CN115786763A - Copper-carbon composite material, preparation method and application thereof, and conductive product - Google Patents
Copper-carbon composite material, preparation method and application thereof, and conductive product Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 131
- AHADSRNLHOHMQK-UHFFFAOYSA-N methylidenecopper Chemical compound [Cu].[C] AHADSRNLHOHMQK-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000010949 copper Substances 0.000 claims abstract description 109
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 105
- 229910052802 copper Inorganic materials 0.000 claims abstract description 104
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 69
- 239000011159 matrix material Substances 0.000 claims abstract description 22
- 238000005275 alloying Methods 0.000 claims abstract description 7
- 239000013078 crystal Substances 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 51
- 238000000034 method Methods 0.000 claims description 29
- 238000000137 annealing Methods 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 18
- 239000010936 titanium Substances 0.000 claims description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 12
- 239000011651 chromium Substances 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 10
- 239000002041 carbon nanotube Substances 0.000 claims description 10
- 229910052804 chromium Inorganic materials 0.000 claims description 10
- 229910021389 graphene Inorganic materials 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052726 zirconium Inorganic materials 0.000 claims description 10
- 239000011575 calcium Substances 0.000 claims description 9
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000004917 carbon fiber Substances 0.000 claims description 6
- 238000004804 winding Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 description 19
- 239000000956 alloy Substances 0.000 description 19
- 229910052799 carbon Inorganic materials 0.000 description 15
- 239000000843 powder Substances 0.000 description 15
- 238000007731 hot pressing Methods 0.000 description 13
- 238000005096 rolling process Methods 0.000 description 13
- 238000005266 casting Methods 0.000 description 11
- 238000005229 chemical vapour deposition Methods 0.000 description 9
- 238000010907 mechanical stirring Methods 0.000 description 8
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- 230000000052 comparative effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000004663 powder metallurgy Methods 0.000 description 7
- IUYOGGFTLHZHEG-UHFFFAOYSA-N copper titanium Chemical compound [Ti].[Cu] IUYOGGFTLHZHEG-UHFFFAOYSA-N 0.000 description 6
- 229910000881 Cu alloy Inorganic materials 0.000 description 5
- 238000003723 Smelting Methods 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 238000003475 lamination Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical compound [Cr].[Cu] GXDVEXJTVGRLNW-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000000265 homogenisation Methods 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
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- 238000010791 quenching Methods 0.000 description 4
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- 238000006243 chemical reaction Methods 0.000 description 3
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- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- HAUBPZADNMBYMB-UHFFFAOYSA-N calcium copper Chemical compound [Ca].[Cu] HAUBPZADNMBYMB-UHFFFAOYSA-N 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- XTYUEDCPRIMJNG-UHFFFAOYSA-N copper zirconium Chemical compound [Cu].[Zr] XTYUEDCPRIMJNG-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 229910001325 element alloy Inorganic materials 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000009689 gas atomisation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The application provides a copper-carbon composite material, a preparation method and application thereof, and a conductive product. The copper-carbon composite material comprises a copper matrix, a carbon material and intermediate elements capable of alloying with the carbon material, wherein the carbon material is dispersed among copper crystal grains of the copper matrix, the compactness of the copper-carbon composite material is 99.9%, and the electric conductivity of the copper-carbon composite material is not less than 105%. The copper-carbon composite material has the characteristics of high density and high conductivity.
Description
Technical Field
The application relates to a conductive material, in particular to a copper-carbon composite material, a preparation method and application thereof, and a conductive product.
