CN114606492A - High-temperature-resistant medium-entropy alloy coating composite metal connector and preparation method thereof - Google Patents

High-temperature-resistant medium-entropy alloy coating composite metal connector and preparation method thereof Download PDF

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CN114606492A
CN114606492A CN202210231614.5A CN202210231614A CN114606492A CN 114606492 A CN114606492 A CN 114606492A CN 202210231614 A CN202210231614 A CN 202210231614A CN 114606492 A CN114606492 A CN 114606492A
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entropy alloy
temperature
alloy coating
coating
metal connector
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CN114606492B (en
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郭平义
殷童
邵勇
潘家琛
王冬朋
崔文宁
王宇鑫
汤雁冰
何震
郭云霞
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Jiangsu University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • C23C26/02—Coating not provided for in groups C23C2/00 - C23C24/00 applying molten material to the substrate
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/10—Oxidising
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/241—Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes
    • H01M8/2425—High-temperature cells with solid electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/2465—Details of groupings of fuel cells
    • H01M8/2483—Details of groupings of fuel cells characterised by internal manifolds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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  • Mechanical Engineering (AREA)
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  • Organic Chemistry (AREA)
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  • Life Sciences & Earth Sciences (AREA)
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Abstract

The invention discloses a high-temperature-resistant intermediate-entropy alloy coating composite metal connector and a preparation method thereof, wherein the composite metal connector comprises a deposition substrate material and an intermediate-entropy alloy coating, the intermediate-entropy alloy coating is divided into three layers, the outer layer is a Cu-rich oxide, the middle layer is a CoFe oxide, and the inner layer is a Ni-rich oxide; the preparation method of the composite metal connector comprises the following steps: pretreating a ferritic stainless steel material; then arc melting the CuNiCoFe intermediate entropy alloy with the face-centered cubic structure, and then carrying out spark deposition on the ferrite stainless steel to obtain an intermediate entropy alloy coating; finally at high temperature and high oxygen pressureThe composite high-temperature corrosion-resistant conductive coating is obtained in the environment. The composite metal connector of the high-temperature-resistant medium-entropy alloy coating utilizes the delayed diffusion effect of the medium-high-entropy alloy, and is favorable for inhibiting the external diffusion of Cr element and CrO in the ferritic stainless steel matrix3Or CrO2(OH)2The composite coating has high conductivity, matched thermal expansion coefficient and good high-temperature corrosion resistance, and solves the problem that the composite coating is easy to peel off.

Description

High-temperature-resistant medium-entropy alloy coating composite metal connector and preparation method thereof
Technical Field
The invention belongs to the technical field of solid oxide fuel cells, and particularly relates to a high-temperature-resistant medium-entropy alloy coating composite metal connector and a preparation method thereof.
Background
The solid oxide fuel cell is a full solid energy conversion device for converting electric energy and heat energy into chemical energy, and renewable energy sources such as solar energy, wind energy, geothermal energy and the like are used as electric energy and heat energy sources to carry out high-temperature synergistic electrolysis reaction of carbon dioxide and water to prepare synthesis gas. In practical application, a single solid oxide fuel cell is low in voltage and power, and cannot meet the electricity demand in life at all, so that each single cell is required to be stacked and connected to form a cell stack so as to obtain high voltage and power, and meanwhile, a connector material isolates oxygen on the cathode side of one single cell from fuel gas on the anode side of another single cell, so that the connector material plays a crucial role in the cell stack, and the performance of the connector material directly affects the stability and the power of the cell stack.
With the operating temperature of the solid oxide fuel cellThe temperature is reduced to 600-800 ℃ at 1000 ℃, so that the connector material can be selected from metal and alloy materials with lower cost and good machining performance and electrical conductivity, and the ferritic stainless steel becomes the most potential connector material at present due to the advantages of good electrical and thermal conductivity, matching of thermal expansion coefficient with other components, low price and the like. However, the ferritic stainless steel has serious oxidative corrosion in the working environment of the solid oxide fuel cell, especially in the high-temperature oxidizing environment of the cathode, and the volatilization of Cr element causes CrO generated on the surface of the cathode3Or CrO2(OH)2The out-diffusion will cause a decrease in the performance of the battery.
