WO2022253114A1 - Method for preparing bright high-conductivity graphene/copper composite material - Google Patents

Method for preparing bright high-conductivity graphene/copper composite material Download PDF

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WO2022253114A1
WO2022253114A1 PCT/CN2022/095458 CN2022095458W WO2022253114A1 WO 2022253114 A1 WO2022253114 A1 WO 2022253114A1 CN 2022095458 W CN2022095458 W CN 2022095458W WO 2022253114 A1 WO2022253114 A1 WO 2022253114A1
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deposition
graphene
copper
composite material
deposition solution
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PCT/CN2022/095458
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French (fr)
Chinese (zh)
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魏坤霞
王少鹏
魏伟
储富强
杜庆柏
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常州大学
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    • 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
    • C25D3/38—Electroplating: Baths therefor from solutions 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
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • 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
    • 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
    • C25D7/0614—Strips or foils
    • 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
    • H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal

Definitions

  • the invention belongs to the technical field of signal transmission, and in particular relates to a preparation method of a bright high-conductivity graphene/copper composite material.
  • the purpose of the present invention is to provide a graphene/copper deposition solution and electrodeposition method with reasonable ratio, green environmental protection, cost saving and controllable coating thickness, so as to prepare a bright high Conductive graphene/copper composites.
  • Graphene is known as an ideal reinforcement material for metal matrix composites because of its superior mechanical properties (Young's modulus of single-layer graphene reaches 1TPa and tensile strength reaches 130GPa). Evenly disperse graphene in copper sulfate pentahydrate solution to form copper sulfate pentahydrate/graphene composite electrodeposition solution. On the one hand, it can not only improve the material performance, but on the other hand, the deposition solution can be recycled and save costs.
  • the graphene/copper composite material is prepared by using the deposition solution provided by the invention in conjunction with the process of the invention, and the obtained graphene/copper composite coating has a flat and bright surface, uniform thickness, high bonding strength with the substrate, and is not easy to fall off.
  • a kind of preparation method of bright type highly conductive graphene/copper composite material, concrete implementation is as follows:
  • the deposition solution A is composed according to the mass concentration: copper sulfate pentahydrate 100-200g/L, graphene 0.1-0.8g/L, sodium lauryl sulfate 0.1-0.8g/L, gelatin 5-25mg/L, and The amount is deionized water;
  • the preparation method of electrodeposition solution A is: mix graphene with sodium lauryl sulfate for ultrasonic dispersion, and then perform high-speed homogeneous dispersion at a speed of 3000-6000r/min; mix gelatin with copper sulfate pentahydrate solution for mechanical After stirring, mix with the graphene solution, and then use an electric mixer to stir and disperse uniformly at high speed to obtain the deposition solution A.
  • the deposition solution B is composed according to the mass concentration: 100-200 g/L of copper sulfate pentahydrate, 3-20 mg/L of polyacrylamide, 6-40 mg/L of thiourea, and the balance is deionized water.
  • the preparation method of electrodeposition solution B is: mix polyacrylamide and thiourea for ultrasonic dispersion, mix with copper sulfate pentahydrate, use electric mixer to stir and high-speed homogeneous dispersion, the speed is 1000-3000r/min, to obtain deposition solution B .
  • the direct current electrodeposition method is used for electrodeposition, and the deposition method is alternate deposition liquid deposition.
  • the process parameters in the electrodeposition process are: the temperature of the electrodeposition solution is 20-35° C., and the pH is 1-3.
  • the deposition method in the electrodeposition process is alternate deposition solution deposition, that is, first deposit in deposition solution A for 20-60 minutes, wash and dry in absolute ethanol and deionized water, and then deposit in deposition solution B for 10-30 minutes to obtain bright type highly conductive graphene/copper composites.
  • the composite material prepared by the method of the invention is a wire or a foil material, the electrical conductivity is 61-115% IACS, and the surface roughness (Ra) is 0.807-4.211 ⁇ m.
  • the coating adhesion test refer to and meet the standard of the Ministry of Aerospace Industry of the People's Republic of China - Copper Coating Technical Conditions (QJ454-88), the coating does not appear peeling, peeling off, etc., indicating that the coating adhesion is good.
  • the present invention has the following advantages compared with the prior art:
  • the invention provides a graphene/copper deposition solution with reasonable proportion, cost saving and controllable coating thickness, and an electrodeposition method.
  • the invention adopts the alternate deposition method, on the one hand, to increase the conductivity of the composite material, and on the other hand, to reduce the surface roughness of the composite material through the leveling effect of the deposition liquid, thereby reducing the loss of high-frequency signals during transmission.
  • the process parameters and coating thickness of the graphene/copper composite material are controllable during the preparation process, and can be directly applied to industrial production preparation.
  • Figure 1 is a process flow chart for preparing bright and highly conductive graphene/copper composite materials by electrodeposition.
  • the graphene/copper deposition solution is called A, and it consists of: copper sulfate pentahydrate 100g/L, graphene 0.1g/L, gelatin 5mg/L, sodium lauryl sulfate 0.1g/L, and the balance by mass concentration It is deionized water; the pure copper deposition solution is called B, which is composed of copper sulfate pentahydrate 100g/L, polyacrylamide 3mg/L, thiourea 6mg/L, and the balance is deionized water.
  • the electrodeposition process environment is: the temperature of the deposition solution is 20° C., and the pH of the deposition solution is 3.
  • the method used is direct current electrodeposition, and the deposition method is alternate deposition solution deposition, that is, deposit in deposition solution A for 20 minutes, wash and dry in absolute ethanol and deionized water, and then deposit in deposition solution B for 10 minutes.
  • the surface of the prepared graphene/copper composite wire is basically flat, the coating thickness is uniform, the surface roughness (Ra) is 2.675 ⁇ m, the leveling ability of the deposition solution is 3.1%, and the conductivity of the composite wire is 87% IACS.
  • the prepared bright high-conductivity graphene/copper composite wire is bent several times at any position, referring to and reaching the standard of the Ministry of Aerospace Industry of the People's Republic of China-copper coating technical conditions (QJ454-88), the results show that 5 times of 90° After bending, the plating layer did not appear to peel off or fall off, indicating that the plating layer has good adhesion.
  • the graphene/copper deposition solution is called A, and it is composed of copper sulfate pentahydrate 120g/L, graphene 0.2g/L, gelatin 10mg/L, sodium lauryl sulfate 0.2g/L, and the balance It is deionized water;
  • the pure copper deposition solution is called B, which is composed of copper sulfate pentahydrate 120g/L, polyacrylamide 6mg/L, thiourea 12mg/L, and the balance is deionized water.
  • the electrodeposition process environment is as follows: the temperature of the deposition solution is 25° C., and the pH of the deposition solution is 2.5.
  • the method used is direct current electrodeposition, and the deposition method is alternate deposition solution deposition, that is, deposit in deposition solution A for 30 minutes, wash and dry in absolute ethanol and deionized water, and then deposit in deposition solution B for 15 minutes.
  • the surface of the graphene/copper composite wire prepared under such a ratio, process environment and electrodeposition parameters is flat and bright, the thickness of the coating is uniform, the surface roughness (Ra) is 2.583 ⁇ m, and the leveling ability of the deposition solution is 6.4%.
  • the composite wire The conductivity is 93% IACS.
  • the plating layer did not peel off or fall off, indicating that the bonding force of the plating layer was good.
  • the graphene/copper deposition solution is called A, and it consists of: copper sulfate pentahydrate 140g/L, graphene 0.4g/L, gelatin 15mg/L, sodium lauryl sulfate 0.4g/L, and the balance by mass concentration It is deionized water; the pure copper deposition solution is called B, which is composed of copper sulfate pentahydrate 140g/L, polyacrylamide 10mg/L, thiourea 20mg/L, and the balance is deionized water.
