimensional porous skeleton are attached with a graphene layer. Compared with the prior art in which a graphene deposition layer is formed on the outer surface of the copper body or graphene is deposited in porous copper of only one particle size, the small-particle-size graphene-three-dimensional porous copper skeleton described in the present application is filled in the second pores of the large-particle-size graphene-three-dimensional porous copper skeleton, which can further increase the contact area with graphene, thereby increasing the content of graphene in the composite conductor material, improving the uniform and orderly distribution of graphene in copper, effectively preventing the problems of graphene agglomeration and disordered distribution, and thereby improving the conductivity and wear resistance of the composite conductor material.

[0045] In some embodiments, the material of the three-dimensional porous copper skeleton includes copper or a first copper alloy.

[0046] In some embodiments, the first copper alloy includes copper and a doping element, and the doping element includes one or more of nickel, bismuth, antimony, tellurium, zirconium, silicon, and molybdenum.

[0047] In some embodiments, the mass ratio of copper to the doping element in the first copper alloy is (50-68):(1-1.5), for example, (52-66):(1-1.5), (54-64):(1-1.5), (56-62):(1-1.5), (58-60):(1-1.5), etc. Within the mass ratio range, when used in electrical contact conductors, the addition of nickel, bismuth, antimony, and tellurium can improve welding resistance, the addition of silicon, nickel, and zirconium can improve corrosion resistance, and nickel and molybdenum can improve wear resistance. The addition of doping elements has a certain effect on electrical conductivity, but the addition of graphene can improve overall electrical conductivity. In addition, the addition of graphene can significantly improve the corrosion resistance, wear resistance, thermal conductivity, and electrical conductivity of the conductor.

[0048] When the composite conductor material is applied to copper wires, no doping elements are required. By adding graphene, the electrical conductivity, thermal conductivity and corrosion resistance of the copper wires can be improved.

[0049] When the first copper alloy contains nickel, the mass ratio of copper to nickel is (50-68):(0.1-0.65), for example, (52-67):(0.1-0.65), (54-66):(0.1-0.65), (55-65):(0.1-0.65), (56-62):(0.1-0.65), (58-60):(0.1-0.65), etc. Within this ratio range, the composite conductor material can have excellent welding resistance, wear resistance, electrical conductivity, and thermal conductivity.

[0050] When the first copper alloy contains bismuth, the mass ratio of copper to bismuth is (50-68):(0.05-0.18), for example, (52-67):(0.05-0.18), (54-66):(0.05-0.18), (55-65):(0.05-0.18), (56-62):(0.05-0.18), (58-60):(0.05-0.18), etc. Within this ratio range, the composite conductor material can have good welding resistance, electrical conductivity, and thermal conductivity.

[0051] When the first copper alloy contains antimony, the mass ratio of copper to antimony is (50-68):(0.05-0.2), for example, (52-67):(0.05-0.2), (54-66):(0.05-0.2), (55-65):(0.05-0.2), (56-62):(0.05-0.2), (58-60):(0.05-0.2), etc. Within this ratio range, the composite conductor material can have excellent welding resistance, electrical conductivity, and thermal conductivity.

[0052] When the first copper alloy contains tellurium, the mass ratio of copper to tellurium is (50-68):(0.05-0.19), for example, (52-67):(0.05-0.19), (54-66):(0.05-0.19), (55-65):(0.05-0.19), (56-62):(0.05-0.19), (58-60):(0.05-0.19), etc. Within this ratio range, the composite conductor material can have good welding resistance, electrical conductivity, and thermal conductivity.

[0053] When the first copper alloy contains zirconium, the mass ratio of copper to zirconium is (50-68):(0.05-0.25), for example, (52-67):(0.05-0.25), (54-66):(0.05-0.25), (55-65):(0.05-0.25), (56-62):(0.05-0.25), (58-60):(0.05-0.25), etc. Within this ratio range, the composite conductor material can have good corrosion resistance, electrical conductivity, and thermal conductivity.

[0054] When the first copper alloy contains silicon, the mass ratio of copper to silicon is (50-68):(0.05-0.4), for example, (52-67):(0.05-0.4), (54-66):(0.05-0.4), (55-65):(0.05-0.4), (56-62):(0.05-0.4), (58-60):(0.05-0.4), etc. Within this ratio range, the composite conductor material can have excellent corrosion resistance, electrical conductivity, and thermal conductivity.

[0055] When the first copper alloy contains molybdenum, the mass ratio of copper to molybdenum is (50-68):(0.1-0.45), for example, (52-67):(0.1-0.45), (54-66):(0.1-0.45), (55-65):(0.1-0.45), (56-62):(0.1-0.45), (58-60):(0.1-0.45), etc. Within this ratio range, the composite conductor material can have good wear resistance, electrical conductivity, and thermal conductivity.

[0056] In some embodiments, the number of graphene layers is 3 to 6, for example, 4 or 5. Within the above range of the number of layers, the graphene structure can be guaranteed to be complete and orderly and evenly distributed.

