CN114606492B - 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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CN114606492B
CN114606492B CN202210231614.5A CN202210231614A CN114606492B CN 114606492 B CN114606492 B CN 114606492B CN 202210231614 A CN202210231614 A CN 202210231614A CN 114606492 B CN114606492 B CN 114606492B
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entropy alloy
medium
coating
temperature
alloy coating
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CN114606492A (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

Abstract

The invention discloses a high-temperature-resistant medium-entropy alloy coating composite metal connector and a preparation method thereof, wherein the composite metal connector comprises a deposition matrix material and a medium-entropy alloy coating, the medium-entropy alloy coating is divided into three layers, the outer layer is Cu-rich oxide, the middle layer is CoFe oxide, and the inner layer is Ni-rich oxide; the preparation method of the composite metal connector comprises the following steps: pre-treating a ferrite stainless steel material; then arc melting the surface-centered cubic structure CuNiCoFe medium entropy alloy, and then depositing a medium entropy alloy coating on the ferrite stainless steel by electric spark; finally, the composite high-temperature corrosion-resistant conductive coating is obtained in a high-temperature high-oxygen pressure environment. The high-temperature-resistant medium-entropy alloy coating composite metal connector prepared by the invention utilizes the delayed diffusion effect of the medium-high-entropy alloy, and is beneficial to inhibiting the out-diffusion and CrO of Cr element in a ferrite stainless steel matrix 3 Or CrO (CrO) 2 (OH) 2 The composite coating is generated, has higher conductivity, matched thermal expansion coefficient and good high-temperature corrosion resistance, and solves the problem that the composite coating is easy to peel.

