CN114594120A - Preparation method of nitrogen-doped graphene/copper wire high-current-carrying composite material - Google Patents

Preparation method of nitrogen-doped graphene/copper wire high-current-carrying composite material Download PDF

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CN114594120A
CN114594120A CN202111653433.3A CN202111653433A CN114594120A CN 114594120 A CN114594120 A CN 114594120A CN 202111653433 A CN202111653433 A CN 202111653433A CN 114594120 A CN114594120 A CN 114594120A
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copper wire
nitrogen
doped graphene
composite material
current
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郑辉
邵辉顺
丁志文
徐海波
张阳
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Hangzhou Dianzi University
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Hangzhou Dianzi University
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
    • G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
    • G01N23/225—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material using electron or ion
    • G01N23/2251—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material using electron or ion using incident electron beams, e.g. scanning electron microscopy [SEM]
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65—Raman scattering
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
    • G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
    • G01N23/2202—Preparing specimens therefor
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
    • G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
    • G01N23/227—Measuring photoelectric effect, e.g. photoelectron emission microscopy [PEEM]
    • G01N23/2273—Measuring photoelectron spectrum, e.g. electron spectroscopy for chemical analysis [ESCA] or X-ray photoelectron spectroscopy [XPS]
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means

Abstract

The invention discloses a preparation method of a nitrogen-doped graphene/copper wire high-current-carrying composite material, which comprises the following steps of: (1) putting a copper wire with a certain diameter into a microwave tube furnace, and introducing hydrogen to perform annealing treatment; (2) plating the annealed copper wire obtained in the step (1) with a nano metal nickel film by electron beam evaporation; (3) coating silk fibroin organic carbon source on the surface of the obtained copper-nickel material by using a device shown in the following diagram, and drying; (4) and (4) putting the dried sample in the step (3) into a microwave tube furnace, starting vacuum, introducing nitrogen gas for plasma heat treatment, and converting silk fibroin into nitrogen-doped graphene and coating the nitrogen-doped graphene on the surface of a copper wire to obtain the nitrogen-doped graphene composite copper wire high-current-carrying composite material. The method solves the problem that the fibroin solution on the small-size filamentous material is difficult to be uniformly coated, ensures that the nitrogen-doped graphene converted from fibroin can uniformly coat the whole copper wire, and improves the current-carrying capacity of the copper wire.