  • the electrodeposition process environment is: the temperature of the deposition solution is 30° C., and the pH of the deposition solution is 2.
  • the method used is direct current electrodeposition, and the deposition method is alternate deposition solution deposition, that is, deposit in deposition solution A for 40 minutes, wash and dry with absolute ethanol and deionized water, and then deposit in deposition solution B for 20 minutes.
  • the surface of the graphene/copper composite wire prepared under such a ratio, process environment and electrodeposition parameters is flat and bright, the thickness of the coating is uniform, the surface roughness (Ra) is 2.373 ⁇ m, and the leveling ability of the deposition solution is 14.1%.
  • the composite wire The conductivity is 96% IACS. In addition, after the composite wire was bent 5 times at 90° at any position, the coating did not peel off or fall off, indicating that the coating had good adhesion.
  • the graphene/copper deposition solution is called A, and it is composed of copper sulfate pentahydrate 200g/L, graphene 0.6g/L, gelatin 20mg/L, sodium lauryl sulfate 0.6g/L, and the balance It is deionized water;
  • the pure copper deposition solution is called B, which is composed of copper sulfate pentahydrate 100g/L, polyacrylamide 20mg/L, thiourea 30mg/L, and the balance is deionized water.
  • the electrodeposition process environment is: the temperature of the deposition solution is 30° C., and the pH of the deposition solution is 1.
  • the method used is direct current electrodeposition method, and the deposition method is alternate deposition solution deposition, that is, first deposit in deposition solution A for 25 minutes, wash and dry in absolute ethanol and deionized water, and then deposit in deposition solution B for 15 minutes.
  • the surface of the graphene/copper composite wire prepared under such a ratio, process environment and electrodeposition parameters is flat and bright, the thickness of the coating is uniform, the surface roughness (Ra) is 1.497 ⁇ m, and the leveling ability of the deposition solution is 45.8%.
  • the composite wire The conductivity is 115% IACS. In addition, after the composite wire was bent 90° five times at any position, the coating did not peel off or fall off, indicating that the coating had good adhesion.
  • the graphene/copper deposition solution is called A, and it is composed of copper sulfate pentahydrate 200g/L, graphene 0.8g/L, gelatin 20mg/L, sodium lauryl sulfate 0.8g/L, and the balance It is deionized water;
  • the pure copper deposition solution is called B, which is composed of copper sulfate pentahydrate 100g/L, polyacrylamide 20mg/L, thiourea 20mg/L, and the balance is deionized water.
  • the electrodeposition process environment is: the temperature of the deposition solution is 35° C., and the pH of the deposition solution is 1.
  • the method used is direct current electrodeposition, and the deposition method is alternate deposition solution deposition, that is, deposit in deposition solution A for 30 minutes, wash and dry with absolute ethanol and deionized water, and then deposit in deposition solution B for 25 minutes.
  • the surface of the graphene/copper composite wire prepared under such a ratio, process environment and electrodeposition parameters is flat and bright, the thickness of the coating is uniform, the surface roughness (Ra) is 1.885 ⁇ m, and the leveling ability of the deposition solution is 31.8%.
  • the composite wire The conductivity is 111% IACS. In addition, after the composite wire was bent 90° five times at any position, the coating did not peel off or fall off, indicating that the coating had good adhesion.
  • the graphene/copper deposition solution is called A, and it consists of: copper sulfate pentahydrate 200g/L, graphene 0.6g/L, gelatin 20mg/L, sodium lauryl sulfate 0.6g/L, and the balance by mass concentration It is deionized water; the pure copper deposition solution is called B, which is composed of copper sulfate pentahydrate 100g/L, polyacrylamide 20mg/L, thiourea 30mg/L, and the balance is deionized water.
  • the electrodeposition process environment is: the temperature of the deposition solution is 30° C., and the pH of the deposition solution is 2.
  • the method used is direct current electrodeposition method, and the deposition method is alternate deposition solution deposition, that is, first deposit in deposition solution A for 25 minutes, wash and dry in absolute ethanol and deionized water, and then deposit in deposition solution B for 15 minutes.
  • the surface of the graphene/copper composite wire prepared under such a ratio, process environment and electrodeposition parameters is flat and bright, the thickness of the coating is uniform, the surface roughness (Ra) is 2.053 ⁇ m, and the leveling ability of the deposition solution is 25.7%.
  • the composite wire The conductivity is 106% IACS. In addition, after the composite wire was bent 90° five times at any position, the coating did not peel off or fall off, indicating that the coating had good adhesion.
  • the graphene/copper deposition solution is called A, and it consists of: copper sulfate pentahydrate 200g/L, graphene 0.6g/L, gelatin 20mg/L, sodium lauryl sulfate 0.6g/L, and the balance by mass concentration It is deionized water; the pure copper deposition solution is called B, which is composed of copper sulfate pentahydrate 100g/L, polyacrylamide 25mg/L, thiourea 30mg/L, and the balance is deionized water.
  • the electrodeposition process environment is: the temperature of the deposition solution is 30° C., and the pH of the deposition solution is 1.
  • the method used is direct current electrodeposition method, and the deposition method is alternate deposition solution deposition, that is, first deposit in deposition solution A for 25 minutes, wash and dry in absolute ethanol and deionized water, and then deposit in deposition solution B for 15 minutes.
  • the surface of the graphene/copper composite wire prepared under such a ratio, process environment and electrodeposition parameters is smooth and bright, the thickness of the coating is uniform, the surface roughness (Ra) is 2.217 ⁇ m, and the leveling ability of the deposition solution is 19.7%.
  • the composite wire The conductivity is 103% IACS. In addition, after the composite wire was bent 90° five times at any position, the coating did not peel off or fall off, indicating that the coating had good adhesion.
  • the graphene/copper deposition solution is called A, and it consists of: copper sulfate pentahydrate 200g/L, graphene 0.6g/L, gelatin 20mg/L, sodium lauryl sulfate 0.6g/L, and the balance by mass concentration It is deionized water; the pure copper deposition solution is called B, which is composed of copper sulfate pentahydrate 100g/L, polyacrylamide 20mg/L, thiourea 30mg/L, and the balance is deionized water.
  • the electrodeposition process environment is: the temperature of the deposition solution is 30° C., and the pH of the deposition solution is 1.5.
  • the method used is direct current electrodeposition method, and the deposition method is alternate deposition solution deposition, that is, first deposit in deposition solution A for 25 minutes, wash and dry in absolute ethanol and deionized water, and then deposit in deposition solution B for 15 minutes.
  • the graphene/copper composite foil prepared under such a ratio, process environment and electrodeposition parameters has a flat and bright surface, a uniform coating thickness, a surface roughness (Ra) of 0.807 ⁇ m, and a leveling ability of the deposition solution of 47.3%.
  • the composite foil The conductivity is 110% IACS. In addition, after the composite foil was bent 90° five times at any position, the coating did not peel off or fall off, indicating that the coating had good adhesion.
  • the graphene/copper deposition solution is called A, and it consists of: copper sulfate pentahydrate 100g/L, graphene 0.1g/L, gelatin 5mg/L, sodium lauryl sulfate 0.1g/L, and the balance by mass concentration for deionized water.
  • the electrodeposition process environment is: the temperature of the deposition solution is 20° C., and the pH of the deposition solution is 3.
  • the method adopted is the direct current electrodeposition method, and the deposition method is to deposit only in the deposition solution A for 30 minutes.
  • the graphene/copper composite wire prepared under such a ratio, process environment and electrodeposition parameters has a large number of raised particles on the surface, the thickness of the coating is uneven, the surface roughness (Ra) is 2.668 ⁇ m, and the leveling ability of the deposition solution is 3.4 %, the conductivity of the composite wire is 76% IACS.
  • the coating of the composite wire 50 times and bending 90° five times at the same position some parts of the coating appeared peeling or falling off, indicating that the bonding force of the coating was poor.
