CN117758102A - Method for preparing high-quality graphene-copper composite powder and high-strength high-conductivity composite material based on graphene limited-domain growth - Google Patents
Method for preparing high-quality graphene-copper composite powder and high-strength high-conductivity composite material based on graphene limited-domain growth Download PDFInfo
- Publication number
- CN117758102A CN117758102A CN202311651347.8A CN202311651347A CN117758102A CN 117758102 A CN117758102 A CN 117758102A CN 202311651347 A CN202311651347 A CN 202311651347A CN 117758102 A CN117758102 A CN 117758102A
- Authority
- CN
- China
- Prior art keywords
- copper
- graphene
- powder
- composite
- composite material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 95
- 239000000843 powder Substances 0.000 title claims abstract description 53
- 239000010949 copper Substances 0.000 title claims abstract description 52
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title abstract description 30
- 229910021389 graphene Inorganic materials 0.000 title abstract description 28
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000005245 sintering Methods 0.000 claims abstract description 26
- 239000011246 composite particle Substances 0.000 claims abstract description 24
- 238000005096 rolling process Methods 0.000 claims description 17
- 238000005098 hot rolling Methods 0.000 claims description 14
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 12
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 12
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 12
- 239000005642 Oleic acid Substances 0.000 claims description 12
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 12
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 12
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 12
- 238000002490 spark plasma sintering Methods 0.000 claims description 12
- 239000005416 organic matter Substances 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 10
- 238000005097 cold rolling Methods 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000003763 carbonization Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 150000001345 alkine derivatives Chemical class 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 238000010000 carbonizing Methods 0.000 claims description 4
- 238000000641 cold extrusion Methods 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 238000001192 hot extrusion Methods 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 2
- 238000010622 cold drawing Methods 0.000 claims description 2
- 238000007731 hot pressing Methods 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 17
- 238000011065 in-situ storage Methods 0.000 abstract description 10
- 238000006555 catalytic reaction Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 238000004804 winding Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 21
- 239000000463 material Substances 0.000 description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- CBFCDTFDPHXCNY-UHFFFAOYSA-N icosane Chemical compound CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 2
- YZAZXIUFBCPZGB-QZOPMXJLSA-N (z)-octadec-9-enoic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O YZAZXIUFBCPZGB-QZOPMXJLSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- ZVDBUOGYYYNMQI-UHFFFAOYSA-N dodec-1-yne Chemical compound CCCCCCCCCCC#C ZVDBUOGYYYNMQI-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229940038384 octadecane Drugs 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000992 sputter etching Methods 0.000 description 1
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
A method for preparing high-quality graphene-copper composite powder and high-strength high-conductivity composite material based on graphene limited-domain growth belongs to the field of copper-based composite materials. The invention aims at the problems of poor quality of graphene prepared by an in-situ growth method and poor electrical property of a composite material. According to the invention, copper powder and an organic carbon source are used as raw materials, the copper powder is pressed into a sheet shape through deformation, and layered composite particles formed by closely stacking the sheet-shaped copper powder/organic matters are formed, the organic matters are uniformly confined between the sheet-shaped copper layers, in the high-temperature heat treatment process, the organic matters are decomposed, the products are fully contacted with the copper surface in a confined space, the composite powder is obtained through copper surface catalysis and graphene self-catalysis, and then the graphene-copper composite material is obtained through sintering and/or deformation. The composite material has high strength, high electrical conductivity and high thermal conductivity, and low temperature coefficient of resistance compared with annealed pure copper, and can be widely used in the fields of transmission wires, motor windings, transformers, large-scale integrated circuits, lead frames and the like.
Description
Technical Field
The invention belongs to the field of copper-based composite materials, and relates to a graphene-copper composite material with high electrical property, a method for preparing high-quality graphene-copper composite powder based on limited-domain growth, and a method for preparing a high-strength high-conductivity composite material based on graphene limited-domain growth.