Background
Copper materials have been widely used in the power electronics industry. However, as the power density of electronic devices and the like is gradually increased, higher and higher requirements are made on the conductivity of the material. Since the conductivity of the material is positively correlated with the electron transfer rate, increasing the overall transfer rate of electrons in copper is an important way to further increase the conductivity of copper. The electron mobility in carbon materials such as carbon nano tubes, graphene and the like can reach 2 multiplied by 10 at room temperature 5 cm 2 V.s, the electron mobility of copper is about 50cm 2 V · s. However, the carrier concentration inside the carbon material is much lower than that of copper, by about three orders of magnitude, which results in poor electrical conductivity when the carbon material is used alone as a conductor. Based on this, if high concentration electrons in copper are transmitted in the carbon material, the conductivity of the copper material is greatly improved. In the existing method for compounding copper and carbon, the copper and the carbon cannot be compounded by a melt casting method due to large difference of material properties, and the copper and the carbon are compounded by a method of laminating hot pressing after chemical vapor deposition or powder metallurgy. However, in the copper-carbon composite material obtained by laminating and hot-pressing after chemical vapor deposition, the carbon layer is generally on the surface of the copper foil, and high conductivity can be realized only by multi-layer pressing; the copper-carbon composite material obtained by the method is generally in a sheet structure, and the application range is limited. The copper-carbon composite material obtained by the powder metallurgy method has low density and is difficult to obtain high conductivity. Therefore, at present, a high density and high conductivity of copper and carbon material dispersed and fused cannot be obtainedCopper-carbon composite material.
Disclosure of Invention
The application provides a copper-carbon composite material, a preparation method, application and a conductive product thereof, so as to obtain the copper-carbon composite material with high density and high conductivity.
In a first aspect, the present application provides a copper-carbon composite material comprising a copper matrix, a carbon material and an intermediate element capable of alloying with the carbon material, wherein the carbon material is dispersed among copper grains of the copper matrix, the compactness of the copper-carbon composite material can reach 99.9%, and the electrical conductivity of the copper-carbon composite material is equal to or greater than 105% iacs.
The copper-carbon composite material comprises a copper matrix, a carbon material and an intermediate element, wherein the intermediate element is an element capable of alloying with the carbon material, and due to the existence of the intermediate element, part of the surface of the carbon material can be subjected to an alloying reaction with the intermediate element firstly, so that the wettability of the carbon material and copper is increased in the preparation process, and the dispersibility of the carbon material in the copper matrix is improved. The copper-carbon composite material of the present application can be obtained by melt casting, and therefore, has a high density up to 99.9% and a high electrical conductivity, which may be equal to or greater than 105% IACS, and in some cases up to 110% IACS. Wherein the conductivity of the standard annealed pure copper is 100%.
In an optional implementation mode, the mass proportion of the carbon material in the copper-carbon composite material is 0.5-2%. Since the carbon material has a relatively low density, which is much lower than that of copper, when the mass percentage of the carbon material in the copper-carbon composite material is in the range of 0.5 to 2%, the dispersion density of the carbon material in copper can be remarkably increased, and the electrical conductivity of the copper-carbon composite material can be further increased.
In an alternative implementation, the carbon material includes at least one of carbon nanotubes, carbon powder, graphite powder, graphene, or carbon fibers.
In an optional implementation mode, the mass proportion of the intermediate element in the copper-carbon composite material is 0.5-1.2%. By controlling the addition amount of the intermediate element, the carbon material can be uniformly dispersed in the copper-carbon composite material, and the electric conductivity of the copper-carbon composite material is not influenced.
In an alternative implementation, the solid solubility of the intermediate element in the copper is less than or equal to 1%. By selecting the element with the room-temperature solid solubility of less than 1 percent in copper as the intermediate element, the intermediate element can be prevented from forming an alloy with the copper and influencing the conductivity of the copper-carbon composite material. Wherein the room temperature solid solubility is the solid solubility at 25 +/-5 ℃.
In an alternative implementation, the intermediate element includes at least one of chromium, zirconium, titanium, calcium, or iron. In an optional implementation mode, the intermediate element comprises chromium, and the mass ratio of the chromium in the copper-carbon composite material is 0.3-0.5%. In an optional implementation mode, the intermediate element comprises zirconium, and the mass ratio of the zirconium in the copper-carbon composite material is 0.1-0.2%. In an optional implementation mode, the intermediate element comprises titanium, and the mass ratio of the titanium in the copper-carbon composite material is 0.1-0.2%. In an optional implementation mode, the intermediate element comprises calcium, and the mass ratio of the titanium in the copper-carbon composite material is 0.1-0.15%.