  • the pure copper deposition solution is called B, which is composed of copper sulfate pentahydrate 100g/L, polyacrylamide 20mg/L, thiourea 30mg/L, and the balance is deionized water.
  • the electrodeposition process environment is: the temperature of the deposition solution is 30° C., and the pH of the deposition solution is 1.
  • the method adopted is the direct current electrodeposition method, and the deposition method is only deposited in the deposition solution B for 40 minutes.
  • the surface of the graphene/copper composite wire prepared under such a ratio, process environment and electrodeposition parameters is smooth, the thickness of the coating is uniform, the surface roughness (Ra) is 2.266 ⁇ m, the leveling ability of the deposition solution is 18%, and the composite wire is conductive.
  • the rate is 99% IACS.
  • the coating did not peel off or fall off, indicating that the coating had good adhesion.
  • the pure copper deposition solution is called A, and it is composed of copper sulfate pentahydrate 200g/L, gelatin 20mg/L, sodium lauryl sulfate 0.8g/L, and the balance is deionized water; graphene/copper
  • the deposition solution is called B, which is composed of copper sulfate pentahydrate 100g/L, graphene 0.8g/L, polyacrylamide 20mg/L, thiourea 20mg/L, and the balance is deionized water.
  • the electrodeposition process environment is: the temperature of the deposition solution is 35° C., and the pH of the deposition solution is 1.
  • the method used is direct current electrodeposition, and the deposition method is alternate deposition solution deposition, that is, deposit in deposition solution B for 30 minutes, and then deposit in deposition solution A for 25 minutes after washing and drying with absolute ethanol and deionized water.
  • the graphene/copper composite wire prepared under such a ratio, process environment and electrodeposition parameters has many raised particles on the surface, the thickness of the coating is uneven, the surface roughness (Ra) is 3.088 ⁇ m, and the leveling ability of the deposition solution is -11.8%, the conductivity of the composite wire is 77% IACS.
  • the coating part appeared peeling or falling off, indicating that the bonding force of the coating was poor.
  • graphene/copper deposition solution which consists of: copper sulfate pentahydrate 280g/L, graphene 0.4g/L, gelatin 15mg/L, sodium lauryl sulfate 0.4g/L, polyacrylamide 10mg according to mass concentration /L, thiourea 20mg/L, and the balance is deionized water.
  • the electrodeposition process environment is: the temperature of the deposition solution is 30° C., and the pH of the deposition solution is 2.
  • the method used is the direct current electrodeposition method, and the deposition time is 60 minutes.
  • the graphene/copper composite wire prepared under such a ratio, process environment and electrodeposition parameters has a large number of protruding particles on the surface, the thickness of the coating is uneven and the color is black, the surface roughness (Ra) is 4.211 ⁇ m, and the deposition solution is uniform.
  • the leveling capacity is -52.5%, and the conductivity of the composite wire is 61% IACS.
  • the composite wire was bent 5 times at 90° at any position, most of the plating layer appeared peeling or falling off, indicating that the bonding force of the plating layer was poor.

Abstract

The present invention belongs to the technical field of signal transmission, and particularly relates to a method for preparing a bright high-conductivity graphene/copper composite material. In view of the technical problem of bright high-conductivity graphene/copper composite materials being difficult to prepare, provided are a green and environmentally friendly cost-saving graphene/copper deposition solution with a rational ratio and a controllable plating thickness, and an electrodeposition method for preparing a bright high-conductivity graphene/copper composite material having high bonding strength to a substrate and having a smooth surface. First, a graphene/copper deposition solution A containing gelatin and sodium lauryl sulfate as additives is prepared; and then, a pure copper deposition solution B containing polyacrylamide and thiourea as additives is prepared. Deposition is performed by means of alternately depositing the deposition solutions, so as to obtain a bright high-conductivity graphene/copper composite material. The composite material prepared in the present invention has relatively high conductivity while having a smooth and bright surface; in addition, the plating layer has a uniform thickness, the bonding strength to a substrate is high, and the composite material is less prone to being peeled off and detaching.

Description

一种光亮型高导电石墨烯/铜复合材料的制备方法A kind of preparation method of bright type highly conductive graphene/copper composite material 技术领域technical field
本发明属于信号传输技术领域，具体涉及一种光亮型高导电石墨烯/铜复合材料的制备方法。The invention belongs to the technical field of signal transmission, and in particular relates to a preparation method of a bright high-conductivity graphene/copper composite material.
背景技术Background technique
在当今时代，随着5G通信、云计算、大数据等技术的迅速发展，大批量数据的高速传输和实时处理已经成为瓶颈技术。在PCB中铜导体的趋肤效应和高密度化发展带来的铜导线尺寸细小化(导线的粗糙度占比率越来越大)，因此信号高速/高频化使信号传输越来越集中于导线“表层”，其结果使信号传输在粗糙度层发生“驻波”、“反射”等造成传输信号损失或“失真”，严重时会造成信号传输失败，因此应采用合适的方法来降低铜导线表面粗糙度从而减少高频信号传输过程中的损耗。In today's era, with the rapid development of 5G communication, cloud computing, big data and other technologies, high-speed transmission and real-time processing of large quantities of data has become a bottleneck technology. The skin effect of the copper conductor in the PCB and the development of high density bring about the miniaturization of the size of the copper wire (the roughness of the wire is increasing), so the high-speed/high-frequency signal makes the signal transmission more and more concentrated The "surface layer" of the wire, as a result, the "standing wave" and "reflection" of the signal transmission in the roughness layer will cause the loss or "distortion" of the transmission signal, and in severe cases, the signal transmission will fail. Therefore, appropriate methods should be used to reduce copper The roughness of the wire surface reduces the loss during high-frequency signal transmission.
目前，石墨烯/金属基复合材料的制备方法有很多种，主要包括粉末冶金法、化学气相沉积法和电沉积法等多种方法，其中，电沉积法是通过氧化还原反应的方式将石墨烯均匀的沉积在金属基体表面，具有工艺简单、镀层厚度可控等优点，但电沉积法还存在以下问题：(1)电沉积液成分及工艺参数会直接影响制备的复合材料的组织和性能；(2)石墨镀层与基体结合较差，易脱落、易氧化，这些问题限制了电沉积法在制备石墨烯/金属基复合材料方面的应用。At present, there are many methods for preparing graphene/metal matrix composites, mainly including powder metallurgy, chemical vapor deposition, and electrodeposition. Uniform deposition on the surface of the metal substrate has the advantages of simple process and controllable coating thickness, but the electrodeposition method still has the following problems: (1) The composition and process parameters of the electrodeposition solution will directly affect the structure and performance of the prepared composite material; (2) The graphite coating is poorly bonded to the substrate, and is easy to fall off and oxidize. These problems limit the application of the electrodeposition method in the preparation of graphene/metal matrix composites.
发明内容Contents of the invention
本发明的目的在于提供一种配比合理、绿色环保、节约成本、镀层厚度可控的石墨烯/铜沉积液以及电沉积方法，从而制备一种与基体结合强度高且表面平整的光亮型高导电石墨烯/铜复合材料。The purpose of the present invention is to provide a graphene/copper deposition solution and electrodeposition method with reasonable ratio, green environmental protection, cost saving and controllable coating thickness, so as to prepare a bright high Conductive graphene/copper composites.
