CN108396346A - A kind of preparation method and application of graphene copper/steel composite material - Google Patents
A kind of preparation method and application of graphene copper/steel composite material Download PDFInfo
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- CN108396346A CN108396346A CN201810114829.2A CN201810114829A CN108396346A CN 108396346 A CN108396346 A CN 108396346A CN 201810114829 A CN201810114829 A CN 201810114829A CN 108396346 A CN108396346 A CN 108396346A
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- graphene
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- composite material
- steel composite
- graphene copper
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Links
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 96
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 94
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 92
- 239000010949 copper Substances 0.000 title claims abstract description 92
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 68
- 239000010959 steel Substances 0.000 title claims abstract description 68
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims description 16
- 238000000034 method Methods 0.000 claims abstract description 31
- 238000009713 electroplating Methods 0.000 claims abstract description 29
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 15
- 238000007747 plating Methods 0.000 claims abstract description 14
- 239000004020 conductor Substances 0.000 claims abstract description 12
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 230000005540 biological transmission Effects 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- 239000004615 ingredient Substances 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 18
- 238000000576 coating method Methods 0.000 abstract description 18
- 230000001681 protective effect Effects 0.000 abstract description 4
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 239000003792 electrolyte Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- 210000001367 artery Anatomy 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 210000003462 vein Anatomy 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/18—Electroplating using modulated, pulsed or reversing current
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0607—Wires
Abstract
Electroplating bath components of the present invention include：220~280g/L of copper sulphate, 0.1~3.0g/L of graphene, 0.1~6.0g/ of nonionic surfactant and deionized water.It is using sinusoidal impulse, electrical parameter in electroplating process：Current density range is 500~3000A/m2, pulse current frequency 250Hz, pulse width 25s；The plating time used is 0.5~4.0h；The temperature of plating solution is 20~70 DEG C, and pH is 2.0~5.0.Copper sulphate graphene plating solution used is nontoxic, can be recycled, cost-effective, environmentally protective；The graphene copper coating surface of acquisition is bright, high with the bond strength of steel core wire；The volume ratio of graphene copper is 10~25% in obtained graphene copper/steel composite material, and the conductivity of composite material is apparently higher than traditional inner conductor copper-clad steel composite material, is suitable for making the coaxial cable inside conductor of transmission high-frequency signal.
Description
Technical field
The invention belongs to steel core wire surface fine chemical technology fields, and in particular to a kind of graphene copper/steel composite material
Preparation method and application.
Background technology
In recent years, with the rapid development of communication transmission facility, communication coaxial cable answering in terms of transmitting high-frequency signal
With more and more universal.Coaxial cable will produce kelvin effect when transmitting high-frequency signal, and kelvin effect is with the increasing of signal frequency
Add and increases.So-called kelvin effect refers to when frequency transmission signal is up to few kilohertz or up to ten thousand hertz, and signal will be same
The outer surface of shaft cable inner wire and the inner surface of outer conductor are transmitted；And signal frequency is higher, and skin depth is smaller.For
The effective rate of utilization of inner wire is improved, saves copper product, inner conductor is frequently with copper covered steel wire.Copper clad steel composite wood
Material is to coat the bimetallic material of layers of copper on the surface of steel, it is combined the high intensity of steel with the good electric conductivity of copper and corrosion resistance
Together.In addition, Copper covered steel material is also extensively used for power circuit, rail line and power cable shield circuit etc.
Field.
Currently, due to Copper covered steel material purposes and quality requirement difference, manufacturing technique method mainly has following 4 kinds：Electricity
Plating method, molten copper infusion process, double copper strips crimping and tube-weld cladding technique.Wherein, galvanoplastic are that copper is equably plated to the surface of steel.