In a second aspect, the present application provides a method for preparing the copper-carbon composite material of the first aspect, the method comprising the steps of: carrying out vacuum melting on a copper source and an intermediate element source substance to obtain a molten liquid; placing a carbon material coated by a copper source or a carbon material coated by an intermediate element source substance into the molten liquid, and cooling to obtain an ingot; and annealing and thermally treating the cast ingot to obtain the copper-carbon composite material.
According to the preparation method, the molten liquid of copper and the intermediate alloy is obtained, then the carbon material is added into the molten liquid, and the carbon material can be subjected to an alloying reaction with the intermediate element of the intermediate element source substance, so that after the carbon material is added into the molten liquid, part of the surface of the carbon material is firstly combined with the intermediate element after being contacted with the intermediate element to form a partially alloyed carbon composite body, and the carbon composite body can have higher density under the action of the intermediate element, so that the wettability with the molten copper can be increased, the carbon material can be dispersed in the molten copper, and further the melt casting of the copper-carbon composite material is realized. Compared with the copper-carbon composite material obtained by a powder metallurgy or electro-deposition method, the copper-carbon composite material obtained by the melting casting method has higher density, and further has higher conductivity. The preparation method of the application is a melt casting method, so the preparation method can be combined with a copper industrialization method to realize large-scale mass production.
In an optional implementation manner, the temperature of the vacuum melting is 1400-1600 ℃.
In an optional implementation mode, the annealing temperature is 900-1000 ℃, and the annealing time is 20-30 h.
In an optional implementation mode, the temperature of the heat treatment is 400-600 ℃, the time of the heat treatment is 3-5 h, and the atmosphere of the heat treatment is hydrogen atmosphere.
In the data in the above possible implementations of the present application, for example, the density, the electrical conductivity, the mass ratio of the carbon material, the mass ratio of the intermediate element, and various temperatures and times during the preparation process of the copper-carbon composite material, the values within the error range of the engineering measurement should be understood as being within the range defined in the present application.
In a third aspect, the present application provides a use of a copper-carbon composite material that can be used to prepare an electrically conductive article. The conductive article may be, for example, an inductor, a winding, a circuit board, an antenna, or the like.
In a fourth aspect, the present application provides an electrically conductive article that can be formed using the copper-carbon composite of the first aspect of the present application. The conductive article includes, but is not limited to, components such as inductors, wires, windings, circuit boards, or antennas.
Technical effects that can be achieved by the third aspect to the fourth aspect of the present application may be described with reference to corresponding effects in the first aspect, and details are not repeated here.
Drawings
Fig. 1 is a micro-topography of the copper-carbon composite of example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more clear, the present application will be further described in detail with reference to the accompanying drawings.
The terminology used in the following examples is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the specification of this application and the appended claims, the singular forms "a", "an", "the" and "the" are intended to include the plural forms as well, such as "one or more", unless the context clearly indicates otherwise.
Reference throughout this specification to "one embodiment" or "some embodiments," or the like, means that a particular feature, structure, or characteristic described in connection with the embodiment is included in one or more embodiments of the present application. Thus, appearances of the phrases "in one embodiment," "in some embodiments," "in other embodiments," or the like, in various places throughout this specification are not necessarily all referring to the same embodiment, but rather "one or more but not all embodiments" unless specifically stated otherwise. The terms "comprising," "including," "having," and variations thereof mean "including, but not limited to," unless otherwise specifically stated.
The following terms are explained for the sake of convenience.
IACS: international annealed copper standard, which is an international annealed copper standard, has a conductivity of 24%. IACS is used to characterize the electrical conductivity of a metal or alloy (referenced to standard annealed pure copper). The conductivity of standard annealed pure copper is generally defined as 100% IACS.
In the existing method for compounding copper and carbon, the fusion of the copper and the carbon is generally realized by a powder metallurgy and a hot-pressing manner of lamination after chemical vapor deposition. However, the industrialized production method of copper is a melt casting method, and the production mode of lamination and hot pressing after powder metallurgy or chemical vapor deposition is not compatible with the industrialized route of copper, so that large-scale mass production is difficult to realize. In the process of melting and casting, because the density difference between the carbon material and the copper is very large, and the copper liquid is difficult to wet the surface of the carbon material at high temperature, the uniform mixing of the carbon material and the molten copper liquid is very difficult to realize. Therefore, at present, a highly conductive copper-carbon composite material cannot be obtained by a melt casting method.
