阅读说明：本技术 一种高寿铜基复合材料 (High-service-life copper-based composite material ) 是由 赵玉平 于 2020-11-22 设计创作，主要内容包括：本发明提供一种高寿铜基复合材料,所述复合材料依下至上分别为：铜合金基材、多孔铜层、晶种铜层、刺状铜、铜氧化层,其中所述铜合金为铜镍合金,铜基表面水热形成有刺状铜,能够显著提高电极材料的比表面积和活性位点,电极稳定好,获得的刺状铜不易剥离脱落；能够在在保证高乙烯转化率的同时提高其寿命。(The invention provides a long-life copper-based composite material, which comprises the following components in parts by weight: the copper alloy is a copper-nickel alloy, and the spine copper is formed on the surface of the copper base in a hydrothermal mode, so that the specific surface area and active sites of an electrode material can be remarkably improved, the stability of the electrode is good, and the obtained spine copper is not easy to peel off; the service life of the catalyst can be prolonged while high ethylene conversion rate is ensured.)

1. The long-life copper-based composite material is characterized in that the copper-based composite material is in a thorn shape, and the composite material comprises the following components in parts by weight: the copper-based composite material comprises a copper alloy substrate, a porous copper layer, a seed copper layer, thorn-shaped copper and a copper oxidation layer, wherein the copper alloy is a copper-nickel alloy, the porous copper layer is obtained by electrochemically reducing copper, the seed copper layer is obtained by electroless chemical reduction, the thorn-shaped copper is obtained by a hydrothermal method, the copper oxidation layer is obtained by an inorganic oxidation method, the copper oxide layer is attached to the surface of the thorn-shaped copper, the length of a thorn-shaped object in the copper-based composite material is 3-5 mu m, and the diameter of the thorn-shaped object is 300-500 nm.

2. An advanced life copper-based composite material as claimed in claim 1, wherein said copper-nickel alloy has a nickel content of 5-10 wt.%.

3. A long-life copper-based composite material according to claim 2, wherein said copper-nickel alloy is subjected to a polishing and degreasing treatment, the polishing being: sanding with 200#, 600#, 1200# sandpaper in sequence, wherein the degreasing is 15g/L Na₂CO₃、 10g/L Na₃PO₄ ^.12H₂O、10 g/L Na₂SiO₃At a temperature of 50 deg.C^oC, time 2 min.

4. A long-life copper-based composite material according to claim 1, wherein said electrochemical reduction of copper uses an electrolyte of: 140-150g/L CuSO₄ ^.5H₂O；30-35g/L H₂SO₄；40-45g/L Cl^-；0.5-1g/L APEO。

5. A long-life copper-based composite material according to claim 1, wherein said parameters for electrochemically reducing copper are: temperature is 25-30 DEG C^oC; the direct current constant voltage is-13V, and the time is 5s-10 s.

6. A long-lived copper-based composite material as claimed in claim 1, characterised in that the electroless chemical reduction uses a solution: 3-5M anhydrous copper acetate in 300-350 deg.C^oAnd C, keeping the state of non-sealing for 15-20 min.

7. A long-life copper-based composite material according to claim 1, wherein said copper-based composite material is selected from the group consisting of copper, aluminum, copper, aluminum, copperThe hydrothermal temperature of the hydrothermal method is 110-120-^oC, the time is 12-24 h.

8. The method of claim 1, wherein the solution system used for hydrothermal and electroless chemical reduction is compatible with the reaction vessel and does not require replacement.

9. The durable copper-based composite material according to claim 1, wherein the copper oxide layer is formed using a solution of a mixture of ammonia and copper carbonate.

10. The durable copper-based composite material as claimed in claim 9, wherein the concentration of ammonia water is 100-120ml/L of 25wt.% ammonia water solution, 40g/L of copper carbonate, the time is 3-5min, and the temperature is 15-20%^oC。

Technical Field

The invention belongs to the field of electrochemistry, and particularly relates to a high-service-life copper-based composite material which is particularly suitable for preparing ethylene by electrocatalytic reduction of carbon dioxide.

