CN117884607A - Preparation method of carbon-copper alloy electrode material and carbon-copper alloy electrode material - Google Patents

Abstract

The invention provides a preparation method of a carbon-copper alloy electrode material and the carbon-copper alloy electrode material, wherein the method comprises the following steps: mixing, namely uniformly mixing tungsten carbide particles with carbon-based material powder according to a preset proportion; compression molding, namely compression molding the mixture of the tungsten carbide particles and the carbon-based material; heating and roasting, namely heating and roasting the green body; copper dipping, namely carrying out copper dipping treatment on the carbon-based blank; wherein the mixing process can also comprise dispersing and rolling after copper leaching. The carbon copper alloy electrode material with better conductivity and mechanical strength is realized, and the interface wettability of the carbon copper alloy electrode material can be obviously improved; the impregnability of the carbon copper alloy electrode material can be obviously improved, the impregnability is excellent, and the carbon copper alloy electrode material is more suitable for high-performance electrochemical devices.

Description

Preparation method of carbon-copper alloy electrode material and carbon-copper alloy electrode material

Technical Field

The invention belongs to the technical field of materials, and particularly relates to a preparation method of a carbon-copper alloy electrode material and the carbon-copper alloy electrode material.

Background

The carbon-copper alloy electrode material is widely used in the fields of welding, electronic packaging and the like due to excellent electrical conductivity and good thermal conductivity.

Existing methods of carbon-copper composite preparation generally involve impregnating a copper melt into a porous carbon matrix, but often suffer from interfacial defects due to non-wettability between carbon and copper, which is insufficient to meet more demanding application standards. Therefore, there is a need for improved interfacial wetting and impregnation that reduces defects in the composite.

Disclosure of Invention

The invention aims to provide a preparation method of a carbon-copper alloy electrode material and the carbon-copper alloy electrode material, which adopt carbon-based powder and tungsten carbide particles as raw materials, realize the carbon-copper alloy electrode material with better conductivity and mechanical strength through the processes of mixing, high-temperature sintering and the like, have excellent interface wetting and impregnation performance, reduce the defects in a composite material and are suitable for high-performance electrochemical devices.

The technical scheme provided by the invention is as follows:

a preparation method of a carbon copper alloy electrode material comprises the following steps:

step 1: mixing, namely uniformly mixing tungsten carbide particles with carbon-based material powder according to a preset proportion;

the particle size of the tungsten carbide particles is 0.1-20 microns, and the carbon-based material powder adopts a porous carbon matrix with proper porosity matched with the tungsten carbide particles; the volume ratio of the tungsten carbide particles to the porous carbon matrix is as follows: 1 to 5: 95-99;

Step 2: compression molding, namely compression molding the mixture of the tungsten carbide particles and the carbon-based material;

cold press molding is adopted, and the pressure is 10-20 MPa; obtaining a green body for standby;

step 3: heating and roasting, namely heating and roasting the green body;

heating to 450-550 ℃ in heating equipment, roasting, preserving heat for 30-60 minutes, and cooling to room temperature to obtain a carbon-based blank for later use;

step 4: copper dipping, namely carrying out copper dipping treatment on the carbon-based blank;

placing the carbon-based blank in a copper melt with the copper flow rate of 0.1-2.0 cm/s, and preserving the heat for 2-4 hours at the temperature of 920-960 ℃; and cooling to room temperature to obtain the carbon copper alloy electrode material.

A preparation method of a carbon copper alloy electrode material comprises the following steps:

step 1: mixing, namely uniformly mixing tungsten carbide particles with carbon-based material powder according to a preset proportion;

the particle size of the tungsten carbide particles is 0.1-20 microns, the carbon-based material powder adopts active carbon powder, and the particle size is 1-20 microns; the mass ratio of the tungsten carbide particles to the activated carbon powder is as follows: 1:2 to 6; putting tungsten carbide particles and active carbon powder into a dispersion solution for dispersion treatment, mechanically stirring for 1.5-3 hours, and then performing ultrasonic dispersion for 30-60 minutes;

step 2: compression molding, namely compression molding the tungsten carbide particles after the dispersion treatment and activated carbon powder;

Stamping and forming, wherein the pressure is 5-15 MPa; obtaining a green body for standby;

step 3: heating and roasting, namely heating and roasting the green body;

heating to 150-220 ℃ in heating equipment, roasting, preserving heat for 20-60 minutes, and cooling to room temperature to obtain a carbon-based blank for later use;

step 4: copper dipping, namely carrying out copper dipping treatment on the carbon-based blank;

placing the carbon-based blank in a copper melt with the copper flow rate of 0.1-2.0 cm/s, and preserving the heat for 2-4 hours at the temperature of 920-960 ℃; cooling to room temperature to obtain a copper-immersed carbon-based blank;

step 5: repeatedly rolling the copper-immersed carbon-based blank for 15-20 times under the rolling pressure of 20-200 MPa; adding 0.1-0.3% of graphene in the rolling process; and obtaining the carbon copper alloy electrode material.

The activated carbon powder in the step 1 comprises activated carbon with high specific surface area;

and/or the number of the groups of groups,

the dispersion solution in the step 1 comprises sodium chloride and potassium chloride aqueous solution; the weight ratio of the sodium chloride to the potassium chloride is 0.5-5:1; the content of sodium chloride and potassium chloride in the water is 0.01-0.1% w/v.

The pressure in the stamping forming process in the step 2 is 10MPa; or increasing the pressure in the stamping forming process in the step 2, starting from 5MPa, increasing 1MPa for each stamping for 1 time until reaching 15MPa, and then finishing the subsequent times of 15MPa pressure stamping;

And/or;

the copper leaching process in the step 4 comprises the steps of carrying out vacuum copper leaching in stages, firstly carrying out copper leaching under the vacuum degree of 10 < -3 > to 10 < -4 > millibar, and then completing copper leaching under the vacuum degree of 10 < -4 > to 10 < -5 > millibar; or the copper leaching process in the step 4 comprises full-stage vacuum copper leaching, wherein the vacuum degree is 10 < -3 > to 10 < -5 > millibars;

and/or;

in the rolling process of the step 5, repeatedly rolling the copper-immersed porous carbon matrix for 15 times, and adding graphene required for increasing conductivity in the first 5 times; graphene required to optimize the material structure was added in the last 10 times.

A preparation method of a carbon copper alloy electrode material comprises the following steps:

step 1: mixing, namely uniformly mixing tungsten carbide particles with carbon-based material powder according to a preset proportion;

the particle size of the tungsten carbide particles is 0.1-20 microns, the carbon-based material powder adopts graphite powder, and the particle size is 1-20 microns; the mass ratio of the tungsten carbide particles to the graphite powder is as follows: 1:2 to 10; putting tungsten carbide particles and graphite powder into a dispersion solution for dispersion treatment, mechanically stirring for 1.5-5 hours, and then performing ultrasonic dispersion for 30-90 minutes;

step 2: compression molding, namely compression molding the tungsten carbide particles after the dispersion treatment and graphite powder;

Stamping and forming, wherein the pressure is 5-24 MPa; obtaining a green body for standby;

step 3: heating and roasting, namely heating and roasting the green body;

heating to 150-220 ℃ in heating equipment, roasting, preserving heat for 20-60 minutes, and cooling to room temperature to obtain a carbon-based blank for later use;

step 4: copper dipping, namely carrying out copper dipping treatment on the carbon-based blank;

placing the carbon-based blank into a copper melt with the copper flow rate of 0.1-2.0 cm/s to dip copper, and preserving heat for 2-4 hours at 920-960 ℃; cooling to room temperature to obtain a copper-immersed porous carbon matrix;

step 5: repeatedly rolling the copper-immersed porous carbon matrix for 15-20 times under the rolling pressure of 20-200 MPa; adding 0.1-5% of graphene in the rolling process; and obtaining the carbon copper alloy electrode material.

The graphite powder in the step 1 is conductive graphite powder;

and/or the number of the groups of groups,

the dispersion solution in the step 1 comprises sodium chloride and potassium chloride aqueous solution; the weight ratio of the sodium chloride to the potassium chloride is 0.5-5:1; the content of sodium chloride and potassium chloride in the water is 0.01-0.1% w/v.

The pressure in the stamping forming process in the step 2 is 15MPa; or increasing the pressure in the stamping forming process in the step 2, starting from 5MPa, increasing 3MPa for each stamping 1 time until reaching 24MPa, and then finishing the subsequent times of 24MPa pressure stamping;

And/or;

the heating process in the heating roasting in the step 3 adopts a heating rate of 5 ℃/min until the roasting temperature is reached, the temperature is kept for 30 minutes, and then the temperature is cooled to the room temperature in a controlled cooling mode;

and/or;

the copper leaching process in the step 4 comprises pressure copper leaching, wherein the pressure range is 5MPa to 20 MPa; or, the copper leaching process in the step 4 comprises the steps of carrying out vacuum copper leaching in stages, wherein the vacuum degree is 10 < -3 > to 10 < -5 > millibar, carrying out copper leaching at the low temperature of 800-900 ℃ and preserving heat for 1-2 hours; then copper is immersed at a high temperature of 950-1000 ℃ and the temperature is kept for 2-3 hours, thus completing copper immersion;

and/or;

in the rolling process of the step 5, repeatedly rolling the copper-immersed porous carbon matrix for 15 times, and adding graphene required for increasing conductivity in the first 5 times; and adding graphene required for enhancing the structure density in the last 10 times.

A preparation method of a carbon copper alloy electrode material comprises the following steps:

step 1: mixing, namely uniformly mixing tungsten carbide particles with carbon-based material powder according to a preset proportion;

the particle size of the tungsten carbide particles is 0.1-20 microns, carbon-based material powder adopts carbon nano tube powder, and the particle size is 1-20 microns; the mass ratio of the tungsten carbide particles to the carbon nano tube powder is as follows: 1: 6-10; putting tungsten carbide particles and carbon nano tube powder into a dispersion solution for dispersion treatment, mechanically stirring for 1.5-2 hours, and then performing ultrasonic dispersion for 120-150 minutes;

Step 2: compression molding, namely compression molding the tungsten carbide particles after the dispersion treatment and carbon nano tube powder;

stamping and forming to obtain a green body under the pressure of 25MPa for later use;

step 3: heating and roasting, namely heating and roasting the green body;

heating to 100-120 ℃ in heating equipment, roasting, preserving heat for 20-60 minutes, and cooling to room temperature to obtain a carbon-based blank for later use;

step 4: copper dipping, namely carrying out copper dipping treatment on the carbon-based blank;

placing the carbon-based blank into a copper melt with the copper flow rate of 0.1-2.0 cm/s, carrying out vacuum copper leaching, and preserving heat for 2-4 hours at 920-960 ℃; the vacuum degree is 10 < -3 > to 10 < -5 > millibars, and the porous carbon matrix immersed with copper is obtained after cooling to room temperature;

step 5: repeatedly rolling the copper-immersed porous carbon matrix for 15-20 times under the rolling pressure of 20-200 MPa; adding 0.1-5% of graphene in the rolling process; and obtaining the carbon copper alloy electrode material.

The dispersion solution in the step 1 comprises sodium chloride and potassium chloride aqueous solution; the weight ratio of the sodium chloride to the potassium chloride is 0.5-5:1; the content of sodium chloride and potassium chloride in water is 0.01-0.1% w/v;

and/or;

and in the rolling process of the step 5, the porous carbon substrate immersed with copper is repeatedly rolled for 15 times, wherein the added amount of graphene is increased by 0.2% each time in the first 7 times, and the added amount of graphene is increased by 0.1% each time in the last 8 times.

The carbon copper alloy electrode material is prepared by the method.

According to the technical scheme provided by the invention, the preparation method of the carbon-copper alloy electrode material and the carbon-copper alloy electrode material provided by the embodiment of the invention realize the carbon-copper alloy electrode material with better conductivity and mechanical strength through taking carbon-based powder and tungsten carbide particles as raw materials, specific mixing, high-temperature sintering and other processes, and the carbon-copper alloy electrode material has excellent interface wetting and impregnation properties, and is more suitable for a high-performance electrochemical device.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.

Fig. 1 is a flowchart of a method for preparing a carbon-copper alloy electrode material according to an embodiment of the present invention.

Detailed Description

The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention.

The terms that may be used herein will first be described as follows:

7"," 3 to 5 and 7"," 2 and 5 to 7", etc. Unless otherwise indicated, numerical ranges recited herein include both their endpoints and all integers and fractions within the numerical range.

The terms "center," "longitudinal," "transverse," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," etc. refer to an orientation or positional relationship based on that shown in the drawings, merely for ease of description and to simplify the description, and do not explicitly or implicitly indicate that the apparatus or element in question must have a particular orientation, be constructed and operated in a particular orientation, and therefore should not be construed as limiting the present disclosure.

Embodiments of the present invention will be described in further detail below with reference to the accompanying drawings.

Example 1

As shown in fig. 1, a preparation method of a carbon copper alloy electrode material includes:

step 1: mixing, namely uniformly mixing tungsten carbide particles with carbon-based material powder according to a preset proportion;

The particle size of the tungsten carbide particles is 0.1-20 microns, and the carbon-based material powder adopts a porous carbon matrix with proper open porosity matched with the tungsten carbide particles; the proper open porosity here refers to a porous carbon matrix with an open porosity of between 20% and 60%; the volume ratio of the tungsten carbide particles to the porous carbon matrix is as follows: 1 to 5: 95-99;

tungsten carbide is a compound composed of tungsten and carbon, is a black hexagonal crystal, has metallic luster, has hardness similar to that of diamond, and is a good conductor of electricity and heat. Tungsten carbide is insoluble in water, hydrochloric acid and sulfuric acid and is easily dissolved in mixed acid of nitric acid and hydrofluoric acid; pure tungsten carbide is fragile, and if a small amount of metals such as titanium, cobalt and the like are doped, the brittleness can be reduced; tungsten carbide, which is used as a steel cutting tool, is often added with titanium carbide, tantalum carbide or a mixture thereof to improve antiknock capability. The tungsten carbide has stable chemical property, and the tungsten carbide powder is applied to hard alloy production materials.

The particle size of the tungsten carbide particles is in the range of 0.1-20 microns, the mixing efficiency of the tungsten carbide particles with smaller particle size and carbon-based powder can be improved, and the interface wetting of the electrode material can be improved by adding the tungsten carbide particles;

The porous carbon matrix is a porous carbon matrix, and is a carbon material with a high-porosity structure. It is typically formed by incorporating microscopic to nanoscale pore structures in the carbon material. These pores can provide a large specific surface area that facilitates the adsorption of gases, liquids or other substances, making them useful in a wide range of adsorption, catalytic and electrochemical applications. Porous carbon matrices with suitable open porosities between 20% and 60% are employed, these porosities being relatively large, suitable for adsorption or storage of larger particles. As for matching with tungsten carbide particles of 0.2-0.5 microns, the open porosity may need to be larger to ensure adequate space.

Step 2: compression molding, namely compression molding the mixture of the tungsten carbide particles and the carbon-based material;

the pressing adopts processes such as stamping, the example adopts cold press molding, the mixture of tungsten carbide particles and carbon-based materials is put into a steel mold for cold pressing, and the pressure is controlled to be 10-20 MPa; obtaining a green body for standby; the size and shape of the green body are related to market demand and the design of the mold, and can be designed by itself.

Step 3: heating and roasting, namely heating and roasting the green body;

Heating to 450-550 ℃ in heating equipment, roasting, preserving heat for 30-60 minutes, and cooling to room temperature to obtain a carbon-based blank for later use;

here, the heating apparatus may use a muffle furnace; the muffle furnace is a general heating device, also called a box furnace, and the working principle of the muffle furnace is based on the resistance heating effect; the heat-insulating material consists of a heating element, an insulating material, a heat-insulating layer and a shell; when an electric current is passed through the heating element, it generates a significant amount of heat; the insulating material is used for isolating the heating element so as to prevent heat loss; the heat preservation layer can help the muffle furnace to keep a higher temperature, so that the heating efficiency is improved; this is a common device known in the art.

Step 4: copper dipping, namely carrying out copper dipping treatment on the carbon-based blank;

placing the carbon-based blank in a copper melt at a copper flow rate of 0.1-2.0 cm/s, and preserving heat for 2-4 hours at 920-960 ℃; and cooling to room temperature to obtain the carbon copper alloy electrode material. The copper-leaching treatment is to deposit copper on the carbon-based green body by electrochemical reduction.

The following are examples of embodiments to name a few:

example 1:

step 1: mixing tungsten carbide particles with the granularity of 1-10 micrometers and a porous carbon matrix of which the open porosity is 20-60 percent, and uniformly mixing according to the volume ratio of 1:99; tungsten carbide particles of 5 microns may be used herein.

Step 2: compression molding, namely, carrying out cold compression molding on a mixture of tungsten carbide particles and carbon-based materials in a steel mold under the pressure of 15MPa to obtain a green body;

step 3: heating and roasting, namely heating the green body to 500 ℃ in a muffle furnace, and preserving heat for 30 minutes to ensure that tungsten carbide particles are well combined with a porous carbon matrix to obtain a carbon-based green body;

step 4: copper dipping, namely placing the cooled carbon-based blank into a copper solution with the copper flow rate of 0.2-2 cm/s, and preserving the heat for 2 hours at 960 ℃ for dipping; cooling in natural environment after finishing the dipping treatment, and obtaining the carbon-copper alloy electrode material.

Example 2:

based on example 1, the properties of the composite material can be optimized by varying the volume ratio of tungsten carbide particles to the carbon matrix. For example, by adjusting the volume ratio of carbonized particles to the carbon matrix to 5:95, the maximum copper flow rate can be further reduced, which is 0.1 cm/s, to achieve a more uniform copper melt flow. The other steps are the same.

Example 3:

on the basis of example 1, the holding time and temperature can be varied during the impregnation step, such as by lowering the holding temperature to 920 ℃ and extending the holding time to 4 hours, better copper melt flow control and a more uniform composite structure can be achieved. The other steps are the same.

Example two

As shown in fig. 1, a preparation method of a carbon copper alloy electrode material includes:

step 1: mixing, namely uniformly mixing tungsten carbide particles with carbon-based material powder according to a preset proportion;

the particle size of the tungsten carbide particles is 0.1-20 microns, the carbon-based material powder adopts active carbon powder, and the particle size is 1-20 microns; the mass ratio of the tungsten carbide particles to the activated carbon powder is as follows: 1:2 to 6;

here, the activated carbon powder may be a general activated carbon powder, or may be a high specific surface area activated carbon powder; the high specific surface area is referred to herein as a specific surface area of up to 3000m ² The activated carbon powder is prepared from carbon-containing raw materials such as wood, coal, petroleum coke and the like through pyrolysis and activation processing, and has developed pore structure, larger specific surface area and rich surface chemical groups, and is collectively called as a carbon material with stronger specific adsorption capacity.

In the example, tungsten carbide particles and active carbon powder are put into a dispersion solution for dispersion treatment, and after mechanical stirring for 1.5-3 hours, ultrasonic dispersion is carried out for 30-60 minutes; the mechanical stirring adopts a well-known mechanical stirring process, belongs to a well-known technology and is not repeated.

Here, the dispersion solution includes aqueous solutions of sodium chloride and potassium chloride; the weight ratio of the sodium chloride to the potassium chloride is 1-5:1; the content of sodium chloride and potassium chloride in the water is 0.01-0.1% (w/v, mass/volume).

Sodium chloride and potassium chloride are common chemical raw materials and are not described in detail.

Ultrasonic dispersion, wherein the mechanical vibration effect generated by the propagation of ultrasonic waves in liquid is that the interaction among particles is reduced, so that the particles are dispersed; when ultrasonic waves pass through liquid, an effect of alternately propagating compression waves and sparse waves is generated; the compressed and sparse regions created by this alternating propagation produce high frequency, high pressure, high temperature, high velocity localized liquid motion, resulting in collisions, shearing and crushing of the particles, resulting in uniform dispersion of the particles.

Step 2: compression molding, namely compression molding the tungsten carbide particles after the dispersion treatment and activated carbon powder;

pressing by adopting processes such as stamping and the like, wherein the mixture of tungsten carbide particles and carbon-based materials is put into a steel die for stamping, and the pressure is controlled to be 5-15 MPa; obtaining a green body for standby; the size and shape of the green body are related to market demand and the design of the mold, and can be designed by itself.

Here, in the press forming process, different pressures, for example, 10MPa, may be used according to different processes; or the pressure is increased in the stamping forming process, 1MPa is increased from 5MPa for each stamping time until 15MPa, and then the subsequent times of 15MPa pressure stamping are completed.

The press molding is a process molding method for obtaining a workpiece of a desired shape and size by applying an external force to a powder material, a plate, a strip, a tube, a profile, etc. by a press and a die to cause plastic deformation.

Step 3: heating and roasting, namely heating and roasting the green body;

heating the green body to 150-220 ℃ in heating equipment, roasting, preserving heat for 20-60 minutes, and cooling to room temperature to obtain a carbon-based green body for later use; here, the heating apparatus may use a muffle furnace.

Step 4: copper dipping, namely carrying out copper dipping treatment on the carbon-based blank;

placing the carbon-based blank in a copper melt with the copper flow rate of 0.1-2.0 cm/s, and preserving heat for 2-4 hours at the temperature of 920-960 ℃; cooling to room temperature to obtain a copper-immersed carbon-based blank;

here, the copper leaching process can be selected to be full-stage vacuum copper leaching according to different processes; the vacuum degree is 10 < -3 > to 10 < -5 > millibars; or selecting staged vacuum copper leaching, pre-soaking copper under 10 < -3 > -10 < -4 > millibar vacuum degree, and then completing copper leaching under 10 < -4 > -10 < -5 > millibar vacuum degree.

Step 5: repeatedly rolling the copper-immersed carbon-based blank for 15-20 times under the rolling pressure of 20-200 MPa; adding 0.1-5% of graphene in the rolling process; and obtaining the carbon copper alloy electrode material. The graphene material may be a single-layer or multi-layer graphene. The rolling may be performed to obtain a copper alloy electrode material with extremely high densification.

Here, in the rolling process, the porous carbon matrix immersed with copper can be repeatedly rolled for 15 times according to different processes, and single-layer graphene with the concentration of graphene required for increasing conductivity of 0.1-5% of the material is added in the first 5 times; and adding multiple layers of graphene with the mass ratio of 0.2-0.8% required by optimizing the material structure in the last 10 times.

Graphene is a kind of graphene with sp ² New materials with hybridized linked carbon atoms closely packed into a monolayer two-dimensional honeycomb lattice structure. The structure of graphene is very stable. The connection between the carbon atoms inside the graphene is flexible, and when external force is applied to the graphene, the carbon atom faces are bent and deformed, so that the carbon atoms do not need to be rearranged to adapt to the external force, and the structure is kept stable. This stable lattice structure gives graphene excellent thermal conductivity; in addition, electrons in graphene are not scattered due to lattice defects or the introduction of foreign atoms when moving in an orbit. Because the interatomic force is very strong, even if surrounding carbon atoms collide, the interference of electrons in the graphene is very small; meanwhile, the graphene has aromaticity and aromatic hydrocarbon property.

The following are examples of embodiments:

example 4:

step 1: mixing, namely mixing tungsten carbide particles with the granularity of 1-20 microns with activated carbon powder with the granularity of 1-20 microns according to the mass ratio of 1:5 to prepare carbon-based powder; for example, tungsten carbide particles with the size of 6 microns and activated carbon powder with the size of 6 microns can be selected;

dispersing the mixed sodium chloride and potassium chloride according to the mass ratio of 1:1 are mixed with water to prepare a dispersion solution, wherein the content of sodium chloride and potassium chloride in the water is 0.01-0.1% (w/v, mass/volume). Mechanically stirring the carbon-based powder in the dispersing solution for 2 hours, and then performing ultrasonic dispersion for 30 minutes;

step 2: press molding, namely press molding the mixture of the dispersed tungsten carbide particles and the activated carbon powder in a steel mold, and performing press molding under the pressure of 10MPa to obtain a green body;

step 3: heating and roasting, namely roasting and heating the green body in a muffle furnace at 150 ℃ for 20 minutes, and cooling to room temperature after roasting to obtain a modified porous carbon matrix, namely a carbon-based green body;

step 4: copper dipping, carrying out full-stage vacuum copper dipping treatment on the carbon-based blank in a vacuum environment, placing the cooled carbon-based blank in a copper solution with a copper flow rate of 0.1-0.3 cm/s, and preserving heat for 2 hours at 965 ℃ with a vacuum degree of 10 < -3 > to 10 < -5 > millibars;

Step 5: repeatedly rolling the carbon-based blank subjected to copper leaching for 15 times under the rolling pressure of 120MPa; and (3) uniformly adding 0.1% of graphene in mass ratio in each rolling process, and finally obtaining the carbon copper alloy electrode material with extremely high densification degree.

Example 5:

step 1: mixing tungsten carbide particles with the granularity of 1-20 microns and active carbon powder with the granularity of 1-20 microns and high specific surface area according to the mass ratio of 1:3 to prepare carbon-based powder; for example, 10 micrometer tungsten carbide particles and active carbon powder with high specific surface area and granularity of 10 micrometers can be selected;

dispersing the mixed sodium chloride and potassium chloride according to a mass ratio of 2:3 mixing with water to obtain a dispersion solution, wherein the content of sodium chloride and potassium chloride in the water is 0.01-0.1% (w/v, mass/volume). Mechanically stirring the carbon-based powder in the dispersion solution for 3 hours, and then performing ultrasonic dispersion for 30 minutes;

step 2: press forming, namely press forming the mixture of the dispersed tungsten carbide particles and the active carbon powder with high specific surface area in a steel mould, adopting stamping processing, starting from 5MPa pressure, increasing 1MPa to 15MPa for each stamping, and press forming to obtain a green body;

step 3: heating and roasting, namely roasting and heating the green body in a muffle furnace at 200 ℃ and preserving heat for 40 minutes to obtain a carbon-based green body so as to realize better porous structure and mechanical stability;

Step 4: copper is immersed, the carbon-based embryo is subjected to stage vacuum copper immersing treatment in a vacuum environment, and the copper flow rate of the copper solution is 0.5-1.0 cm/s. Firstly, pre-soaking copper under the vacuum with the vacuum degree of 10 < -3 > -10 < -4 > millibars, then finishing the final copper soaking process under the vacuum with the vacuum degree of 10 < -4 > -10 < -5 > millibars, wherein the copper soaking temperature is set to 950 ℃ and the temperature is kept for 2 hours;

step 5: repeatedly rolling the carbon-based blank subjected to copper leaching for 15 times under the rolling pressure of 50MPa; and adding graphene in the rolling process according to staged addition, pressing graphene required by adding conductivity for the first 5 times, and optimizing the structure of the material for the last 10 times, so as to finally obtain the carbon-copper alloy electrode material.

Example III

As shown in fig. 1, a preparation method of a carbon copper alloy electrode material includes:

step 1: mixing, namely uniformly mixing tungsten carbide particles with carbon-based material powder according to a preset proportion;

the particle size of the tungsten carbide particles is 0.1-20 microns, the carbon-based material powder adopts graphite powder, and the particle size is 1-20 microns; the mass ratio of the tungsten carbide particles to the graphite powder is as follows: 1:2 to 10;

the graphite powder may be natural graphite, artificial graphite or expanded graphite, the expanded graphite powder having a particle size of 1 to 20 μm, and the expanded graphite is a specially treated graphite material which is usually expanded or oxidized at high temperature to increase the interlayer spacing thereof, thereby improving the conductivity and other characteristics thereof. Expanded graphite is often used in the preparation of electrode materials because of its excellent electrical and thermal conductivity, and is suitable for many applications. In the preparation method, the use of the expanded graphite can help to improve the performance of the carbon-copper alloy electrode material. Or may be a conductive graphite powder.

In the example, tungsten carbide particles and graphite powder are put into a dispersion solution for dispersion treatment, and after mechanical stirring for 1.5-5 hours, ultrasonic dispersion is carried out for 30-90 minutes;

here, the dispersion solution includes aqueous solutions of sodium chloride and potassium chloride; the weight ratio of the sodium chloride to the potassium chloride is 1-5:1; the content of sodium chloride and potassium chloride in the water is 0.01-0.1% (w/v, mass/volume).

Step 2: compression molding, namely compression molding the tungsten carbide particles and graphite powder;

pressing by adopting processes such as stamping and the like, wherein the example adopts stamping and forming, and a mixture of tungsten carbide particles and carbon-based materials is put into a steel die for stamping, and the pressure is controlled to be 5-24 MPa; obtaining a green body for standby; the size and shape of the green body are related to market demand and the design of the mold, and can be designed by itself.

Here, in the press forming process, different pressures, for example, 15MPa, may be used according to different processes; or the pressure is increased in the stamping forming process, from 5MPa, 3MPa is increased for each stamping 1 time until 24MPa, and then 15MPa pressure stamping for the subsequent times is completed.

Step 3: heating and roasting, namely heating and roasting the green body;

Heating the green body to 150-220 ℃ in heating equipment, roasting, preserving heat for 20-60 minutes, and cooling to room temperature to obtain a carbon-based green body for later use; here, the heating apparatus may use a muffle furnace.

In the embodiment, step heating can be adopted, the heating process in the heating equipment adopts a heating rate of 5 ℃/min until the roasting temperature, the heat is preserved for 30 minutes, and then the temperature is cooled to the room temperature in a controlled cooling mode.

Step 4: copper dipping, namely carrying out copper dipping treatment on the carbon-based blank;

placing the carbon-based blank into a copper melt with the copper flow rate of 0.1-2.0 cm/s to dip copper, and preserving heat for 2-4 hours at 920-960 ℃; cooling to room temperature to obtain the copper-immersed carbon-based blank.

The copper immersing process can be carried out by selecting pressurized copper immersing according to different processes, and the pressure range can be between 5MPa and 20 MPa.

In addition, the staged vacuum copper leaching can be selected according to different processes in the copper leaching process, and the specific parameters are as follows:

under the vacuum with the vacuum degree of 10 < -3 > -10 < -5 > millibar, copper is firstly immersed at the low temperature of 800 ℃ to 900 ℃ and the temperature is kept for 1 to 2 hours; then copper is immersed at the high temperature of 950 ℃ to 1000 ℃ and the heat preservation is carried out for 2 to 3 hours, thus completing copper immersion.

These parameters can be fine tuned and optimized according to specific process requirements and experimental results to ensure that the desired properties of the carbon copper alloy electrode material are obtained. In practice, proper equipment and control is ensured to maintain the desired temperature, pressure and vacuum.

Step 5: repeatedly rolling the copper-immersed carbon-based blank for 15-20 times under the rolling pressure of 20-200 MPa; adding 0.1-5% of graphene in the rolling process; and obtaining the carbon copper alloy electrode material. The graphene material may be a single-layer or multi-layer graphene. The rolling may be performed to obtain a copper alloy electrode material with extremely high densification.

Here, in the rolling process, the porous carbon substrate immersed with copper can be repeatedly rolled for 15 times according to different processes, and graphene required for increasing conductivity is added in the first 5 times; and adding graphene required for enhancing the structure density in the last 10 times.

The following are three examples of embodiments:

example 6:

step 1: mixing tungsten carbide particles with the granularity of 1-20 microns and graphite powder with the granularity of 1-20 microns according to the mass ratio of 1:8 to prepare carbon-based powder; for example, 7 microns of tungsten carbide particles and graphite powder with the granularity of 7 microns can be selected;

dispersing the mixed sodium chloride and potassium chloride according to the mass ratio of 1:1 are mixed with water to prepare a dispersion solution, wherein the content of sodium chloride and potassium chloride in the water is 0.01-0.1% (w/v, mass/volume). Mechanically stirring the carbon-based powder in the dispersing solution for 1 hour, and then performing ultrasonic dispersion for 60 minutes;

Step 2: press molding, namely press molding the dispersed carbon-based powder in a steel mold, and performing press molding under the pressure of 15MPa to obtain a green body;

step 3: heating and roasting, namely roasting and heating the green body in a muffle furnace at 180 ℃ for 20 minutes, and cooling to room temperature after roasting to accurately control the generation of a porous structure so as to obtain a carbon-based green body;

step 4: copper is immersed, the carbon-based blank is immersed in copper melt with copper flow rate of 0.1-1.0 cm/s, copper immersing treatment is carried out on the carbon-based blank in vacuum environment to ensure copper permeability, the copper immersing temperature is set to 950 ℃ and the copper immersing temperature is kept for 2 hours under vacuum with vacuum degree of 10 < -3 > to 10 < -5 > millibars;

step 5: and (3) rolling, namely repeatedly pressing the carbon-based blank subjected to copper leaching for 15 times, and uniformly adding 0.3% of graphene in mass ratio in each pressing process to finally obtain the carbon-copper alloy electrode material with better conductivity.

Example 7:

step 1: mixing tungsten carbide particles with the granularity of 1-20 microns and conductive graphite powder with the granularity of 1-20 microns according to the mass ratio of 1:2 to prepare carbon-based powder; for example, tungsten carbide particles with the particle size of 3 microns and conductive graphite powder with the particle size of 3 microns can be selected;

Dispersing the mixed sodium chloride and potassium chloride according to the mass ratio of 1:1 and water to prepare the solvent, wherein the content of sodium chloride and potassium chloride in the water is 0.01-0.1% (w/v, mass/volume). Mechanically stirring the carbon-based powder in a solvent for 4 hours, and then performing ultrasonic dispersion for 90 minutes; the mechanical stirring here employs a temperature-controlled stirrer, the stirring temperature being controlled at 40℃in order to achieve a highly homogeneously dispersed mixture.

Step 2: press forming, namely press forming the dispersed carbon-based powder in a steel mold, wherein the pressure is increased from 5MPa to 24MPa each time, and press forming is carried out to obtain a green body;

step 3: heating and roasting, namely roasting and heating the green body in a muffle furnace at 180 ℃ for 20 minutes, wherein step heating is adopted in the example, the heating process in heating equipment is carried out at a heating rate of 5 ℃/min until the roasting temperature is reached, the temperature is kept for 30 minutes, and then cooling to room temperature is carried out in a controlled cooling mode, so as to obtain a carbon-based green body;

step 4: copper is immersed, the carbon-based blank is immersed in copper melt with copper flow rate of 0.1-2 cm/s, copper immersing treatment is carried out on the carbon-based blank in a vacuum environment, in the copper immersing process, staged vacuum copper immersing is selected, copper immersing is carried out at low temperature of 800-900 ℃ under vacuum with vacuum degree of 10 < -3 > -10 < -5 > mbar, and heat preservation is carried out for 1-2 hours; then copper is immersed at the high temperature of 950 ℃ to 1000 ℃ and the heat preservation is carried out for 2 to 3 hours, thus completing copper immersion. Ensure thorough copper immersion and densification of the material.

Step 5: rolling, repeatedly pressing the carbon-based blank subjected to copper impregnation treatment for 15 times, selecting the porous carbon substrate subjected to copper impregnation for 15 times in the example,adding graphene required for increasing conductivity in the first 5 times; and adding graphene required for enhancing the structure density in the last 10 times. Or, uniformly adding 0.3% of graphene in mass ratio in each pressing process, wherein the graphene adopts micro-porosity of 5-50% and porous specific surface area of 1000m ² And/g graphene, and finally obtaining the carbon copper alloy electrode material with better conductivity.

Example IV

As shown in fig. 1, a preparation method of a carbon copper alloy electrode material includes:

step 1: mixing, namely uniformly mixing tungsten carbide particles with carbon-based material powder according to a preset proportion;

the particle size of the tungsten carbide particles is 0.1-20 microns, carbon-based material powder adopts carbon nano tube powder, and the particle size is 1-20 microns; the mass ratio of the tungsten carbide particles to the carbon nano tube powder is as follows: 1: 6-10;

the carbon nanotube is one kind of one-dimensional quantum material with special structure, and has radial nanometer size and axial micron size, and two ends of the nanotube are sealed basically. Carbon nanotubes mainly consist of layers to tens of layers of coaxial round tubes of carbon atoms arranged in a hexagonal manner. The layer-to-layer distance is kept constant, about 0.34nm, and the diameter is typically 2-20 nm.

In the example, tungsten carbide particles and carbon nano tube powder are put into a dispersion solution for dispersion treatment, and after mechanical stirring for 1.5-2 hours, ultrasonic dispersion is carried out for 120-150 minutes;

here, the dispersion solution includes aqueous solutions of sodium chloride and potassium chloride; the weight ratio of the sodium chloride to the potassium chloride is 1-5:1; the content of sodium chloride and potassium chloride in the water is 0.1-0.1% (w/v, mass/volume).

Step 2: compression molding, namely compression molding the tungsten carbide particles after the dispersion treatment and carbon nano tube powder;

pressing to obtain a green body by adopting processes such as stamping and forming, namely putting the mixture of the dispersed tungsten carbide particles and the carbon-based material into a steel die for stamping, wherein the pressure is controlled to be 25 MPa; the size and shape of the green body are related to market demand and the design of the mold, and can be designed by itself.

Step 3: heating and roasting, namely heating and roasting the green body;

heating to 100-120 ℃ in heating equipment, roasting, preserving heat for 20-60 minutes, and cooling to room temperature to obtain a carbon-based blank for later use; here, the heating apparatus may use a muffle furnace.

Step 4: copper dipping, namely carrying out copper dipping treatment on the carbon-based blank;

Placing the carbon-based blank into a copper melt with the copper flow rate of 0.1-2.0 cm/s, carrying out vacuum copper leaching, and preserving heat for 2-4 hours at 920-960 ℃; cooling to room temperature under the vacuum degree of 10 < -3 > to 10 < -4 > millibar to obtain a copper-immersed carbon-based blank;

step 5: repeatedly rolling the copper-immersed porous carbon matrix for 15-20 times under the rolling pressure of 20-200 MPa; adding 0.1-5% of graphene in the rolling process; and obtaining the carbon copper alloy electrode material. The graphene material may be a single-layer or multi-layer graphene. The rolling may be performed to obtain a copper alloy electrode material with extremely high densification.

Here, in the rolling process, the porous carbon substrate immersed in copper can be repeatedly rolled for 15 times according to different processes, the graphene addition amount accounting for 0.2% of the total amount is increased every time in the first 7 times, the graphene addition amount accounting for 0.1% of the total amount is increased every time in the last 8 times, and the specific graphene addition amount accounting for the total amount in percentage: rolling for the 1 st time: 5.5%; rolling for the 2 nd time; 5.7% 3 rd pass rolling: 5.9%; rolling for the 4 th time: 6.1%; rolling for the 5 th time: 6.3%; and (6) rolling: 6.5%; rolling for the 7 th time: 6.7%; 8 th rolling: 6.8%; and 9, rolling: 6.9%; rolling for the 10 th time: 7.0%; 11 th rolling: 7.1%; 12 th rolling: 7.2%; 13 th rolling: 7.3%; rolling for the 14 th time: 7.5%; 15 th rolling: the balance. And finally, the total amount of the graphene is 100%.

The following is a third example for the embodiment:

example 8:

step 1: mixing tungsten carbide particles with the granularity of 1-20 microns and carbon nano tube powder with the granularity of 1-20 microns according to the mass ratio of 1:10 to prepare carbon-based powder; for example, 3 micron tungsten carbide particles and carbon nanotube powder with the particle size of 3 micron can be selected.

Dispersing the mixed sodium chloride and potassium chloride according to the mass ratio of 1:1 are mixed with water to prepare a dispersion solution, wherein the content of sodium chloride and potassium chloride in the water is 0.01-0.1% (w/v, mass/volume). Mechanically stirring the carbon-based powder in the dispersing solution for 2 hours, and then performing ultrasonic dispersion for 60 minutes;

step 2: press molding, namely press molding the dispersed carbon-based powder in a steel mold, and performing press molding under the pressure of 25MPa to obtain a green body;

step 3: heating and roasting, namely roasting and heating the green body in a muffle furnace at 100 ℃ for 20 minutes, and cooling to room temperature after roasting to ensure the structural integrity of the carbon material to the greatest extent, so as to obtain a carbon-based green body;

step 4: copper immersion

The carbon-based blank is placed in a copper melt with the copper flow rate of 0.1-1.0 cm/s for vacuum copper leaching, and the temperature is kept at 920-960 ℃ for 2-4 hours.

The vacuum level can be adjusted between 10-3 and 10-5 mbar depending on the process and experimental requirements.

Cooling to room temperature to obtain the copper-immersed carbon-based blank.

Step 5: rolling

Repeatedly pressing the carbon-based blank subjected to copper leaching for 15 times. Different graphene adding strategies are adopted, and specific parameters are as follows:

in the first 7 times, the graphene addition amount of 0.2% was increased each time to gradually increase the graphene content.

In the last 8 times, the graphene addition amount of 0.1% was maintained to maintain a stable content.

The total amount of graphene added was 100%.

This strategy aims at providing the material with a well-defined structure and performance, and finally obtaining the carbon-copper alloy electrode material with better conductivity.

Example five

The method of any one of embodiments one to four is used for preparing a carbon-copper alloy electrode material.

In summary, the carbon-based powder and the tungsten carbide particles are used as raw materials, and the specific mixing, high-temperature sintering and other processes are adopted to realize the carbon-copper alloy electrode material with better conductivity and mechanical strength, so that the interface wettability of the carbon-copper alloy electrode material can be obviously improved; the impregnability of the carbon copper alloy electrode material can be obviously improved, the impregnability is excellent, and the carbon copper alloy electrode material is more suitable for high-performance electrochemical devices.

The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions easily contemplated by those skilled in the art within the scope of the present invention should be included in the scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.

Claims (10)

1. The preparation method of the carbon-copper alloy electrode material is characterized by comprising the following steps of:

step 1: mixing, namely uniformly mixing tungsten carbide particles with carbon-based material powder according to a preset proportion;

the particle size of the tungsten carbide particles is 0.1-20 microns, and the carbon-based material powder adopts a porous carbon matrix with proper porosity matched with the tungsten carbide particles; the volume ratio of the tungsten carbide particles to the porous carbon matrix is as follows: 1 to 5: 95-99;

step 2: compression molding, namely compression molding the mixture of the tungsten carbide particles and the carbon-based material;

cold press molding is adopted, and the pressure is 10-20 MPa; obtaining a green body for standby;

step 3: heating and roasting, namely heating and roasting the green body;

heating to 450-550 ℃ in heating equipment, roasting, preserving heat for 30-60 minutes, and cooling to room temperature to obtain a carbon-based blank for later use;

Step 4: copper dipping, namely carrying out copper dipping treatment on the carbon-based blank;

placing the carbon-based blank in a copper melt with the copper flow rate of 0.1-2 cm/s, and preserving heat for 2-4 hours at the temperature of 920-960 ℃; and cooling to room temperature to obtain the carbon copper alloy electrode material.

2. The preparation method of the carbon-copper alloy electrode material is characterized by comprising the following steps of:

step 1: mixing, namely uniformly mixing tungsten carbide particles with carbon-based material powder according to a preset proportion;

the particle size of the tungsten carbide particles is 0.1-20 microns, the carbon-based material powder adopts active carbon powder, and the particle size is 1-20 microns; the mass ratio of the tungsten carbide particles to the activated carbon powder is as follows: 1:2 to 6; putting tungsten carbide particles and active carbon powder into a dispersion solution for dispersion treatment, mechanically stirring for 1.5-3 hours, and then performing ultrasonic dispersion for 30-60 minutes;

step 2: compression molding, namely compression molding the tungsten carbide particles after the dispersion treatment and activated carbon powder;

stamping and forming, wherein the pressure is 5-15 MPa; obtaining a green body for standby;

step 3: heating and roasting, namely heating and roasting the green body;

heating to 150-220 ℃ in heating equipment, roasting, preserving heat for 20-60 minutes, and cooling to room temperature to obtain a carbon-based blank for later use;

Step 4: copper dipping, namely carrying out copper dipping treatment on the carbon-based blank;

placing the carbon-based blank in a copper melt with the copper flow rate of 0.1-2.0 cm/s, and preserving the heat for 2-4 hours at the temperature of 920-960 ℃; cooling to room temperature to obtain a copper-immersed carbon-based blank;

step 5: repeatedly rolling the copper-immersed carbon-based blank for 15-20 times under the rolling pressure of 20-200 MPa; adding 0.1-0.3% of graphene in the rolling process; and obtaining the carbon copper alloy electrode material.

3. The method for preparing the carbon-copper alloy electrode material according to claim 2, characterized in that: the activated carbon powder in the step 1 comprises activated carbon with high specific surface area;

and/or the number of the groups of groups,

the dispersion solution in the step 1 comprises sodium chloride and potassium chloride aqueous solution; the weight ratio of the sodium chloride to the potassium chloride is 0.5-5:1; the content of sodium chloride and potassium chloride in the water is 0.01-0.1% w/v.

4. The method for preparing the carbon-copper alloy electrode material according to claim 2, characterized in that: the pressure in the stamping forming process in the step 2 is 10MPa; or increasing the pressure in the stamping forming process in the step 2, starting from 5MPa, increasing 1MPa for each stamping for 1 time until reaching 15MPa, and then finishing the subsequent times of 15MPa pressure stamping;

And/or;

the copper leaching process in the step 4 comprises the steps of carrying out vacuum copper leaching in stages, firstly carrying out copper leaching under the vacuum degree of 10 < -3 > to 10 < -4 > millibar, and then completing copper leaching under the vacuum degree of 10 < -4 > to 10 < -5 > millibar; or the copper leaching process in the step 4 comprises full-stage vacuum copper leaching, wherein the vacuum degree is 10 < -3 > to 10 < -5 > millibars;

and/or;

in the rolling process of the step 5, repeatedly rolling the copper-immersed porous carbon matrix for 15 times, and adding graphene required for increasing conductivity in the first 5 times; graphene required to optimize the material structure was added in the last 10 times.

5. The preparation method of the carbon-copper alloy electrode material is characterized by comprising the following steps of:

step 1: mixing, namely uniformly mixing tungsten carbide particles with carbon-based material powder according to a preset proportion;

the particle size of the tungsten carbide particles is 0.1-20 microns, the carbon-based material powder adopts graphite powder, and the particle size is 1-20 microns; the mass ratio of the tungsten carbide particles to the graphite powder is as follows: 1:2 to 10; putting tungsten carbide particles and graphite powder into a dispersion solution for dispersion treatment, mechanically stirring for 1.5-5 hours, and then performing ultrasonic dispersion for 30-90 minutes;

step 2: compression molding, namely compression molding the tungsten carbide particles after the dispersion treatment and graphite powder;

Stamping and forming, wherein the pressure is 5-24 MPa; obtaining a green body for standby;

step 3: heating and roasting, namely heating and roasting the green body;

heating to 150-220 ℃ in heating equipment, roasting, preserving heat for 20-60 minutes, and cooling to room temperature to obtain a carbon-based blank for later use;

step 4: copper dipping, namely carrying out copper dipping treatment on the carbon-based blank;

placing the carbon-based blank into a copper melt with the copper flow rate of 0.1-2.0 cm/s to dip copper, and preserving heat for 2-4 hours at 920-960 ℃; cooling to room temperature to obtain a copper-immersed porous carbon matrix;

step 5: repeatedly rolling the copper-immersed porous carbon matrix for 15-20 times under the rolling pressure of 20-200 MPa; adding 0.1-5% of graphene in the rolling process; and obtaining the carbon copper alloy electrode material.

6. The method for preparing a carbon-copper alloy electrode material according to claim 5, wherein: the graphite powder in the step 1 is conductive graphite powder;

and/or the number of the groups of groups,

the dispersion solution in the step 1 comprises sodium chloride and potassium chloride aqueous solution; the weight ratio of the sodium chloride to the potassium chloride is 0.5-5:1; the content of sodium chloride and potassium chloride in the water is 0.01-0.1% w/v.

7. The method for preparing a carbon-copper alloy electrode material according to claim 5, wherein: the pressure in the stamping forming process in the step 2 is 15MPa; or increasing the pressure in the stamping forming process in the step 2, starting from 5MPa, increasing 3MPa for each stamping 1 time until reaching 24MPa, and then finishing the subsequent times of 24MPa pressure stamping;

And/or;

the heating process in the heating roasting in the step 3 adopts a heating rate of 5 ℃/min until the roasting temperature is reached, the temperature is kept for 30 minutes, and then the temperature is cooled to the room temperature in a controlled cooling mode;

and/or;

the copper leaching process in the step 4 comprises pressure copper leaching, wherein the pressure range is 5MPa to 20 MPa; or, the copper leaching process in the step 4 comprises the steps of carrying out vacuum copper leaching in stages, wherein the vacuum degree is 10 < -3 > to 10 < -5 > millibar, carrying out copper leaching at the low temperature of 800-900 ℃ and preserving heat for 1-2 hours; then copper is immersed at a high temperature of 950-1000 ℃ and the temperature is kept for 2-3 hours, thus completing copper immersion;

and/or;

in the rolling process of the step 5, repeatedly rolling the copper-immersed porous carbon matrix for 15 times, and adding graphene required for increasing conductivity in the first 5 times; and adding graphene required for enhancing the structure density in the last 10 times.

8. The preparation method of the carbon-copper alloy electrode material is characterized by comprising the following steps of:

step 1: mixing, namely uniformly mixing tungsten carbide particles with carbon-based material powder according to a preset proportion;

the particle size of the tungsten carbide particles is 0.1-20 microns, carbon-based material powder adopts carbon nano tube powder, and the particle size is 1-20 microns; the mass ratio of the tungsten carbide particles to the carbon nano tube powder is as follows: 1: 6-10; putting tungsten carbide particles and carbon nano tube powder into a dispersion solution for dispersion treatment, mechanically stirring for 1.5-2 hours, and then performing ultrasonic dispersion for 120-150 minutes;

Step 2: compression molding, namely compression molding the tungsten carbide particles after the dispersion treatment and carbon nano tube powder;

stamping and forming to obtain a green body under the pressure of 25MPa for later use;

step 3: heating and roasting, namely heating and roasting the green body;

heating to 100-120 ℃ in heating equipment, roasting, preserving heat for 20-60 minutes, and cooling to room temperature to obtain a carbon-based blank for later use;

step 4: copper dipping, namely carrying out copper dipping treatment on the carbon-based blank;

placing the carbon-based blank into a copper melt with the copper flow rate of 0.1-2.0 cm/s, carrying out vacuum copper leaching, and preserving heat for 2-4 hours at 920-960 ℃; the vacuum degree is 10 < -3 > to 10 < -5 > millibars, and the porous carbon matrix immersed with copper is obtained after cooling to room temperature;

step 5: repeatedly rolling the copper-immersed porous carbon matrix for 15-20 times under the rolling pressure of 20-200 MPa; adding 0.1-5% of graphene in the rolling process; and obtaining the carbon copper alloy electrode material.

9. The method for preparing the carbon-copper alloy electrode material according to claim 8, wherein: the dispersion solution in the step 1 comprises sodium chloride and potassium chloride aqueous solution; the weight ratio of the sodium chloride to the potassium chloride is 0.5-5:1; the content of sodium chloride and potassium chloride in water is 0.01-0.1% w/v;

And/or;

and in the rolling process of the step 5, the porous carbon substrate immersed with copper is repeatedly rolled for 15 times, wherein the added amount of graphene is increased by 0.2% each time in the first 7 times, and the added amount of graphene is increased by 0.1% each time in the last 8 times.

10. A carbon copper alloy electrode material, characterized in that it is produced by the method according to any one of claims 1 to 9.