Background
Copper and copper alloys are widely used in the fields of electronic devices, aerospace, etc., and are used as electric contact materials, wires, heat dissipation materials, etc. because of their excellent electric conductivity, thermal conductivity, and workability. With the continuous progress and development of the fields of integrated circuits, lead frames, special wires and the like, people put forward higher requirements on the electrical property and mechanical property of copper materials, and compared with copper alloying and ceramic particle reinforcement, the graphene reinforced copper-based composite material with high Young modulus, high electron mobility and super large specific surface area is expected to prepare materials with electrical and mechanical properties exceeding those of pure copper.
The preparation methods of the graphene-copper composite material reported at present comprise a ball milling method, an electrodeposition method, a molecular level mixing method, a layer accumulating rolling method, an in-situ growth method and the like. The in-situ growth method has the characteristics of uniform dispersion of the reinforcement, firm interface combination, low raw material price, simple process and the like, has great development potential, however, the quality of the in-situ authigenic graphene is often poor, and the mechanical property of the material can be improved to a certain extent, but the electrical property of the material is negatively influenced. Therefore, the development of the preparation method of the graphene-copper composite material with simple process, good graphene quality, and mechanical property and electrical property exceeding those of pure copper materials is of great research significance and practical value.
Disclosure of Invention
Aiming at the problems of poor quality of graphene and poor electrical property of a composite material prepared by an in-situ growth method, the invention provides a method for preparing high-quality graphene-copper composite powder and a high-strength high-conductivity composite material based on graphene limited-domain growth.
The invention takes copper powder with 100-8000 meshes and organic matters as raw materials, uniformly coats the organic carbon source on the surface of the copper powder through a coating process, and then carries out deformation treatment on the powder, in the process, the copper powder is pressed into a sheet shape, and meanwhile, lamellar composite particles (particle diameter is 10-20000 mu m) formed by tightly stacking sheet copper powder/organic matters are uniformly limited between copper sheet layers. And then in the carbonization heat treatment process of the composite particles, the products of organic matter decomposition are contacted with the large-area flat copper surface in the confined space, and are converted into graphene with fewer defects and high crystallization degree under the catalysis of the copper surface and the self-catalysis of the graphene. Finally, the graphene-copper composite material with excellent mechanical property and electrical property is obtained through sintering and/or deformation.
In order to realize the technical problems, the invention adopts the following technical scheme:
the invention aims to provide graphene-copper composite powder with high electrical performance, wherein the composite powder is prepared by carbonizing lamellar composite particles formed by tightly stacking flaky copper powder and organic matters, the content of the organic matters is 0.01-5 wt%, the number of carbon atoms in organic matters molecules is 5-2000, the diameter-thickness ratio of the flaky copper powder is greater than or equal to 10:1, and the average thickness of the flaky copper powder is 0.1-100 mu m.
Further defined, carbonizing using a heat treatment; the carbonization temperature of the heat treatment is 600-1050 ℃. The carbonization process of the heat treatment is carried out in a hydrogen-argon mixed atmosphere, wherein the volume of hydrogen in the hydrogen-argon mixed atmosphere accounts for 10% -20%.
Further defined, the organic matter is one or more of alkane, alkene, alkyne, aromatic hydrocarbon and organic matter containing oxygen and/or nitrogen. The alkane can be any proportion of one or more of tridecane, octadecane, eicosane, polyethylene, polypropylene and the like, the alkyne can be any proportion of one or more of dodecyne, tridecetne, octadecetylene, eicosyne, polyacetylene and the like, the aromatic hydrocarbon can be any proportion of one or more of benzene, trimethylbenzene, toluene, pyrene, naphthalene, anthracene, polystyrene and the like, and the oxygen-containing and/or nitrogen-containing organic matter can be any proportion of one or more of oleic acid, dimer acid, lauric acid, methyl dodecacarbonate, polymethyl pyrrolidone, polymethyl methacrylate, polyvinyl alcohol and the like.
Further defined, the organic matter is oleic acid.
