CN110391035A - A kind of graphene/copper contact material and preparation method thereof - Google Patents

A kind of graphene/copper contact material and preparation method thereof Download PDF

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Publication number
CN110391035A
CN110391035A CN201810343832.1A CN201810343832A CN110391035A CN 110391035 A CN110391035 A CN 110391035A CN 201810343832 A CN201810343832 A CN 201810343832A CN 110391035 A CN110391035 A CN 110391035A
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graphene
copper powder
copper
contact material
powder body
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CN110391035B (en
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林正得
戴丹
江南
侯宝森
李双艺
褚伍波
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Ningbo Institute of Material Technology and Engineering of CAS
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Ningbo Institute of Material Technology and Engineering of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/14—Treatment of metallic powder
    • B22F1/142—Thermal or thermo-mechanical treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/14—Treatment of metallic powder
    • B22F1/145—Chemical treatment, e.g. passivation or decarburisation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form

Abstract

The present invention relates to a kind of graphene/copper contact materials and preparation method thereof.A kind of graphene that overall performance is very excellent/copper powder body material can be prepared using fluidized bed as reaction unit and using gas phase carbon source as reaction raw materials in the method.Further, the method is sinterable that a kind of graphene that comprehensive performance is very excellent/copper contact material is made using the graphene/copper powder body material as raw material.

Description

A kind of graphene/copper contact material and preparation method thereof
Technical field
The present invention relates to Material Fields, more particularly to a kind of graphene/copper contact material and preparation method thereof.
Background technique
Electrical contact is also referred to as contact, as important contact element in instrument and meter, electric switch.Electrical contact material palpus Meet various requirements such as mechanical property, electrical contact performance, chemical property, processing performance, specifically includes the conduction having had Property and thermal conductivity, low contact resistance, excellent resistance fusion welding can etc..Common electrical contact material is usually silver and silver-base alloy With copper and acid bronze alloy.Wherein, since silver-colored yield and resource are limited, silver and silver-base alloy higher cost, while silver and silver Based alloy easily vulcanizes, is easy to wear, and especially resistance fusion welding can be poor, in high load in use, electrical contact that surface may occur is molten Change condensation and cannot normally disconnect and accident occurs.Use copper and acid bronze alloy substitute silver and silver-base alloy as electrical contact material at For current fashion trend.
The electric conductivity and heating conduction of fine copper are also once used as electrical contact material, but pure all close to silver In use, intensity is easy decline to copper, and in addition its chemical property is more active than silver, and corrosion resistance is bad, is easy to happen table Face oxidation process, causes contact resistance to be gradually increased, and needs to develop suitable acid bronze alloy thus to solve the property that fine copper faces The bad problem of energy.
Acid bronze alloy is that another phase is introduced into Copper substrate to be prepared, and common electric contact material of copper-based alloy is copper Tungsten alloy, copper-tungsten have excellent electrical and thermal conductivity performance, can add other micro metals again thereto, can be into one Step improves its various aspects of performance, but the corrosion resistance of copper-tungsten is bad, the surface oxidation of copper oxide and tungsten oxide easy to form Layer reduces contact resistance.
Graphene is since discovery in 2004, with performances such as its excellent mechanical property and conductive and heat-conductives, causes extensively It attractes attention.Nearly ten years, graphene is used as reinforced phase to realize that the research of enhancing organism material emerges one after another.The hair of University Of Tianjin A kind of method (CN for preparing graphene/copper composite material in Copper Powder Surface supported solid carbon source with infusion process of bright patent 105081312 A) flake copper powder surface dip loading solid carbon source PMMA is used, graphene is grown in copper sheet surface in situ to prepare Graphene/copper powder compounded material, this method are needed to the disagreeableness organic solvent of environment.The patent of invention of University Of Tianjin is in copper The method (104874803 A of CN) that powder surface in situ catalytic solid carbon source prepares graphene/copper composite material is prepared by ball milling Polymethyl methacrylate, is then catalysed and reduced into tube furnace by finely dispersed copper-polymethylmethacrylate powder Graphene prepares graphene/copper composite powder.A kind of Novel high-conductivity of the patent of invention of Duan Mianjun etc., high strength graphite alkene/ Copper product and preparation method thereof (103614583 A of CN) utilizes ball milling mixing method explosive sintering mixed-powder, forms densification, With the composite material than fine copper higher intensity and conductivity.The patent of invention high-strength highly-conductive graphene of Institutes Of Technology Of Jiangxi is copper-based Composite material and preparation method (103952588 A of CN) is gone back in the sulfuric acid solution that graphene oxide is added with hydrazine hydrate Original goes out copper nanoparticle and graphene, restores under hydrogen atmosphere after dry, finally prepares graphene with plasma sintering method Cu-base composites.But that there are density is small due to graphene, is easy to reunite and the problems such as preparation process median surface combines, Constrain the development of graphene/metallic composite.