Aiming at the problem of volatilization of Cr in an alloy connector, depositing a high-temperature corrosion-resistant coating on the surface of a metal connector is an important means. The protective coating acts by adhering to the surface of the alloy, has excellent conductivity, can protect the alloy from high-temperature corrosion, and can effectively inhibit outward diffusion of Cr element, so that the preparation of the coating needs to pay attention to the following aspects: the degradation of the coating is prevented, namely, the mutual diffusion of the coating and the matrix alloy at the interface is avoided, so that the oxidation-resistant elements in the coating are quickly consumed; the combination between the coating and the substrate, the coating must exist stably on the surface of the alloy; the preparation mode of the coating is selected, and the difficulty degree and the preparation condition in the preparation are controlled.
The invention adopts an electric spark deposition coating technology, a pulse power supply used by the electric spark deposition coating technology is a relaxation type pulse generator, and a direct current power supply, a current-limiting resistor and an energy-storage capacitor form a charging loop; the energy storage capacitor, the electrode and the workpiece form a discharge loop. The electrode is connected with the anode, and the workpiece is connected with the cathode. The discharge frequency is controlled by a set of thyristor circuit, and different discharge frequencies are obtained by adjusting the size of the control angle. When the high-entropy alloy coating is in work, the electrode rotates at a high speed, the electrode is infinitely close to a substrate to enable a discharge loop to form a passage, the electrode is melted to form the coating during discharge, and the high-entropy alloy coating prepared through metallurgical bonding has high bonding strength and lower porosity, does not cause large thermal deformation to the substrate, and has specific advantages.
The high-entropy alloy is characterized in that each main element in the alloy has high atomic percentage, but the highest content of the element cannot exceed 35 percent, and the high-entropy alloy is characterized by the combined action of the elements forming the high-entropy alloy in the whole view. The characteristics of the delayed diffusion effect and the serious lattice distortion effect caused by various elements in the high-entropy alloy enable the high-entropy alloy to have excellent structural stability and mechanical properties. The definition of high entropy alloys is based on the composition of one and the entropy of the mixing of the other. High entropy alloys are defined as alloys containing at least five major elements, if based on composition. CuNiCoFe alloy is a four-component alloy, referred to herein as a medium entropy alloy, which still has the four core effects of a high entropy alloy: thermodynamic high entropy effect, kinetic delayed diffusion effect, severe lattice distortion effect of the structure and cocktail effect of performance.
The delayed diffusion effect of the high-entropy alloy means that the phase change in the high-entropy alloy requires the synergistic diffusion of many different kinds of atoms to complete the division of the components among the phases. The vacancy concentration in the high-entropy alloy is limited because each vacancy of the crystal in the high-entropy alloy is also related to the mixing enthalpy and the mixing entropy, a certain equilibrium vacancy concentration is generated in the alloy due to competition between the mixing enthalpy and the mixing entropy, the vacancies in the full-solution matrix are actually surrounded and contended by different element atoms in the diffusion process, the vacancies or atoms are all migrated by a fluctuating diffusion path, the diffusion speed is slow, the activation energy is high, and therefore, the diffusion phase change is slow in the high-entropy alloy. The characteristic is favorable for inhibiting the outward diffusion of Cr element in the ferritic stainless steel matrix and improving the high-temperature resistance of the fuel cell metal connector. Researches show that the ultra-fine grain high-entropy alloy can obtain more excellent comprehensive performance, which is the basis point of the invention.
Disclosure of Invention
The invention aims to improve the high-temperature oxidation resistance of the metal connecting material of the solid oxide fuel cell and prevent chromium compounds CrO at high temperature3Or CrO2(OH)2The cathode poisoning phenomenon caused by volatilization provides a high-temperature-resistant medium-entropy alloy coating composite metal connector and a preparation method thereof.
The technical scheme of the invention is as follows:
a composite metal connector of a high-temperature-resistant medium-entropy alloy coating comprises a deposition base material and a medium-entropy alloy coating, wherein the deposition base material is ferritic stainless steel; the medium-entropy alloy coating is divided into three layers, wherein the outer layer is rich in Cu oxide, the middle layer is CoFe oxide, and the inner layer is rich in Ni oxide.
Further, the medium entropy alloy matrix of the medium entropy alloy coating is CuNiCoFe, and the molar concentrations of the elements are respectively 25 at.%, 25 at.% and 25 at.%.
Further, the thickness of the medium-entropy alloy coating is 10-20 mu m.
The invention provides a preparation method of the high-temperature-resistant medium-entropy alloy coating composite metal connector, which comprises the following steps of:
preprocessing the surface of a ferritic stainless steel substrate: pre-grinding, cleaning with acetone, drying and sealing;
arc melting CuNiCoFe intermediate entropy alloy, controlling the concentration of Cu, Ni, Co and Fe;
processing and pre-grinding the smelted intermediate entropy alloy to prepare an alloy electrode, and depositing a CuNiCoFe intermediate entropy alloy coating on the surface of the matrix by adopting an electric spark technology;
and fourthly, pre-oxidizing the CuNiCoFe intermediate entropy alloy coating in a high-temperature high-oxygen pressure environment to obtain the composite high-temperature corrosion-resistant conductive coating metal connector.
And step three, adopting an electric spark deposition technology, wherein the deposition voltage is about 200V, and protecting with argon.
And step three, obtaining the ultra-fine grain entropy alloy coating by adopting an electric spark deposition technology, wherein the ultra-fine grain entropy alloy coating is metallurgically bonded with the matrix.
The high-temperature high-oxygen pressure environment adopted in the step IV is 750-950 ℃, the oxygen partial pressure is 104-105 Pa, and the time is 50 h, and the composite high-temperature corrosion-resistant conductive coating can be applied to a solid oxide fuel cell connector material.
The technical scheme of the invention can produce the following beneficial effects:
(1) the CuNiCoFe intermediate entropy alloy coating prepared by the method effectively blocks the outward diffusion of Cr element in a ferritic stainless steel matrix, and can improve the high temperature resistance of a fuel cell metal connector; and has high conductivity and thermal expansion coefficient matched with the metal connector, and can be used as a high-temperature corrosion-resistant conductive protective coating.
(2) By adopting the preparation method that the electric spark technology is adopted to prepare the ultra-fine crystal intermediate entropy alloy coating, and the coating is formed through high-temperature thermal growth, the metallurgical bonding of the substrate and the intermediate entropy alloy coating has higher bonding strength and low porosity, the adhesion between the composite coating and the metal stainless steel substrate is increased, and the problem that the composite coating is easy to peel off is solved.
Drawings
FIG. 1 is a sectional view of a composite coating obtained by thermal growth of the medium-entropy alloy coating prepared in example 1 of the present invention in a high-temperature high-oxygen pressure environment.
FIG. 2 shows the surface morphology of the CuNiCoFe entropy alloy after the arc melting in the embodiment 1 of the invention.
FIG. 3 is a cross-sectional view of a composite coating obtained by thermal growth of the medium-entropy alloy coating prepared in example 4 of the present invention in a high-temperature high-oxygen pressure environment.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and the embodiments.
As shown in fig. 1-3, the invention is a composite metal connector of high temperature resistant medium entropy alloy coating and a preparation method thereof, wherein the composite metal connector comprises a deposition base material and a medium entropy alloy coating, wherein the deposition base material is ferritic stainless steel; the alloy elements of the medium-entropy alloy coating are Cu, Ni, Co and Fe.
