CN109666915B - Preparation method of composite metal layer plated carbon nanotube/graphene composite material - Google Patents

Preparation method of composite metal layer plated carbon nanotube/graphene composite material Download PDF

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CN109666915B
CN109666915B CN201910094137.0A CN201910094137A CN109666915B CN 109666915 B CN109666915 B CN 109666915B CN 201910094137 A CN201910094137 A CN 201910094137A CN 109666915 B CN109666915 B CN 109666915B
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graphene
carbon nanotube
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metal layer
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CN109666915A (en
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甘雪萍
赵琪
周科朝
李周
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Central South University
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
    • C23C16/08—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metal halides
    • C23C16/14—Deposition of only one other metal element
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/38—Coating with copper
    • C23C18/40—Coating with copper using reducing agents

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Abstract

The invention provides a preparation method of a composite metal layer plated carbon nanotube/graphene composite material, which comprises the following steps: uniformly mixing the carbon nano tube and the graphene, pretreating, adding the mixture into a dispersing agent, and preparing a carbon nano tube/graphene film; under an inert atmosphere, taking the film as a substrate, introducing reaction source gases of tungsten hexafluoride and molybdenum hexafluoride, introducing reducing gas, and reacting to obtain a tungsten-molybdenum-plated carbon nanotube/graphene laminated material; adding the layered material into copper plating solution, adding a reducing agent, and reacting to obtain a precursor of the composite metal layer plated carbon nanotube/graphene composite material; and sintering the precursor to obtain the composite metal layer plated carbon nanotube/graphene composite material. According to the method, the surface of the carbon nanotube/graphene film is plated with tungsten and molybdenum, so that the interface wettability between carbon and copper is greatly improved, the interface bonding strength is enhanced, and the mechanical property, the electrical property and the friction resistance of the composite material are improved.

Description

Preparation method of composite metal layer plated carbon nanotube/graphene composite material
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a preparation method of a composite metal layer plated carbon nanotube/graphene composite material.
Background
With the rapid development of the electrified railway, the performance requirements of current receiving parts of electric locomotives are higher. The pantograph slide plate of the electric locomotive is an important current collecting component for leading the electric energy into the locomotive. The pantograph slide plate is an electric contact material which requires high electric conduction, wear resistance and wear reduction. The developed countries have a long history of research on pantograph pan materials, and the European and American countries have advanced achievements in theoretical research, application research and the like of the pantograph pan materials. The pantograph slide plate mainly goes through the stages of a metal slide plate, a powder metallurgy slide plate, a carbon slide plate, a composite slide plate and a conductive ceramic slide plate. The copper/carbon composite material has excellent performance, becomes a necessary key material in high-tech fields, and is widely applied to the fields of pantograph slide plates, electric brushes and the like. At present, the copper/carbon composite material developed in China has certain differences from developed countries in Europe and America in the aspects of variety, performance, preparation technology and the like, so the development of the high-performance copper/carbon composite material is a problem which needs to be solved urgently by a plurality of key projects in China.
The main factors affecting the overall performance of the copper/carbon composite are the properties of the carbon-based material itself and the interfacial problems between copper and carbon. The poor structural strength and performance of the carbon-based material can directly influence the performance of the finally prepared composite material; meanwhile, copper and carbon do not generate chemical reaction or diffusion, the combination between the copper and the carbon mainly realizes interface combination in a mechanical mode, the combination force is very weak, and the application of the copper/carbon composite material is limited to the maximum extent by the interface combination force.
At present, the main method for regulating and controlling the interfacial bonding force between copper and a carbon-based material is surface modification of the carbon-based material. The surface modification of the carbon-based material is to plate a metal layer which can chemically react with carbon, diffuse or dissolve with carbon on the surface of the carbon-based material by using methods such as chemical plating, electroplating, magnetron sputtering, molecular blending and the like. However, in the existing methods of chemical plating, electroplating, molecular blending, etc., because different metal salt solutions have different requirements for temperature and reducing agent, it is difficult to plate a composite metal plating layer containing multiple metals, and functional additives containing elements such as nickel, phosphorus, etc., such as a reducing agent hypophosphite, are required to be added in the plating process, which can lead to the introduction of other impurity elements such as nickel, phosphorus, etc., into the composite material, thereby greatly affecting the comprehensive performance of the composite material. And the magnetron sputtering is difficult to realize industrial production due to the problems of complex equipment, high maintenance cost and the like. Therefore, in order to improve the interface bonding force between copper and carbon and improve the comprehensive performance of the copper/carbon composite material, a novel preparation method of the copper/carbon composite material is provided.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects and shortcomings mentioned in the background technology and provide a preparation method of a composite metal layer plated carbon nanotube/graphene composite material.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a preparation method of a composite metal layer plated carbon nanotube/graphene composite material comprises the following steps:
(1) uniformly mixing the carbon nano tube and the graphene to obtain a mixed material; the mixed material is sequentially subjected to acidification treatment, sensitization treatment and activation treatment, so that the surface activity of the carbon-based material is enhanced, then the mixed material is added into a dispersing agent, suspension is obtained after ultrasonic treatment, and a carbon nano tube/graphene film is obtained through suction filtration, so that the prepared film can prevent powder from being blown up by inert gas to pollute the whole reaction bin in the vapor deposition process, can prevent the phenomenon of raw material waste caused by easy taking away of reduced airflow due to fine particles of the powdery nano material, and is favorable for uniformly depositing a plated metal layer on the surface of the carbon material;
(2) under an inert atmosphere, taking the carbon nanotube/graphene film obtained in the step (1) as a substrate, introducing reaction source gases of tungsten hexafluoride and molybdenum hexafluoride, introducing reducing gas, and performing chemical vapor deposition reaction to obtain a tungsten-molybdenum-plated carbon nanotube/graphene laminated material;
(3) adding the tungsten and molybdenum plated carbon nanotube/graphene laminated material obtained in the step (2) into a copper plating solution, adding a reducing agent, carrying out chemical plating reaction, and washing and drying after the reaction is finished to obtain a composite metal layer plated carbon nanotube/graphene composite material precursor;
(4) and (4) sintering the precursor of the composite metal layer plated carbon nanotube/graphene composite material obtained in the step (3) to obtain the composite metal layer plated carbon nanotube/graphene composite material.
In the preparation method, preferably, in the step (1), the purity of the carbon nanotube is 95-99.9%, the purity of the graphene is 95-99.9%, the mass ratio of the carbon nanotube to the graphene is 4:1-1:1, the ratio of the mass of the mixture to the volume of the dispersant is 1:150-300g/mL, and the thickness of the carbon nanotube/graphene film is 1-30 μm.
The carbon nanotube composite material has the advantages of light weight, good conductivity, good stability and the like, shows excellent mechanical properties and unique electrical properties by utilizing the special structure of the carbon nanotube with smaller diameter and higher length-diameter ratio, simultaneously takes the advantages of light weight, small density, good thermal stability, good conductivity and the like of the graphene, and takes the composite carbon-based material formed by mixing the carbon nanotube and the graphene as a reinforcement to enhance the conductivity, mechanical properties and friction resistance of the composite material.
In the above preparation method, preferably, in the step (2), the volume ratio of the tungsten hexafluoride to the molybdenum hexafluoride is 1:4 to 4: 1.
In the preparation method, preferably, in the step (2), the temperature of the chemical vapor deposition reaction is 400-. According to the preparation method, the tungsten-molybdenum metal layer is plated on the surface of the carbon nano tube/graphene film substrate by Chemical Vapor Deposition (CVD), the deposition speed and the deposition quality are effectively improved by controlling the deposition parameters within the range of the preparation method, the metal tungsten-molybdenum coating with high density, high purity and controllable thickness can be obtained, and the interface performance between copper and carbon can be improved after copper is plated subsequently. In the above preparation method, preferably, in the step (3), the electroless plating reaction is performed in a water bath at 40-90 ℃.
In the above preparation method, preferably, in the step (3), the copper plating solution uses copper sulfate as a main salt, and the concentration of the main salt is 15-40 g/L.
In the above preparation method, preferably, the reducing agent in step (3) is at least one of hydrazine hydrate, formaldehyde, dextrose, potassium sodium tartrate, hydrazine sulfate, ethylenediamine, glyoxal, sodium borohydride, lactol, triethanolamine, glycerol, tannic acid, and metol; in the step (1), the dispersant is at least one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and hexadecyl trimethyl ammonium bromide.
In the above preparation method, preferably, in the step (2), the reducing gas is hydrogen, and the inert atmosphere is argon.
In the above preparation method, preferably, in the step (4), the sintering is vacuum hot-pressing sintering or spark plasma sintering; in the vacuum hot-pressing sintering process, the temperature is increased to 700 ℃ and 950 ℃ at the speed of 10-20 ℃/min, and the vacuum degree is controlled to be less than or equal to 10-3Pa, the pressure is 30-50MPa, and the heat preservation time is 3-6 h; in the sintering process of the discharge plasma, the temperature is raised to 850 ℃ and 950 ℃ at the speed of 50-100 ℃/min, and the vacuum degree is controlled to be less than or equal to 10-3Pa, pressure of 30-50MPa, and heat preservation time of20-30min。
In the above preparation method, preferably, in the step (1), the acidification treatment includes the following specific operation steps:
adding the mixed material into acid liquor, carrying out reflux reaction for 1-3h at 60-80 ℃, diluting with deionized water after the reaction is finished, washing to be neutral, and separating and drying to obtain an acidified mixed material; the ratio of the mass of the mixed material to the volume of the acid liquor is 2:100g/mL-4:100g/mL, and the acid liquor is formed by mixing 98% by mass of concentrated sulfuric acid and 65% by mass of concentrated nitric acid according to the volume ratio of 3: 1;
the sensitization treatment comprises the following specific operation steps:
adding the acidified mixed material into a sensitizing solution for ultrasonic treatment, diluting with deionized water, washing to be neutral, separating and drying to obtain a sensitized mixed material; the ratio of the mass of the mixed material to the volume of the sensitizing solution is 2:100g/mL-4:100g/mL, and the sensitizing solution is prepared from 100mL of deionized water, 2-5mL of concentrated hydrochloric acid with mass fraction of 37% and 2-5g of SnCl2Mixing to obtain a mixture;
the activation treatment comprises the following specific operation steps:
adding the sensitized mixed material into an activating solution for ultrasonic treatment, diluting with deionized water and washing to be neutral, then diluting with deionized water and washing to be neutral, and separating and drying to obtain an activated mixed material; the ratio of the mass of the mixed material to the volume of the activating solution is 2:100g/mL-4:100g/mL, and the activating solution is prepared from 100mL of deionized water, 2-5mL of concentrated hydrochloric acid with mass fraction of 37% and 0.01-0.1g of PdCl2Mixing the components.
According to the technical scheme, the metal tungsten and the molybdenum are both strong carbide forming elements, so that a layer of metal tungsten and molybdenum is deposited on the surface of the carbon nano tube/graphene film material by adopting a chemical vapor deposition method, then copper is chemically plated on the surface of the modified carbon nano tube/graphene film material plated with the metal tungsten and molybdenum, and finally vacuum hot-pressing sintering or SPS sintering is carried out near the melting point of copper. The method can improve the wettability between copper and carbon, improve the structural strength of the composite material and obtain the composite metal layer plated carbon nanotube/graphene copper-based composite material with high comprehensive performance.
Compared with the prior art, the invention has the advantages that:
(1) according to the preparation method, the surface of the carbon nano tube/graphene film is plated with tungsten and molybdenum, so that the interface wettability between carbon and copper is greatly improved, and the interface bonding strength is greatly enhanced, so that the mechanical property, the electrical property and the friction resistance of the composite material are improved.
(2) According to the preparation method, the chemical vapor deposition method is adopted to plate high-density and high-purity metal tungsten and molybdenum on the surface of the carbon nano tube/graphene film, so that the comprehensive performance of the composite material is improved, and meanwhile, the thickness of the metal tungsten and molybdenum coating layer can be regulated and controlled through regulating and controlling the reaction time and the reaction temperature.
(3) According to the preparation method disclosed by the invention, the carbon nano tube and the graphene are mixed to form the composite carbon matrix, so that more nucleation sites can be provided for the formation of a subsequent composite coating, and the formation of the composite coating is facilitated.
(4) According to the preparation method, the surface of the carbon nano tube/graphene film material is metallized, so that sintering is facilitated, and after vacuum hot-pressing sintering or spark plasma sintering, a uniform and continuous structure is formed by a metal phase in the composite material, so that the comprehensive performance of the composite material is further improved.
(5) The preparation method disclosed by the invention is simple and short in process, simple to operate, strong in controllability and easy to realize continuous and large-scale production.
Detailed Description
In order to facilitate an understanding of the present invention, the present invention will be described more fully and in detail with reference to the preferred embodiments, but the scope of the present invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
the invention relates to a preparation method of a composite metal layer plated carbon nanotube/graphene composite material, which comprises the following steps:
(1) mixing the carbon nano tube and the graphene uniformly by adopting a 3D powder mixer according to the mass ratio of 4:1 for 3 hours, wherein the purity of the carbon nano tube is 99 percent, and the purity of the graphene is 99 percent to obtain a mixed material;
(2) adding the mixed material into acid liquor, heating and refluxing for 2h in a water bath kettle at 80 ℃, then diluting with deionized water and washing to neutrality, and separating and drying to obtain an acidified mixed material; the ratio of the mass of the mixed material to the volume of the acid liquor is 2:100g/mL, and the acid liquor is formed by mixing 98% of concentrated sulfuric acid and 65% of concentrated nitric acid according to the volume ratio of 3: 1;
(3) adding the acidified mixed material into a sensitizing solution for ultrasonic treatment for 30min, diluting with deionized water, washing to be neutral, separating, and drying at 70 ℃ for 24h to obtain a sensitized mixed material; the ratio of the mass of the mixed material to the volume of the sensitizing solution is 2:100g/mL, and the sensitizing solution is prepared from 100mL of deionized water, 2mL of concentrated hydrochloric acid with the mass fraction of 37 percent, and 2g of SnCl2Mixing the components;
(4) adding the sensitized mixed material into an activating solution for ultrasonic treatment for 30min, diluting with deionized water and washing to be neutral, then diluting with deionized water and washing to be neutral, and separating and drying to obtain an activated mixed material; the ratio of the mass of the mixed material to the volume of the activating solution is 2:100g/mL, and the activating solution is prepared from 100mL of deionized water, 2mL of concentrated hydrochloric acid with the mass fraction of 37 percent and 0.01g of PdCl2Mixing the components;
(5) adding the activated mixed material into a dispersing agent cetyl trimethyl ammonium bromide, wherein the ratio of the mass of the mixed material to the volume of the dispersing agent is 1:200g/mL, performing ultrasonic treatment to obtain a suspension, and performing suction filtration to obtain a carbon nanotube/graphene film with the thickness of 10 micrometers;
(6) under the argon atmosphere, taking the carbon nano tube/graphene film obtained in the step (5) as a matrix, introducing reaction source gases of tungsten hexafluoride and molybdenum hexafluoride, wherein the volume ratio of the tungsten hexafluoride to the molybdenum hexafluoride is 1:4, and introducing a reducing gas H2Carrying out chemical vapor deposition reaction at 400 ℃ for 1min to obtain the tungsten-molybdenum-plated carbon nanotube/graphene laminated material;
(7) adding the tungsten-molybdenum plated carbon nanotube/graphene laminated material obtained in the step (6) into a copper sulfate solution with the concentration of 20g/L, adding a reducing agent hydrazine hydrate, carrying out chemical plating reaction under the condition of a water bath at 60 ℃, and washing and drying after the reaction is finished to obtain a precursor of the composite metal layer plated carbon nanotube/graphene composite material;
(8) putting the precursor of the composite metal layer plated carbon nanotube/graphene composite material in the step (7) into a mould of a spark plasma sintering system for sintering, wherein the heating rate is 50 ℃/min, the sintering temperature is 850 ℃, the heat preservation time is 20min, the sintering pressure is 35MPa, and the vacuum degree is less than or equal to 10-3And Pa, obtaining the composite metal layer plated carbon nanotube/graphene composite material.
Example 2:
the invention relates to a preparation method of a composite metal layer plated carbon nanotube/graphene composite material, which comprises the following steps:
(1) mixing the carbon nano tube and the graphene uniformly by adopting a 3D powder mixer according to the mass ratio of 3:1 for 3 hours, wherein the purity of the carbon nano tube is 99%, and the purity of the graphene is 99%, so as to obtain a mixed material;
(2) adding the mixed material into acid liquor, heating and refluxing for 2h in a water bath kettle at 80 ℃, then diluting with deionized water and washing to neutrality, and separating and drying to obtain an acidified mixed material; the ratio of the mass of the mixed material to the volume of the acid liquor is 3:100g/mL, and the acid liquor is formed by mixing 98% by mass of concentrated sulfuric acid and 65% by mass of concentrated nitric acid according to the volume ratio of 3: 1;
(3) adding the acidified mixture into a sensitizing solution for ultrasonic treatment for 30min, diluting with deionized water, and mixingWashing to be neutral, separating and drying at 70 ℃ for 24h to obtain a sensitized mixed material; the ratio of the mass of the mixed material to the volume of the sensitizing solution is 3:100g/mL, and the sensitizing solution is prepared from 100mL of deionized water, 5mL of concentrated hydrochloric acid with the mass fraction of 37 percent, and 5g of SnCl2Mixing the components;
(4) adding the sensitized mixed material into an activating solution for ultrasonic treatment for 30min, diluting with deionized water and washing to be neutral, then diluting with deionized water and washing to be neutral, and separating and drying to obtain an activated mixed material; the ratio of the mass of the mixed material to the volume of the activating solution is 2:100g/mL, and the activating solution is prepared from 100mL of deionized water, 5mL of concentrated hydrochloric acid with the mass fraction of 37 percent and 0.1g of PdCl2Mixing the components;
(5) adding the activated mixed material into dispersant sodium dodecyl benzene sulfonate, wherein the ratio of the mass of the mixed material to the volume of the dispersant is 1:200g/mL, performing ultrasonic treatment to obtain a suspension, and performing suction filtration to obtain a carbon nanotube/graphene film with the thickness of 15 micrometers;
(6) under the argon atmosphere, taking the carbon nano tube/graphene film obtained in the step (5) as a matrix, introducing reaction source gases of tungsten hexafluoride and molybdenum hexafluoride, wherein the volume ratio of the tungsten hexafluoride to the molybdenum hexafluoride is 1:2, and introducing a reducing gas H2Carrying out chemical vapor deposition reaction at 500 ℃ for 3min to obtain the tungsten-molybdenum-plated carbon nanotube/graphene laminated material;
(7) adding the tungsten-molybdenum plated carbon nanotube/graphene laminated material obtained in the step (6) into a copper sulfate solution with the concentration of 20g/L, adding a reducing agent hydrazine hydrate, carrying out chemical plating reaction in a water bath at 70 ℃, and washing and drying after the reaction is finished to obtain a precursor of the composite metal layer plated carbon nanotube/graphene composite material;
(8) putting the precursor of the composite metal layer plated carbon nanotube/graphene composite material in the step (7) into a mould of a spark plasma sintering system for sintering, wherein the heating rate is 100 ℃/min, the sintering temperature is 850 ℃, the heat preservation time is 30min, the sintering pressure is 50MPa, and the vacuum degree is less than or equal to 10-3Pa, obtaining composite metal layer coated carbonNanotube/graphene composite materials.
Example 3:
the invention relates to a preparation method of a composite metal layer plated carbon nanotube/graphene composite material, which comprises the following steps:
(1) mixing the carbon nano tube and the graphene uniformly by adopting a 3D powder mixer according to the mass ratio of 2:1 for 3 hours, wherein the purity of the carbon nano tube is 99%, and the purity of the graphene is 99%, so as to obtain a mixed material;
(2) adding the mixed material into acid liquor, heating and refluxing for 2h in a water bath kettle at 80 ℃, then diluting with deionized water and washing to neutrality, and separating and drying to obtain an acidified mixed material; the ratio of the mass of the mixed material to the volume of the acid liquor is 4:100g/mL, and the acid liquor is formed by mixing 98% by mass of concentrated sulfuric acid and 65% by mass of concentrated nitric acid according to the volume ratio of 3: 1;
(3) adding the acidified mixed material into a sensitizing solution for ultrasonic treatment for 30min, diluting with deionized water, washing to be neutral, separating, and drying at 70 ℃ for 24h to obtain a sensitized mixed material; the ratio of the mass of the mixed material to the volume of the sensitizing solution is 4:100g/mL, and the sensitizing solution is prepared from 100mL of deionized water, 4mL of concentrated hydrochloric acid with the mass fraction of 37 percent, and 4g of SnCl2Mixing the components;
(4) adding the sensitized mixed material into an activating solution for ultrasonic treatment for 30min, diluting with deionized water and washing to be neutral, then diluting with deionized water and washing to be neutral, and separating and drying to obtain an activated mixed material; the ratio of the mass of the mixed material to the volume of the activating solution is 4:100g/mL, and the activating solution is prepared from 100mL of deionized water, 4mL of concentrated hydrochloric acid with the mass fraction of 37 percent and 0.05g of PdCl2Mixing the components;
(5) adding the activated mixed material into dispersing agent sodium dodecyl sulfate, wherein the ratio of the mass of the mixed material to the volume of the dispersing agent is 1:200g/mL, performing ultrasonic treatment to obtain a suspension, and performing suction filtration to obtain a carbon nanotube/graphene film with the thickness of 30 micrometers;
(6) under the argon atmosphere, taking the carbon nano tube/graphene film obtained in the step (5) as a substrate, and introducing a reaction sourceGas tungsten hexafluoride and molybdenum hexafluoride, the volume ratio of tungsten hexafluoride to molybdenum hexafluoride is 2:1, and reducing gas H is introduced2Carrying out chemical vapor deposition reaction at the reaction temperature of 600 ℃ for 5min to obtain the tungsten-molybdenum-plated carbon nanotube/graphene laminated material;
(7) adding the tungsten-molybdenum plated carbon nanotube/graphene laminated material obtained in the step (6) into a copper sulfate solution with the concentration of 30g/L, adding a reducing agent hydrazine hydrate, carrying out chemical plating reaction under the condition of 80 ℃ water bath, and washing and drying after the reaction is finished to obtain a precursor of the composite metal layer plated carbon nanotube/graphene composite material;
(8) putting the precursor of the composite metal layer plated carbon nanotube/graphene composite material in the step (7) into a mould of a spark plasma sintering system for sintering, wherein the heating rate is 100 ℃/min, the sintering temperature is 850 ℃, the heat preservation time is 30min, the sintering pressure is 50MPa, and the vacuum degree is less than or equal to 10-3And Pa, obtaining the composite metal layer plated carbon nanotube/graphene composite material.