石墨烯因其优越的机械性能(单层石墨烯杨氏模量达到1TPa，抗拉强度达到130GPa)被称为金属基复合材料理想的增强体材料。将石墨烯均匀分散在五水合硫酸铜溶液中，形成五水合硫酸铜/石墨烯复合电沉积液，一方面既可以提升材料性能，另一方面，沉积液可以循环使用、节约成本。使用本发明提供的沉积液配合本发明的工艺制备石墨烯/铜复合材料，获得的石墨烯/铜复合材料镀层表面平整光亮，厚度均匀，且与基体结合强度高，不易脱落。Graphene is known as an ideal reinforcement material for metal matrix composites because of its superior mechanical properties (Young's modulus of single-layer graphene reaches 1TPa and tensile strength reaches 130GPa). Evenly disperse graphene in copper sulfate pentahydrate solution to form copper sulfate pentahydrate/graphene composite electrodeposition solution. On the one hand, it can not only improve the material performance, but on the other hand, the deposition solution can be recycled and save costs. The graphene/copper composite material is prepared by using the deposition solution provided by the invention in conjunction with the process of the invention, and the obtained graphene/copper composite coating has a flat and bright surface, uniform thickness, high bonding strength with the substrate, and is not easy to fall off.
本发明的技术解决方案是：Technical solution of the present invention is:
一种光亮型高导电石墨烯/铜复合材料的制备方法，具体实施如下：A kind of preparation method of bright type highly conductive graphene/copper composite material, concrete implementation is as follows:
(1)配制石墨烯/铜沉积液，称为A，其中，将明胶和十二烷基硫酸钠作为添加剂加入到A中；(1) prepare graphene/copper deposition liquid, be referred to as A, wherein, gelatin and sodium lauryl sulfate are joined in A as additive;
沉积液A按照质量浓度的组成为：五水合硫酸铜100～200g/L，石墨烯0.1～0.8g/L，十二烷基硫酸钠0.1～0.8g/L，明胶5～25mg/L，余量为去离子水；The deposition solution A is composed according to the mass concentration: copper sulfate pentahydrate 100-200g/L, graphene 0.1-0.8g/L, sodium lauryl sulfate 0.1-0.8g/L, gelatin 5-25mg/L, and The amount is deionized water;
电沉积溶液A的配制方法为：将石墨烯与十二烷基硫酸钠混合进行超声分散，再进行高速匀质分散，速度为3000～6000r/min；将明胶与五水合硫酸铜溶液混合进行机械搅拌后再与石墨烯溶液混合，然后采用电动搅拌机搅拌及高速匀质分散，得到沉积液A。The preparation method of electrodeposition solution A is: mix graphene with sodium lauryl sulfate for ultrasonic dispersion, and then perform high-speed homogeneous dispersion at a speed of 3000-6000r/min; mix gelatin with copper sulfate pentahydrate solution for mechanical After stirring, mix with the graphene solution, and then use an electric mixer to stir and disperse uniformly at high speed to obtain the deposition solution A.
(2)配制纯铜沉积液，称为B，其中，将聚丙烯酰胺和硫脲作为添加剂加入到B中；(2) preparing a pure copper deposition solution, called B, wherein polyacrylamide and thiourea are added to B as additives;
沉积液B按照质量浓度的组成为：五水合硫酸铜100～200g/L，聚丙烯酰胺3～20mg/L，硫脲6～40mg/L，余量去离子水。The deposition solution B is composed according to the mass concentration: 100-200 g/L of copper sulfate pentahydrate, 3-20 mg/L of polyacrylamide, 6-40 mg/L of thiourea, and the balance is deionized water.
电沉积溶液B的配制方法为：将聚丙烯酰胺和硫脲混合进行超声分散后与五水合硫酸铜混合，采用电动搅拌机搅拌及高速匀质分散，速度为1000-3000r/min，得到沉积液B。The preparation method of electrodeposition solution B is: mix polyacrylamide and thiourea for ultrasonic dispersion, mix with copper sulfate pentahydrate, use electric mixer to stir and high-speed homogeneous dispersion, the speed is 1000-3000r/min, to obtain deposition solution B .
(3)采用直流电沉积法进行电沉积，沉积方式为交替沉积液沉积。(3) The direct current electrodeposition method is used for electrodeposition, and the deposition method is alternate deposition liquid deposition.
电沉积过程中的工艺参数为：电沉积液温度20～35℃，pH为1～3。The process parameters in the electrodeposition process are: the temperature of the electrodeposition solution is 20-35° C., and the pH is 1-3.
电沉积过程中的沉积方式为交替沉积液沉积，即先在沉积液A中沉积20～60min，经无水乙醇和去离子水清洗烘干后再在沉积液B中沉积10～30min，得到光亮型高导电石墨烯/铜复合材料。The deposition method in the electrodeposition process is alternate deposition solution deposition, that is, first deposit in deposition solution A for 20-60 minutes, wash and dry in absolute ethanol and deionized water, and then deposit in deposition solution B for 10-30 minutes to obtain bright type highly conductive graphene/copper composites.
本发明方法制备的复合材料为导线或箔材，导电率为61～115％IACS，表面粗糙度(Ra)为0.807～4.211μm。经过镀层结合力测试，参考并达到中华人民共和国航天工业部标准-铜镀层技术条件(QJ454-88)，镀层未出现剥离、脱落等现象，说明镀层结合力良好。The composite material prepared by the method of the invention is a wire or a foil material, the electrical conductivity is 61-115% IACS, and the surface roughness (Ra) is 0.807-4.211 μm. After the coating adhesion test, refer to and meet the standard of the Ministry of Aerospace Industry of the People's Republic of China - Copper Coating Technical Conditions (QJ454-88), the coating does not appear peeling, peeling off, etc., indicating that the coating adhesion is good.
由于上述技术方案的运用，本发明与现有技术相比具有下列优点：Due to the application of the above-mentioned technical solution, the present invention has the following advantages compared with the prior art:
本发明提供了一种配比合理、节约成本、镀层厚度可控的石墨烯/铜沉积液，以及电沉积方法。本发明采用交替沉积方式一方面可以提高复合材料的导电率，另一方面可以通过沉积液整平作用降低复合材料表面粗糙度，从而可以减少高频信号在传输过程中的损耗。此外，石墨烯/铜复合材料在制备过程中工艺参数及镀层厚度可控，可直接应用于工业生产制备。The invention provides a graphene/copper deposition solution with reasonable proportion, cost saving and controllable coating thickness, and an electrodeposition method. The invention adopts the alternate deposition method, on the one hand, to increase the conductivity of the composite material, and on the other hand, to reduce the surface roughness of the composite material through the leveling effect of the deposition liquid, thereby reducing the loss of high-frequency signals during transmission. In addition, the process parameters and coating thickness of the graphene/copper composite material are controllable during the preparation process, and can be directly applied to industrial production preparation.
附图说明Description of drawings
图1为电沉积法制备光亮型高导电石墨烯/铜复合材料的工艺流程图。Figure 1 is a process flow chart for preparing bright and highly conductive graphene/copper composite materials by electrodeposition.
具体实施方式Detailed ways
下面结合实施例对本发明作进一步详述，这些实施仅用于说明本发明而不用于限制本发明范围：以下实施例均以配制1L的沉积液为例。The present invention will be further described in detail below in conjunction with the examples, and these implementations are only used to illustrate the present invention and are not intended to limit the scope of the present invention: the following examples all take the preparation of 1 L of deposition solution as an example.
实施例1Example 1
石墨烯/铜沉积液称为A，其按质量浓度组成为：五水合硫酸铜100g/L，石墨烯0.1g/L，明胶5mg/L，十二烷基硫酸钠0.1g/L，余量为去离子水；纯铜沉 积液称为B，其按质量浓度组成为：五水合硫酸铜100g/L，聚丙烯酰胺3mg/L，硫脲6mg/L，余量为去离子水。The graphene/copper deposition solution is called A, and it consists of: copper sulfate pentahydrate 100g/L, graphene 0.1g/L, gelatin 5mg/L, sodium lauryl sulfate 0.1g/L, and the balance by mass concentration It is deionized water; the pure copper deposition solution is called B, which is composed of copper sulfate pentahydrate 100g/L, polyacrylamide 3mg/L, thiourea 6mg/L, and the balance is deionized water.
电沉积工艺环境为：沉积液温度20℃，沉积液pH为3。采用的方法为直流电沉积法，沉积方式为交替沉积液沉积，即先在沉积液A中沉积20min，经无水乙醇和去离子水清洗烘干后再在沉积液B中沉积10min。The electrodeposition process environment is: the temperature of the deposition solution is 20° C., and the pH of the deposition solution is 3. The method used is direct current electrodeposition, and the deposition method is alternate deposition solution deposition, that is, deposit in deposition solution A for 20 minutes, wash and dry in absolute ethanol and deionized water, and then deposit in deposition solution B for 10 minutes.
制备的石墨烯/铜复合导线表面基本平整，镀层厚度均匀，表面粗糙度(Ra)为2.675μm，沉积液整平能力为3.1％，复合导线导电率为87％IACS。The surface of the prepared graphene/copper composite wire is basically flat, the coating thickness is uniform, the surface roughness (Ra) is 2.675 μm, the leveling ability of the deposition solution is 3.1%, and the conductivity of the composite wire is 87% IACS.
将制备的光亮型高导电石墨烯/铜复合导线在任意位置进行数次弯折，参考并达到中华人民共和国航天工业部标准-铜镀层技术条件(QJ454-88)，结果表明，5次90°弯折后镀层未出现剥离、脱落等现象，说明镀层结合力良好。The prepared bright high-conductivity graphene/copper composite wire is bent several times at any position, referring to and reaching the standard of the Ministry of Aerospace Industry of the People's Republic of China-copper coating technical conditions (QJ454-88), the results show that 5 times of 90° After bending, the plating layer did not appear to peel off or fall off, indicating that the plating layer has good adhesion.
其中，沉积液整平能力L的测试方法为粗糙度法,其中L＝(R-R 0)/R，R为基体电沉积前的粗糙度，R 0为电沉积后镀层的粗糙度。 Among them, the test method of the leveling ability L of the deposition solution is the roughness method, where L=(RR 0 )/R, R is the roughness of the substrate before electrodeposition, and R 0 is the roughness of the coating after electrodeposition.
实施例2Example 2
石墨烯/铜沉积液称为A,其按质量浓度组成为：五水合硫酸铜120g/L，石墨烯0.2g/L，明胶10mg/L，十二烷基硫酸钠0.2g/L，余量为去离子水；纯铜沉积液称为B，其按质量浓度组成为：五水合硫酸铜120g/L，聚丙烯酰胺6mg/L，硫脲12mg/L，余量为去离子水。The graphene/copper deposition solution is called A, and it is composed of copper sulfate pentahydrate 120g/L, graphene 0.2g/L, gelatin 10mg/L, sodium lauryl sulfate 0.2g/L, and the balance It is deionized water; the pure copper deposition solution is called B, which is composed of copper sulfate pentahydrate 120g/L, polyacrylamide 6mg/L, thiourea 12mg/L, and the balance is deionized water.
电沉积工艺环境为：沉积液温度25℃，沉积液pH为2.5。采用的方法为直流电沉积法，沉积方式为交替沉积液沉积，即先在沉积液A中沉积30min，经无水乙醇和去离子水清洗烘干后再在沉积液B中沉积15min。The electrodeposition process environment is as follows: the temperature of the deposition solution is 25° C., and the pH of the deposition solution is 2.5. The method used is direct current electrodeposition, and the deposition method is alternate deposition solution deposition, that is, deposit in deposition solution A for 30 minutes, wash and dry in absolute ethanol and deionized water, and then deposit in deposition solution B for 15 minutes.
在此种配比及工艺环境和电沉积参数下制备的石墨烯/铜复合导线表面平整光亮，镀层厚度均匀，表面粗糙度(Ra)为2.583μm，沉积液整平能力为6.4％,复合导线导电率为93％IACS。此外将复合导线在任意位置进行5次90°弯折后， 镀层未出现剥离或脱落现象，说明镀层结合力良好。The surface of the graphene/copper composite wire prepared under such a ratio, process environment and electrodeposition parameters is flat and bright, the thickness of the coating is uniform, the surface roughness (Ra) is 2.583 μm, and the leveling ability of the deposition solution is 6.4%. The composite wire The conductivity is 93% IACS. In addition, after the composite wire was bent at 90° five times at any position, the plating layer did not peel off or fall off, indicating that the bonding force of the plating layer was good.
实施例3Example 3
石墨烯/铜沉积液称为A，其按质量浓度组成为：五水合硫酸铜140g/L，石墨烯0.4g/L，明胶15mg/L，十二烷基硫酸钠0.4g/L，余量为去离子水；纯铜沉积液称为B,其按质量浓度组成为：五水合硫酸铜140g/L，聚丙烯酰胺10mg/L，硫脲20mg/L，余量为去离子水。The graphene/copper deposition solution is called A, and it consists of: copper sulfate pentahydrate 140g/L, graphene 0.4g/L, gelatin 15mg/L, sodium lauryl sulfate 0.4g/L, and the balance by mass concentration It is deionized water; the pure copper deposition solution is called B, which is composed of copper sulfate pentahydrate 140g/L, polyacrylamide 10mg/L, thiourea 20mg/L, and the balance is deionized water.
电沉积工艺环境为：沉积液温度30℃，沉积液pH为2。采用的方法为直流电沉积法，沉积方式为交替沉积液沉积，即先在沉积液A中沉积40min，经无水乙醇和去离子水清洗烘干后再在沉积液B中沉积20min。The electrodeposition process environment is: the temperature of the deposition solution is 30° C., and the pH of the deposition solution is 2. The method used is direct current electrodeposition, and the deposition method is alternate deposition solution deposition, that is, deposit in deposition solution A for 40 minutes, wash and dry with absolute ethanol and deionized water, and then deposit in deposition solution B for 20 minutes.
在此种配比及工艺环境和电沉积参数下制备的石墨烯/铜复合导线表面平整光亮，镀层厚度均匀，表面粗糙度(Ra)为2.373μm，沉积液整平能力为14.1％，复合导线导电率为96％IACS。此外将复合导线在任意位置进行5次90°弯折后，镀层未出现剥离或脱落现象，说明镀层结合力良好。The surface of the graphene/copper composite wire prepared under such a ratio, process environment and electrodeposition parameters is flat and bright, the thickness of the coating is uniform, the surface roughness (Ra) is 2.373 μm, and the leveling ability of the deposition solution is 14.1%. The composite wire The conductivity is 96% IACS. In addition, after the composite wire was bent 5 times at 90° at any position, the coating did not peel off or fall off, indicating that the coating had good adhesion.
实施例4Example 4
石墨烯/铜沉积液称为A,其按质量浓度组成为：五水合硫酸铜200g/L，石墨烯0.6g/L，明胶20mg/L，十二烷基硫酸钠0.6g/L，余量为去离子水；纯铜沉积液称为B,其按质量浓度组成为：五水合硫酸铜100g/L，聚丙烯酰胺20mg/L，硫脲30mg/L，余量为去离子水。The graphene/copper deposition solution is called A, and it is composed of copper sulfate pentahydrate 200g/L, graphene 0.6g/L, gelatin 20mg/L, sodium lauryl sulfate 0.6g/L, and the balance It is deionized water; the pure copper deposition solution is called B, which is composed of copper sulfate pentahydrate 100g/L, polyacrylamide 20mg/L, thiourea 30mg/L, and the balance is deionized water.
电沉积工艺环境为：沉积液温度30℃，沉积液pH为1。采用的方法为直流电沉积法，沉积方式为交替沉积液沉积，即先在沉积液A中沉积25min，经无水乙醇和去离子水清洗烘干后再在沉积液B中沉积15min。The electrodeposition process environment is: the temperature of the deposition solution is 30° C., and the pH of the deposition solution is 1. The method used is direct current electrodeposition method, and the deposition method is alternate deposition solution deposition, that is, first deposit in deposition solution A for 25 minutes, wash and dry in absolute ethanol and deionized water, and then deposit in deposition solution B for 15 minutes.
在此种配比及工艺环境和电沉积参数下制备的石墨烯/铜复合导线表面平整光亮，镀层厚度均匀，表面粗糙度(Ra)为1.497μm，沉积液整平能力为45.8％， 复合导线导电率为115％IACS。此外将复合导线在任意位置进行5次90°弯折后，镀层未出现剥离或脱落现象，说明镀层结合力良好。The surface of the graphene/copper composite wire prepared under such a ratio, process environment and electrodeposition parameters is flat and bright, the thickness of the coating is uniform, the surface roughness (Ra) is 1.497 μm, and the leveling ability of the deposition solution is 45.8%. The composite wire The conductivity is 115% IACS. In addition, after the composite wire was bent 90° five times at any position, the coating did not peel off or fall off, indicating that the coating had good adhesion.
实施例5Example 5
石墨烯/铜沉积液称为A,其按质量浓度组成为：五水合硫酸铜200g/L，石墨烯0.8g/L，明胶20mg/L，十二烷基硫酸钠0.8g/L，余量为去离子水；纯铜沉积液称为B,其按质量浓度组成为：五水合硫酸铜100g/L，聚丙烯酰胺20mg/L，硫脲20mg/L，余量为去离子水。The graphene/copper deposition solution is called A, and it is composed of copper sulfate pentahydrate 200g/L, graphene 0.8g/L, gelatin 20mg/L, sodium lauryl sulfate 0.8g/L, and the balance It is deionized water; the pure copper deposition solution is called B, which is composed of copper sulfate pentahydrate 100g/L, polyacrylamide 20mg/L, thiourea 20mg/L, and the balance is deionized water.
电沉积工艺环境为：沉积液温度35℃，沉积液pH为1。采用的方法为直流电沉积法，沉积方式为交替沉积液沉积，即先在沉积液A中沉积30min，经无水乙醇和去离子水清洗烘干后再在沉积液B中沉积25min。The electrodeposition process environment is: the temperature of the deposition solution is 35° C., and the pH of the deposition solution is 1. The method used is direct current electrodeposition, and the deposition method is alternate deposition solution deposition, that is, deposit in deposition solution A for 30 minutes, wash and dry with absolute ethanol and deionized water, and then deposit in deposition solution B for 25 minutes.
在此种配比及工艺环境和电沉积参数下制备的石墨烯/铜复合导线表面平整光亮，镀层厚度均匀，表面粗糙度(Ra)为1.885μm，沉积液整平能力为31.8％，复合导线导电率为111％IACS。此外将复合导线在任意位置进行5次90°弯折后，镀层未出现剥离或脱落现象，说明镀层结合力良好。The surface of the graphene/copper composite wire prepared under such a ratio, process environment and electrodeposition parameters is flat and bright, the thickness of the coating is uniform, the surface roughness (Ra) is 1.885 μm, and the leveling ability of the deposition solution is 31.8%. The composite wire The conductivity is 111% IACS. In addition, after the composite wire was bent 90° five times at any position, the coating did not peel off or fall off, indicating that the coating had good adhesion.
实施例6Example 6
石墨烯/铜沉积液称为A，其按质量浓度组成为：五水合硫酸铜200g/L，石墨烯0.6g/L，明胶20mg/L，十二烷基硫酸钠0.6g/L，余量为去离子水；纯铜沉积液称为B,其按质量浓度组成为：五水合硫酸铜100g/L，聚丙烯酰胺20mg/L，硫脲30mg/L，余量为去离子水。The graphene/copper deposition solution is called A, and it consists of: copper sulfate pentahydrate 200g/L, graphene 0.6g/L, gelatin 20mg/L, sodium lauryl sulfate 0.6g/L, and the balance by mass concentration It is deionized water; the pure copper deposition solution is called B, which is composed of copper sulfate pentahydrate 100g/L, polyacrylamide 20mg/L, thiourea 30mg/L, and the balance is deionized water.
电沉积工艺环境为：沉积液温度30℃，沉积液pH为2。采用的方法为直流电沉积法，沉积方式为交替沉积液沉积，即先在沉积液A中沉积25min，经无水乙醇和去离子水清洗烘干后再在沉积液B中沉积15min。The electrodeposition process environment is: the temperature of the deposition solution is 30° C., and the pH of the deposition solution is 2. The method used is direct current electrodeposition method, and the deposition method is alternate deposition solution deposition, that is, first deposit in deposition solution A for 25 minutes, wash and dry in absolute ethanol and deionized water, and then deposit in deposition solution B for 15 minutes.
在此种配比及工艺环境和电沉积参数下制备的石墨烯/铜复合导线表面平 整光亮，镀层厚度均匀，表面粗糙度(Ra)为2.053μm，沉积液整平能力为25.7％，复合导线导电率为106％IACS。此外将复合导线在任意位置进行5次90°弯折后，镀层未出现剥离或脱落现象，说明镀层结合力良好。The surface of the graphene/copper composite wire prepared under such a ratio, process environment and electrodeposition parameters is flat and bright, the thickness of the coating is uniform, the surface roughness (Ra) is 2.053 μm, and the leveling ability of the deposition solution is 25.7%. The composite wire The conductivity is 106% IACS. In addition, after the composite wire was bent 90° five times at any position, the coating did not peel off or fall off, indicating that the coating had good adhesion.
实施例7Example 7
石墨烯/铜沉积液称为A，其按质量浓度组成为：五水合硫酸铜200g/L，石墨烯0.6g/L，明胶20mg/L，十二烷基硫酸钠0.6g/L，余量为去离子水；纯铜沉积液称为B，其按质量浓度组成为：五水合硫酸铜100g/L，聚丙烯酰胺25mg/L，硫脲30mg/L，余量为去离子水。The graphene/copper deposition solution is called A, and it consists of: copper sulfate pentahydrate 200g/L, graphene 0.6g/L, gelatin 20mg/L, sodium lauryl sulfate 0.6g/L, and the balance by mass concentration It is deionized water; the pure copper deposition solution is called B, which is composed of copper sulfate pentahydrate 100g/L, polyacrylamide 25mg/L, thiourea 30mg/L, and the balance is deionized water.
电沉积工艺环境为：沉积液温度30℃，沉积液pH为1。采用的方法为直流电沉积法，沉积方式为交替沉积液沉积，即先在沉积液A中沉积25min，经无水乙醇和去离子水清洗烘干后再在沉积液B中沉积15min。The electrodeposition process environment is: the temperature of the deposition solution is 30° C., and the pH of the deposition solution is 1. The method used is direct current electrodeposition method, and the deposition method is alternate deposition solution deposition, that is, first deposit in deposition solution A for 25 minutes, wash and dry in absolute ethanol and deionized water, and then deposit in deposition solution B for 15 minutes.
在此种配比及工艺环境和电沉积参数下制备的石墨烯/铜复合导线表面平整光亮，镀层厚度均匀，表面粗糙度(Ra)为2.217μm，沉积液整平能力为19.7％，复合导线导电率为103％IACS。此外将复合导线在任意位置进行5次90°弯折后，镀层未出现剥离或脱落现象，说明镀层结合力良好。The surface of the graphene/copper composite wire prepared under such a ratio, process environment and electrodeposition parameters is smooth and bright, the thickness of the coating is uniform, the surface roughness (Ra) is 2.217 μm, and the leveling ability of the deposition solution is 19.7%. The composite wire The conductivity is 103% IACS. In addition, after the composite wire was bent 90° five times at any position, the coating did not peel off or fall off, indicating that the coating had good adhesion.