In order to solve the technical problem, the application provides a copper-carbon composite material. The copper-carbon composite material can be prepared by a melt casting process. The copper-carbon composite material of the embodiments of the present application may include a copper matrix, a carbon material, and an intermediate element.
Wherein, the material of the copper matrix can be pure copper, and the purity can be more than 99%. In the copper-carbon composite material, copper crystal grains in a copper matrix are closely packed.
In the copper-carbon composite material, the carbon material is dispersed among the copper crystal grains. The carbon material includes, but is not limited to, at least one of carbon nanotube, carbon powder, graphite powder, graphene, or carbon fiber. Wherein, when the carbon material is selected from carbon nano tubes or carbon fibers, the diameter of the selected carbon nano tubes or carbon fibers is 2-4 nm, and the length of the selected carbon nano tubes or carbon fibers is 10-20 mu m. When the carbon material comprises carbon powder or graphite powder, the particle size of the selected carbon powder or graphite powder is less than 500 meshes. When the carbon material includes graphene, the number of layers of graphene selected is 2 to 10.
In the copper-carbon composite material of the present application, at least part of the surface of the carbon material may be bonded with the intermediate element to form a carbon material-intermediate element composite. The intermediate elements can be dispersed among the copper grains and can also enter the interior of the copper grains to form copper alloy with the copper.
Because at least part of the surface of the carbon material is combined with the intermediate element to form the carbon material-intermediate element composite, and the intermediate element has higher wettability with copper, the carbon material can be more uniformly dispersed among crystal grains of the copper under the action of the intermediate element and cannot be gathered on the surface of the copper, and the uniform compounding of the copper-carbon composite material can be realized by a melt casting method. The copper-carbon composite material of the examples of the present application can have a compactness of 99.9% and an electrical conductivity of 105% or more, in some cases 110% or even 115% or more, iacs.
In an optional embodiment, the mass ratio of the carbon material in the copper-carbon composite material is 0.5-2%. The mass ratio of the carbon material in the copper-carbon composite material directly influences the electric conductivity of the copper-carbon composite material. The content of the carbon material is too low, so that the migration of electrons in the copper matrix is not facilitated, the electron mobility of the copper-carbon composite material is reduced, and the electric conductivity of the copper-carbon composite material is further reduced. In the copper-carbon composite material, the density of the copper-carbon composite material can be influenced by the excessively high content of the carbon material, so that the concentration of carriers in the copper-carbon composite material is influenced, and the improvement of the electric conductivity of the copper-carbon composite material is not facilitated. As an illustrative example, the mass percentage of the carbon material in the copper-carbon composite material may be, for example, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, or 2.0%.
In an alternative embodiment, the mass ratio of the intermediate element in the copper-carbon composite material is 0.5-1.2%. Illustratively, the mass fraction of the intermediate element in the copper-carbon composite includes, but is not limited to, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, or 1.2%. Since the intermediate element is an element capable of undergoing an alloying reaction with the carbon material, the intermediate element generally has poor electrical properties and has low electrical conductivity relative to copper. Therefore, if the amount of the intermediate element is too large, the conductivity of the copper-carbon composite material is directly lowered, and if the amount of the intermediate element is too small, the dispersion requirement of the carbon material cannot be satisfied. Therefore, by controlling the addition amount of the intermediate element, the dispersibility of the carbon material in the copper matrix can be effectively improved without reducing the conductivity of the copper-carbon composite material, and the carbon material can be more uniformly dispersed in the copper matrix.