Galvanoplastic are because it has the advantages that simple for process, copper consumption is less, production cost is low etc., so application range is relatively broad.But
There is also following deficiencies for galvanoplastic：1. being mixed with impurity in layers of copper, the electric conductivity of layers of copper is reduced；2. cyanide electroplate liquid is toxic,
It is unfavorable for environmental protection；3. the bond quality between layers of copper and steel core is poor.These disadvantages limit the application of galvanoplastic.
Traditional inner conductor is up to that (IACS is indicated at 20 DEG C 40%IACS with Copper covered steel material conductivity
International Annealed Copper Standard conductivity).It can be seen that the conductivity of traditional inner conductor copper clad steel is not high,
Need to be further improved its conductivity.
Invention content
The steel core reasonable, environmentally protective, cost-effective, thickness of coating is controllable is matched the purpose of the present invention is to provide a kind of
Line plates graphene copper solution, and uses it for preparing graphene copper/steel composite material to improve the conductivity of material.
Graphene because its superior mechanical performance (Young's modulus of 1TPa and the tensile strength of 130GPa), it is good electrically
(resistivity is about 10 to energy-6Ω cm) as the ideal reinforced phase of metal-base composites.Therefore, by graphene dispersion in (cyanogen
The substitute of compound solution) in copper-bath, copper sulphate-graphene electroplate liquid is formed, cyanide solution can be both eliminated
Harmfulness, and can be recycled, it is not only cost-effective but also environmentally protective.Copper sulphate-graphene electroplate liquid is used for steel core
Line is electroplated, and graphene copper/steel composite material is made, the graphene copper coating surface of acquisition is bright, and thickness is uniform, and and steel
The bond strength of core wire is high.In addition, the conductivity of the graphene copper/steel composite material obtained by this method significantly improves.
Technical solution of the invention is：
The preparation method of graphene copper/steel composite material, specific preparation method are as follows：
(1) electroplating solution of graphene copper/steel composite material is prepared；
(2) it uses the electroplating solution of step (1) that steel core wire is electroplated, graphene copper/steel composite material is made；Plating
Used in the process of pulse pattern be sinusoidal impulse.
Wherein, the electroplating solution of graphene copper/steel composite material of step (1), electroplating bath components press its mass concentration packet
It includes：220~280g/L of copper sulphate, 0.1~3.0g/L of graphene, 0.1~6.0g/L of nonionic surfactant, surplus be go from
Sub- water, wherein the mass ratio of graphene powder and nonionic surfactant is 1:1~1:2.
The preparation method of the electroplating solution of graphene copper/steel composite material is：By the graphene solution containing surfactant
It is mixed with copper/saturated copper sulphate solution, first high speed dispersor is used to stir after mixing, then carry out ultrasonic disperse, obtain graphene
The electroplating solution of copper/steel composite material.Such preparation method makes the copper ion in solution play barrier and separation graphene
Effect, prevent the reunion of graphene and dispersion uneven.
Used in step (2) electroplating process the electrical parameter of sinusoidal impulse for：Current density range is 500~3000A/m2,
Pulse current frequency is 250Hz, pulse width 25s.
The process environments of electroplating solution are：The temperature of electroplating solution controls between 20~70 DEG C, electroplating solution pH ranges
It is 2.0~5.0；Time used in electroplating process is 0.5~4.0h.
The pulse pattern of electroplating technology selection of the present invention is sinusoidal impulse.The common pulse of field of electroplating is rectangular pulse,
But according to rectangular pulse in electroplating process, current density can mutate (current density is bigger, and coating crystal grain is more tiny),
It is easy to keep coating microstructure uneven.And the present invention is electroplated using sinusoidal impulse, coating microstructure is uniform.
In addition, the present invention also controls graphite in graphene copper/steel composite material in electroplating process by adjusting plating solution pH
The volume ratio of alkene copper coating.
Copper sulphate-graphene plating solution used in the present invention is nontoxic, and plating solution proportioning is reasonable, can be recycled, not only saves into
This, and it is environmentally protective；It is bright with its graphene copper coating surface obtained and high with the bond strength of steel core wire.