The invention aims to provide a preparation method of graphene-copper composite powder with high electrical property, which is characterized by comprising the following steps:
copper powder with the particle size of 100-8000 meshes is taken and then coated by organic matters;
then deforming to the thickness of 0.1-100 μm, pressing the copper powder into sheet shape, forming layered composite particles formed by closely stacking sheet copper powder/organic matters, and uniformly restricting the organic matters between the sheet copper layers;
and then heating the composite particles to 600-1050 ℃ for carbonization, decomposing organic matters in the high-temperature heat treatment process, fully contacting the product with the copper surface in a limited space, and obtaining the graphene-copper composite powder through copper surface catalysis and graphene self-catalysis.
Wherein the organic matter is one or more of alkane, alkene, alkyne, aromatic hydrocarbon and organic matter containing oxygen and/or nitrogen, which are mixed in any proportion; the number of carbon atoms in the organic molecule is 5-2000.
The method comprises the steps of carrying out deformation (cold rolling and double-phase pressing) treatment on copper powder coated with organic matters, microscopically obtaining copper powder with a diameter-thickness ratio of more than or equal to 10:1 (initial diameter of copper powder is 1-10000 mu m, average thickness of copper powder after deformation is 0.1-100 mu m), macroscopically forming layered composite particles (diameter of composite particles is 10-20000 mu m, thickness of composite particles is 1-20000 mu m), and the content range of the organic matters in the composite particles: 0.01wt.% to 5wt.%.
Further defined is a deformation process using cold rolling, two-phase pressing.
Further defined is that the same particle size copper powder encapsulates different proportions of organics or that the different particle size copper powder encapsulates the same proportions of organics.
Further defined, the cold rolling is performed at a reduction of 50% to 99%.
Further defined, the bi-directional pressing pressure is 30-500MPa.
The invention aims to provide a preparation method of a graphene-copper composite material, which specifically comprises the steps of preparing the graphene-copper composite powder by any of the above or any of the above methods, and performing one or a combination of sintering and deformation to obtain the composite material.
Further defined, the sintering temperature is 700 ℃ to 900 ℃.
Further limiting, sintering by adopting spark plasma sintering, vacuum hot pressing and high-temperature sintering; the deformation is hot rolling, cold rolling, hot extrusion, cold extrusion and drawing.
Further defined, the hot rolling temperature is 300-900 ℃ and the lower rolling amount is 30% -99%.
Further defined, the cold rolled reduction is 30% -99%.
Still further defined, the hot extrusion temperature is 300 ℃ to 950 ℃ and the extrusion ratio is (2 to 50): 1.
still further defined, the extrusion ratio of the cold extrusion is (2-50): 1.
still further defined, the draw ratio is (2-50): 1, a step of; the drawing temperature is between room temperature and 900 ℃.
Further defined, the composite material is a block, a plate, a bar, a wire.
The invention utilizes the powder deformation process to prepare lamellar composite particles which are tightly stacked by flaky copper powder/organic matters, and limits the organic matters in the composite particles. In the subsequent carbonization treatment process, the decomposition products of the organic matters are fully contacted with the flat copper sheet layer and are effectively catalyzed to form high-quality graphene, so that the problem of poor quality of the graphene on the copper powder surface in the traditional in-situ growth method is solved. Finally, preparing the high-strength high-conductivity high-quality graphene-copper composite material through subsequent sintering and material deformation.
Compared with the prior art, the invention has the following beneficial effects:
the method is simple, is easy for mass production, has high graphene quality of in-situ growth, high strength of graphene-copper composite material, high electrical conductivity and thermal conductivity, and lower temperature coefficient of resistance than annealed pure copper, and can be widely applied to the fields of transmission wires, motor windings, transformers, large-scale integrated circuits, lead frames and the like.
For a further understanding of the nature and the technical aspects of the present invention, reference should be made to the following detailed description of the invention and the accompanying drawings, which are provided for reference and illustration only and are not intended to limit the invention.