Summary of the invention
The purpose of the present invention is to provide a kind of graphene with excellent electrical and thermal conductivity performance/copper contact material and its Preparation method.
The first aspect of the present invention provides a kind of preparation method of graphene/copper contact material, the method includes Following steps:
1) copper powder is added in fluidized bed；
2) gas phase carbon source is passed through the fluidized bed after the methane cracking device of the fluidized bed is decomposed into hydrocarbon atom In；
3) fluidized gas is passed through into the fluidized bed to fluidize copper powder；
4) it under the action of the step 2) hydrocarbon atom and the step 3) fluidized gas, is heat-treated in the fluidized bed Copper powder through fluidizing obtains graphene/copper powder body material；
5) graphene described in sintering processes/copper powder body material obtains graphene/copper contact material.
In another preferred example, the cracking temperature of the gas phase carbon source is 800-1200 DEG C, preferably 900-1100 DEG C.
In another preferred example, the gas phase carbon source is selected from the group: methane, ethane, propane, ethylene, propylene, acetylene, third Alkynes, or combinations thereof.
In another preferred example, the partial size of the copper powder is 5nm-500 μm, preferably 8nm-200 μm, more preferably 10nm- 120μm。
In another preferred example, the partial size of the copper powder is 5nm-500nm, preferably 8nm-300nm, more preferably 10nm- 120nm。
In another preferred example, the partial size of the copper powder is 500nm-200 μm, preferably 800nm-150 μm, more preferably 10 μm -120 μm, more preferably 50 μm -110 μm.
In another preferred example, the shape of the copper powder is selected from the group: spherical, sheet, dendroid, spherical or its group It closes.
In another preferred example, the copper powder is selected from the group: electrolytic copper powder, atomized copper powder, bronze powder, brass powder or its Combination.
In another preferred example, in step 3), the fluidized gas is selected from the group: hydrogen, argon gas, nitrogen, helium, krypton Gas, or combinations thereof.
In another preferred example, in step 4), the treatment temperature of the heat treatment is 500-1000 DEG C, preferably 550- 900 DEG C, preferably 600-800 DEG C.
In another preferred example, in step 4), processing time of the heat treatment under the treatment temperature is 0.1-3 Hour, preferably 0.2-1 hours.
In another preferred example, it is further comprised the steps of: after step 4)
4 ') continue to be passed through fluidized gas, and stop being passed through the hydrocarbon atom, and stop heating the fluidized bed so that fluidisation The temperature of bed is quickly reduced to room temperature, and the graphene/copper powder body material is made.
In another preferred example, rate of temperature fall is 20 DEG C/min-300 DEG C/min, preferably 50 DEG C/min-200 DEG C/min, More preferably 100 DEG C/min-200 DEG C/min.
In another preferred example, rate of temperature fall is 20 DEG C/min-80 DEG C/min, preferably 30 DEG C/min-70 DEG C/min, more 40 DEG C/min-60 DEG C/min in good ground.
In another preferred example, described " room temperature " refers to 20-40 DEG C, preferably 25-35 DEG C.
In another preferred example, the graphene/copper powder body material has one or more features selected from the group below:
1) graphene/copper powder body material partial size be 5nm-500 μm, preferably 8nm-200 μm, more preferably 10nm-120 μm；
2) graphene/copper powder body material is coated on the graphite of the Copper Powder Surface comprising the copper powder as core and entirely Alkene clad；
3) graphene/copper powder body material conductivity is the 94%-99.9% of fine copper electrical conductivity of powdered material, preferably Ground is the 96%-99.9%, the more preferably 98%-99.9% for fine copper electrical conductivity of powdered material of fine copper electrical conductivity of powdered material；
4) graphene/copper powder body material thermal conductivity is the 94%-99.9% of fine copper powder material thermal conductivity, preferably Ground is the 96%-99.9%, the more preferably 98%-99.9% for fine copper powder material thermal conductivity of fine copper powder material thermal conductivity；
5) graphene/copper powder body material antioxygenic property is 3 times of the antioxygenic property of fine copper.
In another preferred example, the graphene/copper powder body material phosphorus content is 0.01-2wt%, preferably 0.05-0.9wt%, more preferably 0.1-0.5wt%.