Example 4:
the invention relates to a preparation method of a composite metal layer plated carbon nanotube/graphene composite material, which comprises the following steps:
(1) mixing the carbon nano tube and the graphene uniformly by using a 3D powder mixer according to the mass ratio of 1:1 for 3 hours, wherein the purity of the carbon nano tube is 99.9%, and the purity of the graphene is 99.9%, so as to obtain a mixed material;
(2) adding the mixed material into acid liquor, heating and refluxing for 2h in a water bath kettle at 80 ℃, then diluting with deionized water and washing to neutrality, and separating and drying to obtain an acidified mixed material; the ratio of the mass of the mixed material to the volume of the acid liquor is 2:100g/mL, and the acid liquor is formed by mixing 98% by mass of concentrated sulfuric acid and 65% by mass of concentrated nitric acid according to the volume ratio of 3: 1;
(3) adding the acidified mixed material into a sensitizing solution for ultrasonic treatment for 30min, diluting with deionized water, washing to be neutral, separating, and drying at 70 ℃ for 24h to obtain a sensitized mixed material; the ratio of the mass of the mixed material to the volume of the sensitizing solution is 4:100g/mL,the sensitizing solution is prepared from 100mL of deionized water, 5mL of concentrated hydrochloric acid with the mass fraction of 37 percent and 5g of SnCl2Mixing the components;
(4) adding the sensitized mixed material into an activating solution for ultrasonic treatment for 30min, diluting with deionized water and washing to be neutral, then diluting with deionized water and washing to be neutral, and separating and drying to obtain an activated mixed material; the ratio of the mass of the mixed material to the volume of the activating solution is 4:100g/mL, and the activating solution is prepared from 100mL of deionized water, 3mL of concentrated hydrochloric acid with the mass fraction of 37 percent and 0.02g of PdCl2Mixing the components;
(5) adding the activated mixed material into a dispersing agent cetyl trimethyl ammonium bromide, wherein the ratio of the mass of the mixed material to the volume of the dispersing agent is 1:200g/mL, performing ultrasonic treatment to obtain a suspension, and performing suction filtration to obtain a carbon nanotube/graphene film with the thickness of 50 micrometers;
(6) under the argon atmosphere, taking the carbon nano tube/graphene film obtained in the step (5) as a matrix, introducing reaction source gases of tungsten hexafluoride and molybdenum hexafluoride, wherein the volume ratio of the tungsten hexafluoride to the molybdenum hexafluoride is 4:1, and introducing a reducing gas H2Carrying out chemical vapor deposition reaction at 800 ℃ for 10min to obtain the tungsten-molybdenum-plated carbon nanotube/graphene laminated material;
(7) adding the tungsten-molybdenum plated carbon nanotube/graphene laminated material obtained in the step (6) into a copper sulfate solution with the concentration of 40g/L, adding a reducing agent hydrazine hydrate, carrying out chemical plating reaction under the condition of 80 ℃ water bath, and washing and drying after the reaction is finished to obtain a precursor of the composite metal layer plated carbon nanotube/graphene composite material;
(8) carrying out vacuum hot-pressing sintering on the composite metal layer plated carbon nanotube/graphene composite material precursor obtained in the step (7), wherein the heating rate is 20 ℃/min, the sintering temperature is 950 ℃, the heat preservation time is 6h, the sintering pressure is 50MPa, and the vacuum degree is less than or equal to 10-3And Pa, obtaining the composite metal layer plated carbon nanotube/graphene composite material.
Comparative example 1:
a preparation method of a composite metal layer plated carbon nanotube/graphene composite material comprises the following steps:
(1) mixing the carbon nano tube and the graphene uniformly by adopting a 3D powder mixer according to the mass ratio of 3:1 for 3 hours, wherein the purity of the carbon nano tube is 99%, and the purity of the graphene is 99%, so as to obtain a mixed material;
(2) adding the mixed material into acid liquor, heating and refluxing for 2h in a water bath kettle at 80 ℃, then diluting with deionized water and washing to neutrality, and separating and drying to obtain an acidified mixed material; the ratio of the mass of the mixed material to the volume of the acid liquor is 3:100g/mL, and the acid liquor is formed by mixing 98% by mass of concentrated sulfuric acid and 65% by mass of concentrated nitric acid according to the volume ratio of 3: 1;
(3) adding the acidified mixed material into a sensitizing solution for ultrasonic treatment for 30min, diluting with deionized water, washing to be neutral, separating, and drying at 70 ℃ for 24h to obtain a sensitized mixed material; the ratio of the mass of the mixed material to the volume of the sensitizing solution is 3:100g/mL, and the sensitizing solution is prepared from 100mL of deionized water, 5mL of concentrated hydrochloric acid with the mass fraction of 37 percent, and 5g of SnCl2Mixing the components;
(4) adding the sensitized mixed material into an activating solution for ultrasonic treatment for 30min, diluting with deionized water and washing to be neutral, then diluting with deionized water and washing to be neutral, and separating and drying to obtain an activated mixed material; the ratio of the mass of the mixed material to the volume of the activating solution is 2:100g/mL, and the activating solution is prepared from 100mL of deionized water, 5mL of concentrated hydrochloric acid with the mass fraction of 37 percent and 0.1g of PdCl2Mixing the components;
(5) adding the activated mixed material into a dispersing agent, wherein the ratio of the mass of the mixed material to the volume of the dispersing agent is 1:200g/mL, performing ultrasonic treatment to obtain a suspension, and performing suction filtration to obtain a carbon nanotube/graphene film with the thickness of 15 micrometers;
(6) adding the carbon nanotube/graphene film obtained in the step (5) into a chemical nickel-tungsten plating solution (containing 15g/L of nickel sulfate and 10g/L of sodium tungstate), adding excessive reducing agent sodium hypophosphite, reacting, performing the reaction under the condition of 80 ℃ water bath, and repeatedly washing the carbon nanotube/graphene film with deionized water to be neutral after the reaction is finished to obtain the carbon nanotube/graphene layered material with the surface coated with nickel, tungsten and phosphorus;
(7) adding the nickel-tungsten-phosphorus-plated carbon nanotube/graphene laminated material in the step (6) into a copper sulfate solution with the concentration of 30/L, adding a reducing agent hydrazine hydrate, carrying out chemical plating reaction in a water bath at 80 ℃, and washing and drying after the reaction is finished to obtain a composite metal layer-plated carbon nanotube/graphene composite material precursor;
(8) and (3) performing vacuum hot-pressing sintering on the composite metal layer plated carbon nanotube/graphene composite material precursor obtained in the step (7), wherein the heating rate is 10 ℃/min, the sintering temperature is 850 ℃, the heat preservation time is 3h, the sintering pressure is 30MPa, and the vacuum degree is less than or equal to 10-3And Pa, obtaining the composite metal layer plated carbon nanotube/graphene composite material.
The composite metal layer plated carbon nanotube/graphene composite materials prepared in the above examples 1 to 4 and comparative example 1 of the present invention were tested for their relevant properties, and the test results are shown in table 1.
TABLE 1 Properties of composite metal layer-plated carbon nanotube/graphene composite materials prepared in examples 1 to 4 and comparative example 1
Numbering Conductivity (MS/m) Coefficient of friction Tensile Strength (MPa)
Example 1 20.3 0.21 189
Example 2 24.5 0.17 186
Example 3 27.6 0.12 221
Example 4 22.9 0.18 194
Comparative example 1 19.5 0.31 156
As can be seen from table 1, the composite metal layer plated carbon nanotube/graphene composite material prepared by the method of the present invention has excellent mechanical properties, electrical conductivity and friction properties.

Claims (7)

1. A preparation method of a composite metal layer plated carbon nanotube/graphene composite material for a pantograph pan is characterized by comprising the following steps:
(1) uniformly mixing the carbon nano tube and the graphene to obtain a mixed material; sequentially carrying out acidification treatment, sensitization treatment and activation treatment on the mixed material, then adding the mixed material into a dispersing agent, carrying out ultrasonic treatment to obtain a suspension, and carrying out suction filtration to obtain a carbon nano tube/graphene film;
(2) under an inert atmosphere, taking the carbon nanotube/graphene film obtained in the step (1) as a substrate, introducing reaction source gases of tungsten hexafluoride and molybdenum hexafluoride, introducing reducing gas, and performing chemical vapor deposition reaction to obtain a tungsten-molybdenum-plated carbon nanotube/graphene laminated material;
(3) adding the tungsten and molybdenum plated carbon nanotube/graphene laminated material obtained in the step (2) into a copper plating solution, adding a reducing agent, carrying out chemical plating reaction, and washing and drying after the reaction is finished to obtain a composite metal layer plated carbon nanotube/graphene composite material precursor;
(4) sintering the composite metal layer plated carbon nanotube/graphene composite material precursor obtained in the step (3) to obtain a composite metal layer plated carbon nanotube/graphene composite material;
in the step (2), the temperature of the chemical vapor deposition reaction is 400-; the volume ratio of the tungsten hexafluoride to the molybdenum hexafluoride is 1:4-4: 1; the reducing gas is hydrogen, and the inert atmosphere is argon and/or nitrogen.
2. The preparation method according to claim 1, wherein in the step (1), the purity of the carbon nanotube is 95-99.9%, the purity of the graphene is 95-99.9%, the mass ratio of the carbon nanotube to the graphene is 4:1-1:1, the ratio of the mass of the mixture to the volume of the dispersant is 1:150-300g/mL, and the thickness of the carbon nanotube/graphene film is 1-30 μm.
3. The method according to claim 1, wherein in the step (3), the electroless plating reaction is carried out in a water bath at 40 to 90 ℃.
4. The production method according to claim 1, wherein in the step (3), the copper plating solution uses copper sulfate as a main salt, and the concentration of the main salt is 15 to 40 g/L.
5. The method according to claim 1, wherein in the step (3), the reducing agent is at least one of hydrazine hydrate, formaldehyde, dextrose, potassium sodium tartrate, hydrazine sulfate, ethylenediamine, glyoxal, sodium borohydride, lactol, triethanolamine, glycerol, tannic acid, and metol; in the step (1), the dispersant is at least one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and hexadecyl trimethyl ammonium bromide.
6. The production method according to claim 1, wherein in the step (4), the sintering is vacuum hot-press sintering or spark plasma sintering; in the vacuum hot-pressing sintering process, the temperature is increased to 800-950 ℃ at the speed of 10-20 ℃/min, and the vacuum degree is controlled to be less than or equal to 10-3Pa, the pressure is 30-50MPa, and the heat preservation time is 3-6 h; in the sintering process of the discharge plasma, the temperature is raised to 850 ℃ and 950 ℃ at the speed of 50-100 ℃/min, and the vacuum degree is controlled to be less than or equal to 10-3Pa, pressure of 30-50MPa, and heat preservation time of 20-30 min.
7. The preparation method according to claim 1, wherein in the step (1), the acidification treatment comprises the following specific operation steps:
adding the mixed material into acid liquor, carrying out reflux reaction for 1-3h at 60-80 ℃, diluting with deionized water after the reaction is finished, washing to be neutral, and separating and drying to obtain an acidified mixed material; the ratio of the mass of the mixed material to the volume of the acid liquor is 2:100g/mL-4:100g/mL, and the acid liquor is formed by mixing 98% by mass of concentrated sulfuric acid and 65% by mass of concentrated nitric acid according to the volume ratio of 3: 1;
the sensitization treatment comprises the following specific operation steps:
adding the acidified mixed material into a sensitizing solution for ultrasonic treatment, diluting with deionized water, washing to be neutral, separating and drying to obtain a sensitized mixed material; the ratio of the mass of the mixed material to the volume of the sensitizing solution is 2:100g/mL-4:100g/mL, and the sensitizing solution is prepared from 100mL of deionized water, 2-5mL of concentrated hydrochloric acid with mass fraction of 37% and 2-5g of SnCl2Mixing to obtain a mixture;
the activation treatment comprises the following specific operation steps:
adding the sensitized mixed material into an activating solution for ultrasonic treatment, diluting with deionized water and washing to neutrality, separating,Drying to obtain an activated mixed material; the ratio of the mass of the mixed material to the volume of the activating solution is 2:100g/mL-4:100g/mL, and the activating solution is prepared from 100mL of deionized water, 2-5mL of concentrated hydrochloric acid with mass fraction of 37% and 0.01-0.1g of PdCl2Mixing the components.
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