Drawings
FIG. 1 (a) shows a composite powder of 200 mesh copper powder,
FIG. 1 (b) is a cross-sectional SEM image of a composite particle 1 obtained by rolling copper powder,
FIG. 1 (c) is a cross-sectional SEM image of a composite particle 2 obtained by rolling copper powder,
FIG. 1 (d) is an SEM image of the front side of the composite particle 1;
FIG. 1 (e) is an SEM image of the front side of composite particles 2;
FIG. 2 is a graph of Raman spectrum measurements after 72h of corrosion of the composite powder and the comparative powder with a dilute nitric acid solution;
FIG. 3 is SEM and TEM of corrosion products of composite powder 1;
FIG. 4 is a mechanical property test of a composite material and a comparative material;
FIG. 5 is a graph showing electrical performance measurements at 20℃to 180℃for the composite and the comparative materials;
FIG. 6 is a fitted view of the surfaces of composite 1, composite 2, comparative 1 and comparative 2;
fig. 7 is a representation of composite material 2 for ion thinning and TEM.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will facilitate a further understanding of the present patent by those skilled in the art and are not intended to limit the invention in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present patent.
Example 1: the preparation method for preparing the high-quality graphene-copper composite powder based on graphene domain-limited growth comprises the following steps:
and step 1, 10000 parts of 200-mesh copper powder are taken and respectively coated with 1 part, so as to obtain oleic acid coated powder 1.
And 2, continuously rolling the oleic acid coated powder 1, and rolling copper powder with an initial thickness of 5 mu m to a thickness of 500nm to obtain composite particles 1 with different oleic acid contents.
And 3, placing the composite particles 1 in a hydrogen-argon mixed atmosphere (wherein the volume of hydrogen accounts for 16.9%), heating to 1000 ℃ at the speed of 10 ℃/min, preserving heat for 3min, and then rapidly cooling to room temperature to obtain the composite powder 1.
And 4, placing the composite powder 1 in an SPS sintering furnace for SPS sintering, wherein the sintering pressure is 40MPa, heating to 700 ℃ at a speed of 100 ℃/min, and preserving heat for 5min to obtain the sintered composite material. And then carrying out hot rolling deformation on the sintered composite material, wherein the hot rolling temperature is 500 ℃, and the lower rolling quantity is 80%. A composite material 1 was obtained.
Example 2: the preparation method for preparing the high-quality graphene-copper composite powder based on graphene domain-limited growth comprises the following steps:
and step 1, 10000 parts of 200-mesh copper powder are taken and respectively coated with 2 parts, so as to obtain oleic acid coated powder 2.
And 2, continuously rolling the oleic acid coated powder 2, and rolling copper powder with an initial thickness of 5 mu m to a thickness of 500nm to obtain composite particles 2 with different oleic acid contents.
And 3, placing the composite particles 2 in a hydrogen-argon mixed atmosphere (wherein the volume of hydrogen accounts for 16.9%), heating to 1000 ℃ at the speed of 10 ℃/min, preserving heat for 3min, and then rapidly cooling to room temperature to obtain the composite powder 2.
And 4, placing the composite powder 2 in an SPS sintering furnace for SPS sintering, wherein the sintering pressure is 40MPa, heating to 700 ℃ at a speed of 100 ℃/min, and preserving heat for 5min to obtain the sintered composite material. And then carrying out hot rolling deformation on the sintered composite material, wherein the hot rolling temperature is 500 ℃, and the lower rolling quantity is 80%. Composite material 2 is obtained.
Comparative example 1: the preparation method for preparing the high-quality graphene-copper composite powder based on graphene domain-limited growth comprises the following steps:
and step 1, 10000 parts of 200-mesh copper powder are taken and respectively coated with 1 part, so as to obtain oleic acid coated powder.
And 2, placing the oleic acid coated powder in a hydrogen-argon mixed atmosphere (the volume of hydrogen accounts for 16.9%), heating to 1000 ℃ at the speed of 10 ℃/min, preserving heat for 3min, and then rapidly cooling to room temperature to obtain the composite powder.