实施例8Example 8
石墨烯/铜沉积液称为A，其按质量浓度组成为：五水合硫酸铜200g/L，石墨烯0.6g/L，明胶20mg/L，十二烷基硫酸钠0.6g/L，余量为去离子水；纯铜沉积液称为B,其按质量浓度组成为：五水合硫酸铜100g/L，聚丙烯酰胺20mg/L，硫脲30mg/L，余量为去离子水。The graphene/copper deposition solution is called A, and it consists of: copper sulfate pentahydrate 200g/L, graphene 0.6g/L, gelatin 20mg/L, sodium lauryl sulfate 0.6g/L, and the balance by mass concentration It is deionized water; the pure copper deposition solution is called B, which is composed of copper sulfate pentahydrate 100g/L, polyacrylamide 20mg/L, thiourea 30mg/L, and the balance is deionized water.
电沉积工艺环境为：沉积液温度30℃，沉积液pH为1.5。采用的方法为直流电沉积法，沉积方式为交替沉积液沉积，即先在沉积液A中沉积25min，经无水乙醇和去离子水清洗烘干后再在沉积液B中沉积15min。The electrodeposition process environment is: the temperature of the deposition solution is 30° C., and the pH of the deposition solution is 1.5. The method used is direct current electrodeposition method, and the deposition method is alternate deposition solution deposition, that is, first deposit in deposition solution A for 25 minutes, wash and dry in absolute ethanol and deionized water, and then deposit in deposition solution B for 15 minutes.
在此种配比及工艺环境和电沉积参数下制备的石墨烯/铜复合箔表面平整光亮，镀层厚度均匀，表面粗糙度(Ra)为0.807μm，沉积液整平能力为47.3％，复合箔导电率为110％IACS。此外将复合箔在任意位置进行5次90°弯折后，镀层未出现剥离或脱落现象，说明镀层结合力良好。The graphene/copper composite foil prepared under such a ratio, process environment and electrodeposition parameters has a flat and bright surface, a uniform coating thickness, a surface roughness (Ra) of 0.807 μm, and a leveling ability of the deposition solution of 47.3%. The composite foil The conductivity is 110% IACS. In addition, after the composite foil was bent 90° five times at any position, the coating did not peel off or fall off, indicating that the coating had good adhesion.
对比实施例1Comparative Example 1
石墨烯/铜沉积液称为A，其按质量浓度组成为：五水合硫酸铜100g/L，石墨烯0.1g/L，明胶5mg/L，十二烷基硫酸钠0.1g/L，余量为去离子水。The graphene/copper deposition solution is called A, and it consists of: copper sulfate pentahydrate 100g/L, graphene 0.1g/L, gelatin 5mg/L, sodium lauryl sulfate 0.1g/L, and the balance by mass concentration for deionized water.
电沉积工艺环境为：沉积液温度20℃，沉积液pH为3。采用的方法为直流电沉积法，沉积方式为只在沉积液A中沉积30min。The electrodeposition process environment is: the temperature of the deposition solution is 20° C., and the pH of the deposition solution is 3. The method adopted is the direct current electrodeposition method, and the deposition method is to deposit only in the deposition solution A for 30 minutes.
在此种配比及工艺环境和电沉积参数下制备的石墨烯/铜复合导线表面有大量凸起颗粒，镀层厚度不均匀，表面粗糙度(Ra)为2.668μm，沉积液整平能力为3.4％，复合导线导电率为76％IACS。此外采用透明胶带对复合导线镀层进行50次粘贴及在同一位置进行5次90°弯折后，镀层部分位置出现剥离或脱落现象，说明镀层结合力较差。The graphene/copper composite wire prepared under such a ratio, process environment and electrodeposition parameters has a large number of raised particles on the surface, the thickness of the coating is uneven, the surface roughness (Ra) is 2.668 μm, and the leveling ability of the deposition solution is 3.4 %, the conductivity of the composite wire is 76% IACS. In addition, after using scotch tape to paste the coating of the composite wire 50 times and bending 90° five times at the same position, some parts of the coating appeared peeling or falling off, indicating that the bonding force of the coating was poor.
对比实施例2Comparative Example 2
纯铜沉积液称为B,其按质量浓度组成为：五水合硫酸铜100g/L，聚丙烯酰胺20mg/L，硫脲30mg/L，余量为去离子水。The pure copper deposition solution is called B, which is composed of copper sulfate pentahydrate 100g/L, polyacrylamide 20mg/L, thiourea 30mg/L, and the balance is deionized water.
电沉积工艺环境为：沉积液温度30℃，沉积液pH为1。采用的方法为直流电沉积法，沉积方式为只在沉积液B中沉积40min。The electrodeposition process environment is: the temperature of the deposition solution is 30° C., and the pH of the deposition solution is 1. The method adopted is the direct current electrodeposition method, and the deposition method is only deposited in the deposition solution B for 40 minutes.
在此种配比及工艺环境和电沉积参数下制备的石墨烯/铜复合导线表面平整，镀层厚度均匀，表面粗糙度(Ra)为2.266μm，沉积液整平能力为18％，复合导线导电率为99％IACS。此外将复合导线在任意位置进行5次90°弯折后，镀层未出现剥离或脱落现象，说明镀层结合力良好。The surface of the graphene/copper composite wire prepared under such a ratio, process environment and electrodeposition parameters is smooth, the thickness of the coating is uniform, the surface roughness (Ra) is 2.266 μm, the leveling ability of the deposition solution is 18%, and the composite wire is conductive. The rate is 99% IACS. In addition, after the composite wire was bent 90° five times at any position, the coating did not peel off or fall off, indicating that the coating had good adhesion.
对比实施例3Comparative Example 3
纯铜沉积液称为A，其按质量浓度组成为：五水合硫酸铜200g/L，明胶20mg/L，十二烷基硫酸钠0.8g/L，余量为去离子水；石墨烯/铜沉积液称为B，其按质量浓度组成为：五水合硫酸铜100g/L，石墨烯0.8g/L，聚丙烯酰胺20mg/L，硫脲20mg/L,余量为去离子水。The pure copper deposition solution is called A, and it is composed of copper sulfate pentahydrate 200g/L, gelatin 20mg/L, sodium lauryl sulfate 0.8g/L, and the balance is deionized water; graphene/copper The deposition solution is called B, which is composed of copper sulfate pentahydrate 100g/L, graphene 0.8g/L, polyacrylamide 20mg/L, thiourea 20mg/L, and the balance is deionized water.
电沉积工艺环境为：沉积液温度35℃，沉积液pH为1。采用的方法为直流电沉积法，沉积方式为交替沉积液沉积，即先在沉积液B中沉积30min，经无水乙醇和去离子水清洗烘干后再在沉积液A中沉积25min。The electrodeposition process environment is: the temperature of the deposition solution is 35° C., and the pH of the deposition solution is 1. The method used is direct current electrodeposition, and the deposition method is alternate deposition solution deposition, that is, deposit in deposition solution B for 30 minutes, and then deposit in deposition solution A for 25 minutes after washing and drying with absolute ethanol and deionized water.
在此种配比及工艺环境和电沉积参数下制备的石墨烯/铜复合导线表面有较多凸起颗粒，镀层厚度不均匀，表面粗糙度(Ra)为3.088μm，沉积液整平能力为-11.8％，复合导线导电率为77％IACS。此外将复合导线在任意位置进行5次90°弯折后，镀层部分位置出现剥离或脱落现象，说明镀层结合力较差。The graphene/copper composite wire prepared under such a ratio, process environment and electrodeposition parameters has many raised particles on the surface, the thickness of the coating is uneven, the surface roughness (Ra) is 3.088 μm, and the leveling ability of the deposition solution is -11.8%, the conductivity of the composite wire is 77% IACS. In addition, after the composite wire was bent 90° five times at any position, the coating part appeared peeling or falling off, indicating that the bonding force of the coating was poor.