Technical Field

CO₂Chemical structure is stable, therefore CO₂The molecules are very difficult to activate and thus difficult to participate in the reaction, so that

Conventionally, it is converted by severe reaction conditions (e.g., high temperature and high pressure). In general, researchers have used chemical reforming, mineralization, enzymatic catalysis, and photocatalytic and electrocatalytic approaches to overcome the larger CO2The activation energy barrier of (1). In these methods, H is not required due to mild conditions of electrochemical reduction reaction₂The reaction pH is close to neutral as a raw material, and excellent clean energy compatibility has been attracting attention.

Electrochemical reduction is a means of reducing CO2 under relatively mild ambient conditions by applying an electric current such that CO2 is reduced at the cathode surface. Electrochemical reduction has the following advantages: the reduction product can be controlled by adjusting the electrolysis voltage, the electrolysis temperature and the electrolyte type; the electrolyte is convenient to recover; the electrolytic cell has simple structure and is convenient to manufacture, and is generally carried out at normal temperature; the electric energy for electrolysis can be generated from renewable energy sources such as solar energy, wind energy and geothermal energy; the electrochemical reaction system is compact and modularized, can be adjusted according to requirements, and is easy to be used in industrial factories.

Due to many factors, such as the types of electrodes, the types of solvents, the electrolysis voltage, the pressure, the temperature, etc., affecting the electrochemical reduction of CO2, the obtained products are also various, such as methanol, formic acid, methane, carbon monoxide, ethylene, etc., and various metals are classified into four major groups according to the distribution rule of the products.

(I) Copper (Cu) as a unique catalyst shows remarkable catalytic performance and can convert CO into CO₂Conversion to hydrocarbons and oxygenates, being the only one capable of converting CO with significant efficiency₂Metal electrocatalysts for reduction to hydrocarbons or oxygenated hydrocarbons, such as methane, ethylene, ethanol and propanol.

(II) the second metal, noble metals such as gold (Au), silver (Ag), zinc (Zn), palladium (Pd) and gallium (Ga), is selective for carbon monoxide (CO) and is mainly produced from CO.

(III) the third metal, tin (Sn), lead ((Pb), mercury (Hg), indium (In), cadmium (Cd), etc., which are mainly used for producing formate, is used for producing formic acid (HCOOH) and formate ((HCOO)^-) The most preferred catalyst of (1).

(N) a fourth metal selected from nickel (Ni), iron (Fe), platinum (Pt) and titanium (Ti), which reacts only with hydrogen evolution under a stable condition to generate hydrogen (H)₂) Without CO₂The reducing power of (c).

Among the various catalysts for electrochemical reduction of COZ, copper is considered to be the most promising catalyst for the formation of hydrocarbon compounds such as methane and ethylene. In recent years, highly selective copper-based electrocatalysts have attracted much attention from both domestic and foreign researchers because of their high energy density and ability to produce ethylene as a chemical raw material.

CN202010628183 discloses a dendritic copper electrode with hydrophobic surface, and its preparation method and application. The copper electrode provided by the invention comprises a gas diffusion layer and a copper layer deposited on the surface of the gas diffusion layer; the copper layer has a dendritic microstructure. The surface of the copper electrode provided by the invention consists of regular copper dendrites, the copper electrode shows good hydrophobicity, can effectively prevent the excessive contact of electrolyte, avoids the electrode from flooding and improves the stability of the electrode; and the dendritic copper can also efficiently enrich cations in the electrolyte to form a local high electric field, so that the carbon-carbon coupling rate is improved, and the electrode shows excellent electro-catalytic CO2 reduction activity.