In another preferred example, the graphene coated layer with a thickness of 0.03nm-3.5nm, preferably 0.05nm- 2.0nm, more preferably 0.06nm-1.0nm, most preferably 0.06nm-0.3nm.
In another preferred example, in step 5), the treatment temperature of the sintering processes is 800-1100 DEG C, preferably 850-1050℃。
In another preferred example, in step 5), processing time of the sintering processes under the treatment temperature is 0.1-3 hours, preferably 0.3-1 hours.
In another preferred example, in step 5), the sintering processes carry out under 1-100Pa back end vacuum, preferably 3-50Pa, more preferably 4-10Pa.
The second aspect of the present invention, provides a kind of graphene/copper contact material, and the contact material is using this The preparation of method described in invention first aspect.
In another preferred example, the contact material has one or more features selected from the group below:
1) conductivity of the contact material is 50MS/m-58MS/m, preferably 56MS/m-58MS/m, more preferably 57MS/m-58MS/m；
2) thermal conductivity of the contact material is 360W/mK-400W/mK, preferably 380W/mK-400W/mK, more Good ground 390W/mK-400W/mK；
3) coefficient of friction of the contact material is 0.01-0.2, preferably 0.03-0.15；
4) tensile strength of the contact material is 200-500MPa；
5) contact material under abrasive wear conditions 200 DEG C oxidation 24 hours after, the graphene/copper contact material Contact resistance be copper billet contact resistance 50%.
It should be understood that above-mentioned each technical characteristic of the invention and having in below (eg embodiment) within the scope of the present invention It can be combined with each other between each technical characteristic of body description, to form a new or preferred technical solution.As space is limited, In This no longer tires out one by one states.
Detailed description of the invention
Fig. 1 is graphene/copper powder body 1 Raman results.
Fig. 2 is copper powder (a) and graphene/copper powder body 1 (b) SEM result.
Fig. 3 is graphene/copper powder body C1 SEM result.
Specific embodiment
The present inventor's in-depth study by long-term, by adjusting graphene/copper powder body, preparation process is unexpectedly made It is standby to obtain a kind of graphene with excellent electrical and thermal conductivity performance/copper powder body.Specifically, by using fluidized bed as reaction dress It sets, and uses gas phase carbon source, a kind of powder of graphene uniform coated copper is prepared in the present invention, and the conductivity of the powder is high Up to the 99% of the conductivity of fine copper, thermal conductivity is up to the 98.7% of the thermal conductivity of fine copper, and the powder flows in a fluidized bed Change, is not easy to be bonded；Airflow field and uniform temperature fields are controllable, easily prepared high-quality graphene, and graphene is in the cladding of copper powder Area is up to 100%.The method does not have to addition dispersing agent, and graphene/copper powder purity is high of preparation is free from foreign meter.The stone Black alkene/copper powder body conductivity and thermal conductivity are all up to the 99% of fine copper.Further, by graphene described in sintering processes/ A kind of graphene/copper contact material of excellent combination property is prepared in copper powder body, the present invention.On this basis, inventor Complete the present invention.
Reaction unit-fluidized bed
Fluidized bed plant includes system of bf body, temperature system and air flow system.System of bf body includes furnace chamber system, fluidisation Bed system and methane cracking system.Furnace chamber system offer prepares environment, and fluidized system is to guarantee that copper powder is anti-under fluidized state It answers, forms good gas-solid contact, realize all standing of Copper Powder Surface graphene.Methane cracking system provides carbon source.Temperature system It is made of temperature elevation system and temperature control system, heating uses Segmented heating.In temperature control system, 4 points of fluidized bed center and outside Thermometric, it is ensured that temperature is uniform during the deposition process for coating, reaches Copper Powder Surface graphene coating uniformity.Jet system Including gas path pipe, valve and gas flow measurement and control module.
This preparation system has gaseous carbon sources cracker and fluidizer, guarantees that gaseous carbon sources are sufficiently split at high temperature Solution, prepares graphene/copper powder under low temperature and fluidized state, realizes all standing of Copper Powder Surface graphene, and the graphene of preparation/ Copper powder uniform, controllable.
Preparation method
Graphene/copper contact material method is prepared the present invention provides a kind of, described method includes following steps:
(1) copper powder is placed in fluidized bed；
(2) gaseous carbon sources (gas phase carbon source) are passed through the methane cracking device below fluidized bed, make gaseous carbon sources at high temperature Sufficiently it is cracked into carbon and hydrogen atom；
(3) carbon and hydrogen atom are passed through the fluidized bed；
(4) fluidized gas is passed through fluidized bed, under fluidization conditions so that fluidisation copper powder at low temperature with carbon, hydrogen atom into Row reaction；With
(5) optionally the copper powder is cooled down, so that graphene/copper powder body material of surface coated graphite alkene be made Material:
(6) graphene described in sintering processes/copper powder body material obtains the graphene/copper contact material.
