CN110102758B - Cu-X/C composite material and preparation method thereof - Google Patents

Cu-X/C composite material and preparation method thereof Download PDF

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CN110102758B
CN110102758B CN201910451447.3A CN201910451447A CN110102758B CN 110102758 B CN110102758 B CN 110102758B CN 201910451447 A CN201910451447 A CN 201910451447A CN 110102758 B CN110102758 B CN 110102758B
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composite material
carbon material
plating solution
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CN110102758A (en
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甘雪萍
袁月
赵琪
周科朝
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Central South University
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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
    • B22F1/17—Metallic particles coated with metal
    • 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
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • 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
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
    • C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
    • C23C18/1886—Multistep pretreatment
    • C23C18/1893—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
    • 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
    • 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
    • C23C18/48—Coating with alloys

Abstract

The invention provides a Cu-X/C composite material and a preparation method thereof. The preparation method comprises the following steps: sequentially carrying out oil removal, coarsening, sensitization and activation on the carbon material; adding the activated carbon material into a Cu-X plating solution, adjusting the pH value with an alkali solution, slowly adding a reducing agent until the solution is clear, cleaning the solution to be neutral with deionized water, and drying the solution to obtain a Cu-X coated carbon material; adding a Cu-X coated carbon material into a copper plating solution, adjusting the pH value with an alkali solution, then slowly adding a reducing agent, stirring until the solution is clear, then washing with deionized water to be neutral, and drying to obtain a Cu-X/C composite material precursor; and sintering the precursor to obtain the Cu-X/C composite material. The Cu-X/C composite material prepared by the preparation method has a uniform and continuous space three-dimensional network structure, and has the characteristics of high density, and excellent friction performance, electric conduction and heat conduction performance and mechanical performance.

Description

Cu-X/C composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a Cu-X/C composite material and a preparation method thereof.
Background
The Cu/C composite material is a novel material with ideal comprehensive performance, has excellent electric and thermal conductivity of metal copper and copper alloy, and has good self-lubricating property and corrosion resistance of carbon material, so that the Cu/C composite material is widely applied to electrode materials and the like in sliding plates, motor brushes and electronic elements for pantograph of electric vehicles, and greatly prolongs the service life of parts and the service life of equipment. Due to the special working conditions of these materials, they are required to have good friction properties, electrical and thermal conductivity and mechanical properties. At present, a liquid phase impregnation method and a powder metallurgy method are usually adopted to prepare a Cu/C composite material, but the wettability of Cu and C is poor, and the thermal expansion characteristic is greatly different, so that the bonding property between the Cu and the C is poor, and the mechanical property of the prepared Cu/C composite material is poor; in addition, in the process of preparing the Cu/C composite material, the carbon material is easy to agglomerate, so that the carbon material is dispersed in the composite material unevenly, and the electric and heat conducting performance, the mechanical property and the friction performance of the composite material are influenced to a certain extent. Therefore, there is a need to develop a method for improving the overall performance of the Cu/C composite material.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects and shortcomings in the background art and provide a Cu-X/C composite material and a preparation method thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a preparation method of a Cu-X/C composite material, wherein X in the Cu-X/C composite material is at least one of Cr, Mo and W, and the preparation method comprises the following steps:
(1) sequentially carrying out oil removal, coarsening, sensitization and activation on the carbon material;
(2) adding the activated carbon material obtained in the step (1) into a Cu-X plating solution, adjusting the pH value with an alkali solution, slowly adding a reducing agent until the solution is clear, cleaning the solution to be neutral with deionized water, and drying the solution to obtain a Cu-X coated carbon material;
(3) adding the Cu-X coated carbon material obtained in the step (2) into a copper plating solution, adjusting the pH value with an alkali solution, slowly adding a reducing agent, stirring until the solution is clear, then washing with deionized water to be neutral, and drying to obtain a Cu-X/C composite material precursor;
(4) and (4) sintering the precursor of the Cu-X/C composite material obtained in the step (3) to obtain the Cu-X/C composite material.
In the above preparation method, preferably, in the step (2), the Cu-X plating solution contains a main salt and a complexing agent, and the main salt is CuSO4And a soluble salt containing X, the soluble salt containing X being CrCl3、Na2MoO4、H4Na2O6At least one of W, KNaC as complexing agent4H4O6·4H2O and EDTA.
The above preparation method is preferably Cu-The volume of the X plating solution is measured, the concentration of the main salt is 20-30g/L, the concentration of the complexing agent is 30-100g/L, and CuSO4And soluble salt containing X in a mass ratio of 1: 1-2: 1, KNaC4H4O6·4H2The mass ratio of O to EDTA is 1:1-4: 5.
We find that the bonding strength of the copper-carbon composite interface can be effectively improved by introducing the modified metal X, but the modified metal X is difficult to be plated on the surface of the carbon material independently, if a Cu-X alloy plating layer is plated, X can be co-deposited with Cu, and then the modified metal X can be plated on the carbon material easily, and the plated Cu-X alloy can enhance the bonding strength of the copper substrate and the carbon interface. By adopting the Cu-X plating solution formula, the uniform and compact Cu-X alloy plating layer can be ensured to be obtained by plating, meanwhile, the plating process is stably carried out, and the plating efficiency is high. If the concentration of the main salt is out of the range of the invention, the plating is difficult to start, and if the concentration of the main salt is lower than the range of the invention, the plating efficiency is low; if the concentration of the complexing agent is outside the range of the present invention, the reaction will be slow, and if the concentration is below the range of the present invention, the complexing agent will be difficult to complex with the main salt to form a precipitate.
In the above preparation method, preferably, in the step (3), the copper plating solution contains a main salt, a complexing agent and a stabilizer, and the main salt is CuSO4·5H2O, a source of copper ions for the plating; the complexing agent is KNaC4H4O6·4H2A mixture of O and EDTA; the stabilizer is K4Fe(CN)6·3H2O, the appearance of the coating can be improved, and the deposition speed is reduced; based on the volume of the copper plating solution, the concentration of the main salt is 15-25g/L, the concentration of the stabilizer is 1-1.5g/L, the concentration of the complexing agent is 30-36g/L, and KNaC4H4O6·4H2The mass ratio of O to EDTA is 1:1-4: 5.
The copper plating layer is further plated on the surface of the Cu-X alloy plating layer, so that the content of a copper matrix can be improved, and the electric conductivity, the heat conductivity and the mechanical property of the composite material are effectively improved. By adopting the formula of the copper plating solution, the uniform and compact metal copper layer can be ensured to be plated, meanwhile, the plating process is stably carried out, and the plating efficiency is high. If the concentration of the main salt is out of the range of the invention, the plating is difficult to start, and if the concentration of the main salt is lower than the range of the invention, the plating efficiency is low; if the concentration of the complexing agent is outside the range of the present invention, the reaction will be slow, and if the concentration is below the range of the present invention, the complexing agent will be difficult to complex with the main salt to form a precipitate.
In the above production method, preferably, in the step (2), the temperature of the Cu — X plating solution is maintained at 50 to 60 ℃. The temperature of the Cu-X plating solution is required to be controlled within the scope of the invention, if the temperature is beyond the scope of the invention, metal powder such as copper, molybdenum powder and the like can be generated in the reaction system and can not be plated on the carbon material, and if the temperature is lower than the scope of the invention, the plating is slower or even can not be plated, and the reaction efficiency is low.
In the above production method, preferably, in the step (3), the temperature of the copper plating solution is maintained at 50 to 60 ℃.
In the above preparation method, preferably, in the step (2) and the step (3), the reducing agent is C2H2O3At least one of formaldehyde, hydrazine and sodium borohydride, wherein the concentration of the reducing agent is 10-13 ml/L; more preferably, the reducing agent is C2H2O3And/or hydrazine, the two reducing agents have strong reducibility, are safe and environment-friendly, and can obtain a relatively pure metal coating.