In an alternative embodiment, the intermediate element has a room temperature solid solubility in the copper matrix of less than or equal to 1%. The solid solubility of the intermediate element in the copper matrix is too high, so that the intermediate element is too much to enter the copper matrix and cannot be separated out, the lattice structure of the copper matrix is affected, and the conductivity of the copper-carbon composite material is reduced. In the embodiment of the application, by selecting the intermediate element with low solid solubility, in the preparation process of the copper-carbon composite material, part of the intermediate element can be precipitated from the copper matrix through operations such as heat treatment and the like, so that the copper-carbon composite material can keep higher conductivity.
Illustratively, the intermediate element includes at least one of chromium, zirconium, titanium, calcium, or iron. When the intermediate element comprises chromium, the mass ratio of the chromium in the copper-carbon composite material is 0.3-0.5%. Illustratively, the mass fraction of chromium in the copper-carbon composite includes, but is not limited to, 0.3%, 0.35%, 0.4%, 0.45%, or 0.5%.
When the intermediate element comprises zirconium, the mass proportion of the zirconium in the copper-carbon composite material is 0.1-0.2%. Illustratively, the mass fraction of zirconium in the copper-carbon composite includes, but is not limited to, 0.1%, 0.11%, 0.12%, 0.13%, 0.14%, 0.15%, 0.16%, 0.17%, 0.18%, 0.19%, or 0.2%. When the intermediate element comprises titanium, the mass ratio of the titanium in the copper-carbon composite material is 0.1-0.2%. Illustratively, the mass fraction of titanium in the copper-carbon composite material includes, but is not limited to, 0.1%, 0.11%, 0.12%, 0.13%, 0.14%, 0.15%, 0.16%, 0.17%, 0.18%, 0.19%, or 0.2%. When the intermediate element comprises calcium, the mass ratio of the calcium in the copper-carbon composite material is 0.1-0.15%. Illustratively, the mass percentage of calcium in the copper-carbon composite includes, but is not limited to, 0.1%, 0.11%, 0.12%, 0.13%, 0.14%, or 0.15%.
Based on the same technical concept, the embodiment of the application also provides a preparation method of the copper-carbon composite material. The preparation method of the copper-carbon composite material of the embodiment of the application can comprise the following steps S11 to S13.
S11, carrying out vacuum melting on the copper source and the intermediate element source substance to obtain molten liquid. Wherein the temperature of the vacuum melting is 1400-1600 ℃.
And S12, placing the carbon material coated with the copper source or the carbon material coated with the intermediate element source substance into the molten liquid, and cooling to obtain an ingot.
And S13, annealing and heat treating the cast ingot to obtain the copper-carbon composite material. The annealing temperature is 900-1000 ℃, and the annealing time is 20-30 h. The temperature of the heat treatment is 400-600 ℃, the time of the heat treatment is 3-5 h, and the atmosphere of the heat treatment is hydrogen atmosphere.
Wherein, after the ingot is annealed, the ingot can be selectively added into a rolling process to obtain the required section.
It is understood that in the embodiments of the present application, the copper source includes, but is not limited to, elemental copper, electrolytic copper, and the like. The intermediate element source substance includes element simple substance or intermediate element alloy, such as copper-chromium intermediate alloy Cu-10Cr, copper-zirconium intermediate alloy Cu-50Zr, copper-titanium intermediate alloy Cu-50Ti or copper-calcium intermediate alloy Cu-50Ca, etc. When the carbon material is coated with the copper source, the copper source may coat the carbon material in the form of a sheet. Also, when the carbon material is coated with the intermediate element source substance, the intermediate element source substance may coat the carbon material in the form of flakes. The carbon material is coated by the copper source or the intermediate element source substance, so that the carbon material can enter molten liquid, and an effective dispersion effect is realized.
In the preparation method of the embodiment of the application, the intermediate element is added in the copper smelting process at a high temperature to form carbide with part of the surface of the carbon material, so that the wetting of the copper liquid and the surface of the carbon material is improved, the uniform dispersion of the carbon material in the copper liquid can be realized, and the electric conductivity of the obtained copper-carbon composite material is greatly improved.
The specific properties and the specific preparation process of the copper-carbon composite material of the present application are further described in detail with specific examples.