And step 3, placing the composite powder in an SPS sintering furnace for SPS sintering, wherein the sintering pressure is 40MPa, heating to 700 ℃ at a speed of 100 ℃/min, and preserving heat for 5min to obtain the sintered composite material. And then carrying out hot rolling deformation on the sintered composite material, wherein the hot rolling temperature is 500 ℃, and the lower rolling quantity is 80%. Comparative material 1 was obtained.
Comparative example 2: the preparation method for preparing the high-quality graphene-copper composite powder based on graphene domain-limited growth comprises the following steps:
and step 1, 10000 parts of 200-mesh copper powder are taken and respectively coated with 2 parts, so as to obtain oleic acid coated powder.
And 3, placing the oleic acid coated powder in a hydrogen-argon mixed atmosphere (the volume of hydrogen accounts for 16.9%), heating to 1000 ℃ at the speed of 10 ℃/min, preserving heat for 3min, and then rapidly cooling to room temperature to obtain the composite powder.
And step 3, placing the composite powder in an SPS sintering furnace for SPS sintering, wherein the sintering pressure is 40MPa, heating to 700 ℃ at a speed of 100 ℃/min, and preserving heat for 5min to obtain the sintered composite material. And then carrying out hot rolling deformation on the sintered composite material, wherein the hot rolling temperature is 500 ℃, and the lower rolling quantity is 80%. Comparative material 2 was obtained.
Comparative example 3: the preparation method for preparing the high-quality graphene-copper composite powder based on graphene domain-limited growth comprises the following steps:
and step 1, 10000 parts of 200-mesh copper powder are taken, continuous rolling is carried out, and copper powder with the initial thickness of 5 mu m is rolled to the thickness of 500nm.
And 2, placing in a hydrogen-argon mixed atmosphere (wherein the volume of hydrogen is 16.9%), heating to 1000 ℃ at the speed of 10 ℃/min, preserving heat for 3min, and then rapidly cooling to room temperature.
And step 3, placing the mixture in an SPS sintering furnace for SPS sintering, wherein the sintering pressure is 40MPa, heating to 700 ℃ at a speed of 100 ℃/min, and preserving heat for 5min. And then hot rolling deformation is carried out, the hot rolling temperature is 500 ℃, and the lower rolling quantity is 80%. Comparative material 3 was obtained.
The following tests are adopted to verify the effects of the invention:
composite powder of raw material 200-mesh copper powder is shown in fig. 1 (a), and cross-section SEM images of composite particles 1 and 2 obtained by rolling the powder are shown in fig. 1 (b, c), wherein the composite particles can be formed by tightly stacking smooth and flat flake copper powder with the thickness of 300-700 nm, and fig. 1 (d, e) are SEM images of the front surfaces of the composite particles, and the smooth and flat surfaces provide a basis for the growth of two-dimensional graphene.
The composite powder and the contrast powder are corroded for 72 hours by using a dilute nitric acid solution with the concentration of 15%, the corrosion product is filtered and dried in a suction way, and the test result (shown in figure 2) of the Raman spectrum shows that the graphene in the composite powder prepared by the limited-area growth method has higher crystallization degree, fewer defects and 2690cm -1 A 2D peak appears nearby. Wherein SEM and TEM of the corrosion product of composite powder 1 (as in fig. 3) illustrate the presence of in situ self-generated few-layer graphene.
The composite material and the comparative material were subjected to mechanical property test, and the results are shown in fig. 4. It can be found that the Yield Strengths (YS) of the composite material 1 and the composite material 2 prepared by the finite field growth method are 258+/-5.5 MPa and 292+/-5.3 MPa, which are respectively improved by 17.3 percent and 23.7 percent compared with the comparison samples 1 (YS: 220+/-10.7 MPa) and 2 (YS: 236+/-14.3 MPa); compared with a comparative sample 3 (YS: 210+ -3.1 MPa), the two types of the composite material are respectively improved by 22.8 percent and 39.1 percent.