In another preferred example, the copper is powder.
In another preferred example, (average) partial size of the copper powder be 10nm-1000 μm, preferably 20nm-800 μm, more 25nm-550 μm of good ground.
In another preferred example, the partial size of the copper powder is 10nm-920 μm.
In another preferred example, the purity of the copper powder is 99-99.99%, preferably 99.5-99.99%.
In another preferred example, the shape of the copper powder is selected from the group: spherical, sheet, dendroid, spherical.
In another preferred example, the copper powder is selected from the group: electrolytic copper powder, atomized copper powder, bronze powder, brass powder or its Combination.
In another preferred example, the gaseous carbon sources are selected from the group: methane, acetylene, ethane, propane, ethylene, propylene, third Alkynes, or combinations thereof.
In another preferred example, the temperature that the gaseous carbon sources sufficiently crack at high temperature is 800~1200 DEG C.
In another preferred example, the methane cracking device includes methane cracking chamber, is located at the intracavitary portion of the methane cracking Methane cracking heater strip and be connected with the methane cracking chamber gaseous carbon sources entrance and hydrocarbon atom outlet；Wherein, The hydrocarbon atom outlet is connected with the hydrocarbon atom entrance of the fluidized bed.
In another preferred example, the fluidized gas is argon gas and/or hydrogen.
In another preferred example, it is 400~800 DEG C that the copper powder Yu carbon, hydrogen atom of fluidisation, which carry out the temperature of low-temp reaction, compared with 600-800 DEG C of good ground.
In another preferred example, in step (6), the treatment temperature of the sintering processes is 700-1200 DEG C, preferably 750-1150℃。
In another preferred example, processing time of the sintering processes under the treatment temperature is 10-100min, preferably Ground 20-80min, more preferably 25-70min.
In another preferred example, the sintering processes are selected from the group: hot pressed sintering processing, cold-rolled sintered processing or its group It closes.
In another preferred example, in the graphene/copper powder body material, the graphene coated layer with a thickness of 0.03nm-3.5nm, preferably 0.05nm-2.0nm, more preferably 0.06nm-1.0nm, most preferably 0.06nm-0.3nm.
It should be understood that the method for the invention can effectively overcome existing graphene/copper contact material and its technology of preparing to deposit Deficiency, such as the disadvantages of resistance to oxidation does not cause not arc ablation resistance, graphene and weak copper interface binding power.
More specifically, the present invention integrates heated filament methane cracking device in fluidized bed CVD equipment, utilize tantalum wire (2200 DEG C) It cracks methane and generates high-activity carbon hydrogen compound active group, then high-activity carbon hydrogen compound active group is sent by low temperature by carrier gas In fluidizing chamber, it is made to reset to form graphene in intracavitary Copper Powder Surface.The temperature for fluidizing cavity is controlled at 700 DEG C hereinafter, remote low In the fusing point of copper, the adhesion problem of copper powder in high growth temperature technology is efficiently solved.And copper powder is living with height under fluidized state Property hydrocarbon active group forms comprehensive contact, solves the gas as caused by copper powder unsettled bulk in traditional CVD method The bad problem of affixed touching, realizes the uniform growth high-quality graphene coating on Copper Powder Surface.It reburns and forms graphene/copper electricity Contact composite material.The conductivity of the contact material is not less than the 97% of the conductivity of fine copper；And thermal conductivity is not less than The 98.2% of the thermal conductivity of fine copper；Under abrasive wear conditions 200 DEG C oxidation 24 hours after, the contact resistance of the contact material is small In the 60% of the contact resistance of copper billet.
Graphene/copper contact material
The present invention also provides a kind of graphene/copper contact material, the contact material is using the method system Standby.
In another preferred example, in the graphene/copper powder body material, packet of the graphene coated layer to the copper powder Rate >=95% is covered, preferably 98%, preferably 100% cladding.
In the present invention, due to as reaction unit and using gas phase carbon source, gained graphite using fluidized bed simultaneously In alkene/copper powder body material, the thickness of the graphene coated layer is highly uniform.