Example 1
Pretreating the surface of a ferritic stainless steel 430SS substrate, grinding the surface to 2000# by using water-grinding abrasive paper, cleaning and drying the surface by using distilled water and acetone, and storing the surface in a sealed bag. The method comprises the steps of arc melting CuNiCoFe intermediate entropy alloy, pre-weighing pure metal Cu, Ni, Co and Fe blocks, and respectively preparing the pure metal Cu, Ni, Co and Fe blocks according to the mixture ratio of 25 at.%, 25 at.% and 25 at.%. The method is characterized in that a vacuum induction furnace is adopted to smelt CuNiCoFe medium-entropy alloy, when the vacuum degree reaches 2Pa, an electric furnace of a diffusion pump is electrified for heating, a hot chamber is used for feeding materials, and a heating switch is started. Processing and pre-grinding the smelted CuNiCoFe intermediate entropy alloy, preparing an alloy electrode, depositing a CuNiCoFe intermediate entropy alloy coating on the surface of a substrate by adopting an electric spark technology, wherein the deposition voltage is about 200V, continuously introducing argon gas as protective gas to obtain an ultra-fine crystal intermediate entropy alloy coating, and the ultra-fine crystal intermediate entropy alloy coating is metallurgically combined with the substrate, and the thickness of the prepared intermediate coating is controlled to be about 10 mu m. And thermally growing the intermediate entropy alloy coating in a high-temperature high-oxygen pressure environment, setting the temperature to be 750 ℃, the oxygen partial pressure to be 104 Pa and the oxidation time to be 50 h to obtain the composite high-temperature corrosion-resistant conductive coating metal connector, wherein the obtained composite coating is divided into three layers, the outer side is rich in Cu oxide, the middle layer is CoFe oxide, and the inner side is rich in Ni oxide. The high-temperature conductivity of the chromium-containing iron oxide is lower than 100S/cm at 800 ℃, and the chromium-containing iron oxide has excellent high-temperature oxidation resistance and can effectively prevent the volatilization of chromium compounds at high temperature.
Example 2
Pretreating the surface of a ferritic stainless steel 430SS substrate, grinding the surface to 1500# by using water-grinding abrasive paper, cleaning and drying the surface by using distilled water and acetone, and storing the surface in a sealed bag. The method comprises the steps of arc melting CuNiCoFe intermediate entropy alloy, pre-weighing pure metal Cu, Ni, Co and Fe blocks, and respectively preparing the pure metal Cu, Ni, Co and Fe blocks according to the mixture ratio of 25 at.%, 25 at.% and 25 at.%. The method is characterized in that a vacuum induction furnace is adopted to smelt CuNiCoFe medium entropy alloy, when the vacuum degree reaches 5Pa, an electric furnace of a diffusion pump is electrified for heating, a hot chamber is used for feeding materials, and a heating switch is started. Processing and pre-grinding the smelted CuNiCoFe intermediate entropy alloy, preparing an alloy electrode, depositing a CuNiCoFe intermediate entropy alloy coating on the surface of a substrate by adopting an electric spark technology, wherein the deposition voltage is about 200V, continuously introducing argon gas as protective gas to obtain an ultra-fine crystal intermediate entropy alloy coating, and the ultra-fine crystal intermediate entropy alloy coating is metallurgically combined with the substrate, and the thickness of the prepared intermediate coating is controlled to be about 15 mu m. And thermally growing the intermediate entropy alloy coating in a high-temperature high-oxygen pressure environment, setting the temperature to be 750 ℃, the oxygen partial pressure to be 104 Pa and the oxidation time to be 50 h to obtain the composite high-temperature corrosion-resistant conductive coating metal connector, wherein the obtained composite coating is divided into three layers, the outer side is rich in Cu oxide, the middle layer is CoFe oxide, and the inner side is rich in Ni oxide. The high-temperature conductivity of the chromium-containing composite material is lower than 100S/cm at 800 ℃, the high-temperature oxidation resistance is excellent, and the volatilization of chromium compounds at high temperature can be effectively prevented.
Example 3
Pretreating the surface of a ferritic stainless steel 430SS substrate, grinding the surface to 2000# by using water-grinding abrasive paper, cleaning and drying the surface by using distilled water and acetone, and storing the surface in a sealed bag. The method comprises the steps of arc melting CuNiCoFe intermediate entropy alloy, pre-weighing pure metal Cu, Ni, Co and Fe blocks, and respectively preparing the pure metal Cu, Ni, Co and Fe blocks according to the mixture ratio of 25 at.%, 25 at.% and 25 at.%. The method is characterized in that a vacuum induction furnace is adopted to smelt CuNiCoFe medium-entropy alloy, when the vacuum degree reaches 2Pa, an electric furnace of a diffusion pump is electrified for heating, a hot chamber is used for feeding materials, and a heating switch is started. Processing and pre-grinding the smelted CuNiCoFe intermediate entropy alloy, preparing an alloy electrode, depositing a CuNiCoFe intermediate entropy alloy coating on the surface of a substrate by adopting an electric spark technology, wherein the deposition voltage is about 200V, continuously introducing argon gas as protective gas to obtain an ultra-fine crystal intermediate entropy alloy coating, and the ultra-fine crystal intermediate entropy alloy coating is metallurgically combined with the substrate, and the thickness of the prepared intermediate coating is controlled to be about 20 mu m. And thermally growing the intermediate entropy alloy coating in a high-temperature high-oxygen pressure environment, setting the temperature to be 950 ℃, the oxygen partial pressure to be 105 Pa and the oxidation time to be 50 h to obtain the composite high-temperature corrosion-resistant conductive coating metal connector, wherein the obtained composite coating is divided into three layers, the outer side is rich in Cu oxide, the middle layer is CoFe oxide, and the inner side is rich in Ni oxide. The high-temperature conductivity of the chromium-containing composite material is lower than 100S/cm at 800 ℃, the high-temperature oxidation resistance is excellent, and the volatilization of chromium compounds at high temperature can be effectively prevented.
Example 4
Pretreating the surface of a ferritic stainless steel 430SS substrate, grinding the surface to 2000# by using water-grinding abrasive paper, cleaning and drying the surface by using distilled water and acetone, and storing the surface in a sealed bag. The method comprises the steps of arc melting CuNiCoFe medium entropy alloy, pre-weighing pure metal Cu, Ni, Co and Fe blocks, and respectively preparing the pure metal Cu, Ni, Co and Fe blocks according to the proportion of 25 at.%, 25 at.% and 25 at.%. The method is characterized in that a vacuum induction furnace is adopted to smelt CuNiCoFe medium-entropy alloy, when the vacuum degree reaches 2Pa, an electric furnace of a diffusion pump is electrified for heating, a hot chamber is used for feeding materials, and a heating switch is started. Processing and pre-grinding the smelted CuNiCoFe intermediate entropy alloy, preparing an alloy electrode, depositing a CuNiCoFe intermediate entropy alloy coating on the surface of a substrate by adopting an electric spark technology, wherein the deposition voltage is about 200V, continuously introducing argon gas as protective gas to obtain an ultra-fine crystal intermediate entropy alloy coating, and metallurgically combining the ultra-fine crystal intermediate entropy alloy coating with the substrate, wherein the thickness of the prepared intermediate coating is controlled to be about 18 mu m. And thermally growing the intermediate entropy alloy coating in a high-temperature high-oxygen pressure environment, setting the temperature to be 850 ℃, the oxygen partial pressure to be 105 Pa and the oxidation time to be 50 h to obtain the composite high-temperature corrosion-resistant conductive coating metal connector, wherein the obtained composite coating is divided into three layers, the outer side is rich in Cu oxide, the middle layer is CoFe oxide, and the inner side is rich in Ni oxide. The high-temperature conductivity of the chromium-containing composite material is lower than 100S/cm at 800 ℃, the high-temperature oxidation resistance is excellent, and the volatilization of chromium compounds at high temperature can be effectively prevented.
Example 5
Pretreating the surface of a ferritic stainless steel 430SS matrix, grinding the surface to 1800#, cleaning and drying the surface by using distilled water and acetone, and storing the surface in a sealed bag. The method comprises the steps of arc melting CuNiCoFe intermediate entropy alloy, pre-weighing pure metal Cu, Ni, Co and Fe blocks, and respectively preparing the pure metal Cu, Ni, Co and Fe blocks according to the mixture ratio of 25 at.%, 25 at.% and 25 at.%. The method is characterized in that a vacuum induction furnace is adopted to smelt CuNiCoFe medium-entropy alloy, when the vacuum degree reaches 2Pa, an electric furnace of a diffusion pump is electrified for heating, a hot chamber is used for feeding materials, and a heating switch is started. Processing and pre-grinding the smelted CuNiCoFe intermediate entropy alloy, preparing an alloy electrode, depositing a CuNiCoFe intermediate entropy alloy coating on the surface of a substrate by adopting an electric spark technology, wherein the deposition voltage is about 200V, continuously introducing argon gas as protective gas to obtain an ultra-fine crystal intermediate entropy alloy coating, and the ultra-fine crystal intermediate entropy alloy coating is metallurgically combined with the substrate, and the thickness of the prepared intermediate coating is controlled to be about 12 mu m. And thermally growing the intermediate entropy alloy coating in a high-temperature high-oxygen pressure environment, setting the temperature at 800 ℃, the oxygen partial pressure at 104 Pa and the oxidation time at 50 h to obtain the composite high-temperature corrosion-resistant conductive coating metal connector, wherein the composite coating is divided into three layers, the outer side is rich in Cu oxide, the middle layer is CoFe oxide, and the inner side is rich in Ni oxide. The high-temperature conductivity of the chromium-containing composite material is lower than 100S/cm at 800 ℃, the high-temperature oxidation resistance is excellent, and the volatilization of chromium compounds at high temperature can be effectively prevented.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention in any way. It will be understood by those skilled in the art that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (8)

1. The composite metal connector is characterized by comprising a deposition base material and a medium-entropy alloy coating, wherein the deposition base material is ferritic stainless steel; the medium-entropy alloy coating is divided into three layers, wherein the outer layer is rich in Cu oxide, the middle layer is CoFe oxide, and the inner layer is rich in Ni oxide.
2. The high temperature resistant mid-entropy alloy coating composite metal interconnect of claim 1, wherein the mid-entropy alloy matrix of the mid-entropy alloy coating is CuNiCoFe, and the molar concentrations of each element are 25 at.%, and 25 at.%, respectively.
3. The high-temperature-resistant intermediate-entropy alloy coating composite metal connector according to claim 2, wherein the thickness of the CuNiCoFe intermediate-entropy alloy coating is 10-20 μm.
4. A method for preparing the high temperature resistant intermediate entropy alloy coating composite metal connector according to claim 1, characterized by comprising the following steps:
preprocessing the surface of a ferritic stainless steel substrate: pre-grinding, cleaning with acetone, drying and sealing;
arc melting CuNiCoFe intermediate entropy alloy, controlling the concentration of Cu, Ni, Co and Fe;
processing and pre-grinding the smelted intermediate entropy alloy to prepare an alloy electrode, and depositing a CuNiCoFe intermediate entropy alloy coating on the surface of the matrix by adopting an electric spark technology;
and fourthly, pre-oxidizing the CuNiCoFe intermediate entropy alloy coating in a high-temperature high-oxygen pressure environment to obtain the composite high-temperature corrosion-resistant conductive coating metal connector.
5. The preparation method of the composite metal connector with the high-temperature-resistant medium-entropy alloy coating according to claim 4, wherein an electric spark deposition technology is adopted in the step three, the deposition voltage is about 200V, and argon is used for protection.
6. The method for preparing the composite metal connector of the high-temperature-resistant intermediate-entropy alloy coating layer according to claim 4, wherein the ultra-fine grain intermediate-entropy alloy coating layer is obtained by adopting an electric spark deposition technology in the step (iii), and the ultra-fine grain intermediate-entropy alloy coating layer is metallurgically bonded with the substrate.
7. The preparation method of the high-temperature-resistant intermediate-entropy alloy coating composite metal connector as claimed in claim 6, wherein the high-temperature and high-oxygen-pressure environment adopted in the step (iv) is 750 ℃ to 950 ℃, the oxygen partial pressure is 104 Pa to 105 Pa, and the time is 50 hours.
8. The method for preparing the high-temperature-resistant intermediate-entropy alloy coating composite metal connector as claimed in claim 7, wherein the composite high-temperature-resistant corrosion-resistant conductive coating can be applied to a solid oxide fuel cell connector material.
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