As shown in FIG. 5, the electrical performance tests at 20-180 ℃ of the composite material and the comparative material show that the room temperature conductivities of the composite material 1 and the composite material 2 are 99.7% IACS and 98.6% IACS respectively, which are close to the international standard annealed pure copper, are improved by 2% and 0.8% respectively compared with the comparative material 3, and are improved by 1% and 1.8% respectively compared with the comparative material 1 (98.7% IACS) and the comparative material 2 (96.8 IACS). In addition, the temperature coefficients of resistance of composite 1 and composite 2 were 0.00388 and 0.00371, respectively, and were reduced compared to the control (control 1 (0.00395); control 2 (0.00389) and control 3 (0.00394)). Meanwhile, after the test temperature is 40 ℃ and 80 ℃ respectively, the resistivity of the composite material 1 and the composite material 2 is lower than that of the international annealed pure copper at the same temperature, and at 160 ℃, the conductivity is 103.2% and 102.2% of that of the international annealed pure copper at the same temperature respectively.
The surfaces of the composite 1, the composite 2, the comparative 1 and the comparative 2 were subjected to argon ion etching for 60s and XPS test, and five peaks (sp 2 -C:284.8eV、sp 3 -C285.8 eV, C-O286.8 eV, c=o 287.6eV, O-c=o 289 eV) to fit C1S is shown in fig. 6. The sp2-C content of composite 1 and composite 2 (73.5% and 75.7%, respectively) was found to be 2.6% and 12.8% higher compared to comparative 1 (70.9%) and comparative 2 (62.9%), respectively.
The characterization of ion thinning and TEM of the composite material 2 is shown in fig. 7, it can be seen that the flat graphene layers are arranged in an oriented manner along the copper interface, the lattice spacing of the in-situ self-produced product is 0.35nm, the in-situ self-produced product is shown as a typical graphene lattice, and the area between white arrows in the figure shows that 15 layers of graphene with higher crystallization degree are grown between two copper sheets.
Claims (10)
1. The graphene-copper composite powder with high electrical property is characterized in that the composite powder is prepared by carbonizing lamellar composite particles formed by tightly stacking flaky copper powder and organic matters, wherein the content of the organic matters is 0.01-5 wt%, the number of carbon atoms in organic matter molecules is 5-2000, the diameter-thickness ratio of the flaky copper powder is greater than or equal to 10:1, and the average thickness of the flaky copper powder is 0.1-100 mu m.
2. The composite powder according to claim 1, wherein the carbonization temperature is 600 ℃ to 1050 ℃.
3. The composite powder according to claim 1, wherein the organic matter is one or more of alkane, alkene, alkyne, aromatic hydrocarbon and organic matter containing oxygen and/or nitrogen.
4. The composite powder according to claim 1, wherein the organic substance is oleic acid.
5. The method for preparing a composite powder according to any one of claims 1 to 4, wherein the method is realized by the steps of: taking copper powder with the particle size of 100-8000 meshes, coating the copper powder with an organic matter, and deforming the copper powder until the thickness of the copper powder is 0.1-100 mu m; and carbonizing to obtain graphene-copper composite powder.
6. The method according to claim 5, wherein the deformation treatment is performed by cold rolling or two-phase pressing.
7. The method of claim 6, wherein the cold rolling reduction is 50% -99%; the pressure of the two-way pressing is 30MPa-500MPa.
8. The preparation method of the graphene-copper composite material is characterized in that the graphene-copper composite powder according to any one of claims 1-4 or the graphene-copper composite powder prepared by the method according to any one of claims 5-7 is subjected to one or a combination of sintering and deformation to obtain the composite material.