In another preferred example, the contact material has one or more features selected from the group below:
1) conductivity of the contact material is not less than the 97% of the conductivity of fine copper；
2) thermal conductivity of the contact material is not less than the 98.2% of the thermal conductivity of fine copper；
3) under abrasive wear conditions 200 DEG C after oxidation 24 hours, the contact resistance of the contact material is less than connecing for copper billet The 60% of electric shock resistance.
Compared with prior art, the present invention has following major advantage:
(1) the method as reaction unit and uses gas phase carbon source using fluidized bed, can prepare graphene uniform cladding The powder of copper；
(2) the method is due to, as reaction unit, can effectively avoid the bonding of copper powder in reaction process using fluidized bed；
(3) the method not only facilitates the bonding for avoiding copper powder in reaction process, more conducively due to using gas phase carbon source Prepare graphene/copper powder body of the high quality of overall performance stable homogeneous；
(4) the method has gaseous carbon compared to the preparation method for using gas phase carbon source in CVD furnace, this preparation system Source cracker and fluidizer guarantee that gaseous carbon sources crack at high temperature, prepare graphite under low temperature and copper powder fluidized state Alkene/copper powder guarantees that copper powder reacts under fluidized state, forms good gas-solid contact, realizes all standing of Copper Powder Surface graphene. And this preparation method does not have to dispersing agent, and finely dispersed graphene/copper powder of high-purity can be prepared under fluidized state.
(5) graphene/copper powder body has excellent electrical and thermal conductivity performance, mechanical performance, antioxygenic property；
(6) in the graphene/copper powder body, the graphene coated layer is uniformly wrapped on the Copper Powder Surface, and described There is excellent bond strength, so that gained powder has extraordinary mouldability between graphene coated layer and the copper powder Energy, heating conduction, electric conductivity, antioxygenic property；Material is in electrical contact with graphene/copper obtained by the graphene/copper powder sintering Material also has extraordinary heating conduction, electric conductivity, antioxygenic property, so as to significantly extend the use longevity of contact material Life；
(7) graphene/copper contact material is compared to the preparation method for using gas phase carbon source in CVD furnace, this side For graphene/copper powder of method preparation due to being added without dispersing agent during the preparation process, graphene/copper powder purity and quality are higher, Dispersion is more evenly.
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention Rather than it limits the scope of the invention.In the following examples, the experimental methods for specific conditions are not specified, usually according to conventional strip Part or according to the normal condition proposed by manufacturer.Unless otherwise stated, otherwise percentage and number are calculated by weight.
Unless otherwise defined, it anticipates known to all professional and scientific terms as used herein and one skilled in the art Justice is identical.In addition, any method similar to or equal to what is recorded and material can be applied to the method for the present invention.Wen Zhong The preferred implement methods and materials are for illustrative purposes only.
1 graphene of embodiment/copper powder body 1
1) the copper powder powder of 100nm (100g, atomized copper powder) is added in fluidized bed.
2) methane enters methane cracking device by outer ring tracheae, is heated using tantalum heater strip, and hydrocarbon atom is from netted spray The latasuture of head enters fluidized bed.
3) hydrogen enters fluidized bed, by adjusting mass flowmenter, fluidizes copper powder.Fluidized bed is heated, is heated to 800 ℃。
4) after 800 DEG C keep the temperature 0.5 hour, continue hydrogen fluidized gas, close methane, until temperature drops to room temperature (cooling Speed is 50 DEG C/min), the copper powder of surface coated graphite alkene is obtained, i.e. graphene/copper powder body 1.
It is tested through infrared carbon sulfur analyzer, the graphene/copper powder body 1 purity is very high, and phosphorus content is only 0.1wt% shows that content of the graphene containing carbon in graphene/copper powder body 1 is low, illustrates that graphene number of plies is few, matter Amount is high.
Fig. 1 is graphene/copper powder body 1 Raman results.
It will be seen from figure 1 that being implicitly present in graphene in gained graphene/copper powder body 1.Specifically, in Fig. 1, graphite The characteristic feature peak of alkene is the peak 2D near 2700cm-1 and the peak G near 1580cm-1.
Fig. 2 is copper powder (a) and graphene/copper powder body 1 (b) SEM result.
Figure it is seen that graphene/copper powder body 1 is similar with the partial size of copper powder, it is uniformly dispersed.This shows the graphite Alkene layer is uniformly wrapped on Copper Powder Surface, and the thickness of graphene layer is about 0.07-0.105nm, coverage rate of the graphene layer to copper powder About 100%.