The volume ratio of graphene copper is 10~25% in graphene copper/steel composite material produced by the present invention, and composite wood
The conductivity of material is apparently higher than traditional inner conductor copper-clad steel composite material, is suitable for making transmission high-frequency signal
Coaxial cable inside conductor.
Beneficial effects of the present invention：
(1) sinusoidal impulse is used in electroplating process so that graphene copper coating group in graphene copper/steel composite material
Knit more fine uniform.
(2) matrix of the invention is steel core wire, and biography can be become by carrying out graphene copper/steel composite material after electroplating processes
The coaxial cable inside conductor finished product of defeated high-frequency signal, needs not move through rolling and stretch processing, the not only cost-effective and time, but also prevents
The generation of defect.
(3) volume ratio of graphene copper is 10~25% in graphene copper/steel composite material, and the conductivity of composite material
It is apparently higher than traditional inner conductor copper-clad steel composite material, is suitable for making the coaxial cable of transmission high-frequency signal
Inside conductor.
Specific implementation mode
The present invention is described in further detail with reference to embodiment：Following embodiment is with the graphene copper electrolyte for configuring 1L
Example；
Embodiment 1
The concentration proportioning of graphene copper electrolyte is：Copper sulphate 220g/L, graphene 0.1g/L, nonionic surfactant
The mass ratio of 0.1g/L, graphene powder and nonionic surfactant is 1:1, surplus is deionized water；The technique ring of plating solution
Border is：20 DEG C of temperature, pH value of solution=5.0；Pulse electrical parameter is：Current density 500A/m2, pulse current frequency 250Hz, arteries and veins
It is 25s to rush width, and 0.5h is electroplated, the graphene copper coating surface light prepared under such proportioning and process environments and electrical parameter
Bright, no hole, thickness is uniform.The volume ratio of graphene copper is 10% in graphene copper/steel composite material of acquisition, and graphene
Copper coating and steel core wire interface cohesion are good；In addition, the conductivity of graphene copper/steel composite material is 50.7%IACS.
Embodiment 2
When the concentration proportioning of graphene copper electrolyte is：Copper sulphate 250g/L, graphene 1g/L, nonionic surfactant
The mass ratio of 1.5g/L, graphene and nonionic surfactant is 1:1.5, surplus is deionized water；The process environments of plating solution
For：40 DEG C of temperature, pH value of solution=3.0；Pulse electrical parameter is：Current density 1000A/m2, pulse current frequency 250Hz, arteries and veins
It is 25s to rush width, and 2h is electroplated, and the graphene copper coating surface prepared under such proportioning and process environments and electrical parameter is bright,
Without hole, thickness is uniform.The volume ratio of graphene copper is 15% in graphene copper/steel composite material of acquisition, and graphene copper
Coating and steel core wire interface cohesion are good；In addition, the conductivity of graphene copper/steel composite material is 58.8%IACS.
Embodiment 3
When the concentration proportioning of graphene copper electrolyte is：Copper sulphate 280g/L, graphene 2g/L, nonionic surfactant
The mass ratio of 4g/L, graphene and nonionic surfactant is 1:2, surplus is deionized water；The process environments of plating solution are：Temperature
60 DEG C of degree, pH value of solution=3.0；Pulse electrical parameter is：Current density 2000A/m2, pulse current frequency 250Hz, pulse width
For 25s, 2h is electroplated, the graphene copper coating surface prepared under such proportioning and process environments and electrical parameter is bright, no hole,
Thickness is uniform.The volume ratio of graphene copper is 20% in graphene copper/steel composite material of acquisition, and graphene copper coating and steel
Core wire interface cohesion is good；In addition, the conductivity of graphene copper/steel composite material is 65.5%IACS.