Description

Preparation method of nitrogen-doped graphene/copper wire high-current-carrying composite material
Technical Field
The invention relates to the technical field of high current-carrying composite materials, in particular to a preparation method of a nitrogen-doped graphene/copper wire high current-carrying composite material.
Background
In recent years, with the miniaturization of electronic devices, the development of electronic devices is undergoing paradigm shift miniaturization, which makes electronic devices have greater portability and versatility. At the same time, the functionality and performance of these devices has increased. While the miniaturization of transistor memory devices can keep pace with practical needs, there has been slow progress in the development of conductors (e.g., copper and gold) that power components within the device. This results in higher current densities as device sizes shrink, reaching the limits of today's conventional conductor (e.g., Cu and Au) devices. In fact, the current density devices in these devices have already exceeded the breakdown limits of Cu and Au. Therefore, new conductors with higher current carrying capacity are in great demand.
The requirements of many emerging technical fields on copper materials are higher and higher, particularly, the requirements on high-current-carrying copper materials are greatly met, and one of the methods for realizing the high-strength high-current-carrying copper-based materials is to compound graphene with ultrahigh mechanical property and electrical property with copper to prepare the composite material.
Graphene has the characteristics of ultrahigh carrier mobility and far exceeding the maximum current-carrying capacity of copper, copper and copper alloy have the characteristics of excellent thermal conductivity, electrical conductivity, corrosion resistance and the like, so that the graphene becomes an important industrial metal, and on the basis of the graphene, the graphene is used as a reinforcement to form a novel composite material, so that the mechanical property, the wear resistance, the thermal conductivity, the electrical conductivity, the corrosion resistance and the like are greatly improved, and therefore, the graphene and a copper matrix can be compounded to obtain the composite material, so that the current-carrying capacity of the copper matrix is improved.
The key and difficult point of preparing the high current-carrying graphene/copper wire composite conductor lies in the problem of interface combination between copper and graphene, the wettability of copper wires is poor, so that copper and silk fibroin solution are difficult to coat together in the practical experiment process, and a layer of metal needs to be plated on the surface of copper to form a good interface so as to improve the current-carrying capacity of the graphene/copper wire composite conductor. According to the invention, a nickel film is plated on the surface of the copper wire by electron beam evaporation, so that the wettability of the copper wire is improved; the spinning of silk fibroin solution is carried out on the micron-sized copper wire by using the motor, the problem that the silk fibroin solution on the small-size silk-like material is difficult to paint uniformly is solved, the operation is safe and simple, the cost is low, the nitrogen-doped graphene converted from silk fibroin can be ensured to uniformly coat the whole copper wire, and the carrying capacity of the copper wire is improved.
Disclosure of Invention
The method solves the problems of the graphene copper wire composite technology in the prior art, solves the problem that the fibroin solution on the small-size filamentous material is difficult to uniformly coat, is safe and simple to operate and low in cost, ensures that the nitrogen-doped graphene converted from fibroin can uniformly coat the whole copper wire, and improves the carrying capacity of the graphene/copper wire composite material.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a nitrogen-doped graphene/copper wire high-current-carrying composite material comprises the following steps:
(1) putting a copper wire with a certain diameter into a microwave tube furnace, starting vacuum, and introducing hydrogen for annealing treatment;
(2) plating the annealed copper wire obtained in the step (1) with a nano metal nickel film by electron beam evaporation;
(3) coating silk fibroin solution on the surface of the copper-nickel wire material obtained in the step (2), and drying; the method comprises the following specific steps: two motors with the same power and the same rotating speed are aligned at the same height; a thick copper wire (with the diameter of 500-; welding a sample copper wire on the two motors by using a tin wire; uniformly coating the fibroin solution on the surface of a sample copper wire by using a rubber head dropper; the motor is electrified to realize the self transmission of the copper wire coated with silk fibroin along with the motor; and (5) ending the electrification, taking off the sample, and drying the sample based on the infrared baking lamp.
(4) And (4) putting the sample obtained in the step (3) into a microwave tube furnace, starting vacuum, introducing nitrogen gas for plasma heat treatment, converting silk fibroin into nitrogen-doped graphene and coating the nitrogen-doped graphene on the surface of the copper wire, and finally obtaining the graphene/copper wire composite material.
Preferably, in the step (1), the diameter of the copper wire is more than 20 microns, the hydrogen flow is controlled at 50sccm during annealing of the copper wire, the gas pressure is adjusted to 200-300 Pa, the microwave power is firstly adjusted to 1000W, preheating is carried out for 10 minutes, then the microwave power is adjusted to 1500W, and the reaction time is 15 min.
Preferably, in the step (2), when the nano metal nickel film is subjected to electron beam evaporation plating, the beam current of the electron beam is 150mA, the plating time is 3min, and the thickness of the nickel film is between 5 and 20 nm.
Preferably, in the step (3), the rotating speed of the motor is 17000r/h, the power supply time of the motor is 60s, and the baking time under the infrared baking lamp is 1 h.
Preferably, in the step (4), the flow rate of the nitrogen gas is controlled to be 50sccm, the gas pressure is adjusted to 2000-300 Pa, the microwave power is 2000W, and the reaction time is 25 min. The microwave power has a large influence on the growth of graphene, the higher the power is, the better the crystallinity of the graphene is, but the higher the power is, sp3 hybridization type defects can be generated.
Therefore, the invention has the following beneficial effects: compared with the traditional method, the method is simple and quick in process, steps are simple and steps, and compared with the traditional graphene composite copper wire material, the nitrogen-doped graphene can be uniformly distributed and coated on the surface of the copper wire, and the current carrying capacity is greatly improved.
Drawings
FIG. 1 is an SEM energy spectrum of the surface of the copper wire in example 1 after being plated with the nickel film by the electron beam. A layer of nickel film is deposited on the reaction copper wire and is used for improving the wettability between the graphene and the copper wire.
Fig. 2 is a macro topography, a surface SEM, a cross-section SEM and a raman spectrum of the nitrogen-doped graphene composite surface nickel-coated copper wire in example 1. The nitrogen-doped graphene is uniformly coated on the surface of the copper wire, a good interface is formed between the graphene and the copper wire, and the crystallinity of the graphene is good.
Fig. 3 is a current-carrying test V-I relationship diagram of the nitrogen-doped graphene composite copper wire material and the comparative pure copper wire in example 1.
Fig. 4 is a graph of current carrying values measured for a plurality of times for the nitrogen-doped graphene composite copper wire material and the comparative pure copper wire in example 1.
Fig. 5 is a schematic diagram of the principle of the preparation method of the nitrogen-doped graphene/copper wire high current-carrying composite material.
Detailed Description
The invention is further described with reference to the following figures and detailed description.
Example 1:
(1) as shown in FIG. 5, a copper wire with a diameter of 50 microns is placed in a microwave tube furnace, vacuum is started, hydrogen is introduced, the flow rate of the hydrogen is controlled at 50sccm, the air pressure is adjusted to 200-300 Pa, the microwave power is firstly adjusted to 1000W, preheating is carried out for 10 minutes, then, the microwave power is adjusted to 1500W, and the reaction time is 15 min.
(2) And (2) putting the annealed copper wire obtained in the step (1) into an electron beam evaporation coating device, putting a nickel target material, adjusting the beam current of an electron beam to 150mA, wherein the coating time is 3min, and the thickness of the nickel film is 5-20 nm.
(3) Two motors with the same power and the rotation speed of 17000r/h are placed on equal-height foam and aligned, and the two motors are welded together by a thick copper wire with the diameter of 500 mu m.
(4) And welding the copper wire plated with the nickel film on the two motors.
(5) Uniformly coating the fibroin solution on the surface of a sample copper wire by using a rubber head dropper, supplying power to the sample copper wire by using a No. 5 battery, spin-coating for 60s, disconnecting the connection, stopping supplying power, and taking down the battery.
(6) And (5) placing the sample under an infrared baking lamp for baking for 1 h.
(7) And (3) putting the sample subjected to the step (6) into a plasma microwave, and carrying out high-temperature high-pressure treatment for 25min in an atmosphere of nitrogen (the flow rate is controlled to be 50sccm), wherein the microwave power is 2000W.
(10) Its ampacity was measured by a 2651A digital source meter.
(2) After treatment, the SEM image and the energy spectrum are shown in FIG. 1; (9) after treatment, cooling and taking out a sample, thus obtaining the graphene composite copper wire high current-carrying material, wherein a macro topography picture, a surface SEM picture, a cross-section SEM picture, a Raman spectrum of graphene, a current-carrying test V _ I relation curve diagram and a current-carrying number multiple-measurement graph are respectively shown in figures 2, 3 and 4.
From fig. 1, it can be seen that a nickel film is deposited on the copper wire to improve the wettability between the graphene and the copper wire.
As can be seen from fig. 2, the nitrogen-doped graphene is uniformly coated on the surface of the copper wire, a good interface is formed between the graphene and the copper wire, and the crystallinity of the graphene is good.
From fig. 3 and 4, it can be seen that under the same size and the same processing conditions, the maximum current-carrying capacity of the graphene composite copper wire material is greatly improved compared with that of an annealed pure copper wire.
The above-described embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.