9. The method according to claim 8, wherein the sintering temperature is 700 ℃ to 900 ℃, and sintering is performed by spark plasma sintering, vacuum hot pressing and high temperature sintering; the deformation is hot rolling, cold rolling, hot extrusion, cold extrusion and drawing; the hot rolling temperature is 300-900 ℃, and the lower rolling quantity is 30-99%; the rolling quantity under cold rolling is 30% -99%; the hot extrusion temperature is 300-950 ℃, and the extrusion ratio is (2-50) to 1; the extrusion ratio of the cold extrusion is (2-50) to 1; the drawing ratio is (2-50) to 1, and the drawing temperature is room temperature-900 ℃.
10. The method of claim 8, wherein the composite material is a block, a plate, a bar, or a wire.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311651347.8A CN117758102A (en) | 2023-12-05 | 2023-12-05 | Method for preparing high-quality graphene-copper composite powder and high-strength high-conductivity composite material based on graphene limited-domain growth |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311651347.8A CN117758102A (en) | 2023-12-05 | 2023-12-05 | Method for preparing high-quality graphene-copper composite powder and high-strength high-conductivity composite material based on graphene limited-domain growth |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117758102A true CN117758102A (en) | 2024-03-26 |
Family
ID=90324786
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311651347.8A Pending CN117758102A (en) | 2023-12-05 | 2023-12-05 | Method for preparing high-quality graphene-copper composite powder and high-strength high-conductivity composite material based on graphene limited-domain growth |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117758102A (en) |
-
2023
- 2023-12-05 CN CN202311651347.8A patent/CN117758102A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111145960B (en) | High-strength high-conductivity copper-based composite material and preparation method thereof | |
| CN108573763B (en) | Preparation method of wire and cable conductor, graphene-coated metal powder and conductor | |
| EP3190084A1 (en) | Partially oxidized graphene and preparation method therefor | |
| WO2020047500A1 (en) | Graphene material-metal nanocomposites and processes of making and using same | |
| CN113787788B (en) | Graphene/metal composite material and preparation method and application thereof | |
| CN110331316B (en) | High-strength heat-resistant graphene-aluminum composite conductor material and preparation method thereof | |
| CN102719693A (en) | Graphene and carbon nanotube mixed enhanced metal-matrix composite material and preparation method thereof | |
| CN110157931B (en) | Nano carbon reinforced metal matrix composite material with three-dimensional network structure and preparation method thereof | |
| Kim et al. | A new horizon for hexagonal boron nitride film | |
| CN112011705A (en) | Batch preparation method of nano-carbon reinforced copper-based composite material | |
| CN109365799B (en) | Preparation method of graphene coated metal powder and metal-based-graphene electrical contact | |
| CN110788144B (en) | Metallic copper-graphene laminated composite material and preparation method and device thereof | |
| CN111349905B (en) | Preparation method of enhanced copper-based composite wire | |
| Jia et al. | Preparation and electrical properties of sintered copper powder compacts modified by polydopamine-derived carbon nanofilms | |
| Wang et al. | Interface structure and properties of CNTs/Cu composites fabricated by electroless deposition and spark plasma sintering | |
| CN114054762A (en) | Graphene/metal matrix composite material preparation method based on graphene defect regulation | |
| CN110904356B (en) | Preparation method of network interpenetrating graphene-copper composite material | |
| KR101573241B1 (en) | Three-dimensional Grapheene Structure and Manufacturing method of Thereof and Elctrode using thereof | |
| Zhao et al. | Copper-polydopamine composite derived from bioinspired polymer coating | |
| CN117758102A (en) | Method for preparing high-quality graphene-copper composite powder and high-strength high-conductivity composite material based on graphene limited-domain growth | |
| KR101902256B1 (en) | Cu composite reinforced by 3D graphite or graphene network and preparing method thereof | |
| Zhou et al. | The effect of surface coating treatment on the properties of carbon nanotube reinforced copper matrix composites | |
| CN112011706A (en) | Batch preparation method of carbon nanosheet reinforced copper-based composite material | |
| CN114645149A (en) | Preparation method of in-situ authigenic graphene/copper composite material with composite interface structure | |
| CN114214602A (en) | Continuous preparation method of three-dimensional in-situ graphene reinforced metal matrix composite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |