CN117463999A - Copper-based conductive composite material and preparation method and application thereof - Google Patents
Copper-based conductive composite material and preparation method and application thereof Download PDFInfo
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- CN117463999A CN117463999A CN202311825838.XA CN202311825838A CN117463999A CN 117463999 A CN117463999 A CN 117463999A CN 202311825838 A CN202311825838 A CN 202311825838A CN 117463999 A CN117463999 A CN 117463999A
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- copper
- powder
- transition metal
- based conductive
- conductive composite
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 193
- 239000010949 copper Substances 0.000 title claims abstract description 155
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 149
- 239000002131 composite material Substances 0.000 title claims abstract description 126
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000000843 powder Substances 0.000 claims abstract description 55
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 53
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 41
- 150000003624 transition metals Chemical class 0.000 claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000001257 hydrogen Substances 0.000 claims abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 30
- 239000012298 atmosphere Substances 0.000 claims abstract description 22
- 150000003839 salts Chemical class 0.000 claims abstract description 21
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 150000001879 copper Chemical class 0.000 claims abstract description 15
- -1 saccharide compound Chemical class 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 238000011065 in-situ storage Methods 0.000 claims abstract description 8
- 238000001704 evaporation Methods 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims abstract description 5
- 238000000227 grinding Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 37
- 238000005098 hot rolling Methods 0.000 claims description 21
- 238000005245 sintering Methods 0.000 claims description 21
- 229930006000 Sucrose Natural products 0.000 claims description 16
- 239000005720 sucrose Substances 0.000 claims description 16
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 15
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 9
- 229940010552 ammonium molybdate Drugs 0.000 claims description 9
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 9
- 239000011609 ammonium molybdate Substances 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 5
- 238000009440 infrastructure construction Methods 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- 238000010304 firing Methods 0.000 claims description 4
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims description 3
- 229930091371 Fructose Natural products 0.000 claims description 3
- 239000005715 Fructose Substances 0.000 claims description 3
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- VMKYLARTXWTBPI-UHFFFAOYSA-N copper;dinitrate;hydrate Chemical compound O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O VMKYLARTXWTBPI-UHFFFAOYSA-N 0.000 claims description 3
- CYKLGTUKGYURDP-UHFFFAOYSA-L copper;hydrogen sulfate;hydroxide Chemical compound O.[Cu+2].[O-]S([O-])(=O)=O CYKLGTUKGYURDP-UHFFFAOYSA-L 0.000 claims description 3
- VWYGTDAUKWEPCZ-UHFFFAOYSA-L dichlorocopper;hydrate Chemical compound O.Cl[Cu]Cl VWYGTDAUKWEPCZ-UHFFFAOYSA-L 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 24
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 description 22
- 229910039444 MoC Inorganic materials 0.000 description 22
- 239000011159 matrix material Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 19
- 230000008569 process Effects 0.000 description 15
- 150000001720 carbohydrates Chemical class 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 4
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 4
- 239000004566 building material Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000007731 hot pressing Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 238000010000 carbonizing Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical group O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 238000002490 spark plasma sintering Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011218 binary composite Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000000185 sucrose group Chemical group 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/16—Metallic particles coated with a non-metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Powder Metallurgy (AREA)
Abstract
The embodiment of the invention relates to a copper-based conductive composite material and a preparation method and application thereof, wherein the preparation method comprises the following steps: adding copper powder, soluble copper salt and transition metal oxyacid salt into a first solvent, stirring, and sequentially evaporating, drying and grinding the mixed solution obtained by stirring to obtain first mixture powder; placing the first mixture powder in a hydrogen atmosphere for first roasting, so that a mixed coating containing nano copper and transition metal oxide is formed on the surface of copper powder, and obtaining precursor powder; adding the precursor powder and the saccharide compound into a second solvent, stirring, and sequentially evaporating and drying to obtain second mixture powder; placing the second mixture powder in a hydrogen atmosphere for second roasting, and using a saccharide compound as a carbon source to convert the transition metal oxide into a transition metal carbide and form graphene on the surface of the mixed coating in situ to obtain a copper-based composite powder material; the transition metal oxyates include group VI metal oxyates.
Description
Technical Field
The invention relates to the technical field of nano material preparation, in particular to a copper-based conductive composite material and a preparation method and application thereof.
Background
With the progress of technology and the development of urban design, smart cities have become an important direction for future urban construction. The smart city infrastructure construction comprises an intelligent traffic system, an intelligent water service system, an intelligent power grid system and the like, and the systems increase the requirements of higher mechanical properties and functional characteristics for new generation building materials, and particularly, the conductive materials with higher conductivity and stability are required to support the operation of more systems. Traditional building materials cannot meet the requirements of high-efficiency and stable operation of smart cities due to limited mechanical properties and conductive properties. For example, although pure copper commonly used in a circuit system has good conductivity, the pure copper has low strength, hardness, abrasion resistance and fatigue resistance, and the strength of the pure copper in a soft state after annealing is only 230-290 MPa.
The novel material represented by graphene is introduced into copper to obtain the copper-based composite material, so that the mechanical property of the copper-based material can be enhanced, and meanwhile, the original excellent functional characteristics such as high electrical conductivity and high thermal conductivity can be maintained, so that the application field of the copper-based composite material is greatly widened. However, in the related art, the composite material is prepared by combining the graphene and the copper matrix through a mechanical ball milling process and a discharge plasma sintering method, so that the combination property of the graphene and the copper matrix is poor, and the ideal reinforcing effect is difficult to develop.
Therefore, a new method for forming copper-based composite materials is needed to improve the mechanical properties of copper-based composite materials while maintaining higher electrical conductivity.
Disclosure of Invention
In view of the above technical problems, the present invention provides a copper-based conductive composite material, a preparation method and an application thereof, so as to at least partially solve at least one of the above mentioned technical problems.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
as one aspect of the present invention, there is provided a method for preparing a copper-based conductive composite, comprising: adding copper powder, soluble copper salt and transition metal oxyacid salt into a first solvent, stirring, and sequentially evaporating, drying and grinding the mixed solution obtained by stirring to obtain first mixture powder; placing the first mixture powder in a hydrogen atmosphere for first roasting, so that a mixed coating containing nano copper and transition metal oxide is formed on the surface of copper powder, and obtaining precursor powder; adding the precursor powder and the saccharide compound into a second solvent, stirring, and sequentially evaporating and drying to obtain second mixture powder; placing the second mixture powder in a hydrogen atmosphere for second roasting, and using a saccharide compound as a carbon source to convert the transition metal oxide into a transition metal carbide and form graphene on the surface of the mixed coating in situ to obtain a copper-based composite powder material; the transition metal oxyates include group VI metal oxyates.
According to an embodiment of the present invention, the transition metal oxyacid salt specifically includes ammonium tungstate or ammonium molybdate; the soluble copper salt includes at least one of copper sulfate, copper sulfate hydrate, copper chloride hydrate, copper nitrate, or copper nitrate hydrate.
According to the embodiment of the invention, the temperature of the first roasting is 380-420 ℃; the second roasting temperature is 780-820 ℃; the time of the first roasting and/or the second roasting is greater than or equal to 10 minutes.
According to an embodiment of the present invention, the saccharide compound comprises at least one of fructose, glucose, maltose, sucrose.
According to an embodiment of the invention, the preparation method further comprises hot-press sintering and multi-step hot rolling of the copper-based composite powder material to obtain the copper-based conductive composite material.
According to the embodiment of the invention, the addition mass ratio of the copper powder, the soluble copper salt and the transition metal oxyacid salt is as follows: 1:0.15:0 to 0.004.
According to the embodiment of the invention, the adding mass ratio of the copper powder to the carbohydrate is 1:0.01-0.015.
According to an embodiment of the invention, in the hydrogen atmosphere of the first roasting and the second roasting, the gas flow rate of the hydrogen is more than 100mL/min; and introducing inert gas into the hydrogen atmosphere of the second roasting.
As another aspect of the present invention, there is provided a copper-based conductive composite material prepared by the above-described preparation method.
As a further aspect of the invention there is also provided the use of a copper-based conductive composite as described above in the field of infrastructure construction.
Based on the technical scheme, the copper-based conductive composite material, the preparation method and the application thereof have at least one or a part of the following beneficial effects:
(1) The method comprises the steps of modifying the surface of copper powder, namely attaching transition metal oxyacid salt to the surface of copper powder, and then performing first roasting in hydrogen atmosphere to obtain copper powder covered by transition metal oxide. And then adding a carbohydrate and performing second roasting under the hydrogen atmosphere, so that the carbohydrate reacts with the transition metal oxide to generate transition metal carbide, the transition metal carbide can be ensured to be uniformly distributed at the interface of the copper matrix and the graphene, and the subsequent enhancement of the bonding strength of the graphene and the copper matrix is facilitated. The method has the advantages that the method can ensure that the structure of the graphene is not damaged in the subsequent graphene introduction process, simultaneously better promotes the interface bonding effect of the graphene and the copper matrix, fully plays the reinforcing effect of the graphene on the mechanical property, and avoids the reduction of the conductive property caused by the damage of the loaded transition metal carbide to the graphene structure.
(2) The in-situ interaction of the graphene and the copper matrix is formed based on the copper powder as a template, so that the uniformity of distribution of saccharide compounds on the surface of all copper powder can be ensured, the uniformity of final graphene in the copper matrix is further ensured, and the graphene forms a conductive path in the copper matrix. The method overcomes the damage to the graphene structure in the mixing process in the related technology, avoids the problem of agglomeration caused by uneven distribution of the graphene structure, further improves the mechanical properties of the subsequently prepared copper-based composite material, such as yield strength, tensile strength or elongation at break, and ensures higher conductivity of the subsequently prepared copper-based composite material.
(3) The method has simple steps and lower operation difficulty. In the related art, the process for synthesizing the surface modified graphene generally needs to be carried out on a template or a substrate, but the method is beneficial to taking copper powder as the template, and reduces the process cost and complexity.
Drawings
The present invention is described in further detail below with reference to the accompanying drawings.
FIG. 1 is a flow chart of a method for preparing a copper-based conductive composite according to an embodiment of the present invention;
FIG. 2 is a flow chart of a process for preparing a copper-based conductive composite according to an embodiment of the present invention;
FIG. 3 is a tensile engineering stress-strain curve of the copper-based conductive composite CB-1.6-0.055 of example 1 of the present invention;
FIG. 4 is a tensile engineering stress-strain curve of the copper-based conductive composite CB-1.6-0.11 of example 2 of the present invention;
FIG. 5 is a scanning electron microscope image of the composite reinforcement of example 2 of the present invention after corrosion of the copper-based conductive composite;
FIG. 6 is a scanning electron microscope image of the interface between CB-1.6 and 0.11 of the copper-based conductive composite material of example 2 of the present invention;
FIG. 7 is a tensile engineering stress-strain curve of comparative example 1 using pure copper material CB according to the present invention;
FIG. 8 is a tensile engineering stress-strain graph of comparative example 2 using copper-based conductive composite CB-1.6 of the present invention;
FIG. 9 is an X-ray diffraction pattern of example 2, comparative example 1 and comparative example 2 of the present invention;
FIG. 10 is a tensile engineering stress-strain curve of the copper-based conductive composite CB-1.6-0.165 of example 3 of the present invention;
FIG. 11 is a tensile engineering stress-strain curve of the copper-based conductive composite CB-1.6-0.22 of example 4 of the present invention;
FIG. 12 is a tensile engineering stress-strain graph of comparative example 3 using copper-based conductive composite CB-2.5 of the present invention;
FIG. 13 is a tensile engineering stress-strain curve of the copper-based conductive composite CB-2.5-0.055 of example 5 of the present invention;
FIG. 14 is a tensile engineering stress-strain curve of the copper-based conductive composite CB-2.5-0.11 of example 6 of the present invention;
FIG. 15 is a tensile engineering stress-strain curve of the copper-based conductive composite CB-2.5-0.165 of example 7 of the present invention;
FIG. 16 is a tensile engineering stress-strain curve of the copper-based conductive composite CB-2.5-0.22 of example 8 of the present invention;
fig. 17 is a graph showing the change of the conductivity of the copper-based conductive composite material according to the embodiments 1 to 8 of the present invention with the volume fraction of molybdenum carbide.
In the drawings, the reference numerals specifically have the following meanings:
1-copper powder;
2-transition metal oxide;
3-graphene;
4-transition metal carbide.
Detailed Description
The present invention will be further described in detail below with reference to specific embodiments and with reference to the accompanying drawings, in order to make the objects, technical solutions and advantages of the present invention more apparent.
In the related art, the combination of graphene and a copper matrix is poor, so that the obtained composite material has poor comprehensive performance. If the copper-based composite material is prepared by combining a mechanical ball milling process and a spark plasma sintering method, the Vickers hardness of the copper-based composite material is slightly improved, and meanwhile, the conductivity is reduced to a certain extent to 94 percent IACS. Conductivity is a relatively important consideration index for copper-based conductive composites. The related technology also prepares the copper-based composite material by combining a molecular-level mixing process with a spark plasma sintering method, wherein the tensile strength is 320MPa, but the conductivity is reduced to 88 percent IACS, so that the copper-based composite material is difficult to industrially apply and popularize.
In the process of realizing the invention, it is found that in the process of preparing the copper-based conductive composite material, copper powder, soluble copper salt and transition metal oxyacid salt are firstly mixed and stirred, then baked in a hydrogen atmosphere, so that a uniform coating of transition metal oxide grows on the surface of the copper powder, then a carbohydrate is used as a carbon source, the transition metal carbide is formed by baking in the hydrogen atmosphere, and meanwhile, the carbohydrate is carbonized into graphene. The bonding strength of the subsequent graphene and the copper matrix can be greatly enhanced, transition metal carbide is ensured to be distributed at the interface of the boundary of the copper matrix and the graphene, the prepared graphene can better promote the interface bonding interaction force of the graphene and the copper matrix while ensuring that the structure is not damaged, and the copper-based conductive composite material has higher conductivity while improving the mechanical properties such as tensile strength and the like, thereby being beneficial to industrial popularization.
Specifically, according to some embodiments of the present invention, a method for preparing a copper-based conductive composite is provided, fig. 1 is a flowchart of a method for preparing a copper-based conductive composite according to an embodiment of the present invention, fig. 2 is a flowchart of a process for preparing a copper-based conductive composite according to an embodiment of the present invention, and as shown in fig. 1 to 2, the preparation method includes the following steps S101 to S104.
In step S101, copper powder 1, a soluble copper salt, and a transition metal oxyacid salt are added to a first solvent and stirred, and the mixed solution obtained by stirring is sequentially evaporated, dried, and ground to obtain a first mixture powder.
In step S102, the first mixture powder is placed in a hydrogen atmosphere, and first baking is performed, so that a mixed coating layer containing nano copper and transition metal oxide 2 is formed on the surface of copper powder 1, and precursor powder is obtained.
According to the embodiment of the invention, the transition metal oxyacid salt takes the first solvent as a medium, is firstly dissolved in the first solvent, and then is recrystallized on the surface of copper powder 1 together with copper salt, so that the transition metal oxyacid salt is uniformly distributed on the surface of copper powder 1. Subsequently, the copper salt is reduced to elemental copper in a low temperature hydrogen atmosphere, and in step S102, the first calcination is carried out at a lower temperature, and the transition metal oxyacid salt undergoes a decomposition reaction and is not reduced, so that the transition metal oxyacid salt undergoes a decomposition during the first calcination to form the transition metal oxide 2.
In step S103, the precursor powder and the saccharide compound are added into the second solvent, stirred, and then evaporated and dried sequentially to obtain a second mixture powder.
In step S104, the second mixture powder is placed under a hydrogen atmosphere for second roasting, and the carbohydrate compound is used as a carbon source, so that the transition metal oxide 2 is converted into the transition metal carbide 4, and the graphene 3 is formed on the surface of the mixed coating in situ, so as to obtain the copper-based composite powder material.
According to the embodiment of the invention, the copper powder 1 covered by the transition metal oxide 2 is obtained by modifying the surface of the copper powder 1, that is, attaching a transition metal oxyacid salt to the surface of the copper powder 1, and then performing first baking under a hydrogen atmosphere. And then adding a carbohydrate and performing second roasting under the hydrogen atmosphere, so that the carbohydrate reacts with the transition metal oxide 2 to generate the transition metal carbide 4, the transition metal carbide 4 can be ensured to be uniformly distributed at the interface of the copper matrix and the graphene 3, and the subsequent enhancement of the bonding strength of the graphene 3 and the copper matrix is facilitated. The method has the advantages that the method can ensure that the structure of the graphene 3 is not damaged in the subsequent process of introducing the graphene 3, simultaneously better promote the interface bonding effect of the graphene 3 and the copper matrix, fully exert the strengthening effect of the graphene 3 on the mechanical property of the copper matrix, and avoid the reduction of the conductive property caused by the structural damage of the loaded transition metal carbide 4 to the graphene 3.
Further, the in-situ interaction of the graphene 3 and the copper matrix is formed based on the copper powder 1 as a template, so that the uniformity of distribution of carbohydrate on the surface of all copper powder 1 can be ensured, the uniformity of graphene 3 generated by carbonizing the final carbohydrate in the copper matrix can be ensured, and the graphene 3 forms a conductive path in the copper matrix. The method overcomes the damage to the structure of the graphene 3 in the mixing process of the related technology, avoids the problem of agglomeration caused by uneven distribution of the structure of the graphene 3, further improves the mechanical properties of the subsequently prepared copper-based composite material, such as yield strength, tensile strength or elongation at break, and ensures higher conductivity of the subsequently prepared copper-based composite material. The transition metal oxyates include group VI metal oxyates.
According to an embodiment of the invention, the first solvent and/or the second solvent comprises ethanol or water containing water, preferably ethanol containing water. Wherein water is favorable for the decomposition process of the transition metal oxyacid salt and ethanol is used for accelerating the evaporation and drying speed.
According to an embodiment of the invention, the transition metal oxyacid salt specifically comprises ammonium tungstate or ammonium molybdate, preferably the transition metal oxyacid salt is ammonium molybdate. In the related pre-experiment of the invention, the mechanical property and the electrical conductivity of the prepared copper-based conductive composite material are higher when the ammonium molybdate is used. The soluble copper salt includes at least one of copper sulfate, copper sulfate hydrate, copper chloride hydrate, copper nitrate, or copper nitrate hydrate. Preferably, the soluble copper salt is copper nitrate trihydrate, wherein trihydrate means that each copper nitrate molecule combines with three water molecules to form a stable crystal structure.
According to the embodiment of the invention, the temperature of the first baking is 380-420 ℃, such as 380 ℃, 390 ℃, 400 ℃, 410 ℃, or 420 ℃, but not limited thereto, and is preferably 400 ℃. The second baking temperature is 780-820 ℃, for example 780 ℃, 790 ℃, 800 ℃, 810 ℃ or 820 ℃, but not limited thereto, and preferably 800 ℃. The time of the first roasting and/or the second roasting is greater than or equal to 10 minutes. The first firing is to prepare the transition metal oxide 2 for forming the precursor powder; the second firing is to carbonize the transition metal oxide 2 with the saccharide compound to prepare graphene 3 having higher crystallinity and generate the transition metal carbide 4, and thus the temperature required for the second firing is relatively higher.
According to an embodiment of the present invention, the carbohydrate comprises at least one of fructose, glucose, maltose, sucrose, preferably the carbohydrate is sucrose. In the process of carrying out the related pre-experiment of the invention, the sucrose is found to be relatively low in cost, the sucrose has higher viscosity, the form of wrapping precursor powder is easier to form, and in the experiment, the quality of graphene 3 formed by carbonizing the sucrose is found to be relatively better.
According to an embodiment of the invention, the preparation method further comprises hot-press sintering and multi-step hot rolling of the copper-based composite powder material to obtain the copper-based conductive composite material. The thickness of the copper-based composite powder material is reduced by 20-80%, for example, 20%, 30%, 40%, 50%, 60%, 70% or 80%, but not limited thereto, preferably 50%, by multi-step hot rolling, and the purpose is to further improve the compactibility of the prepared copper-based conductive composite material.
According to the embodiment of the invention, the addition mass ratio of the copper powder 1, the soluble copper salt and the transition metal oxyacid salt is as follows: 1:0.15:0 to 0.004. The addition mass ratio of the copper powder 1 to the soluble copper salt is fixed 1:0.15, and when the addition ratio of the transition metal oxyacid salt to the copper powder 1 is 0-0.004:1, the prepared copper-based conductive composite material has higher mechanical property and better conductive property. For example, but not limited to, 0.001:1, 0.002:1, 0.003:1 or 0.004:1.
Specifically, the added transition metal oxyacid salt takes ammonium molybdate as an example, when the adding mass ratio of ammonium molybdate to copper powder 1 is 0.002:1, that is to say, the volume fraction of molybdenum carbide in the prepared copper-based conductive composite material is 0.11%, the mechanical property of the prepared copper-based conductive composite material is relatively more stable, and the conductivity is better.
According to the embodiment of the invention, the adding mass ratio of the copper powder 1 to the saccharide compound is 1:0.01-0.015, for example, but not limited to, 1:0.01, 1:0.011, 1:0.012, 1:0.013, 1:0.014 or 1:0.015. When the adding mass ratio of the copper powder 1 to the carbohydrate is 1:0.01, namely the volume fraction of the carbohydrate in the prepared copper-based conductive composite material is 1.6%, the mechanical property of the obtained copper-based conductive composite material is relatively more stable, and the conductive property is better.
According to an embodiment of the invention, in the hydrogen atmosphere of the first roasting and the second roasting, the gas flow rate of the hydrogen is more than 100mL/min; for example, but not limited to, 110mL/min, 150mL/min, 200mL/min, 250mL/min, 300mL/min, 350mL/min, 400mL/min may be used. And introducing inert gas into the hydrogen atmosphere of the second roasting. In the whole gas introducing process, the total gas flow rate is usually controlled to be less than 500mL/min, for example, the gas flow rate of hydrogen is 400mL/min and the gas flow rate of inert gas is 50mL/min in the second roasting process, but the inert gas is preferably argon.
According to some embodiments of the present invention, there is also provided a copper-based conductive composite material prepared by the preparation method as described above.
According to the embodiment of the invention, a method for directly synthesizing graphene 3 on copper powder 1 in situ is provided, so that the copper-based conductive composite material with higher strength and higher conductivity is prepared, and the mechanical property of the copper-based conductive composite material is greatly improved while the higher conductivity is maintained.
According to the embodiment of the invention, taking ammonium molybdate and sucrose as examples, when the adding mass ratio of ammonium molybdate to copper powder to sucrose is 0.002:1:0.01, the tensile strength of the copper-based conductive composite material prepared by the preparation method is 330MPa, and the conductivity is 96% IACS.
According to some embodiments of the present invention there is also provided the use of a copper-based conductive composite as described above in the field of infrastructure construction.
According to an embodiment of the invention, infrastructure construction in urban construction comprises traffic systems, water service systems, smart grid systems and the like, and the systems have requirements for higher mechanical properties and higher electric conductivity of building materials. The traditional building materials have lower strength, lower hardness, lower friction and wear degree and lower fatigue resistance due to limited mechanical property and conductivity, for example, the strength of pure copper is only 230-290 MPa in a soft state after annealing. The copper-based conductive composite material prepared by the method is used as an excellent conductive material, can improve the strength, the plasticity, the toughness and the corrosion resistance of the material on the basis of ensuring the original high conductivity of copper, and can be applied to improving the performance and the stability of an infrastructure.
According to the embodiment of the invention, the three-component copper-based conductive composite material is formed by introducing the transition metal carbide into the copper-based conductive composite material, wherein the transition metal carbide is not only distributed on the interface, but also uniformly distributed at a position close to the interface, and the position can be called as an interface gradual transition region, so that the interface combination of the copper-based conductive composite material is improved, and the macroscopic mechanical property of the copper-based conductive composite material is remarkably improved. In addition, the copper-based conductive composite material provided by the embodiment of the invention has the characteristic of strong customization, and can be used for adjusting the components of the copper-based conductive composite material according to different application scene requirements and adjusting the performance of the copper-based conductive composite material to meet different requirements.
The invention is further illustrated by the following examples. In the following detailed description, for purposes of explanation, numerous specific details are set forth in order to provide a thorough explanation of the embodiments of the invention. It may be evident, however, that one or more embodiments may be practiced without these specific details. Moreover, the details of the various embodiments below may be arbitrarily combined into other viable embodiments without conflict.
Example 1:
20g of copper powder 1, 3.025g of copper nitrate trihydrate (Cu (NO) 3 ) 2 ·3H 2 O) and 0.02 g of ammonium molybdate tetrahydrate ((NH) 4 ) 6 Mo 7 O 24 ·4H 2 O), and then added to ethanol aqueous solutions (30 ml of deionized water and 40 ml of ethanol) respectively, and mixed and stirred for more than 30 minutes to obtain a uniform suspension. The above suspension was evaporated under stirring at 80 ℃ and then baked in an oven at 70 ℃ for more than 3 hours to ensure adequate drying. The dried product was then ground to a fine powder.
Subsequently, roasting for 90 minutes in a tube furnace at 400 ℃ under the atmosphere with the hydrogen flow of 200mL/min to obtain MoO 3 @ Cu precursor powder. Through the above steps, a mixed coating of nano copper and molybdenum oxide is formed on the surface of copper powder 1.
The MoO obtained above is subjected to 3 The @ Cu precursor powder and 0.2g sucrose were added to an aqueous ethanol solution (deionized water 20 ml, ethanol 40 ml) respectively, and mixed and stirred for 20 minutes until uniform. Then evaporated with stirring at 75 ℃ and baked in an oven at 70 ℃ for more than 3 hours to ensure adequate drying to give a mixed powder.
And (3) roasting the mixed powder in a tube furnace for 10 minutes at 800 ℃ by using hydrogen and argon atmosphere, wherein the hydrogen flow is 200mL/min and the argon flow is 200mL/min, so as to prepare the ternary copper-based composite powder material (CB-1.6-0.055 composite powder) containing graphene 3 with the volume fraction of 1.6% and molybdenum carbide with the volume fraction of 0.055%.
Loading the CB-1.6-0.055 composite powder material into a graphite mould with an inner diameter of 30 mm, solidifying the composite powder material by using a vacuum hot-pressing sintering system, and adjusting the vacuum degree to be 10 -4 The applied pressure is 50MPa or less, the sintering temperature is 850 ℃, and the sintering time is 1 hour. The hot pressed billet is then further densified by multi-step hot rolling. The single-step hot rolling temperature is 800 ℃, the single reduction thickness is 0.1-0.2 mm, and after the multi-step hot rolling operation, the final accumulation thickness of the CB-1.6-0.055 composite powder material is reduced to 50%, and the copper-based conductive composite material CB-1.6-0.055 is prepared.
Fig. 3 is a tensile engineering stress-strain curve of the copper-based conductive composite CB-1.6 to 0.055 of example 1 of the present invention. As shown in FIG. 3, it was found by examination that the yield strength was 270MPa, the tensile strength was 311MPa, the elongation at break was 12%, and the electrical conductivity was 97% IACS (International annealed copper Standard).
Example 2:
this example 2 is similar to example 1, and the same parts are not repeated except that ammonium molybdate tetrahydrate ((NH) 4 ) 6 Mo 7 O 24 ·4H 2 The adding amount of O) is 0.04g, and finally the ternary copper-based composite powder material with the molybdenum carbide volume fraction of 0.11% is prepared, and after hot-pressing sintering and multi-step hot rolling in the same way as in the example 1, the copper-based conductive composite material CB-1.6-0.11 is finally prepared.
Fig. 4 is a tensile engineering stress-strain curve of the copper-based conductive composite CB-1.6 to 0.11 according to example 2 of the present invention. As shown in FIG. 4, it was found by examination that the yield strength was 303MPa, the tensile strength was 330MPa, the elongation at break was 15%, and the electrical conductivity was 96% IACS.
And corroding the copper matrix in CB-1.6-0.11 by using a mixed solution of hydrochloric acid and ferric trichloride to obtain the composite reinforcement of graphene 3 and molybdenum carbide. Fig. 5 is a scanning electron microscope image of the composite reinforcement after corrosion of the copper-based conductive composite material of example 2 of the present invention. FIG. 6 is a scanning electron microscope image of the interface between CB-1.6 and 0.11 of the copper-based conductive composite material of example 2 of the present invention. As shown in fig. 5, the graphene 3 is loaded with molybdenum carbide nano particles with uniform size, which proves that the graphene 3 loaded with the molybdenum carbide nano particles can realize the structural characteristics of enhancing the performance of copper-based materials. As shown in fig. 6, molybdenum carbide nanoparticles formed at the copper and graphene 3 interface were characterized, indicating an improvement in the copper and graphene 3 interface bonding by the molybdenum carbide nanoparticles.
Comparative example 1:
20g of copper powder 1 was weighed and charged into a graphite mold having an inner diameter of 30 mm. The mixed powder was solidified using a vacuum hot press sintering system. Adjusting the vacuum degree 10 -4 The applied pressure is 50MPa or less, the sintering temperature is 850 ℃, and the sintering time is 1 hour. The hot pressed billet is then further densified by multi-step hot rolling. The single-step hot rolling temperature is 800 ℃, the single reduction thickness is 0.1-0.2 mm, and the pure copper material CB obtained after the multi-step hot rolling operation is used as a comparison. Fig. 7 is a tensile engineering stress-strain curve of comparative example 1 using pure copper material CB according to the present invention. As shown in fig. 7, it was found by examination that the yield strength was 175MPa, the tensile strength was 233MPa, the elongation at break was 25%, and the electrical conductivity was 97% IACS.
Comparative example 2:
20g of copper powder 1 and 0.2g of sucrose are weighed respectively, added into ethanol water solution (deionized water 20 ml and ethanol 40 ml) and stirred for 20 minutes until uniform. Then evaporated with stirring at 75 ℃ and baked in an oven at 70 ℃ for more than 3 hours to ensure adequate drying. Roasting the powder in a tube furnace for 10 minutes at 800 ℃ by using hydrogen and argon atmosphere (the hydrogen flow is 200mL/min and the argon flow is 200 mL/min), and preparing binary copper-based composite powder (CB-1.6 composite powder) containing graphene 3 with the volume fraction of 1.6% of graphene 3.
Curing the binary composite powder material by using a vacuum hot-pressing sintering system, and adjusting the vacuum degree to 10 -4 Under MPa, applying pressure50MPa, a sintering temperature of 850 ℃ and a sintering time of 1 hour. The hot pressed billet is then further densified by multi-step hot rolling. The single-step hot rolling temperature is 800 ℃, the single reduced thickness is 0.1-0.2 mm, and after the multi-step hot rolling operation, the final accumulated thickness of the CB-1.6 composite powder material is reduced to 50%, and the copper-based conductive composite material CB-1.6 is prepared for comparison.
Fig. 8 is a tensile engineering stress-strain graph of comparative example 2 using copper-based conductive composite CB-1.6 according to the present invention. As shown in FIG. 8, it was found by examination that the yield strength was 246MPa, the tensile strength was 275MPa, the elongation at break was 17%, and the electrical conductivity was 93% IACS.
The products prepared in inventive example 2, comparative example 1 and comparative example 2 were subjected to material analysis using X-ray diffraction. FIG. 9 is an X-ray diffraction pattern of example 2, comparative example 1 and comparative example 2 of the present invention, as shown in FIG. 9, the X-ray diffraction of the material contains characteristic peaks of both copper and molybdenum carbide, indicating that the molybdenum carbide is finally formed by the added metal molybdate during the preparation process.
Example 3:
this example 3 is similar to example 1, and the same parts are not repeated except that ammonium molybdate tetrahydrate ((NH) 4 ) 6 Mo 7 O 24 ·4H 2 The adding amount of O) is 0.06g, the ternary copper-based composite powder material with the molybdenum carbide volume fraction of 0.165% is prepared, and the copper-based conductive composite material CB-1.6-0.165 is finally prepared after hot press sintering and multi-step hot rolling in the same way as in the example 1.
Fig. 10 is a tensile engineering stress-strain curve of the copper-based conductive composite CB-1.6 to 0.165 of example 3 of the present invention. As shown in fig. 10, it was found by examination that the yield strength was 274MPa, the tensile strength was 300MPa, the elongation at break was 18%, and the electrical conductivity was 94% IACS.
Example 4:
this example 4 is similar to example 1, and the same parts are not repeated except that ammonium molybdate tetrahydrate ((NH) 4 ) 6 Mo 7 O 24 ·4H 2 The addition amount of O) was 0.08g, preparationThe ternary copper-based composite powder material with the molybdenum carbide volume fraction of 0.22 percent is obtained, and after hot press sintering and multi-step hot rolling, the copper-based conductive composite material CB-1.6-0.22 is finally prepared.
Fig. 11 is a tensile engineering stress-strain curve of the copper-based conductive composite CB-1.6 to 0.22 according to example 4 of the present invention. As shown in fig. 11, it was found by examination that the yield strength was 251MPa, the tensile strength was 285MPa, the elongation at break was 19%, and the electrical conductivity was 93% IACS.
Comparative example 3:
the preparation process of the comparative example 3 is similar to that of the comparative example 2, and the same parts are not repeated, except that the adding amount of sucrose is 0.3g, the ternary copper-based composite powder material with the molybdenum carbide volume fraction of 2.5% is prepared, and after hot press sintering and multi-step hot rolling, the copper-based conductive composite material CB-2.5 is finally prepared as a comparison.
Fig. 12 is a tensile engineering stress-strain graph of comparative example 3 using copper-based conductive composite CB-2.5 according to the present invention. As shown in fig. 12, it was found by examination that the yield strength was 240MPa, the tensile strength was 265MPa, the elongation at break was 17%, and the electrical conductivity was 89% IACS.
Example 5:
the same parts as in example 1 are not repeated, except that the added amount of sucrose is 0.3g, the ternary copper-based composite powder material containing 2.5% of graphene 3 and 0.055% of molybdenum carbide is prepared, and after the same hot press sintering and multi-step hot rolling as in example 1, the copper-based conductive composite CB-2.5-0.055 is finally prepared.
Fig. 13 is a tensile engineering stress-strain curve of the copper-based conductive composite CB-2.5-0.055 of example 5 of the present invention. As shown in fig. 13, it was found by examination that the yield strength was 275MPa, the tensile strength was 304MPa, and the electrical conductivity was 96% IACS.
Example 6:
the same parts as in example 6 and example 2 are not repeated, except that the adding amount of sucrose is 0.3g, the ternary copper-based composite powder material containing 2.5% of graphene 3 and 0.11% of molybdenum carbide is prepared, and after hot press sintering and multi-step hot rolling, the copper-based conductive composite material CB-2.5-0.11 is finally prepared.
Fig. 14 is a tensile engineering stress-strain curve of the copper-based conductive composite CB-2.5-0.11 according to example 6 of the present invention. As shown in fig. 14, it was found by examination that the yield strength was 290MPa, the tensile strength was 305MPa, and the electrical conductivity was 95% IACS.
Example 7:
the same parts as in example 7 are not repeated, except that the added amount of sucrose is 0.3g, the ternary copper-based composite powder material containing 2.5% of graphene 3 and 0.165% of molybdenum carbide is prepared, and after hot press sintering and multi-step hot rolling, the copper-based conductive composite material CB-2.5-0.165 is finally prepared.
Fig. 15 is a tensile engineering stress-strain curve of the copper-based conductive composite CB-2.5-0.165 of example 7 of the present invention. As shown in fig. 15, the yield strength was 280MPa, the tensile strength was 308MPa, and the electrical conductivity was 94% IACS.
Example 8:
the same parts as in example 8 are not repeated, except that the added amount of sucrose is 0.3g, the ternary copper-based composite powder material containing 2.5% of graphene 3 and 0.22% of molybdenum carbide is prepared, and after hot press sintering and multi-step hot rolling, the copper-based conductive composite material CB-2.5-0.22 is finally prepared.
Fig. 16 is a tensile engineering stress-strain curve of the copper-based conductive composite CB-2.5-0.22 of example 8 of the present invention. As shown in fig. 16, it was found from the examination that the yield strength was 294MPa, the tensile strength was 316MPa, and the electrical conductivity was 92% IACS.
Fig. 17 is a graph showing the change of the conductivity of the copper-based conductive composite material according to embodiments 1 to 8 of the present invention along with the volume fraction of molybdenum carbide, as shown in fig. 17, it can be seen that when the volume fraction of graphene 3 synthesized in situ is 1.6% under the condition that other conditions are unchanged, the prepared copper-based conductive composite material has better conductivity than when the volume fraction of graphene 3 is 2.5%.
The mechanical properties of the composite materials prepared in examples 1 to 8 and comparative examples 1 to 3 of the present invention are shown in the following Table 1.
Table 1 mechanical Properties of the composite materials of examples 1 to 8 and comparative examples 1 to 3
According to the data in table 1, the mechanical properties exhibited a change of increasing followed by decreasing with increasing volume content of molybdenum carbide. The conductivity change is combined, so that the conductivity of the material can be improved by a certain content of graphene 3, but the content cannot be too high. Meanwhile, the molybdenum carbide with a certain content is introduced to help to improve the mechanical property of the copper-based conductive composite material, but the content is not too high. In the embodiment of the invention, when the volume fraction of the graphene 3 is 1.6%, and when the volume fraction of the molybdenum carbide is 0.055-0.11%, the mechanical property and the conductivity of the prepared copper-based conductive composite material are in a good state, so that the copper-based conductive composite material can be suitable for industrial popularization.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the invention thereto, but to limit the invention thereto, and any modifications, equivalents, improvements and equivalents thereof may be made without departing from the spirit and principles of the invention.
Claims (10)
1. The preparation method of the copper-based conductive composite material is characterized by comprising the following steps of:
adding copper powder, soluble copper salt and transition metal oxyacid salt into a first solvent, stirring, and sequentially evaporating, drying and grinding the mixed solution obtained by stirring to obtain first mixture powder;
placing the first mixture powder in a hydrogen atmosphere, and performing first roasting to form a mixed coating containing nano copper and transition metal oxide on the surface of copper powder, so as to obtain precursor powder;
adding the precursor powder and the saccharide compound into a second solvent, stirring, and sequentially evaporating and drying to obtain second mixture powder;
placing the second mixture powder in a hydrogen atmosphere for second roasting, and using the carbohydrate compound as a carbon source to convert the transition metal oxide into transition metal carbide and form graphene on the surface of the mixed coating in situ to obtain a copper-based composite powder material;
the transition metal oxyates include group vi metal oxyates.
2. The preparation method according to claim 1, wherein the transition metal oxyacid salt specifically comprises ammonium tungstate or ammonium molybdate; the soluble copper salt includes at least one of copper sulfate, copper sulfate hydrate, copper chloride hydrate, copper nitrate, or copper nitrate hydrate.
3. The preparation method according to claim 1, wherein the temperature of the first firing is 380-420 ℃; the second roasting temperature is 780-820 ℃;
the time of the first roasting and/or the second roasting is more than or equal to 10min.
4. The method according to claim 1, wherein the saccharide compound comprises at least one of fructose, glucose, maltose, sucrose.
5. The method according to any one of claims 1 to 4, further comprising hot press sintering and multi-step hot rolling the copper-based composite powder material to obtain the copper-based conductive composite material.
6. The preparation method according to any one of claims 1 to 4, wherein the copper powder, the soluble copper salt and the transition metal oxyacid salt are added in mass ratio: 1:0.15:0 to 0.004.
7. The method according to any one of claims 1 to 4, wherein the ratio by mass of the copper powder to the saccharide compound is 1:0.01 to 0.015.
8. The production method according to any one of claims 1 to 4, characterized in that in the hydrogen atmosphere of the first calcination and the second calcination, the gas flow rate of hydrogen is more than 100mL/min;
and introducing inert gas into the hydrogen atmosphere of the second roasting.
9. A copper-based conductive composite material, characterized in that it is prepared by the preparation method according to any one of claims 1 to 8.
10. Use of the copper-based conductive composite of claim 9 in the field of infrastructure construction.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030124016A1 (en) * | 2001-12-27 | 2003-07-03 | Byoung Kee Kim | Method of producing tungsten-copper based composite powder and sintered alloys for heat-sink using said composite powder |
| CN104874803A (en) * | 2015-05-06 | 2015-09-02 | 天津大学 | Method for preparing graphene/copper composite material by in-situ catalysis of solid carbon source on surfaces of copper powders |
| CN104934573A (en) * | 2014-03-19 | 2015-09-23 | 苏州格瑞动力电源科技有限公司 | In-situ solid-phase synthesis method of silicon-graphene spheroidal composite material with multilevel structure and application thereof |
| CN105081312A (en) * | 2015-08-17 | 2015-11-25 | 天津大学 | Method for preparing grapheme/copper composite material by loading solid carbon source on copper powder surface in impregnation manner |
| CN109482865A (en) * | 2018-09-12 | 2019-03-19 | 天津大学 | A method of high-content graphene nanometer sheet/carbon/carbon-copper composite material is prepared in situ |
| CN109897985A (en) * | 2019-03-05 | 2019-06-18 | 天津工业大学 | Three-dimensional continuous graphite alkene/carbon/carbon-copper composite material and preparation method thereof |
| CN110125385A (en) * | 2019-04-15 | 2019-08-16 | 中国航发北京航空材料研究院 | A kind of preparation method of the graphene Cu-base composites based on fabricated in situ |
| CN110172607A (en) * | 2019-04-11 | 2019-08-27 | 全球能源互联网欧洲研究院 | A kind of preparation method of graphene enhancing Cu tailings |
| CN110453107A (en) * | 2019-08-01 | 2019-11-15 | 天津大学 | Graphene-tungsten carbide collaboration enhancing Cu-base composites preparation method |
| CN115522095A (en) * | 2021-06-24 | 2022-12-27 | 上海交通大学 | In-situ interface modification method of graphene-copper-based composite material |
-
2023
- 2023-12-28 CN CN202311825838.XA patent/CN117463999B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030124016A1 (en) * | 2001-12-27 | 2003-07-03 | Byoung Kee Kim | Method of producing tungsten-copper based composite powder and sintered alloys for heat-sink using said composite powder |
| CN104934573A (en) * | 2014-03-19 | 2015-09-23 | 苏州格瑞动力电源科技有限公司 | In-situ solid-phase synthesis method of silicon-graphene spheroidal composite material with multilevel structure and application thereof |
| CN104874803A (en) * | 2015-05-06 | 2015-09-02 | 天津大学 | Method for preparing graphene/copper composite material by in-situ catalysis of solid carbon source on surfaces of copper powders |
| CN105081312A (en) * | 2015-08-17 | 2015-11-25 | 天津大学 | Method for preparing grapheme/copper composite material by loading solid carbon source on copper powder surface in impregnation manner |
| CN109482865A (en) * | 2018-09-12 | 2019-03-19 | 天津大学 | A method of high-content graphene nanometer sheet/carbon/carbon-copper composite material is prepared in situ |
| CN109897985A (en) * | 2019-03-05 | 2019-06-18 | 天津工业大学 | Three-dimensional continuous graphite alkene/carbon/carbon-copper composite material and preparation method thereof |
| CN110172607A (en) * | 2019-04-11 | 2019-08-27 | 全球能源互联网欧洲研究院 | A kind of preparation method of graphene enhancing Cu tailings |
| CN110125385A (en) * | 2019-04-15 | 2019-08-16 | 中国航发北京航空材料研究院 | A kind of preparation method of the graphene Cu-base composites based on fabricated in situ |
| CN110453107A (en) * | 2019-08-01 | 2019-11-15 | 天津大学 | Graphene-tungsten carbide collaboration enhancing Cu-base composites preparation method |
| CN115522095A (en) * | 2021-06-24 | 2022-12-27 | 上海交通大学 | In-situ interface modification method of graphene-copper-based composite material |
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