对比实施例4Comparative Example 4
配制石墨烯/铜沉积液，其按质量浓度组成为：五水合硫酸铜280g/L，石墨烯0.4g/L，明胶15mg/L，十二烷基硫酸钠0.4g/L，聚丙烯酰胺10mg/L，硫脲20mg/L，余量为去离子水。Prepare graphene/copper deposition solution, which consists of: copper sulfate pentahydrate 280g/L, graphene 0.4g/L, gelatin 15mg/L, sodium lauryl sulfate 0.4g/L, polyacrylamide 10mg according to mass concentration /L, thiourea 20mg/L, and the balance is deionized water.
电沉积工艺环境为：沉积液温度30℃，沉积液pH为2。采用的方法为直流电沉积法，沉积时间60min。The electrodeposition process environment is: the temperature of the deposition solution is 30° C., and the pH of the deposition solution is 2. The method used is the direct current electrodeposition method, and the deposition time is 60 minutes.
在此种配比及工艺环境和电沉积参数下制备的石墨烯/铜复合导线表面有大量凸起颗粒，镀层厚度不均匀且颜色发黑，表面粗糙度(Ra)为4.211μm，沉积液整平能力为-52.5％，复合导线导电率为61％IACS。此外将复合导线在任意位置进行5次90°弯折后，镀层大部分位置出现剥离或脱落现象，说明镀层结合力较差。The graphene/copper composite wire prepared under such a ratio, process environment and electrodeposition parameters has a large number of protruding particles on the surface, the thickness of the coating is uneven and the color is black, the surface roughness (Ra) is 4.211 μm, and the deposition solution is uniform. The leveling capacity is -52.5%, and the conductivity of the composite wire is 61% IACS. In addition, after the composite wire was bent 5 times at 90° at any position, most of the plating layer appeared peeling or falling off, indicating that the bonding force of the plating layer was poor.
所选实例均为本发明优选的实施方式，但本发明并不限于上述实施方式，在不背离本发明的实质内容的情况下，本领域技术人员能够做出的任何显而易见的改进、替换或变形均属于本发明的保护范围。The selected examples are all preferred implementations of the present invention, but the present invention is not limited to the above-mentioned implementations, without departing from the essence of the present invention, any obvious improvement, replacement or deformation that those skilled in the art can make All belong to the protection scope of the present invention.

Claims (8)

  1. 一种光亮型高导电石墨烯/铜复合材料的制备方法，其特征在于：所述制备方法步骤如下：A preparation method of a bright high-conductivity graphene/copper composite material, characterized in that: the steps of the preparation method are as follows:
    (1)配制石墨烯/铜沉积液，称为A，并将明胶和十二烷基硫酸钠作为添加剂加入到A中；(1) prepare graphene/copper deposition liquid, be referred to as A, and gelatin and sodium lauryl sulfate are joined in A as additive;
    (2)配制纯铜沉积液，称为B，并将聚丙烯酰胺和硫脲作为添加剂加入到B中；(2) prepare pure copper deposition solution, called B, and polyacrylamide and thiourea are added in B as additives;
    (3)采用直流电沉积法进行沉积，沉积方式为交替沉积液沉积。(3) The direct current electrodeposition method is used for deposition, and the deposition method is alternate deposition liquid deposition.
  2. 根据权利要求1所述的光亮型高导电石墨烯/铜复合材料的制备方法，其特征在于：步骤(1)所述的沉积液A按照质量浓度的组成为：五水合硫酸铜100～200g/L，石墨烯0.1～0.8g/L，十二烷基硫酸钠0.1～0.8g/L，明胶5～25mg/L，余量为去离子水。According to the preparation method of bright type highly conductive graphene/copper composite material according to claim 1, it is characterized in that: the deposition liquid A described in step (1) is composed according to the mass concentration: copper sulfate pentahydrate 100～200g/ L, graphene 0.1-0.8g/L, sodium lauryl sulfate 0.1-0.8g/L, gelatin 5-25mg/L, and the balance is deionized water.
  3. 根据权利要求1所述的光亮型高导电石墨烯/铜复合材料的制备方法，其特征在于：步骤(2)所述沉积液B按照质量浓度的组成为：五水合硫酸铜100～200g/L，聚丙烯酰胺3～20mg/L，硫脲6～40mg/L，余量为去离子水。According to the preparation method of bright type high conductivity graphene/copper composite material according to claim 1, it is characterized in that: the composition of the deposition solution B in step (2) according to the mass concentration is: copper sulfate pentahydrate 100～200g/L , polyacrylamide 3~20mg/L, thiourea 6~40mg/L, and the balance is deionized water.
  4. 根据权利要求1所述的光亮型高导电石墨烯/铜复合材料的制备方法，其特征在于：步骤(1)所述的电沉积液的配置方法为：将石墨烯与十二烷基硫酸钠混合进行超声分散，再进行高速匀质分散，速度为3000～6000r/min；将明胶与五水合硫酸铜溶液混合进行机械搅拌后再与石墨烯溶液混合，然后采用电动搅拌机搅拌及高速匀质分散，得到沉积液A。The preparation method of bright type highly conductive graphene/copper composite material according to claim 1, characterized in that: the configuration method of the electrodeposition solution described in step (1) is: graphene and sodium lauryl sulfate Mixing for ultrasonic dispersion, followed by high-speed homogeneous dispersion at a speed of 3000-6000r/min; mixing gelatin with copper sulfate pentahydrate solution for mechanical stirring and then mixing with graphene solution, and then using an electric mixer for stirring and high-speed homogeneous dispersion , to obtain deposition solution A.
  5. 根据权利要求1所述的光亮型高导电石墨烯/铜复合材料的制备方法，其特征在于：步骤(2)所述电沉积液的配置方法为：将聚丙烯酰胺和硫脲混合进行超声分散后再与五水合硫酸铜混合，再采用电动搅拌机搅拌及高速匀质分散，速度为1000～3000r/min，得到沉积液B。The preparation method of bright type highly conductive graphene/copper composite material according to claim 1, characterized in that: the configuration method of the electrodeposition solution described in step (2) is: mixing polyacrylamide and thiourea for ultrasonic dispersion Then mix it with copper sulfate pentahydrate, and then use an electric mixer to stir and disperse uniformly at a high speed at a speed of 1000-3000r/min to obtain the deposition solution B.
  6. 根据权利要求1所述的光亮型高导电石墨烯/铜复合材料的制备方法，其特征在于：步骤(3)所述的电沉积过程中的工艺参数为：电沉积液温度20～35℃，pH为1～3。According to the preparation method of bright type highly conductive graphene/copper composite material according to claim 1, it is characterized in that: the process parameters in the electrodeposition process described in step (3) are: electrodeposition liquid temperature 20～35 ℃, The pH is 1-3.
  7. 根据权利要求1所述的光亮型高导电石墨烯/铜复合材料的制备方法，其特征在于：步骤(3)所述的电沉积过程中的沉积方式为交替沉积液沉积，即先在沉积液A中沉积20～60min，经无水乙醇和去离子水清洗烘干后再在沉积液B中沉积10～30min，得到光亮型高导电石墨烯/铜复合材料。The preparation method of bright type highly conductive graphene/copper composite material according to claim 1, characterized in that: the deposition method in the electrodeposition process described in step (3) is alternate deposition liquid deposition, that is, first in the deposition liquid Deposit in A for 20 to 60 minutes, wash and dry with absolute ethanol and deionized water, and then deposit in deposition solution B for 10 to 30 minutes to obtain a bright high-conductivity graphene/copper composite material.
  8. 根据权利要求1-7任一项所述方法制备的光亮型高导电石墨烯/铜复合材料，其特征在于：所述复合材料为导线或箔材，复合材料的导电率为61～115％IACS，表面粗糙度(Ra)为0.807～4.211μm。According to the bright type highly conductive graphene/copper composite material prepared by the method according to any one of claims 1-7, it is characterized in that: the composite material is a wire or foil material, and the conductivity of the composite material is 61 to 115% IACS , Surface roughness (Ra) is 0.807 ~ 4.211μm.
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