Example 1
The embodiment is a copper-carbon composite material, and the specific preparation process is as follows:
s101, weighing the following raw materials: electrolytic copper, copper titanium master alloy and Carbon Nanotubes (CNTs) were mixed in a ratio of Ti:0.1wt.%, carbon nanotubes: 0.01wt.%, balance Cu.
S102, vacuum melting: putting the electrolytic copper and the copper-titanium intermediate alloy into a graphite crucible of a vacuum smelting furnace, heating to 1500 ℃ in inert gas, and preserving heat for half an hour to reach a molten state.
S103, feeding carbon source: and rapidly adding the CNT powder wrapped by the copper sheet into the alloy molten liquid.
S104, mechanical stirring: mechanical stirring was used to uniformly distribute the CNT powder in the copper melt.
S105, rapid solidification: and solidifying the uniformly dispersed melt to obtain the high-conductivity copper-carbon composite cast ingot.
S106, milling the surface: and removing the surface defects of the obtained copper alloy cast ingot by using a numerical control milling machine.
S107, annealing: the ingot was placed in a 950 ℃ resistance furnace for homogenization treatment for 24 hours.
S108, rolling: and rolling the cast ingot into a plate with the required thickness by using a rolling mill.
S109, heat treatment: and (3) annealing the plate at 500 ℃ for 4h by hydrogen and then quenching to obtain the final copper-carbon composite plate.
Fig. 1 is an SEM image of the copper-carbon composite material obtained in the present example. As shown in fig. 1, it can be observed that a large amount of CNTs are dispersed in the copper matrix and no significant pores are seen at the copper-carbon composite interface. The copper-carbon composite material obtained by the preparation method can obtain higher density, and the CNT can be uniformly dispersed in the matrix.
Example 2
The embodiment is a copper-carbon composite material, and the specific preparation process is as follows:
s101, weighing the following raw materials: electrolytic copper, copper-chromium master alloy and CNT were mixed as per Cr:0.3wt.%, CNT:0.1wt.%, balance Cu.
S102, vacuum melting: putting the electrolytic copper and the copper-titanium intermediate alloy into a graphite crucible of a vacuum smelting furnace, heating to 1600 ℃ in inert gas, and preserving heat for half an hour to reach a molten state.
S103, feeding carbon source: and rapidly adding the CNT powder wrapped by the copper sheet into the alloy molten liquid.
S104, mechanical stirring: mechanical stirring was used to uniformly distribute the CNT powder in the copper melt.
S105, rapid solidification: and solidifying the uniformly dispersed melt to obtain the high-conductivity copper-carbon composite cast ingot.
S106, milling the surface: and removing the surface defects of the obtained copper alloy cast ingot by using a numerical control milling machine.
S107, annealing: the ingot was placed in a resistance furnace at 920 ℃ for homogenization treatment for 8 hours.
S108, rolling: and rolling the cast ingot into a plate with the required thickness by using a rolling mill.
S109, heat treatment: and (3) annealing the plate at 500 ℃ for 4h by hydrogen, and then quenching to obtain the final copper-carbon composite plate.
Example 3
The embodiment is a copper-carbon composite material, and the specific preparation process is as follows:
s101, weighing the following raw materials: electrolytic copper, copper-zirconium master alloy and graphene (Gr) were mixed according to the following ratio Zr:0.1wt.%, gr:1.0wt.%, balance Cu.
S102, vacuum melting: putting the electrolytic copper and the copper-titanium intermediate alloy into a graphite crucible of a vacuum smelting furnace, heating to 1600 ℃ in inert gas, and preserving heat for half an hour to reach a molten state.
S103, feeding carbon source: and rapidly adding the Gr powder wrapped by the copper sheet into the alloy molten liquid.
S104, mechanical stirring: mechanical stirring was used to uniformly distribute the Gr powder in the copper melt.
S105, rapid solidification: and solidifying the uniformly dispersed melt to obtain the high-conductivity copper-carbon composite material cast ingot.
S106, milling the surface: and removing the surface defects of the obtained copper alloy cast ingot by using a numerical control milling machine.
S107, annealing: the ingot was placed in a resistance furnace at 920 ℃ for homogenization treatment for 8 hours.
S108, rolling: and rolling the cast ingot into a plate with the required thickness by using a rolling mill.
S109, heat treatment: and (3) annealing the plate at 500 ℃ for 4h by hydrogen, and then quenching to obtain the final copper-carbon composite plate.
Example 4
The embodiment is a copper-carbon composite material, and the specific preparation process is as follows:
s101, weighing the following raw materials: electrolytic copper, copper-calcium intermediate alloy and graphite powder are mixed according to the proportion of Ca:0.1wt.%, graphite powder: 1.0wt.%, balance Cu.
S102, vacuum melting: putting the electrolytic copper and the copper-titanium intermediate alloy into a graphite crucible of a vacuum smelting furnace, heating to 1400 ℃ in inert gas, and preserving heat for half an hour to reach a molten state.
S103, feeding carbon source: and rapidly adding Gr powder wrapped by the copper sheet into the alloy molten liquid.
S104, mechanical stirring: mechanical stirring was used to uniformly distribute the Gr powder in the copper melt.
S105, rapid solidification: and solidifying the uniformly dispersed melt to obtain the high-conductivity copper-carbon composite cast ingot.
S106, milling the surface: and removing the surface defects of the obtained copper alloy cast ingot by using a numerical control milling machine.
S107, annealing: the ingot was placed in a resistance furnace at 920 ℃ for homogenization treatment for 8 hours.
S108, rolling: and rolling the cast ingot into a plate with the required thickness by using a rolling mill.
S109, heat treatment: and (3) annealing the plate at 500 ℃ for 4h by hydrogen, and then quenching to obtain the final copper-carbon composite plate.
Comparative example 1
The comparative example is a copper-carbon composite material obtained by using a chemical vapor deposition post-lamination hot pressing method, and the specific preparation process is as follows:
s101, electrochemical polishing: and (3) pretreating the original plate-shaped copper substrate by adopting an electrochemical polishing process to obtain the pretreated copper substrate.
S102, chemical vapor deposition: and growing graphene on the upper surface and the lower surface of the pretreated copper substrate by adopting a chemical vapor deposition process to obtain the graphene coated copper substrate.
S103, hot-pressing sintering: and carrying out hot-pressing sintering treatment on at least one piece of graphene-coated copper substrate under the conditions that the sintering temperature is 900 ℃, the sintering pressure is 50MPa and the sintering time is 20min to obtain the copper-carbon composite material prepared by the chemical vapor deposition post-lamination hot-pressing method.
Comparative example 2
The comparative example is a copper-carbon composite material prepared by a powder metallurgy process, and the specific preparation process comprises the following steps:
s101, weighing raw materials: the copper chromium powder produced by gas atomization was mixed with CNT according to the Cr:0.3wt.%, CNT:0.1wt.%, balance Cu.
S102, powder mixing: putting the copper-chromium powder and the CNT into a roller ball mill, adding absolute ethyl alcohol, then putting the steel ball into the roller ball mill, and mixing the mixture for 24 hours by the roller ball mill at the rotating speed of 200r/min to obtain the uniformly mixed composite powder.
S103, hydrogen annealing: and (3) putting the uniformly mixed composite powder into a vacuum tube furnace, and annealing for 4 hours at 500 ℃ by hydrogen to obtain dry composite powder.
S104, vacuum hot pressing: putting the dried composite powder into a graphite mould, wherein the vacuum degree of a vacuum hot-pressing furnace is 10 -4 Pa, raising the temperature to 1050 ℃ at the speed of 30 ℃/min, keeping the temperature and the pressure for 60min after the pressure is raised to 50MPa, and taking out the block after temperature reduction to obtain a hot-pressed block.
S105, heat treatment: and (3) annealing the block obtained by hot pressing at 500 ℃ for 4h by using hydrogen to obtain the final copper-carbon composite material.
The copper-carbon composites of each example and comparative example were tested for electrical conductivity, and the test results are shown in table 1.
The density test method comprises the following steps: the density was measured using the drainage method.
Conductivity test method: the wire was tested for conductivity with reference to GB/T351-2019 and the sheet/foil was tested with reference to ASTM F390-98 (2003).