[0057] In some embodiments, the composite conductor material includes graphene-3D copper skeleton composites of N different particle sizes. In other words, the composite conductor material includes a first graphene-3D copper skeleton composite, a second graphene-3D copper skeleton composite, ..., and an Nth graphene-3D copper skeleton composite, where N is an integer greater than or equal to 2, and the particle size of the first graphene-3D copper skeleton composite > the particle size of the second graphene-3D copper skeleton composite > ... > the Nth graphene-3D copper skeleton composite. By mixing graphene-3D copper skeleton composites of different particle sizes, the contact area between the graphene and the three-dimensional porous copper skeleton can be increased, and the dispersion of the graphene in the three-dimensional porous copper skeleton can be improved, thereby preventing graphene agglomeration and uneven distribution.

[0058] It is understandable that the large-particle graphene-three-dimensional copper skeleton complex can be filled with one or more small-particle graphene-three-dimensional copper skeleton complexes.

[0059] It can be understood that in the complex, the filling method of graphene-three-dimensional copper skeleton complexes of N particle sizes can be: the second hole of the first graphene-three-dimensional copper skeleton complex is filled with the second graphene-three-dimensional copper skeleton complex, the second graphene-three-dimensional copper skeleton complex is filled with the third graphene-three-dimensional copper skeleton complex,..., the N-1th graphene-three-dimensional copper skeleton complex is filled with the Nth graphene-three-dimensional copper skeleton complex.

[0060] It can be understood that the composite conductor material may include: a structure formed by two types of graphene-three-dimensional copper skeleton complexes, for example, a structure formed by the N-1 graphene-three-dimensional copper skeleton complex filled with the N-3 graphene-three-dimensional copper skeleton complex; and / or a structure formed by three types of graphene-three-dimensional copper skeleton complexes, for example, a structure formed by the N-2 graphene-three-dimensional copper skeleton complex filled with the N-1 graphene-three-dimensional copper skeleton complex and the N-1 graphene-three-dimensional copper skeleton complex. The present invention relates to a structure in which the first graphene-three-dimensional copper skeleton complex is filled with an N-th graphene-three-dimensional copper skeleton complex; ····; and / or, a structure formed by graphene-three-dimensional copper skeleton complexes of N types of particle sizes, for example, the first graphene-three-dimensional copper skeleton complex is filled with a second graphene-three-dimensional copper skeleton complex, and the second graphene-three-dimensional copper skeleton complex is filled with a third graphene-three-dimensional copper skeleton complex, ···, and the N-1-th structure graphene-three-dimensional copper skeleton complex is filled with a structure formed by the third graphene-three-dimensional copper skeleton complex.

[0061] In at least one embodiment, the composite conductor material includes a first graphene-three-dimensional copper skeleton composite, a second graphene-three-dimensional copper skeleton composite, a third graphene-three-dimensional copper skeleton composite, and a fourth graphene-three-dimensional copper skeleton composite. The particle size of the first graphene-three-dimensional copper skeleton composite is 10 5 ~5ⅹ10 5 nm, for example, 2×10 5 nm, 3×10 5 nm, 4×10 5 nm, etc.; the particle size of the second graphene-three-dimensional copper skeleton complex is 10 4 ~5ⅹ10 4 nm, for example, 2 x 10 4 nm, 3×10 4 nm, 4×10 4nm, etc.; the particle size of the third graphene-three-dimensional copper skeleton complex is 100-300 nm, for example, it can be 120-280 nm, 150-260 nm, 180-230 nm, etc.; the particle size of the fourth graphene-three-dimensional copper skeleton complex is 50-80 nm, for example, it can be 52-78 nm, 55-70 nm, 60-65 nm, etc.

[0062] In some embodiments, in the composite conductor material, by volume, the first graphene-three-dimensional copper skeleton complex comprises 1 part, the second graphene-three-dimensional copper skeleton complex comprises 1.2-2 parts, the third graphene-three-dimensional copper skeleton complex comprises 2.6-3 parts, and the fourth graphene-three-dimensional copper skeleton complex comprises 4 parts. For example, the ratios may be 1:(1.5-1.8):(2.6-3):4, 1:(1.6-1.7):(2.6-3):4, 1:(1.2-2):(2.8-2.9):4, etc. Within these content ranges, the small-particle graphene-three-dimensional copper skeleton complex is facilitated to uniformly fill the pores of the large-particle graphene-three-dimensional copper skeleton complex, thereby improving the uniform distribution of graphene in the three-dimensional porous copper skeleton.

[0063] In some embodiments, the composite conductor material further comprises copper powder. Among the at least two graphene-three-dimensional copper skeleton composites of different particle sizes, a larger-particle-sized graphene-three-dimensional copper skeleton composite is filled with the copper powder and at least one smaller-particle-sized graphene-three-dimensional copper skeleton composite. The copper powder can provide support and reduce strain damage to the graphene.

[0064] It can be understood that, in some embodiments, each graphene-three-dimensional copper skeleton composite of a particle size is filled with copper powder.

[0065] It can be understood that in other embodiments, only the large-particle graphene-three-dimensional copper skeleton complexes are filled with copper powder, and the small-particle graphene-three-dimensional copper skeleton complexes filled in the large-particle graphene-three-dimensional copper skeleton complexes are not filled with copper powder.

[0066] It can be understood that in other embodiments, only the small-particle graphene-three-dimensional copper skeleton complexes are filled with copper powder, and the large-particle graphene-three-dimensional copper skeleton complexes filled with small-particle graphene-three-dimensional copper skeleton complexes are not filled with copper powder.

[0067] In some embodiments, the mass ratio of the copper powder to the three-dimensional porous copper skeleton is (0.01-0.5):100, for example, (0.01-0.5):100, (0.01-0.5):100, (0.01-0.5):100, (0.01-0.5):100, (0.01-0.5):100, (0.01-0.5):100, etc. Within the mass ratio range, the copper powder can be filled between graphene-three-dimensional copper skeleton complexes of different particle sizes and in the pores of the graphene-three-dimensional copper skeleton. On the one hand, the copper powder can serve as a supporting structure to prevent strain damage to the graphene during pressing, which would prevent it from effectively functioning. On the other hand, the copper powder is dispersed and filled in the gaps of the graphene-three-dimensional copper skeleton, which can prevent agglomeration of graphene and promote uniform and orderly distribution of graphene in the graphene-three-dimensional copper skeleton. The copper powder can also improve the continuous conductivity of the composite conductor material and enhance the performance of the composite conductor material.

[0068] In some embodiments, the copper powder has a particle size of 10 to 30 nm, for example, 12 to 28 nm, 15 to 25 nm, 18 to 24 nm, 19 to 22 nm, 20 to 21 nm, etc. Small-sized copper powder is more easily dispersed in the second pores of the graphene-three-dimensional copper skeleton composite, thereby improving the continuous conductivity of the composite conductor material, providing support, and preventing graphene agglomeration.

[0069] Second, see Figure 1 The present invention also provides a method for preparing the composite conductor material, comprising the following steps:

[0070] Step S11: providing a second copper alloy having at least two particle sizes, wherein the second copper alloy comprises copper and an active metal doped in the copper;

[0071] Step S12: placing the second copper alloy of at least two particle sizes in an acidic solution for an acidic chemical bath to remove active metals in the second copper alloy, thereby obtaining a three-dimensional porous copper skeleton of at least two particle sizes, wherein the three-dimensional porous copper skeleton has a plurality of first pores;

[0072] Step S13: Depositing graphene on the surface of the first pores of the three-dimensional porous copper skeleton of different particle sizes to form a graphene layer bonded to the pore walls of the first pores, thereby obtaining graphene-three-dimensional copper skeleton complexes of at least two particle sizes, wherein the graphene-three-dimensional copper skeleton complexes have second pores, and the pore walls of the second pores are the graphene layers;

[0073] Step S14: mixing the graphene-three-dimensional copper skeleton complexes of different particle sizes, so that the graphene-three-dimensional copper skeleton complexes of small particle size are filled into the second pores of the graphene-three-dimensional copper skeleton complexes of large particle size, to obtain a composite conductor material.

[0074] The preparation method of the composite conductor material described in the present application is to prepare an alloy by preparing copper and an active metal of at least two particle sizes, and remove the active metal in the second copper alloy through an acidic chemical bath to obtain a three-dimensional porous copper skeleton with different particle sizes containing pores. Graphene is deposited on the surface of the first pore of the three-dimensional porous copper skeleton, and small-particle graphene-three-dimensional copper skeleton complexes are filled in the pores of the large-particle graphene-three-dimensional copper skeleton complexes. The pores can increase the contact area with the graphene, thereby increasing the content of graphene in the composite conductor material. The mixing of graphene-three-dimensional copper skeleton complexes of different particle sizes can further improve the uniform dispersion of graphene in the three-dimensional porous copper skeleton, effectively prevent the problems of graphene agglomeration and disordered distribution, and thereby improve the conductivity and wear resistance of the composite conductor material.

[0075] In the step S11:

[0076] In some embodiments, the preparation method of the second copper alloy includes: providing copper and an active metal, mixing, and smelting to obtain the second copper alloy.

[0077] In some embodiments, when the copper and the active metal are mixed and smelted, the copper and the active metal can be added at the same time.

[0078] In other embodiments, when the copper and the active metal are mixed and smelted, the copper can be added in multiple batches. Specifically, a first portion of the copper and active metal is added first, smelted for a period of time, and then the remaining copper is added; or a first portion of the copper and active metal is added first, smelted for a period of time, and then a second portion of the copper is added, and then smelted for a period of time, and then the remaining copper is added. It will be understood that the number of times the copper is added is not limited. Smelting by adding copper in small amounts and multiple times facilitates uniform mixing of the copper and the active metal, promotes a uniform distribution of pores in the three-dimensional porous copper skeleton, and thus improves the uniform dispersion of graphene.

[0079] In some embodiments, after obtaining the second copper alloy, the method further comprises crushing to obtain the second copper alloy with at least two particle sizes.

[0080] In some embodiments, the pulverization method includes one or more of mechanical ball milling and atomization.

[0081] In some embodiments, the active metal includes one or more of aluminum, iron, zinc, and magnesium. These active metals have a stronger ability to gain or lose electrons, are more active in chemical reactions, are non-toxic, and are easily removed by reacting with acidic solutions. It is understood that copper particles of different sizes can be independently selected for the active metal.

[0082] In some embodiments, the mass ratio of copper to the active metal in the second copper alloy is (50-68):(27-45), for example, (52-66):(29-43), (54-64):(31-41), (56-62):(33-39), (58-60):(35-37), etc. Within this mass ratio range, the copper is uniformly distributed in the second copper alloy, and after the active metal is removed by an acidic solution, a three-dimensional porous copper skeleton containing pores can be formed.

[0083] In some embodiments, the second copper alloy further contains a doping element. When the mixed raw material does not contain the doping element, after reacting with the acidic solution to remove the active metal, the material of the three-dimensional porous copper skeleton comprises copper. When the mixed raw material contains the doping element, the doping element does not react with the acidic solution and can remain in the three-dimensional porous copper skeleton, thereby increasing the three-dimensional porous copper skeleton's resistance to welding, corrosion, and wear. The material of the three-dimensional porous copper skeleton comprises the first copper alloy containing copper and the doping element, and the doping element can be selectively added according to actual needs.

[0084] The doping elements are as described above and will not be described again here.

[0085] In some embodiments, the smelting is performed in a vacuum environment with a vacuum degree of 12-16 Pa, for example, 12.5-15.5 Pa, 13-15 Pa, 13.5-14.5 Pa, etc. Within the vacuum degree range, copper and active metals are conducive to uniform mixing to form an alloy.

[0086] In other embodiments, the smelting is performed in an inert gas environment, and the inert gas includes one or more of nitrogen, helium, neon, argon, krypton, xenon, and radon.

[0087] In some embodiments, the smelting temperature is 1400-1500° C., for example, 1410-1490° C., 1420-1480° C., 1430-1470° C., 1440-1460° C., 1450-1455° C., etc.; the smelting time is 50-110 minutes, for example, 55-105 minutes, 60-100 minutes, 65-95 minutes, 70-90 minutes, 75-80 minutes, etc. Under the smelting conditions, the copper and the active metal are melted into a liquid. Unlike solid-solid mixing, the liquid-liquid mixing of the copper and the active metal element is more uniform.

[0088] In the step S12:

[0089] In some embodiments, the acidic solution includes one or more of hydrochloric acid and nitric acid.

[0090] It is understandable that during transportation and storage, the surfaces of copper and active metals are inevitably oxidized to form metal oxides. The acidic solution can not only react with the active metals, but also react with the metal oxides to remove the metal oxides.

[0091] In some embodiments, the mass fraction of the acidic solution is 20% to 40%, for example, 21% to 39%, 22% to 38%, 24% to 35%, 25% to 33%, 28% to 30%, etc. Within this mass fraction range, sufficient reaction with the active metal is facilitated to remove the active metal.

[0092] In some embodiments, the second copper alloy is placed in an acidic solution for an acidic chemical bath and further includes water washing and drying.

[0093] In the step S13:

[0094] In some embodiments, the method of depositing graphene includes a vapor deposition method, which facilitates the graphene to be closely adsorbed on the surface of the three-dimensional porous copper skeleton and the surface of the first pore.

[0095] The vapor deposition method belongs to the existing technology in this field and will not be described in detail here.

[0096] In some embodiments, in the graphene-three-dimensional copper skeleton complex, the number of graphene layers is 3 to 6.

[0097] Step S14:

[0098] In some embodiments, the composite conductor material includes graphene-3D copper skeleton composites of N different particle sizes. In other words, the composite conductor material includes a first graphene-3D copper skeleton composite, a second graphene-3D copper skeleton composite, ..., and an Nth graphene-3D copper skeleton composite, where N is an integer greater than or equal to 2, and the particle size of the first graphene-3D copper skeleton composite > the particle size of the second graphene-3D copper skeleton composite > ... > the Nth graphene-3D copper skeleton composite. By mixing graphene-3D copper skeleton composites of different particle sizes, the contact area between the graphene and the three-dimensional porous copper skeleton can be increased, and the dispersion of the graphene in the three-dimensional porous copper skeleton can be improved, thereby preventing graphene agglomeration and uneven distribution.

[0099] It is understandable that the large-particle graphene-three-dimensional copper skeleton complex can be filled with one or more small-particle graphene-three-dimensional copper skeleton complexes.

[0100] It can be understood that in the complex, the filling method of graphene-three-dimensional copper skeleton complexes of N particle sizes can be: the second hole of the first graphene-three-dimensional copper skeleton complex is filled with the second graphene-three-dimensional copper skeleton complex, the second graphene-three-dimensional copper skeleton complex is filled with the third graphene-three-dimensional copper skeleton complex,..., the N-1th graphene-three-dimensional copper skeleton complex is filled with the Nth graphene-three-dimensional copper skeleton complex.

[0101] It can be understood that the composite conductor material may include: a structure formed by two types of graphene-three-dimensional copper skeleton complexes, for example, a structure formed by the N-1 graphene-three-dimensional copper skeleton complex filled with the N-3 graphene-three-dimensional copper skeleton complex; and / or a structure formed by three types of graphene-three-dimensional copper skeleton complexes, for example, a structure formed by the N-2 graphene-three-dimensional copper skeleton complex filled with the N-1 graphene-three-dimensional copper skeleton complex and the N-1 graphene-three-dimensional copper skeleton complex. The present invention relates to a structure in which the first graphene-three-dimensional copper skeleton complex is filled with an N-th graphene-three-dimensional copper skeleton complex; ····; and / or, a structure formed by graphene-three-dimensional copper skeleton complexes of N types of particle sizes, for example, the first graphene-three-dimensional copper skeleton complex is filled with a second graphene-three-dimensional copper skeleton complex, and the second graphene-three-dimensional copper skeleton complex is filled with a third graphene-three-dimensional copper skeleton complex, ···, and the N-1-th structure graphene-three-dimensional copper skeleton complex is filled with a structure formed by the third graphene-three-dimensional copper skeleton complex.