In addition, after tested, the thermal conductivity of copper powder used in embodiment 1 is 390W/mK, conductivity 98%IACS；And graphite Alkene/copper powder body 1 thermal conductivity is 385W/mK, conductivity 95%IACS, this shows 1 gained graphene of embodiment/copper powder body 1 Thermal conductivity up to the 98.7% of copper powder, conductivity up to copper powder 96.9%.
2 graphenes of embodiment/copper contact material 1
By 1 gained graphene of embodiment/1 hot pressed sintering of copper powder body, back end vacuum is 5Pa, and temperature is 1000 DEG C, when processing Between be 30min, obtain graphene/copper contact material 1.
It is tested through contact resistance tester, obtained by being sintered under the sintering condition described in embodiment 2 of copper powder used in embodiment 1 Under air, after 220 DEG C of oxidation 6h, the contact resistance of the copper billet is 1.11 Ω to copper billet body, and graphene/copper contact material 1 Contact resistance after above-mentioned condition oxidation is 0.72 Ω, is 0.64 times of copper billet, illustrates that graphene/copper contact material 1 has There is preferable inoxidizability.
After tested, graphene/copper contact material 1 conductivity is 57MS/m, is the 98% of the conductivity of fine copper block；Stone Black alkene/copper contact material 1 thermal conductivity is 395W/mK, is the 98.5% of the thermal conductivity of fine copper block；Under abrasive wear conditions 200 DEG C oxidation 24 hours after, the graphene/copper contact material 1 contact resistance be copper billet contact resistance 50%.Graphite Alkene/copper contact material 1 coefficient of friction is 0.1.Graphene/copper contact material 1 tensile strength is 300MPa.
3 graphenes of embodiment/copper powder body 2
1) the copper powder powder of 10nm (200g, atomized copper powder) is added in fluidized bed.
2) ethane enters methane cracking device by outer ring tracheae, is heated using tantalum heater strip, and hydrocarbon atom is from netted spray The latasuture of head enters fluidized bed.
3) hydrogen enters fluidized bed, by adjusting mass flowmenter, fluidizes copper powder.Fluidized bed is heated, is heated to 700 ℃。
4) after 700 DEG C keep the temperature 0.3 hour, continue hydrogen fluidized gas, close ethane, until temperature drops to room temperature (cooling Speed is 40 DEG C/min), the copper powder of surface coated graphite alkene is obtained, i.e. graphene/copper powder body 2.
4 graphenes of embodiment/copper contact material 2
By 3 gained graphene of embodiment/2 hot pressed sintering of copper powder body, back end vacuum is 5Pa, and temperature is 950 DEG C, when processing Between be 20min, obtain graphene/copper contact material 2.
After tested, graphene/copper contact material 2 conductivity is the 98% of the conductivity of fine copper, and graphene/copper electricity connects The thermal conductivity of touching material 2 is the 98.6% of the thermal conductivity of fine copper；Under abrasive wear conditions 200 DEG C oxidation 24 hours after, graphene/copper The contact resistance of contact material 2 is the 55% of the contact resistance of copper billet.Graphene/copper contact material 2 coefficient of friction is 0.05.Graphene/copper contact material 2 tensile strength is 240MPa.
5 graphenes of embodiment/copper powder body 3
1) the copper powder powder of 50nm (300g, electrolytic copper powder) is added in fluidized bed.
2) ethylene enters methane cracking device by outer ring tracheae, is heated using tantalum heater strip, and hydrocarbon atom is from netted spray The latasuture of head enters fluidized bed.
3) argon gas enters fluidized bed, by adjusting mass flowmenter, fluidizes copper powder.Fluidized bed is heated, is heated to 600 ℃。
4) after 600 DEG C keep the temperature 0.5 hour, continue argon gas fluidized gas, close ethylene, until temperature drops to room temperature (cooling Speed is 50 DEG C/min), the copper powder of surface coated graphite alkene is obtained, i.e. graphene/copper powder body 3.
6 graphenes of embodiment/copper contact material 3
It is sintered after 5 gained graphene of embodiment/copper powder body 3 is cold-pressed, back end vacuum is 5Pa, and temperature is 950 DEG C, processing Time is 30min, obtains graphene/copper contact material 3.
After tested, graphene/copper contact material 3 conductivity is the 98.5% of the conductivity of fine copper, graphene/copper electricity The thermal conductivity of contact material 3 is the 98.7% of the thermal conductivity of fine copper；Under abrasive wear conditions 200 DEG C oxidation 24 hours after, graphene/ The contact resistance of copper contact material 3 is the 45% of the contact resistance of copper billet.Graphene/copper contact material 3 coefficient of friction It is 0.03.Graphene/copper contact material 3 tensile strength is 320MPa.
7 graphenes of embodiment/copper powder body 4
1) 100 μm of copper powder powder (100g, atomized copper powder) is added in fluidized bed.
2) methane enters methane cracking device by outer ring tracheae, is heated using tantalum heater strip, and hydrocarbon atom is from netted spray The latasuture of head enters fluidized bed.
3) argon gas enters fluidized bed, by adjusting mass flowmenter, fluidizes copper powder.Fluidized bed is heated, is heated to 750 ℃。
4) after 750 DEG C keep the temperature 0.5 hour, 800 DEG C are warming up to, continues argon gas fluidized gas, keeps the temperature 0.5 hour.
5) continue argon gas fluidized gas, close methane, until temperature drops to room temperature (cooling rate is 60 DEG C/min), wrapped The copper powder of graphene is covered, i.e. graphene/copper powder body 4.
3,5,7 gained graphene of embodiment/copper powder body 2-4 performance and 1 gained graphene of embodiment/copper powder body 1 property It can be similar.
8 graphenes of embodiment/copper contact material 4
It is sintered after 7 gained graphene of embodiment/copper powder body 4 is cold-pressed, back end vacuum is 4Pa, and temperature is 900 DEG C, processing Time is 30min, obtains graphene/copper contact material 4.
After tested, graphene/copper contact material 4 conductivity is the 99% of the conductivity of fine copper；Graphene/copper electricity connects The thermal conductivity of touching material 4 is the 98.5% of the thermal conductivity of fine copper；Under abrasive wear conditions 200 DEG C oxidation 24 hours after, graphene/copper The contact resistance of contact material 4 is the 40% of the contact resistance of copper billet.Graphene/copper contact material 4 coefficient of friction is 0.15.Graphene/copper contact material 4 tensile strength is 400MPa.
1 graphene of comparative example/copper powder body C1
With embodiment 1, difference is: replacing fluidized bed as reaction unit, reaction condition using conventional CVD furnace Are as follows: using the copper powder powder of 100g 100nm and methane as reaction raw materials, kept the temperature at 800 DEG C reaction in 0.5 hour obtain graphene/ Copper powder body C1.
Fig. 3 is graphene/copper powder body C1 SEM result.
From figure 3, it can be seen that gained graphene/copper powder body C1 is bonded into block, graphene is only distributed in block Surface, bulk inner do not have graphene.
In conclusion the present invention is led to as reaction unit using gas phase carbon source as reaction raw materials by using fluidized bed The cracking gas phase carbon source under high temperature (800~1200 DEG C) is crossed, and grows graphite in Copper Powder Surface under low temperature (600-800 DEG C) Alkene, be prepared a kind of graphene coated evenly and completely, graphene/copper powder that dispersibility is excellent, thermal conductivity is excellent Body obtains a kind of graphene/copper electrical contact of excellent combination property with the graphene/further sintering processes of copper powder body Material.
All references mentioned in the present invention is incorporated herein by reference, independent just as each document It is incorporated as with reference to such.In addition, it should also be understood that, after reading the above teachings of the present invention, those skilled in the art can To make various changes or modifications to the present invention, such equivalent forms equally fall within model defined by the application the appended claims It encloses.

Claims (10)

1. a kind of graphene/copper contact material preparation method, which is characterized in that described method includes following steps:
1) copper powder is added in fluidized bed；
2) gas phase carbon source is passed through in the fluidized bed after the methane cracking device of the fluidized bed is decomposed into hydrocarbon atom；
3) fluidized gas is passed through into the fluidized bed to fluidize copper powder；
4) under the action of the step 2) hydrocarbon atom and the step 3) fluidized gas, be heat-treated in the fluidized bed through flowing The copper powder of change obtains graphene/copper powder body material；
5) graphene described in sintering processes/copper powder body material obtains graphene/copper contact material.
2. the method as described in claim 1, which is characterized in that the gas phase carbon source is selected from the group: methane, ethane, propane, second Alkene, propylene, acetylene, propine, or combinations thereof.
3. the method as described in claim 1, which is characterized in that in step 3), the fluidized gas is selected from the group: hydrogen, argon Gas, nitrogen, helium, Krypton, or combinations thereof.
4. the method as described in claim 1, which is characterized in that in step 4), the treatment temperature of the heat treatment is 500- 1000 DEG C, preferably 550-900 DEG C, preferably 600-800 DEG C.
5. method as claimed in claim 4, which is characterized in that in step 4), the heat treatment is under the treatment temperature The processing time be 0.1-3 hours, preferably 0.2-1 hours.