Embodiment 4
When the concentration proportioning of graphene copper electrolyte is：Copper sulphate 280g/L, graphene 3g/L, nonionic surfactant
The mass ratio of 6g/L, graphene and nonionic surfactant is 1:2, surplus is deionized water；The process environments of plating solution are：Temperature
70 DEG C of degree, pH value of solution=1.0；Pulse electrical parameter is：Current density 3000A/m2, pulse current frequency 250Hz, pulse width
For 25s, 4h is electroplated, the graphene copper coating surface prepared under such proportioning and process environments and electrical parameter is bright, no hole,
Thickness is uniform.The volume ratio of graphene copper is 25% in graphene copper/steel composite material of acquisition, and graphene copper coating and steel
Core wire interface cohesion is good；In addition, the conductivity of graphene copper/steel composite material is 70.6%IACS.
Comparative example 1
When the concentration proportioning of graphene copper electrolyte is：Copper sulphate 220g/L, graphene 0.1g/L, nonionic surfactant
The mass ratio of 0.1g/L, graphene and nonionic surfactant is 1:1, surplus is deionized water；The process environments of plating solution are：
20 DEG C of temperature, pH value of solution=5.0；The pulse electrical parameter of rectangular pulse is：Current density 500A/m2, pulse current frequency is
0.5h is electroplated in 250Hz, pulse width 25s, the graphene copper coating prepared under such proportioning and process environments and electrical parameter
Surface is dark, and tissue is coarse.The volume ratio of graphene copper is 10% in graphene copper/steel composite material of acquisition, conductivity
For 25.3%IACS.
The embodiment is the preferred embodiments of the present invention, but present invention is not limited to the embodiments described above, not
Away from the present invention substantive content in the case of, those skilled in the art can make it is any it is conspicuously improved, replace
Or modification all belongs to the scope of protection of the present invention.
Claims (8)
1. a kind of preparation method of graphene copper/steel composite material, it is characterised in that：The preparation method of the composite material is：
(1) electroplating solution of graphene copper/steel composite material is prepared；
(2) it uses the electroplating solution of step (1) that steel core wire is electroplated, graphene copper/steel composite material is made；Wherein, electric
Pulse pattern used in plating process is sinusoidal impulse.
2. the preparation method of graphene copper/steel composite material according to claim 1, it is characterised in that：Step (1) is described
The electroplating solution ingredient of graphene copper/steel composite material include：220~280g/L of copper sulphate, 0.1~3.0g/L of graphene,
0.1~6.0g/L of nonionic surfactant, surplus are deionized water, wherein graphene powder and nonionic surfactant
Mass ratio be 1:1~1:2.
3. the preparation method of graphene copper/steel composite material according to claim 2, it is characterised in that：Step (1) is described
The preparation method of electroplating solution of graphene copper/steel composite material be：By graphene solution and saturation containing surfactant
Copper-bath mixes, and first high speed dispersor is used to stir after mixing, then carries out ultrasonic disperse, it is multiple to obtain graphene copper/steel
The electroplating solution of condensation material.
4. the preparation method of graphene copper/steel composite material according to claim 1, it is characterised in that：Step (2) is described
Electroplating process in sinusoidal impulse electrical parameter be：Current density range is 500~3000A/m2, pulse current frequency is
250Hz, pulse width 25s.
5. the preparation method of graphene copper/steel composite material according to claim 1, it is characterised in that：Step (2) is described
The process environments of electroplating solution be：The temperature of electroplating solution controls between 20~70 DEG C, and electroplating solution pH ranging from 2.0~
5.0。
6. the preparation method of graphene copper/steel composite material according to claim 1, it is characterised in that：Step (2) is described
Electroplating process used in the time be 0.5~4.0h.
7. the preparation method of graphene copper/steel composite material according to claim 1, it is characterised in that：Step (2) is described
The volume ratio of graphene copper is 10~25% in graphene copper/steel composite material obtained.
8. the application of graphene copper/steel composite material made from a kind of method according to claim 1, it is characterised in that：Institute
State the coaxial cable inside conductor that graphene copper/steel composite material is suitable for making transmission high-frequency signal.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109972124A (en) * | 2019-04-22 | 2019-07-05 | 华南理工大学 | A method of copper-graphite alkene composite deposite is prepared on ABS plastic surface |
| CN110408976A (en) * | 2019-08-09 | 2019-11-05 | 常州大学 | A kind of graphene/nanometer twin composite material and preparation method controllable with tissue |
| CN110428939A (en) * | 2019-08-09 | 2019-11-08 | 常州大学 | A kind of preparation method of highly conductive graphene copper/aluminum complex lead |
| CN110802225A (en) * | 2019-10-11 | 2020-02-18 | 广州盛门新材料科技有限公司 | Preparation method of copper-coated graphene |
| CN111041542A (en) * | 2019-11-22 | 2020-04-21 | 上海交通大学 | Composite metal wire with composite electroplated nano carbon metal film and preparation method thereof |
| CN113293417A (en) * | 2021-06-03 | 2021-08-24 | 常州大学 | Preparation method of bright high-conductivity graphene/copper composite material |
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| CN103943170A (en) * | 2014-05-09 | 2014-07-23 | 浙江大学 | Conductor wire core of electric wire in nuclear-sheath structure and preparation method thereof |
| CN103943281A (en) * | 2014-05-09 | 2014-07-23 | 浙江大学 | Preparation method of electric wire and cable with copper-graphene complex phase conductive wire core |
| CN104087993A (en) * | 2014-06-30 | 2014-10-08 | 江西百川电导体有限公司 | Linear traction electro-deposition production technology for large-scale copper-clad steel wire rod used for grounding wire |
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2018
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| CN2196326Y (en) * | 1994-06-06 | 1995-05-03 | 姜荣行 | Steel wire transmission line coated with copper |
| CN103943170A (en) * | 2014-05-09 | 2014-07-23 | 浙江大学 | Conductor wire core of electric wire in nuclear-sheath structure and preparation method thereof |
| CN103943281A (en) * | 2014-05-09 | 2014-07-23 | 浙江大学 | Preparation method of electric wire and cable with copper-graphene complex phase conductive wire core |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109972124A (en) * | 2019-04-22 | 2019-07-05 | 华南理工大学 | A method of copper-graphite alkene composite deposite is prepared on ABS plastic surface |
| CN110408976A (en) * | 2019-08-09 | 2019-11-05 | 常州大学 | A kind of graphene/nanometer twin composite material and preparation method controllable with tissue |
| CN110428939A (en) * | 2019-08-09 | 2019-11-08 | 常州大学 | A kind of preparation method of highly conductive graphene copper/aluminum complex lead |
| WO2021027607A1 (en) * | 2019-08-09 | 2021-02-18 | 常州大学 | Preparation method for highly conductive graphene copper/aluminium composite wire |
| CN110408976B (en) * | 2019-08-09 | 2021-05-25 | 常州大学 | Graphene/nano twin crystal composite material with controllable tissue and preparation method thereof |
| CN110802225A (en) * | 2019-10-11 | 2020-02-18 | 广州盛门新材料科技有限公司 | Preparation method of copper-coated graphene |
| CN110802225B (en) * | 2019-10-11 | 2021-12-17 | 广州盛门新材料科技有限公司 | Preparation method of copper-coated graphene |
| CN111041542A (en) * | 2019-11-22 | 2020-04-21 | 上海交通大学 | Composite metal wire with composite electroplated nano carbon metal film and preparation method thereof |
| CN111041542B (en) * | 2019-11-22 | 2021-03-30 | 上海交通大学 | Composite metal wire with composite electroplated nano carbon metal film and preparation method thereof |
| CN113293417A (en) * | 2021-06-03 | 2021-08-24 | 常州大学 | Preparation method of bright high-conductivity graphene/copper composite material |
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| Publication number | Publication date |
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| CN108396346B (en) | 2020-02-14 |
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