[0102] In at least one embodiment, the composite conductor material includes a first graphene-three-dimensional copper skeleton composite, a second graphene-three-dimensional copper skeleton composite, a third graphene-three-dimensional copper skeleton composite, and a fourth graphene-three-dimensional copper skeleton composite.

[0103] In some embodiments, the process of mixing the graphene-three-dimensional copper skeleton complexes of different particle sizes further includes adding copper powder.

[0104] The first graphene-three-dimensional copper skeleton complex, the second graphene-three-dimensional copper skeleton complex, the third graphene-three-dimensional copper skeleton complex and the fourth graphene-three-dimensional copper skeleton complex and the copper powder are described above and will not be repeated here.

[0105] In some embodiments, the mixing method includes ultrasonic treatment, the frequency of the ultrasonic treatment is 10 to 30 kHz, for example, 12 to 28 kHz, 14 to 26 kHz, 16 to 24 kHz, 18 to 20 kHz, etc.; the duration of the ultrasonic treatment is 2 to 4 hours, for example, 3 hours. Under the conditions of the ultrasonic treatment, the three-dimensional porous copper skeletons of different gradient particle sizes are conducive to uniform mixing; during the mixing process, the small-particle graphene-three-dimensional copper skeleton complex can be filled into the second pores of the large-particle graphene-three-dimensional copper skeleton complex, and the copper powder can be filled into the pores and gaps of the three-dimensional porous copper skeletons of different particle sizes.

[0106] In some embodiments, after obtaining the composite conductor material, ball milling is further performed, wherein the ball milling time is 0.5 to 1 hour, for example, 0.6 to 0.9 hours, 0.7 to 0.8 hours, etc.; the ball-to-material ratio of the ball milling is (4 to 6):1, for example, 5:1, etc.; and the rotation speed of the ball milling is 210 to 240 r / min, for example, 215 to 235 r / min, 220 to 230 r / min, etc. Under the ball milling conditions, the small-particle graphene-three-dimensional copper skeleton complex can be fixed in the second pores of the large-particle graphene-three-dimensional copper skeleton complex, and the ball milling can destroy part of the graphene inside the composite conductor material, exposing the copper, which promotes the fusion between the copper and the copper during the subsequent sintering and pressing process.

[0107] In a third aspect, an embodiment of the present application further provides a conductor, which includes the above-mentioned composite conductor material.

[0108] The conductor described in the present application includes a composite conductor material, which includes graphene-three-dimensional copper skeleton complexes of at least two particle sizes. The second pores of the large-particle graphene-three-dimensional copper skeleton complex accommodate small-particle graphene-three-dimensional copper skeleton complexes, which can increase the contact area between the graphene and the three-dimensional copper skeleton. The composite conductor material contains a high content of uniformly and orderly distributed graphene, which can effectively improve the conductivity of the conductor.

[0109] In some embodiments, the conductor comprises a wire cable or an electrical contact conductor.

[0110] In some embodiments, in the composite conductor material in the wire and cable, the material of the three-dimensional porous copper skeleton includes copper.

[0111] In some embodiments, the method for preparing the wire and cable comprises the following steps:

[0112] Providing the above composite conductor material, pressing and forming it, and then sintering it to obtain a sintered embryonic body;

[0113] hot pressing and melting the sintered green body to obtain a smelted green body;

[0114] The smelted embryo body is placed in a wire drawing die, extruded and drawn, and annealed to obtain wires and cables.

[0115] The contact gaps between different three-dimensional porous copper skeletons are different. During pressing, the outer surface of the composite conductor material will deform, resulting in disordered distribution or agglomeration of some graphene, but the internal deformation of the composite conductor material is relatively small. This is because the large-particle graphene-three-dimensional copper skeleton complex in the composite conductor material is filled with countless small-particle graphene-three-dimensional copper skeleton complexes and contains a certain porosity. The internal deformation of the graphene-three-dimensional copper skeleton complex is more likely to occur in the direction of the voids with less resistance. Graphene and copper are formed by vapor deposition and have strong bonding force. After deformation under less resistance, the graphene deposition layer will not be damaged. In subsequent processing technology, the uniformly and orderly distributed graphene deposition layer will change in an orderly manner with the extension and contraction of the three-dimensional porous copper skeleton.

[0116] In some embodiments, the sintering temperature is 500-700° C., for example, 510-690° C., 520-680° C., 550-650° C., 580-640° C., 600-620° C., etc. Within the sintering temperature range, metal adhesion can be avoided, and the stability and uniform distribution of graphene can be improved.

[0117] In some embodiments, the hot pressing temperature is 220-300° C., for example, 230-295° C., 235-290° C., 240-280° C., 245-270° C., 250-260° C., etc.; the hot pressing pressure is 380-490 MPa, for example, 390-485 MPa, 400-480 MPa, 420-470 MPa, 430-460 MPa, 440-450 MPa, etc. Within the hot pressing temperature range, the density between metal particles is improved, the formation of voids is prevented, and the metal stretching movement is promoted, and a certain stretching and peeling effect is exerted on the agglomeration of graphene, thereby preventing the agglomeration of graphene.

[0118] In some embodiments, in the composite conductor material of the electrical contact conductor, the three-dimensional porous copper skeleton comprises a first copper alloy comprising copper and a dopant element. The dopant element in the first copper alloy can improve the electrical contact conductor's resistance to welding, corrosion, and wear.

[0119] In some embodiments, the method for preparing the electrical contact conductor comprises the following steps:

[0120] Providing the above composite conductor material, pressing and forming it, and then sintering it to obtain a sintered embryonic body;

[0121] The sintered green body is hot pressed and smelted to obtain an electrical contact conductor.

[0122] In some embodiments, the sintering temperature is 500-700° C., for example, 510-690° C., 520-680° C., 550-650° C., 580-640° C., 600-620° C., etc. Within the sintering temperature range, metal adhesion can be avoided, and the stability and uniform distribution of graphene can be improved.

[0123] In some embodiments, the hot pressing temperature is 220-300° C., for example, 230-295° C., 235-290° C., 240-280° C., 245-270° C., 250-260° C., etc.; the hot pressing pressure is 380-490 MPa, for example, 390-485 MPa, 400-480 MPa, 420-470 MPa, 430-460 MPa, 440-450 MPa, etc. Within the hot pressing temperature range, the density between metal particles is improved, the formation of voids is prevented, and the metal stretching movement is promoted, and a certain stretching and peeling effect is exerted on the agglomeration of graphene, thereby preventing the agglomeration of graphene.

[0124] The pressing, melting, extrusion drawing and annealing are related to the prior art in this field and will not be described in detail here.

[0125] The present application will be described in detail below through specific examples. The following examples are only some examples of the present application and are not limitations of the present application.

[0126] Example 1

[0127] This embodiment provides a composite conductor material comprising a graphene-three-dimensional copper skeleton composite of two different particle sizes. The composite conductor material is prepared as follows:

[0128] 50g of copper and 45g of aluminum were weighed and placed in a vacuum melting furnace. The vacuum degree was controlled to be 12Pa and the temperature was 1400°C. The mixture was smelted for 80min and subjected to mechanical ball milling to obtain a second copper alloy with a first particle size and a second particle size. The second copper alloys with different particle sizes were rinsed with water and then placed in 20% hydrochloric acid by mass. After the reaction, the alloys were rinsed with water again and dried to obtain a three-dimensional porous copper skeleton with different particle sizes of copper element. The three-dimensional porous copper skeleton contained a plurality of first pores and a second pore. The particle size of the three-dimensional porous copper skeleton with the first particle size was 10 5 ~5x10 5 nm, and the particle size of the second three-dimensional porous copper skeleton is 10 4 ~5x10 4 nm;

[0129] Graphene was deposited on the surface of the first hole of the three-dimensional porous copper skeleton by vapor deposition. The number of graphene layers was 3 to obtain a first graphene-three-dimensional copper skeleton complex and a second graphene-three-dimensional copper skeleton complex. The two were mixed in a volume ratio of 1:2, and 0.25 g of copper powder with a particle size of 10 to 30 nm was added. The mixture was ultrasonically treated for 2 h, and then ball milled for 0.5 h, with a ball-to-material ratio of 4:1 and a ball milling speed of 210 r / min to obtain a composite conductor material.

[0130] Example 2

[0131] This embodiment is basically the same as Example 1, except that, in this embodiment, 50 g of copper and 45 g of aluminum were weighed, and a third graphene-three-dimensional copper skeleton complex was prepared according to the above-mentioned graphene-three-dimensional copper skeleton preparation method, and the particle size of the third graphene-three-dimensional copper skeleton complex was 100 to 300 nm; the first graphene-three-dimensional copper skeleton complex, the second graphene-three-dimensional copper skeleton complex, and the third graphene-three-dimensional copper skeleton complex were mixed in a volume ratio of 1:2:3.

[0132] Example 3

[0133] This embodiment is basically the same as Example 2, except that, in this embodiment, 50 g of copper and 45 g of aluminum were weighed, and a fourth graphene-three-dimensional copper skeleton complex was prepared according to the above-mentioned graphene-three-dimensional copper skeleton preparation method, and the particle size of the fourth graphene-three-dimensional copper skeleton was 100 to 300 nm; the first graphene-three-dimensional copper skeleton, the second graphene-three-dimensional copper skeleton, the third graphene-three-dimensional copper skeleton and the fourth graphene-three-dimensional copper skeleton were mixed in a volume ratio of 1:2:3:4.

[0134] Example 4

[0135] This embodiment is basically the same as Example 1, except that, in this embodiment, 50 g of copper with a particle size and 45 g of iron are weighed and placed in a vacuum melting furnace. The vacuum degree is controlled to be 12 Pa and the temperature is 1400° C. The furnace is smelted for 80 min and mechanical ball milling is performed to obtain a second copper alloy with a first particle size and a second particle size.

[0136] Example 5

[0137] This embodiment is basically the same as Example 1, except that, in this embodiment, 0.65 g of nickel and 0.25 g of zirconium are also weighed and placed in a vacuum melting furnace; after reacting with hydrochloric acid, a three-dimensional porous copper skeleton made of a copper-nickel-zirconium alloy is obtained.

[0138] Example 6

[0139] This embodiment is basically the same as embodiment 1, except that the number of graphene layers deposited in this embodiment is 4.

[0140] Example 7

[0141] This embodiment is basically the same as embodiment 1, except that the number of graphene layers deposited in this embodiment is 6.

[0142] Example 8

[0143] This embodiment is basically the same as embodiment 1, except that, when preparing the second copper alloys with the first particle size and the second particle size in this embodiment, 60 g of copper and 35 g of aluminum are weighed and placed in a vacuum melting furnace.

[0144] Example 9

[0145] This embodiment is basically the same as embodiment 1, except that, when preparing the second copper alloys with the first particle size and the second particle size in this embodiment, 68 g of copper and 27 g of aluminum are weighed and placed in a vacuum melting furnace.

[0146] Example 10

[0147] This embodiment is substantially the same as embodiment 1, except that, in this embodiment, no copper powder is added when the first graphene-three-dimensional copper skeleton complex and the second graphene-three-dimensional copper skeleton complex are mixed.

[0148] Comparative Example 1

[0149] In the composite conductor material of this comparative example, the three-dimensional porous copper skeleton is replaced by metallic copper.

[0150] Comparative Example 2

[0151] In the composite conductor material of this comparative example, the three-dimensional porous copper skeleton is replaced by a metal copper alloy, which includes copper, nickel and zirconium.

[0152] Wire and cable embodiment

[0153] This embodiment provides a wire and cable, the preparation process of which is as follows:

[0154] The composite conductor material of Example 1 was weighed, cold pressed, and then vacuum sintered at a sintering temperature of 500° C. to obtain a sintered green body.

[0155] Hot pressing the sintered green body at a temperature of 220° C. and a pressure of 380 MPa, and then performing vacuum arc melting to obtain a smelted green body.

[0156] The smelted embryo body is placed in a wire drawing die, extruded and drawn, and annealed to obtain ultra-high conductive wires and cables.

[0157] Wire and cable comparison

[0158] The wire and cable comparative example is basically the same as the wire and cable embodiment, except that, in the wire and cable comparative example, the composite conductor material of comparative example 1 is used to prepare the wire and cable.

[0159] The electrical conductivity of the wires and cables of the embodiment and the comparative example was tested by the eddy current method, and the electrical conductivity of the wires and cables was shown in Table 1.

[0160] Table 1

[0161] Electrical conductivity (% IACS) Wire and cable embodiment 85 Wire and cable comparison 60

[0162] As can be seen from Table 1, the conductivity of the wires and cables prepared using the composite conductor material in this solution is increased by 25% IACS compared with the control example. This is because the graphene is evenly and stably distributed in the composite conductor material provided by this application, which significantly improves the conductivity of the conductor.

[0163] Electrical contact conductor embodiments

[0164] This embodiment provides an electrical contact conductor, the preparation process of which is as follows:

[0165] The composite conductor material of Example 5 was weighed, cold pressed, and then vacuum sintered at a sintering temperature of 500° C. to obtain a sintered green body.

[0166] The sintered green body is hot pressed at a temperature of 220° C. and a pressure of 380 MPa. After the hot pressing is completed, vacuum arc melting is performed to obtain an electrical contact conductor.

[0167] Electrical contact conductor comparison example

[0168] The electric contact conductor comparative example is basically the same as the electric contact conductor embodiment, except that, in the electric contact conductor comparative example, the composite conductor material of comparative example 2 is used to prepare the wire and cable.

[0169] The welding force test was performed on the electrical contact conductors of the embodiment and the comparative example, and the welding force of the wires and cables was obtained as shown in Table 2.

[0170] Table 2

[0171] Welding force (g) Electrical contact conductor embodiments 11 Electrical contact conductor comparison example 4

[0172] As can be seen from Table 2, the welding force of the electrical contact conductor prepared by the composite conductor material in this solution is increased by 7g compared with the comparative example, indicating that the use of the composite conductor material provided by this application to prepare the electrical contact conductor can effectively improve the conductor's anti-welding performance.

[0173] The composite conductor material and preparation method thereof provided in the embodiments of the present application are introduced in detail above. Specific examples are used herein to illustrate the principles and implementation methods of the present application. The description of the above embodiments is only used to help understand the method and core idea of ​​the present application. At the same time, for those skilled in the art, according to the idea of ​​the present application, there may be changes in the specific implementation methods and application scope. In summary, the content of this specification should not be understood as limiting the present application.

Claims

1. A composite conductor material, characterized in that: The invention relates to a graphene-three-dimensional copper skeleton complex comprising at least two particle sizes; the graphene-three-dimensional copper skeleton complex comprising a three-dimensional porous copper skeleton, the three-dimensional porous copper skeleton having a plurality of first pores, and a graphene layer attached to the surface of the first pores; the graphene-three-dimensional copper skeleton complex having a plurality of second pores, and at least a portion of the graphene-three-dimensional copper skeleton complexes with a small particle size among the graphene-three-dimensional copper skeleton complexes with at least two particle sizes being accommodated in the second pores of the graphene-three-dimensional copper skeleton complexes with a large particle size.

2. The composite conductor material according to claim 1, wherein The material of the three-dimensional porous copper skeleton includes copper or a first copper alloy; and / or The number of graphene layers is 3 to 6; and / or The composite conductor material includes a first graphene-three-dimensional copper skeleton complex to an Nth graphene-three-dimensional copper skeleton complex, wherein N is an integer greater than or equal to 2, and the particle size of the first graphene-three-dimensional copper skeleton complex to the Nth graphene-three-dimensional copper skeleton complex decreases successively.

3. The composite conductor material according to claim 2, wherein: The first copper alloy comprises copper and a doping element, wherein the doping element comprises one or more of nickel, bismuth, antimony, tellurium, zirconium, silicon, and molybdenum; and / or The composite conductor material includes a first graphene-three-dimensional copper skeleton complex, a second graphene-three-dimensional copper skeleton complex, a third graphene-three-dimensional copper skeleton complex and a fourth graphene-three-dimensional copper skeleton complex; and / or The composite conductor material further includes copper powder, and the copper powder is filled in the graphene-three-dimensional copper skeleton composite.

4. The composite conductor material according to claim 3, wherein In the first copper alloy, the mass ratio of the copper to the doping element is (50-68): (1-1.5); and / or The particle size of the first graphene-three-dimensional copper skeleton complex is 10 5 ~5ⅹ10 5 nm, and the particle size of the second graphene-three-dimensional copper skeleton complex is 10 4 ~5ⅹ10 4 nm, the particle size of the third graphene-three-dimensional copper skeleton complex is 100-300 nm, and the particle size of the fourth graphene-three-dimensional copper skeleton complex is 50-80 nm; and / or In the composite conductor material, the content of the first graphene-three-dimensional copper skeleton complex is 1 part, the content of the second graphene-three-dimensional copper skeleton complex is 1.2-2 parts, the content of the third graphene-three-dimensional copper skeleton complex is 2.6-3 parts, and the content of the fourth graphene-three-dimensional copper skeleton complex is 4 parts, by volume; and / or The mass ratio of the copper powder to the three-dimensional porous copper skeleton is (0.01-0.5):100; and / or The particle size of the copper powder is 10-30 nm.

5. A method for preparing a composite conductor material, characterized in that: The steps include: providing a second copper alloy of at least two particle sizes, wherein the second copper alloy comprises copper and an active metal doped in the copper; Placing the second copper alloy of at least two particle sizes in an acidic solution for an acidic chemical bath to remove active metals in the second copper alloy, thereby obtaining a three-dimensional porous copper skeleton of at least two particle sizes, wherein the three-dimensional porous copper skeleton has a plurality of first pores; Depositing graphene on the surface of the first pores of the three-dimensional porous copper skeleton with different particle sizes to form a graphene layer bonded to the pore walls of the first pores, thereby obtaining graphene-three-dimensional copper skeleton complexes with at least two particle sizes, wherein the graphene-three-dimensional copper skeleton complexes have second pores, and the pore walls of the second pores are the graphene layers; The graphene-three-dimensional copper skeleton complexes of different particle sizes are mixed, and the graphene-three-dimensional copper skeleton complexes of small particle size are filled into the second pores of the graphene-three-dimensional copper skeleton complexes of large particle size to obtain a composite conductor material.

6. The preparation method according to claim 5, wherein The composite conductor material includes a first graphene-three-dimensional copper skeleton complex to an Nth graphene-three-dimensional copper skeleton complex, wherein N is an integer greater than or equal to 2, and the particle size of the first graphene-three-dimensional copper skeleton complex to the Nth graphene-three-dimensional copper skeleton complex decreases in sequence; and / or The active metal includes one or more of aluminum, iron, zinc and magnesium; and / or The acidic solution includes one or more of hydrochloric acid and nitric acid.

7. The preparation method according to claim 6, wherein The composite conductor material includes a first graphene-three-dimensional copper skeleton complex, a second graphene-three-dimensional copper skeleton complex, a third graphene-three-dimensional copper skeleton complex and a fourth graphene-three-dimensional copper skeleton complex.

8. The preparation method according to claim 7, wherein The particle size of the first graphene-three-dimensional copper skeleton complex is 10 5 ~5ⅹ10 5 nm, and the particle size of the second graphene-three-dimensional copper skeleton complex is 10 4 ~5ⅹ10 4 nm, the particle size of the third graphene-three-dimensional copper skeleton complex is 100-300 nm, and the particle size of the fourth graphene-three-dimensional copper skeleton complex is 50-80 nm.

9. The preparation method according to claim 5, wherein In the graphene-three-dimensional copper skeleton complex, the number of graphene layers is 3 to 6; and / or In the second copper alloy, the mass ratio of the copper to the active metal is (50-68): (27-45); and / or The mass fraction of the acidic solution is 20% to 40%.

10. The preparation method according to claim 5, characterized in that The method of depositing graphene includes a vapor deposition method; and / or The second copper alloy further comprises a doping element; the doping element comprises one or more of nickel, bismuth, antimony, tellurium, zirconium, silicon, and molybdenum; the mass ratio of the copper to the doping element is (50-68): (1-1.5); and / or After obtaining the composite conductor material, the process further includes ball milling. The ball milling time is 0.5-1 hour, the ball-to-material ratio is (4-6):1, and the rotation speed is 210-240 r / min.

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