6. the method as described in claim 1, which is characterized in that further comprised the steps of: after step 4)
4 ') continue to be passed through fluidized gas, and stop being passed through the hydrocarbon atom, and stop heating the fluidized bed so that fluidized bed Temperature is quickly reduced to room temperature, and the graphene/copper powder body material is made.
7. the method as described in claim 1, which is characterized in that the graphene/copper powder body material has selected from the group below one A or multiple features:
1) graphene/copper powder body material partial size is 5nm-500 μm, preferably 8nm-200 μm, more preferably 10nm- 120μm；
2) graphene/copper powder body material is coated on the graphene packet of the Copper Powder Surface comprising the copper powder as core and entirely Coating；
3) graphene/copper powder body material conductivity is the 94%-99.9% of fine copper electrical conductivity of powdered material, preferably The 96%-99.9% of fine copper electrical conductivity of powdered material, the more preferably 98%-99.9% for fine copper electrical conductivity of powdered material；
4) graphene/copper powder body material thermal conductivity is the 94%-99.9% of fine copper powder material thermal conductivity, preferably The 96%-99.9% of fine copper powder material thermal conductivity, the more preferably 98%-99.9% for fine copper powder material thermal conductivity；
5) graphene/copper powder body material antioxygenic property is 3 times of the antioxygenic property of fine copper.
8. the method as described in claim 1, which is characterized in that in step 5), the treatment temperature of the sintering processes is 800-1100 DEG C, preferably 850-1050 DEG C.
9. a kind of graphene/copper contact material, which is characterized in that the contact material is using described in claim 1 Method preparation.
10. contact material as claimed in claim 9, which is characterized in that the contact material has selected from the group below one A or multiple features:
1) conductivity of the contact material is 50MS/m-58MS/m, preferably 56MS/m-58MS/m, more preferably 57MS/ M-58MS/m；
2) thermal conductivity of the contact material is 360W/mK-400W/mK, preferably 380W/mK-400W/mK, more preferably 390W/mK-400W/mK；
3) coefficient of friction of the contact material is 0.01-0.2, preferably 0.03-0.15；
4) tensile strength of the contact material is 200-500MPa；
5) contact material under abrasive wear conditions 200 DEG C oxidation 24 hours after, the graphene/copper contact material connects Electric shock resistance is the 50% of the contact resistance of copper billet.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114974647A (en) * 2021-02-18 2022-08-30 上海新池能源科技有限公司 Ultrahigh-conductivity wire and cable and preparation method thereof
CN115351277A (en) * 2022-08-04 2022-11-18 国网智能电网研究院有限公司 Graphene-copper composite material and preparation method and application thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013093358A1 (en) * 2011-12-22 2013-06-27 Arkema France Method for producing an assembly of carbon nanotubes and graphene
CN103764545A (en) * 2011-09-02 2014-04-30 贝克休斯公司 Method to generate and disperse nanostructures in a composite material
CN105483641A (en) * 2015-12-28 2016-04-13 哈尔滨工业大学 Preparing method of copper-base electric contact material enhanced by in-situ grown graphene
CN106115668A (en) * 2016-06-20 2016-11-16 山东欧铂新材料有限公司 The process for dispersing of a kind of Graphene and graphene composite material
WO2018051105A1 (en) * 2016-09-14 2018-03-22 Metalysis Limited Method of producing a powder

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103764545A (en) * 2011-09-02 2014-04-30 贝克休斯公司 Method to generate and disperse nanostructures in a composite material
WO2013093358A1 (en) * 2011-12-22 2013-06-27 Arkema France Method for producing an assembly of carbon nanotubes and graphene
CN105483641A (en) * 2015-12-28 2016-04-13 哈尔滨工业大学 Preparing method of copper-base electric contact material enhanced by in-situ grown graphene
CN106115668A (en) * 2016-06-20 2016-11-16 山东欧铂新材料有限公司 The process for dispersing of a kind of Graphene and graphene composite material
WO2018051105A1 (en) * 2016-09-14 2018-03-22 Metalysis Limited Method of producing a powder

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114974647A (en) * 2021-02-18 2022-08-30 上海新池能源科技有限公司 Ultrahigh-conductivity wire and cable and preparation method thereof
CN115351277A (en) * 2022-08-04 2022-11-18 国网智能电网研究院有限公司 Graphene-copper composite material and preparation method and application thereof
CN115351277B (en) * 2022-08-04 2024-02-06 国网智能电网研究院有限公司 Graphene copper composite material and preparation method and application thereof

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