Claims (6)

1. A preparation method of a nitrogen-doped graphene/copper wire high-current-carrying composite material is characterized by comprising the following steps:
(1) putting a copper wire with a certain diameter into a microwave tube furnace, starting vacuum, and introducing hydrogen for annealing treatment;
(2) plating the annealed copper wire obtained in the step (1) with a nano metal nickel film by electron beam evaporation;
(3) coating silk fibroin solution on the surface of the copper-nickel wire material obtained in the step (2), and drying; the method comprises the following specific steps: two motors with the same power and the same rotating speed are aligned at the same height; a thick copper wire is fixed between the two motors for connection, so that the two motors can rotate at the same speed; welding a sample copper wire on the two motors by using a tin wire; uniformly coating the fibroin solution on the surface of a sample copper wire by using a rubber head dropper; the motor is electrified to realize the self transmission of the copper wire coated with silk fibroin along with the motor; after the electrification is finished, taking down the sample, and drying the sample based on an infrared drying lamp;
(4) and (4) putting the sample obtained in the step (3) into a microwave tube furnace, starting vacuum, introducing nitrogen gas for plasma heat treatment, converting silk fibroin into nitrogen-doped graphene and coating the nitrogen-doped graphene on the surface of the copper wire, and finally obtaining the graphene/copper wire composite material.
2. The preparation method of the nitrogen-doped graphene/copper wire high current-carrying composite material according to claim 1, wherein in the step (1), the diameter of the copper wire is larger than 20 micrometers, the hydrogen flow rate is controlled at 50sccm during annealing of the copper wire, the gas pressure is adjusted to 200-300 Pa, the microwave power is adjusted to 1000W, the copper wire is preheated for 10 minutes, then the microwave power is adjusted to 1500W, and the reaction time is 15 min.
3. The preparation method of the nitrogen-doped graphene/copper wire high current-carrying composite material according to claim 2, wherein in the step (2), the beam current of an electron beam is 150mA, the plating time is 3min, and the thickness of a nickel film is 5-20 nm.
4. The preparation method of the nitrogen-doped graphene/copper wire high current-carrying composite material according to claim 1, wherein in the step (3), the rotating speed of a motor is 17000r/h, the power supply time of the motor is 60s, and the baking time under an infrared baking lamp is 1 h.
5. The preparation method of the nitrogen-doped graphene/copper wire high current-carrying composite material according to claim 1, wherein in the step (4), the flow rate of nitrogen is controlled at 50sccm, the gas pressure is adjusted to 200-300 Pa, the microwave power is 2000W, and the reaction time is 25 min.
6. The method as claimed in claim 1, wherein in the step (3), the diameter of the copper wire is 500-1000 μm.
CN202111653433.3A 2021-12-30 2021-12-30 Preparation method of nitrogen-doped graphene/copper wire high-current-carrying composite material Pending CN114594120A (en)

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