TABLE 1
As can be seen from the data in table 1, the density and the conductivity of the copper-carbon composite material obtained by the preparation method of the present application are both significantly higher than those of comparative example 2, and also slightly higher than those of the copper-carbon composite material obtained by the post-cvd laminated hot-pressing method of comparative example 1. The copper-carbon composite material can be obtained by a melt casting method, can be fused with the existing preparation process of a copper material, can realize large-scale commercial production compared with a chemical vapor deposition post-lamination hot pressing method and a powder metallurgy method, and has lower production cost.
The copper-carbon composite material provided by the embodiment of the application can be used for manufacturing various conductive products. The conductive article of manufacture includes, but is not limited to, components such as inductors, wires, windings, circuit boards, or antennas.
The above description is only for the specific embodiments of the present application, but the scope of the present application is not limited thereto, and any person skilled in the art can easily think of the changes or substitutions within the technical scope of the present application, and shall be covered by the scope of the present application. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.
Claims (17)
1. The copper-carbon composite material is characterized by comprising a copper matrix, a carbon material and an intermediate element capable of alloying with the carbon material, wherein the carbon material is dispersed among copper crystal grains of the copper matrix, the compactness of the copper-carbon composite material is 99.9%, and the electric conductivity of the copper-carbon composite material is not less than 105% IACS.
2. The copper-carbon composite material according to claim 1, wherein the carbon material is present in the copper-carbon composite material in an amount of 0.5 to 2% by mass.
3. The copper-carbon composite material according to claim 1, wherein the mass ratio of the intermediate element in the copper-carbon composite material is 0.5 to 1.2%.
4. The copper-carbon composite material according to claim 3, wherein the room-temperature solid solubility of the intermediate element in the copper matrix is 1% or less.
5. The copper-carbon composite of claim 3, wherein the intermediate element comprises at least one of chromium, zirconium, titanium, calcium, or iron.
6. The copper-carbon composite material according to any one of claims 1 to 5, wherein the intermediate element comprises chromium, and the mass ratio of the chromium in the copper-carbon composite material is 0.3 to 0.5%.
7. The copper-carbon composite material according to any one of claims 1 to 6, wherein the intermediate element includes zirconium, and the mass ratio of zirconium in the copper-carbon composite material is 0.1 to 0.2%.
8. The copper-carbon composite according to any one of claims 1 to 7, wherein the intermediate element comprises titanium, and the mass ratio of the titanium in the copper-carbon composite is 0.1 to 0.2%.
9. The copper-carbon composite material according to any one of claims 1 to 8, wherein the intermediate element includes calcium, and the mass ratio of the titanium in the copper-carbon composite material is 0.1 to 0.15%.
10. The copper-carbon composite material according to any one of claims 1 to 9, wherein the carbon material comprises at least one of carbon nanotubes, carbon powder, graphite powder, graphene, or carbon fibers.
11. The method of making a copper-carbon composite material according to any one of claims 1 to 10, comprising the steps of:
carrying out vacuum melting on a copper source and an intermediate element source substance to obtain a molten liquid;
placing a carbon material coated by a copper source or a carbon material coated by an intermediate element source substance into the molten liquid, and cooling to obtain an ingot;
and annealing and heat treating the cast ingot to obtain the copper-carbon composite material.
12. The method of claim 11, wherein the vacuum melting temperature is 1400-1600 ℃.
13. The method according to claim 11 or 12, wherein the annealing temperature is 900 to 1000 ℃ and the annealing time is 20 to 30 hours.
14. The method according to any one of claims 11 to 13, wherein the temperature of the heat treatment is 400 to 600 ℃, the time of the heat treatment is 3 to 5 hours, and the atmosphere of the heat treatment is a hydrogen atmosphere.
15. Use of a copper-carbon composite material according to any one of claims 1 to 10 for the preparation of an electrically conductive article.
16. An electrically conductive article formed using the copper-carbon composite material according to any one of claims 1 to 10.
17. The conductive article of claim 16, wherein the conductive article comprises an inductor, a wire, a motor winding, an antenna, or a circuit board.
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