CN201911278128 uses a copper alloy material with an amorphous structure as a catalyst, and performs an electrochemical reaction on CO2 to obtain a carbon-containing compound. The invention adopts the copper alloy material with an amorphous structure as a catalyst to directly prepare carbon-containing compounds such as alcohol, acid, ketone and the like by electrocatalytic reduction of CO 2. The copper alloy material can be prepared into various macroscopic forms such as a block form, a powder form and a film form, can be directly used as an electrocatalytic electrode material to be applied to a CO2 electrocatalytic reduction cell, and simultaneously improves the electrocatalytic activity and stability of the catalyst, thereby improving the performance and efficiency of the electrolytic cell. The synthesis method provided can effectively exert the cooperative catalytic performance among catalysts by regulating and controlling the composition and structure of the copper alloy material with an amorphous structure, further regulate and control the type of products, and selectively obtain different carbon-containing compounds such as alcohol, acid, ketone and the like.

CN201910713686 discloses a copper-based carbon dioxide electrocatalytic material and a preparation method thereof, wherein the method comprises the steps of: mixing an oxidant solution and an organic ligand solution to prepare a mixed solution; putting metal copper into the mixed solution, so that the organic ligand is adsorbed on part of specific crystal faces of the metal copper, and oxidation reaction is carried out on crystal faces of the metal copper which are not adsorbed by the organic ligand; and cleaning the metal copper after the oxidation reaction to remove the organic ligand adsorbed on the crystal face of the metal copper, and performing electrochemical reduction to obtain the OD-Cu carbon dioxide catalytic material with more specific crystal faces. According to the invention, by adding different types and concentrations of organic ligands in the oxidation process, on one hand, the regulation and control of different crystal structure of the OD-Cu material can be realized; on the other hand, the prepared OD-Cu material has the advantages of high surface roughness, high crystal boundary density and the like, and can preferentially expose crystal faces, so that the catalytic activity of the material on CO2 and the selectivity on a multi-carbon product can be remarkably improved.

CN201810661930 discloses a preparation method of flower-shaped copper oxide, which comprises the following steps: A) mixing an oxidant, a morphology control agent, a hydrophilic group surfactant and an alkaline compound in water to obtain an initial solution; the morphology control agent is selected from sodium tungstate, potassium tungstate, sodium molybdate, urea or ethylenediamine; B) and immersing the cleaned copper into the initial solution for hydrothermal reaction to obtain flower-shaped copper oxide. The application also provides a method for photoelectrocatalysis reduction of CO2 by using flower-shaped copper oxide as an electrode. The invention provides a method for preparing flower-shaped copper oxide by taking elemental copper as a copper source, and the flower-shaped copper oxide prepared by the method can be directly used as an electrode for photoelectrocatalytic reduction of CO2 without additional forming treatment.

CN201310254758 discloses a flower-shaped copper oxide/iron oxide nanotube catalyst and a preparation method thereof, wherein firstly a volcanic iron oxide nanotube grows on the upper surface of an iron-based substrate in situ by an electrochemical anodic oxidation method, then copper oxide with a flower-shaped structure is deposited on the iron oxide substrate by a pulse electrodeposition method, and the flower-shaped copper oxide/iron oxide nanotube catalyst is obtained after calcination. The catalyst obtained by the invention has good photoelectrocatalysis performance, and realizes the coupling of two reactions of water cracking and CO2 reduction, and the product is methanol and ethanol after the photoelectrocatalysis reduction of CO2 and gas chromatography detection and analysis.

The following problems are evident from the above patent: (1) as the most excellent ethylene selective catalyst, the catalyst has few research directions aiming at improving the ethylene selectivity, and the ethylene is the most important energy hydrogenation raw material in the chemical production; (2) the life of the electrocatalytic electrode was not studied; (3) the catalytic activity is to be improved.

Disclosure of Invention

Based on the problems, the key problem to be solved by the invention is to provide a high-service-life copper-based composite material, an electrode structure and a preparation technology, wherein the electrode structure and the preparation technology can ensure high ethylene conversion rate and prolong the service life of the copper-based composite material.

The long-life copper-based composite material is in a thorn shape, and the composite material comprises the following components in parts by weight: the copper-based composite material comprises a copper alloy substrate, a porous copper layer, a seed copper layer, thorn-shaped copper and a copper oxidation layer, wherein the copper alloy is a copper-nickel alloy, the porous copper layer is obtained by electrochemically reducing copper, the seed copper layer is obtained by electroless chemical reduction, the thorn-shaped copper is obtained by a hydrothermal method, the copper oxidation layer is obtained by an inorganic oxidation method, the copper oxide layer is attached to the surface of the thorn-shaped copper, the length of a thorn-shaped object in the copper-based composite material is 3-5 mu m, and the diameter of the thorn-shaped object is 300-500 nm.

Further, the nickel content in the copper-nickel alloy is 5-10 wt.%.

Further, the copper-nickel alloy is subjected to polishing and degreasing treatment, and the polishing comprises the following steps: sanding with 200#, 600#, 1200# sandpaper in sequence, wherein the degreasing is 15g/L Na₂CO₃、 10g/L Na₃PO₄ ^.12H₂O、10 g/L Na₂SiO₃At a temperature of 50 deg.C^oC, time 2 min.

Further, the electrochemical reduction copper uses an electrolyte that: 140-150g/L CuSO₄ ^.5H₂O；30-35g/L H₂SO₄；40-45g/L Cl^-；0.5-1g/L APEO。

Further, the parameters of the electrochemical reduction of copper are as follows: temperature is 25-30 DEG C^oC; the direct current constant voltage is-13V, and the time is 5s-10 s.

Further, the solution used for the electroless chemical reduction is: 3-5M anhydrous cupric acetate in glycerol at 300 deg.C-350^oAnd C, keeping the state of non-sealing for 15-20 min.

Further, the hydrothermal temperature of the hydrothermal method is 110-120-^oC, the time is 12-24 h.

Furthermore, the solution system and the reaction kettle used by the hydrothermal method and the solution used by electroless chemical reduction are consistent and do not need to be replaced.

Further, the solution used for the copper oxide layer is a mixed solution of ammonia water and copper carbonate.

Further, the ammonia water has the concentration of 100-120ml/L ammonia water solution with the mass fraction of 25wt.%, 40g/L copper carbonate, the time is 3-5min, and the temperature is 15-20^oC。

(1) Regarding the selection of the substrate: the copper-based alloy is a copper-nickel cupronickel alloy, is a copper-nickel binary alloy, has 5-10 wt% of nickel, has better corrosion resistance on the premise of meeting the mechanical strength, and has nickel in CO₂Without any catalytic reduction of CO in the electrocatalysis process₂The ability of nickel to cause no side reactions and not affect the conversion of the highly selective ethylene of the present invention, if brass (Cu-Zn) or bronze (Cu-Sn) alloy is used, Zn will electrocatalytically produce CO, and tin will electrocatalytically produce formic acid, which is not favorable for the purpose of the present invention.

(2) Regarding the pretreatment of the substrate: grinding and degreasing, wherein grinding: sanding with 200#, 600#, 1200# sandpaper in sequence for smoothing the surface, which aims to reduce roughness, remove macroscopic defects such as scratches, oxide layers, corrosion marks and rusty spots on the surface, improve the surface smoothness and achieve sufficient degreasing degree of 15g/L Na₂CO₃、 10g/L Na₃PO₄ ^.12H₂O、10 g/L Na₂SiO₃At a temperature of 50 deg.C^oC, the time is 2min, the degreasing solution used by the invention does not contain strong-alkaline sodium hydroxide, mainly because Na2CuO is formed by Cu + NaOH + O2₂And Na2CuO₂Can be decomposed into CuO suitable oxide film in water, is not beneficial to robbing the surface, and comprises one-time hot water washing and one-time hot water washingAnd (3) washing with cold water, washing the surface of the workpiece to be plated with deionized water heated to at least 45-50 ℃, removing residual alkali liquor on the surface, and washing with cold deionized water.

(3) Electrochemical deposition reduction is carried out under extremely high negative bias: in the copper-containing solution as electrolyte, copper-base alloy as cathode and inert or pure copper electrode as anode, and the direct current is switched on, the copper ions are reduced at the cathode, but because of the extremely high negative bias applied on the copper-base alloy plate, thus leading to a violent hydrogen evolution reaction, the hydrogen exists in the form of bubbles at the cathode, and because the hydrogen bubbles do not have metal ions at the place where the hydrogen bubbles appear, that is, any copper ion deposition reaction does not occur, so that the reaction of electrodepositing copper to form a compact structure is uniform at the cathode, thereby forming voids, as shown in figures 1, 2, 3 and 4, which, with increasing time, holes with different densities are formed on the surface of the copper base alloy, the density of the holes is closely related to voltage and time, the cathode deposition process can obviously increase the specific surface area of the cathode material, and the specific surface area of the polished copper-based alloy is approximately equal to 0 m.²(ii)/g; after 10s of cathodic deposition, the specific surface rises to 9m²G, if the time is increased, the cathode current density is reasonably adjusted, and the cathode current density can be obtained to be higher than 100m²A/g of three-dimensional porous copper material, but which also provides an active electrocatalytic reduction of CO directly by the above-mentioned method, albeit with a high specific surface area₂The activity, but the catalytic activity conversion, the ethylene selectivity and the Faraday efficiency are all low, and the preparation method can be consulted in the prior art.

The electro-deposition of the invention is carried out for 5s-10s in a very short time, the main purpose is to obtain a porous copper layer, the purpose is to 'dig pit' to facilitate the subsequent seed crystal attachment, and finally obtain the CO2 electro-catalytic material with high bonding strength and long service life through the subsequent hydrothermal reaction 'burying pit'.

The copper-containing electrolyte of the invention: 140-150g/L CuSO₄ ^.5H₂O；30-35g/L H₂SO₄；40-45g/L Cl^-(ii) a 0.5-1g/L APEO, where theoretical CuSO₄ ^.5H₂O may be about 230g/L, but sulfuric acid is caused in consideration of solubilityCopper precipitation, thereby reducing CuSO₄ ^.5H₂O is 140-150 g/L; the sulfuric acid can obviously reduce the resistance of the plating solution in the plating solution, can also prevent the hydrolysis of copper sulfate from forming copper hydroxide precipitate, the concentration of the sulfuric acid is lower than that of the actual copper plating, the sulfuric acid is usually more than 40g/L in the industry, and is beneficial to forming a flat plating layer, and when the concentration of the sulfuric acid is lower, a rough plating layer is easy to form, which is required by the invention; the APEO surfactant is added in the application, and is mainly used for improving the surface tension of the plating solution and avoiding excessive overflow of hydrogen bubbles.

Finally, the process should be optimally at rest without any stirring assistance.

(4) Regarding the high temperature chemical reduction of copper nanowire seeds: the process uses a 3-5M glycerol solution of anhydrous copper acetate, wherein the glycerol has a certain reducibility at normal temperature but no copper sulfate reducibility, and the glycerol solution has the temperature of 300 ℃ to 350 DEG C^oAnd C, under the condition of extremely strong reduction capability, copper sulfate can be reduced into copper polyhedral particles through electroless chemistry, the copper polyhedral particles can be adsorbed into the pits in the step (2) to be used as crystal seeds, the reaction kettle is not sealed in the process, the evaporation loss of the solution needs to be reduced to the greatest extent, and the main density of the process is that the crystal seeds are formed.

(5) The spinous copper-based composite material is obtained by hydrothermal treatment, and the hydrothermal temperature in the process is 110-120 DEG C^oAnd C, the time is 12-24h, before the step (4), the air in the reaction kettle in the step (3) is exhausted by using nitrogen, the nano copper can be shaped and grown by a hydrothermal method, the nano wire is obtained, and the copper-based electrode material with high specific surface area is further obtained.

To further illustrate the above operation, an ultra-fine cupronickel wire was used as the substrate, as shown in fig. 5; electrochemical deposition reduction is carried out by extremely high negative bias to form a porous copper layer on the surface, as shown in figure 6; then forming copper crystals in the pore channels by high-temperature electroless chemical reduction, as shown in figure 7; the spiny copper-based composite material obtained by the hydrothermal treatment is shown in figure 8, and the spiny copper on the surface of the copper material can be more obviously seen from figure 9.

(6) Regarding the oxidation: the purpose of the oxidation is to form CuO_XThe oxidation state metal has rich crystal boundary on the surface of the catalyst, and the specific crystal face shows stronger catalytic activity and selectivity, under the electrocatalytic condition of CO2, the oxide layer is electrochemically reduced to a metal layer, and the process activates the metal catalyst, a specific low coordination active site is formed on the surface of the catalyst, the reaction site of the competitive Hydrogen Evolution Reaction (HER) is blocked, the product selectivity is improved, the reduction activity of the copper-based electrode has strong dependence on the initial thickness of the copper-oxygen layer, the method has the advantages that the thickness of the oxide layer obtained by the method is 0.1-0.2 micron, the concentration of ammonia water is 100-120ml/L ammonia water solution with the mass fraction of 25wt.%, the concentration of copper carbonate is 40g/L, the time is 3-5min, and the temperature is 15-20.^oC, after oxidation, the thorn-shaped structure is slightly converged as shown in figure 10, XPS test is carried out on the oxidized copper oxide base material as shown in figure 11 fitting graph, and CuO is further confirmed_XIs present.

The beneficial technical effects are as follows:

(1) the electrode stability is good, and the obtained thorn-shaped copper is not easy to peel off.

(2) The copper thorn material obviously improves the contact specific surface area of reactants and electrodes and provides rich sites for catalytic reduction of CO 2.

（3）CuO_XThe layer effectively inhibits hydrogen evolution reaction, and the oxidation state is preferentially combined with H ions for reduction, so that the combination reaction of H and H is avoided.

(4) Has extremely high ethylene selectivity.

Drawings

FIG. 1 is a SEM image of electrochemical deposition carried out at-13V under constant flow voltage for 2s according to the present invention.

FIG. 2 is a SEM image of electrochemical deposition carried out at-13V under constant flow voltage for 5s according to the present invention.

FIG. 3 is a SEM image of electrochemical deposition carried out at-13V under constant flow voltage for 7s according to the present invention.

FIG. 4 is a SEM image of electrochemical deposition carried out at-13V under constant flow voltage for 10s according to the present invention.

FIG. 5 is a TEM image of the invention on a copper wire.

FIG. 6 is a 10s TEM image of electrochemical deposition performed at-13V at a constant flow voltage according to the present invention.

FIG. 7 is a TEM image of electroless chemical reduction at high temperature according to the present invention.

Fig. 8 is a TEM image of a water heat of the present invention.

FIG. 9 is an SEM image of a spiny copper-based composite material obtained by the hydrothermal treatment of the present invention.

FIG. 10 is an SEM image of a spiny copper-based composite material obtained by the oxidation treatment of the present invention.

FIG. 11 is an XPS fit of a spiny copper-based composite material obtained by the oxidation treatment of the present invention.

Detailed Description

The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.

Example 1

A long-life copper-based composite material is prepared by the following method:

(1) pretreating the copper-based alloy; the copper-based alloy is a copper-nickel-copper alloy.

Wherein the pretreatment in the step (1) comprises grinding and inorganic degreasing: the grinding is as follows: and sanding by using 200#, 600#, and 1200# sandpaper in sequence.

Defatting to 15g/L Na₂CO₃、 10g/L Na₃PO₄ ^.12H₂O、10 g/L Na₂SiO₃At a temperature of 50 deg.C^oC, time 2 min.

(2) Taking a copper-containing solution as an electrolyte, taking a copper-based alloy as a cathode, and carrying out electrochemical deposition reduction under extremely high negative bias.

Wherein the copper-containing electrolyte in the step (2) comprises copper sulfate, sulfuric acid, chloride ions and a surfactant, the anode is an inert electrode or pure copper, and the copper-containing electrolyte comprises the following components in percentage by weight: 140g/L CuSO₄ ^.5H₂O；30g/L H₂SO₄；40g/L Cl^-(ii) a 0.5g/L APEO; temperature 25^oC; the direct current constant voltage is-13V, and the time is 5 s.

(3) And (3) chemically reducing the copper nanowire seed crystal at high temperature.

Wherein the solution used in the high-temperature chemical reduction in the step (3) is a mixed solution of copper acetate and glycerol, and a glycerol solution of 3M anhydrous copper acetate at the temperature of 300 DEG C^oAnd C, keeping the state of non-sealing for 15 min.

(4) And carrying out hydrothermal treatment to obtain the thorn-shaped copper-based composite material.

Wherein the solution used in the step (4) is consistent with the solution in the step (3) in a closed state, and before the step (4), nitrogen is used for evacuating the air in the reaction kettle in the step (3).

The hydrothermal temperature in the step (4) is 110 DEG C^oC, the time is 12 h.

(5) And (4) oxidizing.

Wherein the oxidizing solution used in the step (5) is a mixed solution of ammonia water and copper carbonate.

The ammonia water concentration is 100ml/L, the mass fraction is 25wt.% of ammonia water solution, 40g/L of copper carbonate, the time is 3min, and the temperature is 15%^oC。

Example 2

A long-life copper-based composite material is prepared by the following method:

(1) pretreating the copper-based alloy; the copper-based alloy is a copper-nickel-copper alloy.

Wherein the pretreatment in the step (1) comprises grinding and inorganic degreasing: the grinding is as follows: and sanding by using 200#, 600#, and 1200# sandpaper in sequence.

Defatting to 15g/L Na₂CO₃、 10g/L Na₃PO₄ ^.12H₂O、10 g/L Na₂SiO₃At a temperature of 50 deg.C^oC, time 2 min.

(2) Taking a copper-containing solution as an electrolyte, taking a copper-based alloy as a cathode, and carrying out electrochemical deposition reduction under extremely high negative bias.

Wherein the copper-containing electrolyte in the step (2) comprises copper sulfate, sulfuric acid, chloride ions and a surfactant, the anode is an inert electrode or pure copper, and the copper-containing electrolyte comprises the following components in percentage by weight: 145g/L CuSO₄ ^.5H₂O；32.5g/L H₂SO₄；42.5g/L Cl^-(ii) a 0.75g/L APEO; temperature 27^oC; the direct current constant voltage is-13V, and the time is 8 s.

(3) And (3) chemically reducing the copper nanowire seed crystal at high temperature.

Wherein the solution used in the high-temperature chemical reduction in the step (3) is a mixed solution of copper acetate and glycerol, and a glycerol solution of 4M anhydrous copper acetate at the temperature of 320 DEG C^oAnd C, in an unsealed state, the time is 17.5 min.

(4) And carrying out hydrothermal treatment to obtain the thorn-shaped copper-based composite material.

Wherein the solution used in the step (4) is consistent with the solution in the step (3) in a closed state, and before the step (4), nitrogen is used for evacuating the air in the reaction kettle in the step (3).

The hydrothermal temperature in the step (4) is 115 DEG^oC, the time is 18 h.

(5) And (4) oxidizing.

Wherein the oxidizing solution used in the step (5) is a mixed solution of ammonia water and copper carbonate.

The ammonia water concentration is 115ml/L, the mass fraction is 25wt.% of ammonia water solution, 40g/L of copper carbonate, the time is 4min, and the temperature is 17.5^oC。

Example 3

A long-life copper-based composite material is prepared by the following method:

(1) pretreating the copper-based alloy; the copper-based alloy is a copper-nickel-copper alloy.

Wherein the pretreatment in the step (1) comprises grinding and inorganic degreasing: the grinding is as follows: and sanding by using 200#, 600#, and 1200# sandpaper in sequence.

Defatting to 15g/L Na₂CO₃、 10g/L Na₃PO₄ ^.12H₂O、10 g/L Na₂SiO₃At a temperature of 50 deg.C^oC, time 2 min.

(2) Taking a copper-containing solution as an electrolyte, taking a copper-based alloy as a cathode, and carrying out electrochemical deposition reduction under extremely high negative bias.

Wherein the copper-containing electrolyte in the step (2) comprises copper sulfate, sulfuric acid, chloride ions anda surfactant, the anode is an inert electrode or pure copper, a copper-containing electrolyte: 150g/L CuSO₄ ^.5H₂O； 35g/L H₂SO₄；45g/L Cl^-(ii) a 1g/L APEO; temperature 30^oC; the direct current constant voltage is-13V, and the time is 10 s.

(3) And (3) chemically reducing the copper nanowire seed crystal at high temperature.

Wherein the solution used in the high-temperature chemical reduction in the step (3) is a mixed solution of copper acetate and glycerol and a glycerol solution of 5M anhydrous copper acetate at the temperature of 350 DEG C^oAnd C, keeping the state of non-sealing for 20 min.

(4) And carrying out hydrothermal treatment to obtain the thorn-shaped copper-based composite material.

Wherein the solution used in the step (4) is consistent with the solution in the step (3) in a closed state, and before the step (4), nitrogen is used for evacuating the air in the reaction kettle in the step (3).

The hydrothermal temperature in the step (4) is 120 DEG^oC, the time is 24 h.

(5) And (4) oxidizing.

Wherein the oxidizing solution used in the step (5) is a mixed solution of ammonia water and copper carbonate.

Ammonia water solution with concentration of 120ml/L and mass fraction of 25wt.%, copper carbonate of 40g/L, time of 5min, and temperature of 20%^oC。

Designated as S-3 sample.

Comparative example 1

A long-life copper-based composite material is prepared by the following method:

(1) pretreating the copper-based alloy; the copper-based alloy is a copper-nickel-copper alloy.

Wherein the pretreatment in the step (1) comprises grinding and inorganic degreasing: the grinding is as follows: and sanding by using 200#, 600#, and 1200# sandpaper in sequence.

Defatting to 15g/L Na₂CO₃、 10g/L Na₃PO₄ ^.12H₂O、10 g/L Na₂SiO₃At a temperature of 50 deg.C^oC, time 2 min.

(2) And (3) chemically reducing the copper nanowire seed crystal at high temperature.

Wherein the solution used in the high-temperature chemical reduction in the step (2) is a mixed solution of copper acetate and glycerol and a glycerol solution of 5M anhydrous copper acetate at the temperature of 350 DEG C^oAnd C, keeping the state of non-sealing for 20 min.

(3) And carrying out hydrothermal treatment to obtain the thorn-shaped copper-based composite material.

Wherein the solution used in the step (3) is consistent with the solution in the step (2) in a closed state, and before the step (3), nitrogen is used for evacuating the air in the reaction kettle in the step (3).

The hydrothermal temperature in the step (3) is 120 DEG^oC, the time is 24 h.

(4) And (4) oxidizing.

Wherein the oxidizing solution used in the step (4) is a mixed solution of ammonia water and copper carbonate.

Ammonia water solution with concentration of 120ml/L and mass fraction of 25wt.%, copper carbonate of 40g/L, time of 5min, and temperature of 20%^oC。

Designated as D-1 sample.

And (3) carrying out mechanical impact test on the ultrasonic oscillation S-3 and the D-1, wherein the test conditions are as follows: and (2) placing the copper-based composite material in a beaker filled with petroleum ether, sealing, oscillating and impacting for 60min in a 40 KHz/100 w ultrasonic cleaning instrument, taking out a sample, drying, and then determining the weight loss, wherein the mass loss of S-3 is 0.27wt.%, and the mass loss of D-1 is 3.89wt.%, so that the influence of the preparation of the porous layer in the step 2 on the service life of the bonding strength of the electrode can be obviously obtained.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.