In the above preparation method, preferably, in the step (2), in order to avoid generation of copper, molybdenum powder, chromium powder and the like and guarantee plating efficiency, the addition amount of the reducing agent is 10-50g/L based on the volume of the Cu-X plating solution.
In the above preparation method, preferably, in the step (3), the reducing agent is added in an amount of 10 to 50g/L based on the volume of the copper plating solution in order to ensure the plating efficiency.
In the above preparation method, preferably, in the step (2) and the step (3), the alkali solution is a NaOH solution, and the pH value is adjusted to 12-13.
In the above preparation method, preferably, in the step (4), spark plasma sintering is performed, and the vacuum degree is controlled to be less than or equal to 10-3Pa, heating rate of 50-100 deg.C/min, sintering temperature of 850-Cooling at a cooling rate of 90-100 deg.C/min.
In the above preparation method, preferably, in the step (1), the carbon material is at least one of graphite, carbon nanotubes, diamond and carbon fiber;
the oil removal is to add the carbon material into alkali liquor and stir the mixture, wherein the alkali liquor is NaOH solution, the concentration of the alkali liquor is 100-150g/L, the stirring time is 30-60min, and the stirring temperature is above 90 ℃;
the coarsening is to add the carbon material after deoiling into acid liquor and stir, wherein the acid liquor is HNO3The concentration of the acid liquor is 10-50 vol.%, the stirring time is 30-60min, and the stirring temperature is above 90 ℃;
the sensitization is to add the coarsened carbon material into a sensitization liquid to be stirred, wherein the sensitization liquid is SnCl2The concentration of the sensitizing solution is 5-20g/L, the pH value is 1-1.5, the stirring time is 20-30min, and the stirring temperature is room temperature;
the activation is to add the sensitized carbon material into an activation solution which is PdCl for stirring treatment2The concentration of the solution and the activating solution is 0.05-2g/L, the activating temperature is 50-60 ℃, and the stirring time is 10-30 min.
The present invention also provides, as a general inventive concept, a Cu-X/C composite material prepared according to the above-described preparation method.
The method comprises the steps of chemically plating a Cu-X alloy coating on the surface of a carbon material, wherein X is at least one of Cr, Mo and W, and then chemically plating Cu to prepare composite powder of the composite coating coated with the carbon material, wherein the composite coating has the characteristics of controllable thickness, uniformity, compactness and good bonding property with the carbon material, and then sintering the composite coating by adopting an SPS (semi-solid solution) method below an alloy melting point to ensure that a metal phase uniformly and tightly coats the carbon material. Cr is generated in the sintering process3C2、Mo2C. WC, and the like, and these carbides have excellent wettability with Cu and low resistivity. The prepared composite material has high density, excellent friction performance, electric conductivity, heat conductivity and mechanical property, and the prepared composite material forms a uniform and continuous space three-dimensional network and the carbon material is uniformly distributed.
Compared with the prior art, the invention has the advantages that:
(1) the composite powder of the composite coating coated with the carbon material is prepared by chemically plating a Cu-X alloy coating on the carbon material, wherein X is at least one of Cr, Mo and W, and then chemically plating Cu, and the composite coating has the characteristics of controllable thickness, uniformity, compactness and good bonding property with the carbon material, and then sintering by adopting an SPS (semi-solid solution) method below an alloy melting point to ensure that a metal phase uniformly and tightly coats the carbon material. Mo formed by sintering2C、Cr3C2The electrical resistivity of carbides such as WC and the like is low, the wettability of the carbides with Cu is excellent, and the finally obtained Cu-X/C composite material has a uniform and continuous space three-dimensional network structure and has the characteristics of high density, and excellent friction performance, electric conductivity, heat conductivity and mechanical property.
(2) The present invention is to form carbide (Mo) of X at the interface between copper and carbon2C、Cr3C2WC, etc.), the wetting angle of carbide and Cu is very small, the wettability between interfaces is very good, and the interface bonding strength between the copper phase and the carbon phase is improved.
(3) The metal coating of the composite material obtained by sintering of the invention contains the dispersed carbide strengthening phase, so that the mechanical property of the material is enhanced.
(4) Along with the increase of the content of the metal phase and the reduction of the porosity, the thermal conductivity of the composite material also can be obviously increased; the Cu phase in the composite material is continuously distributed, and can provide a continuous channel for the transfer of electrons and phonons, so that the good electric and heat conducting properties of Cu are fully exerted.
(5) In the copper/carbon composite material which is not coated with the X metal coating, the interface combination of copper and the carbon material is not firm, carbon particles are easily extruded in the friction process, and the copper matrix is pure copper and has weak plastic deformation resistance. According to the invention, the X-containing alloy plating layer is plated on the surface of the carbon firstly, so that the strength and toughness of the composite material are enhanced, the plastic deformation resistance of the copper matrix can be improved, the possibility of microcracks generated on the copper matrix is reduced, the interface between the copper matrix and the carbon is tightly combined, a continuous solid lubricating layer is generated on the friction surface by the carbon, and the friction performance is greatly improved.
(6) The proportion of the metal plating amount to the carbon material can be adjusted under the same process according to the actual application requirements so as to adapt to different requirements.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is an SEM photograph of a Cu-Mo/C composite material in example 1 of the present invention;
FIG. 2 is an SEM photograph of a Cu-W/C composite material in example 2 of the present invention;
FIG. 3 is an SEM photograph of a Cu-Cr/C composite material in example 3 of the present invention;
FIG. 4 is an SEM photograph of a Cu-W-Mo/C composite material in example 4 of the present invention.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the 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 preparation method of the Cu-Mo/C composite material comprises the following steps:
(1) adding 100g of graphite powder with the particle size of 17 mu m into a NaOH solution with the concentration of 100g/L, stirring at 93 ℃ for 60min, and cleaning with deionized water to be neutral after oil removal;
(2) adding HNO with the concentration of 10 vol.% into the graphite powder subjected to oil removal in the step (1)3Stirring the solution at 95 ℃ for 30min, and cleaning the solution to be neutral by using deionized water after coarsening is finished;
(3) adding the graphite powder coarsened in the step (2) into SnCl with the concentration of 5g/L, pH value of 12Stirring the solution at room temperature for 20min, and cleaning the solution to be neutral by using deionized water after sensitization;
(4) adding PdCl with concentration of 0.05g/L into the sensitized graphite powder obtained in the step (3)2Stirring the solution at 50 ℃ for 15min, and cleaning the solution to be neutral by using deionized water after activation;
(5) adding the activated graphite powder obtained in the step (4) into a prepared Cu-Mo plating solution at 55 ℃, wherein the adding amount of the graphite powder is 5g/L based on the volume of the Cu-Mo plating solution, adjusting the pH value to 12 by using a NaOH solution, slowly adding a reducing agent glyoxylic acid with the concentration of 13ml/L, wherein the adding amount of the glyoxylic acid is 15g/L based on the volume of the Cu-Mo plating solution, stirring until the solution is clear, adjusting the pH value of the solution by using the NaOH solution in the stirring process to keep the pH value at 12, then washing the solution to be neutral by using deionized water, and drying the solution to obtain Cu-Mo coated graphite powder; the Cu-Mo plating solution comprises the following components in concentration by volume: EDTA 20g/L, KNaC4H4O6·H2O 16g/L、CuSO4·5H2O 10g/L、Na2MoO4 10g/L；
(6) Adding the Cu-Mo coated graphite powder obtained in the step (5) into a copper plating solution at 50 ℃, wherein the addition amount of the Cu-Mo coated graphite powder is 5g/L by volume of the copper plating solution, adjusting the pH value to 13 by using NaOH alkali liquor, slowly adding glyoxylic acid with the concentration of 13ml/L by volume of the copper plating solution, and the addition amount of glyoxylic acid serving as a reducing agent is 19g/L until the solution is clear, then washing the solution to be neutral by using deionized water, and drying the solution to obtain a Cu-Mo/C composite material precursor; the copper plating solution comprises the following components in concentration by volume: EDTA 20g/L, KNaC4H4O6·H2O 16g/L、CuSO4·5H2O 15g/L、K4Fe(CN)6·3H2O 1.5g/L；
(7) Putting the precursor of the Cu-Mo/C composite material obtained in the step (6) into a graphite die for spark plasma sintering, and controlling the vacuum degree to be less than or equal to 10-3Pa, the heating rate is 100 ℃/min, the sintering temperature is 850 ℃, the sintering pressure is 35Mpa, the heat preservation time is 10min, and after sintering, cooling is carried out at the cooling speed of 100 ℃/min to obtain the Cu-Mo/C composite material.
The SEM photograph of the Cu — Mo/C composite material prepared in this example is shown in fig. 1, which shows that the composite material has a uniform and continuous three-dimensional network structure and graphite particles are uniformly distributed.
Example 2:
the preparation method of the Cu-W/C composite material comprises the following steps:
(1) adding 100g of graphite powder with the particle size of 17 mu m into a NaOH solution with the concentration of 120g/L, stirring at 95 ℃ for 60min, and cleaning with deionized water to be neutral after oil removal;
(2) adding HNO with the concentration of 30 vol.% into the graphite powder subjected to oil removal in the step (1)3Stirring the solution at 95 ℃ for 30min, and cleaning the solution to be neutral by using deionized water after coarsening is finished;
(3) adding the graphite powder coarsened in the step (2) into SnCl with the concentration of 10g/L, pH value of 1.22Stirring the solution at room temperature for 20min, and cleaning the solution to be neutral by using deionized water after sensitization;
(4) adding PdCl with concentration of 0.5g/L into the sensitized graphite powder obtained in the step (3)2Stirring the solution at 50 ℃ for 15min, and cleaning the solution to be neutral by using deionized water after activation;
(5) adding the activated graphite powder obtained in the step (4) into the prepared Cu-W plating solution at 50 ℃, wherein the adding amount of the graphite powder is 5g/L based on the volume of the Cu-W plating solution, adjusting the pH value to 12 by using NaOH solution, slowly adding a reducing agent glyoxylic acid with the concentration of 13ml/L, wherein the adding amount of the glyoxylic acid is 25g/L based on the volume of the Cu-W plating solution, stirring until the solution is clear, and adjusting the pH value of the solution by using the NaOH solution in the stirring processKeeping the pH value at 12, then washing the graphite powder to be neutral by using deionized water, and drying the graphite powder to obtain Cu-W coated graphite powder; the Cu-W plating solution comprises the following components in concentration by volume: EDTA 50g/L, KNaC4H4O6·H2O 40g/L、CuSO4·5H2O 15g/L、H4Na2O6W 10g/L；
(6) Adding the Cu-W coated carbon material obtained in the step (5) into a copper plating solution at 50 ℃, wherein the addition amount of Cu-W coated graphite powder is 5g/L in terms of the volume of the copper plating solution, adjusting the pH value to 13 by using NaOH alkali liquor, slowly adding glyoxylic acid with the concentration of 13ml/L in terms of the volume of the copper plating solution, and adding a reducing agent glyoxylic acid of 13g/L until the solution is clear, then washing the solution to be neutral by using deionized water, and drying the solution to obtain a Cu-W/C composite material precursor; the copper plating solution comprises the following components in concentration by volume: EDTA 16g/L, KNaC4H4O6·H2O 16g/L、CuSO4·5H2O 18g/L、K4Fe(CN)6·3H2O 1.5g/L；
(7) Putting the precursor of the Cu-W/C composite material obtained in the step (6) into a graphite die for spark plasma sintering, and controlling the vacuum degree to be less than or equal to 10-3Pa, the heating rate is 50 ℃/min, the sintering temperature is 900 ℃, the sintering pressure is 35Mpa, the heat preservation time is 10min, and after sintering, cooling is carried out at the cooling speed of 100 ℃/min to obtain the Cu-W/C composite material.
An SEM photograph of the Cu — W/C composite material prepared in this example is shown in fig. 2, which shows that the composite material has a uniform and continuous three-dimensional network structure and graphite particles are uniformly distributed.
Example 3:
the preparation method of the Cu-Cr/C composite material comprises the following steps:
(1) adding 100g of graphite powder with the particle size of 17 mu m into a NaOH solution with the concentration of 150g/L, stirring at 93 ℃ for 60min, and cleaning with deionized water to be neutral after oil removal;
(2) adding HNO with the concentration of 50 vol.% into the graphite powder subjected to oil removal in the step (1)3Stirring the solution at 92 ℃ for 30min, and cleaning the solution to be neutral by using deionized water after coarsening is finished;
(3) adding SnCl with the concentration of 20g/L, pH value of 1.5 into the roughened graphite powder obtained in the step (2)2Stirring the solution at room temperature for 20min, and cleaning the solution to be neutral by using deionized water after sensitization;
(4) adding the sensitized graphite powder obtained in the step (3) into PdCl with the concentration of 1g/L2Stirring the solution at 50 ℃ for 30min, and cleaning the solution to be neutral by using deionized water after activation;
(5) adding the activated graphite powder obtained in the step (4) into a prepared Cu-Cr plating solution at 50 ℃, wherein the adding amount of the graphite powder is 5g/L calculated by the volume of the Cu-Cr plating solution, adjusting the pH value to 12 by using a NaOH solution, slowly adding glyoxylic acid with the concentration of 13ml/L calculated by the volume of the Cu-Cr plating solution, and adding a reducing agent glyoxylic acid of 30g/L, stirring until the solution is clear, adjusting the pH value of the solution by using the NaOH solution in the stirring process to keep the pH value at 12, then washing the solution to be neutral by using deionized water, and drying the solution to obtain Cu-Cr/C composite graphite powder; the Cu-Cr plating solution comprises the following components in concentration by volume: EDTA 30g/L, KNaC4H4O6·H2O 30g/L、CuSO4·5H2O 17g/L、CrCl3 10g/L；
(6) Adding the Cu-Cr coated graphite powder obtained in the step (5) into a copper plating solution at 50 ℃, wherein the addition amount of the Cu-Cr coated graphite powder is 5g/L in terms of the volume of the copper plating solution, adjusting the pH value to 13 by using NaOH alkali liquor, slowly adding 10ml/L glyoxylic acid in terms of the volume of the copper plating solution, adding 10g/L of glyoxylic acid serving as a reducing agent, stirring until the solution is clear, then washing the solution to be neutral by using deionized water, and drying the solution to obtain a Cu-Cr/C composite material precursor; the copper plating solution comprises the following components in concentration by volume: EDTA 18g/L, KNaC4H4O6·H2O 16g/L、CuSO4·5H2O 17g/L、K4Fe(CN)6·3H2O 1.5g/L；
(7) Filling the precursor of the Cu-Cr/C composite material obtained in the step (6) into a graphite moldThe vacuum degree is controlled to be less than or equal to 10-3Pa, the heating rate is 50 ℃/min, the sintering temperature is 900 ℃, the sintering pressure is 35Mpa, the heat preservation time is 10min, and after sintering, cooling is carried out at the cooling speed of 100 ℃/min to obtain the Cu-Cr/C composite material.
An SEM photograph of the Cu — Cr/C composite material prepared in this example is shown in fig. 3, which shows that the composite material has a uniform and continuous three-dimensional network structure and graphite particles are uniformly distributed.
Example 4:
the preparation method of the Cu-W-Mo/C composite material comprises the following steps:
(1) adding 100g of graphite powder with the particle size of 17 mu m into a NaOH solution with the concentration of 120g/L, stirring at 95 ℃ for 60min, and cleaning with deionized water to be neutral after oil removal;
(2) adding HNO with the concentration of 30 vol.% into the graphite powder subjected to oil removal in the step (1)3Stirring the solution at 95 ℃ for 30min, and cleaning the solution to be neutral by using deionized water after coarsening is finished;
(3) adding the graphite powder coarsened in the step (2) into SnCl with the concentration of 10g/L, pH value of 1.22Stirring the solution at room temperature for 20min, and cleaning the solution to be neutral by using deionized water after sensitization;
(4) adding PdCl with concentration of 0.5g/L into the sensitized graphite powder obtained in the step (3)2Stirring the solution at 50 ℃ for 15min, and cleaning the solution to be neutral by using deionized water after activation;
(5) adding the activated graphite powder obtained in the step (4) into a prepared Cu-W-Mo plating solution at 50 ℃, wherein the adding amount of the graphite powder is 5g/L based on the volume of the Cu-We-Mo plating solution, adjusting the pH value to 12 by using NaOH solution, then slowly adding a reducing agent glyoxylic acid with the concentration of 13ml/L, wherein the adding amount of the glyoxylic acid is 25g/L based on the volume of the Cu-W-Mo plating solution, stirring until the solution is clear, adjusting the pH value of the solution by using the NaOH solution in the stirring process to keep the pH value at 12, then washing the solution to be neutral by using deionized water, and drying to obtain Cu-W-Mo coated graphite powder; the Cu-W-Mo plating solution comprises the following components in concentration by volume: 50g/L of EDTA,KNaC4H4O6·H2O 40g/L、CuSO4·5H2O 15g/L、H4Na2O6W 5g/L、Na2MoO4 5g/L；
(6) Adding the Cu-W-Mo coated graphite powder obtained in the step (5) into a copper plating solution at 50 ℃, wherein the addition amount of the Cu-W-Mo coated graphite powder is 5g/L in terms of the volume of the copper plating solution, adjusting the pH value to 13 by using NaOH alkali liquor, slowly adding glyoxylic acid with the concentration of 13ml/L in terms of the volume of the copper plating solution, adding 13g/L of glyoxylic acid serving as a reducing agent until the solution is clear, cleaning the solution to be neutral by using deionized water, and drying the solution to obtain a Cu-W-Mo/C composite material precursor; the copper plating solution comprises the following components in concentration by volume: EDTA 16g/L, KNaC4H4O6·H2O 16g/L、CuSO4·5H2O 18g/L、K4Fe(CN)6·3H2O 1.5g/L；
(7) Putting the precursor of the Cu-W-Mo/C composite material obtained in the step (6) into a graphite die for spark plasma sintering, and controlling the vacuum degree to be less than or equal to 10-3Pa, the heating rate is 50 ℃/min, the sintering temperature is 900 ℃, the sintering pressure is 35Mpa, the heat preservation time is 10min, and after sintering, cooling is carried out at the cooling speed of 100 ℃/min to obtain the Cu-WMo/C composite material.
The SEM photograph of the Cu-W-Mo/C composite material prepared in this example is shown in FIG. 4, which shows that the composite material has a uniform and continuous three-dimensional network structure and graphite particles are uniformly distributed.
The properties of the Cu-X/C composite materials prepared in the above-mentioned examples 1 to 4 of the present invention were measured, and the results are shown in Table 1.
TABLE 1 Properties of Cu-X/C composites in examples 1-4
Figure BDA0002075275820000081
As can be seen from Table 1, the Cu-X/C composite material prepared by the preparation method disclosed by the invention is low in resistivity, good in electric and heat conductivity, high in density, low in friction coefficient and excellent in mechanical property.

Claims (8)

1. A preparation method of a Cu-X/C composite material, wherein X in the Cu-X/C composite material is at least one of Cr, Mo and W, and is characterized by comprising the following steps:
(1) sequentially carrying out oil removal, coarsening, sensitization and activation on the carbon material;
(2) adding the activated carbon material obtained in the step (1) into a Cu-X plating solution, adjusting the pH value with an alkali solution, slowly adding a reducing agent until the solution is clear, cleaning the solution to be neutral with deionized water, and drying the solution to obtain a Cu-X coated carbon material;
(3) adding the Cu-X coated carbon material obtained in the step (2) into a copper plating solution, adjusting the pH value with an alkali solution, slowly adding a reducing agent, stirring until the solution is clear, then washing with deionized water to be neutral, and drying to obtain a Cu-X/C composite material precursor;
(4) sintering the precursor of the Cu-X/C composite material obtained in the step (3) to obtain a Cu-X/C composite material;
in the step (2), the Cu-X plating solution contains main salt and complexing agent, wherein the main salt is CuSO4And a soluble salt containing X, the soluble salt containing X being CrCl3、Na2MoO4、H4Na2O6At least one of W, KNaC as complexing agent4H4O6•4H2O and EDTA;
based on the volume of the Cu-X plating solution, the concentration of the main salt is 20-30g/L, the concentration of the complexing agent is 30-100g/L, and CuSO4And soluble salt containing X in a mass ratio of 1: 1-2: 1, KNaC4H4O6•4H2The mass ratio of O to EDTA is 1:1-4: 5.
2. The method according to claim 1, wherein in the step (3), the copper plating solution contains a main salt, a complexing agent and a stabilizer, and the main salt is CuSO4·5H2O, KNaC as complexing agent4H4O6·4H2Mixtures of O and EDTA, stabilizersIs K4Fe(CN)6·3H2O; based on the volume of the copper plating solution, the concentration of the main salt is 15-25g/L, the concentration of the stabilizer is 1-1.5g/L, the concentration of the complexing agent is 30-36g/L, and KNaC4H4O6·4H2The mass ratio of O to EDTA is 1:1-4: 5.
3. The production method according to claim 1, wherein in the step (2), the temperature of the Cu — X plating solution is maintained at 50 to 60 ℃; in the step (3), the temperature of the copper plating solution is maintained at 50-60 ℃.
4. The method according to claim 1, wherein in the step (2) and the step (3), the reducing agent is C2H2O3At least one of formaldehyde, hydrazine and sodium borohydride, wherein the concentration of the reducing agent is 10-13 ml/L; in the step (2), the adding amount of the reducing agent is 10-50g/L based on the volume of the Cu-X plating solution; in the step (3), the adding amount of the reducing agent is 10-50g/L based on the volume of the copper plating solution.
5. The method according to claim 1, wherein in the steps (2) and (3), the alkali solution is NaOH solution, and the pH value is adjusted to 12-13.
6. The production method according to claim 1, wherein in the step (4), spark plasma sintering is performed with a degree of vacuum of 10 or less-3Pa, the heating rate is 50-100 ℃/min, the sintering temperature is 850-.
7. The production method according to claim 1, wherein in the step (1), the carbon material is at least one of graphite, carbon nanotube, diamond, and carbon fiber;
the oil removal is to add the carbon material into alkali liquor and stir the mixture, wherein the alkali liquor is NaOH solution, the concentration of the alkali liquor is 100-150g/L, the stirring time is 30-60min, and the stirring temperature is above 90 ℃;
the coarsening is to add the carbon material after deoiling into acid liquor and stir, wherein the acid liquor is HNO3The concentration of the acid liquor is 10-50 vol.%, the stirring time is 30-60min, and the stirring temperature is above 90 ℃;
the sensitization is to add the coarsened carbon material into a sensitization liquid to be stirred, wherein the sensitization liquid is SnCl2The concentration of the sensitizing solution is 5-20g/L, the pH value is 1-1.5, the stirring time is 20-30min, and the stirring temperature is room temperature;
the activation is to add the sensitized carbon material into an activation solution which is PdCl for stirring treatment2The concentration of the solution and the activating solution is 0.05-2g/L, the activating temperature is 50-60 ℃, and the stirring time is 10-30 min.
8. A Cu-X/C composite material produced by the production method according to any one of claims 1 to 7.
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