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 an all-solid-state energy conversion device for converting electric energy and heat energy into chemical energy, and adopts renewable energy sources such as solar energy, wind energy, geothermal energy and the like 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, the voltage and power of a single solid oxide fuel cell are low, and the power requirement in life cannot be met completely, so that each single cell stack is required to be connected to form a cell stack to obtain high voltage and power, and meanwhile, the oxygen on the cathode side of one single cell and the fuel gas on the anode side of the adjacent other single cell are isolated by the connector material, so that the connector material plays a vital role in the cell stack, and the performance of the connector material directly influences the stability and power of the cell stack.
Along with the reduction of the operation temperature of the solid oxide fuel cell from 1000 ℃ to 600-800 ℃, the connector material can be made of metal and alloy materials with lower cost and good mechanical processing performance and electrical conductivity, and the ferritic stainless steel becomes the connector material with the highest potential at present due to the advantages of good electrical conductivity, thermal expansion coefficient matching with other components, low price and the like. However, the ferritic stainless steel has serious oxidation corrosion in the working environment of the solid oxide fuel cell, especially in the high-temperature oxidizing environment of the cathode, and the CrO generated on the surface of the cathode is caused by the volatilization of Cr element 3 Or CrO (CrO) 2 (OH) 2 The out-diffusion will cause degradation of the cell performance.
Aiming at the volatilization problem of the alloy connector Cr, the deposition of a layer of high-temperature corrosion-resistant coating on the surface of the metal connector is an important means. The protective coating acts on the surface of the attached alloy, has excellent conductivity, can protect the alloy from high-temperature corrosion, and can effectively inhibit the outward diffusion of Cr element, so the preparation of the coating needs to take the following aspects into consideration: the degradation of the coating is prevented, namely, the inter-diffusion of the coating and the matrix alloy at the interface is avoided, so that the oxidation-resistant elements in the coating are consumed more quickly; the bond between the coating and the substrate, the coating must be stable on the alloy surface; the preparation mode of the coating is selected, and the difficulty and the preparation condition in the preparation are controlled.
The invention adopts the electric spark deposition coating technology, the pulse power source used by the invention is a relaxation type pulse generator, and a charging loop is formed by the direct current power source, a current limiting resistor and an energy storage capacitor; the energy storage capacitor forms a discharge loop together with the electrode and the workpiece. The electrode is connected with the positive electrode, and the workpiece is connected with the negative electrode. The discharge frequency is controlled by a set of thyristor circuit, and different discharge frequencies are obtained by adjusting the control angle. When in operation, the electrode rotates at a high speed, and approaches the substrate infinitely to form a discharge loop to form a passage, and the electrode melts to form a coating during discharge, so that the high-entropy alloy coating prepared by metallurgical bonding has higher bonding strength and lower void ratio, does not cause larger thermal deformation to the substrate, and has specific advantages.
The high-entropy alloy is characterized in that each main element in the alloy has a high atomic percentage, but the highest content of the elements cannot exceed 35%, and the high-entropy alloy is characterized by the combined action of the elements composing the high-entropy alloy as a whole. The characteristics of the hysteresis diffusion effect and the serious lattice distortion effect caused by various elements in the high-entropy alloy lead the high-entropy alloy to have excellent structural stability and mechanical properties. The definition of high entropy alloys is based on one component and the other on mixed entropy. If based on composition, a high entropy alloy is defined as an alloy comprising at least five major elements. CuNiCoFe alloys are four component alloys, referred to herein as mid-entropy alloys, which still have four core effects of high-entropy alloys: thermodynamic high entropy effects, kinetic delayed diffusion effects, structural severe lattice distortion effects and performance cocktail effects.
The delayed diffusion effect of the high-entropy alloy means that the phase transition in the high-entropy alloy requires many different kinds of atoms to cooperatively diffuse to complete the division of the interphase components. The concentration of vacancies 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 mixing entropy, and competition between the mixing enthalpy and mixing entropy creates a certain equilibrium vacancy concentration in the alloy, during diffusion, vacancies in the whole solute matrix are actually surrounded and contended for by different elemental atoms, either vacancies or atoms are all transported by the fluctuating diffusion path, the diffusion rate is slower, the activation energy is higher, and therefore the diffusion phase transition is slower in the high-entropy alloy. This feature is advantageous in suppressing the out-diffusion of Cr element in the ferritic stainless steel matrix and improving the high temperature resistance of the fuel cell metal connector. Research shows that the superfine crystal high-entropy alloy can obtain more excellent comprehensive performance, and the invention is based on 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 compound CrO at high temperature 3 Or CrO (CrO) 2 (OH) 2 The 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:
the high-temperature-resistant medium-entropy alloy coating composite metal connector comprises a deposition matrix material and a medium-entropy alloy coating, wherein the deposition matrix material is ferrite stainless steel; the medium-entropy alloy coating is divided into three layers, wherein the outer layer is Cu-rich oxide, the middle layer is CoFe oxide, and the inner layer is Ni-rich oxide.
Further, the medium entropy alloy matrix of the medium entropy alloy coating is CuNiCoFe, and the molar concentration of each element is 25 at%, 25 at%, 25 at% and 25 at%, respectively.
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:
(1) pretreatment of the surface of a ferrite stainless steel substrate: pre-grinding, cleaning with acetone, drying and sealing;
(2) arc smelting of the entropy alloy in CuNiCoFe, and controlling the concentration of Cu, ni, co, fe;
(3) processing and pre-grinding the smelted medium entropy alloy to prepare an alloy electrode, and depositing a CuNiCoFe medium entropy alloy coating on the surface of a substrate by adopting an electric spark technology;
(4) and pre-oxidizing the CuNiCoFe medium entropy alloy coating in a high-temperature high-oxygen-pressure environment to obtain the composite high-temperature corrosion-resistant conductive coating metal connector.
And (3) adopting an electric spark deposition technology, wherein the deposition voltage is about 200V, and the argon is used for protection.
The step (3) adopts an electric spark deposition technology to obtain the ultra-fine grain medium entropy alloy coating, and the ultra-fine grain medium entropy alloy coating is metallurgically bonded with the substrate.
The high-temperature high-oxygen pressure environment adopted in the step (4) has the temperature of 750-950 ℃ and the oxygen partial pressure of 10 4 ~10 5 The time is 50 h, and the composite high-temperature corrosion-resistant conductive coating can be applied to solid oxide fuel cell connector materials.
The technical scheme of the invention can produce the following beneficial effects:
(1) The CuNiCoFe medium-entropy alloy coating prepared by the method effectively prevents the outer diffusion of Cr element in a ferrite stainless steel matrix, and can improve the high temperature resistance of the 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) The preparation method of preparing the superfine grain medium-entropy alloy coating by adopting the electric spark technology and then forming the coating by high-temperature thermal growth has the advantages that the metallurgical bonding of the matrix and the medium-entropy alloy coating has higher bonding strength and low porosity, the adhesiveness between the composite coating and the metal stainless steel substrate is increased, and the problem that the composite coating is easy to peel is solved.
Drawings
FIG. 1 is a cross-sectional morphology of a composite coating obtained by thermally growing a medium-entropy alloy coating prepared in example 1 of the present invention in a high-temperature high-oxygen pressure environment.
FIG. 2 is a surface morphology of an entropy alloy in CuNiCoFe after arc melting in example 1 of the present invention.
FIG. 3 is a cross-sectional morphology of a composite coating obtained by thermally growing the medium-entropy alloy coating prepared in example 4 of the present invention in a high-temperature high-oxygen pressure environment.
Description of the embodiments
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and the embodiments, and it is apparent that the described embodiments are some embodiments of the present invention, not all embodiments.
1-3, the invention relates to a high-temperature-resistant medium-entropy alloy coating composite metal connector and a preparation method thereof, wherein the composite metal connector comprises a deposition matrix material and a medium-entropy alloy coating, and the deposition matrix material is ferrite stainless steel; the alloy element of the medium-entropy alloy coating is Cu, ni, co, fe.
Example 1
The surface of the ferrite stainless steel 430SS substrate is pretreated, polished to 2000# by water-abrasive paper, then cleaned and dried by distilled water and acetone, and stored in a sealed bag. The entropy alloy in CuNiCoFe was arc melted, pre-weighed blocks of pure metal Cu, ni, co, fe, in proportions 25 at%, 25 at%, 25 at% and 25 at%, respectively. And smelting the entropy alloy in the CuNiCoFe by adopting a vacuum induction furnace, and electrifying and heating the diffusion pump electric furnace, feeding the materials in a hot chamber and starting a heating switch when the vacuum degree reaches 2 Pa. Processing and pre-grinding the smelted CuNiCoFe medium-entropy alloy to prepare an alloy electrode, depositing a CuNiCoFe medium-entropy alloy coating on the surface of a substrate by adopting an electric spark technology, continuously introducing argon as a shielding gas at a deposition voltage of about 200V to obtain an ultrafine-grain medium-entropy alloy coating, and metallurgically combining the ultrafine-grain medium-entropy alloy coating with the substrate to prepare a medium-coating with a thickness of about 10 mu m. And then thermally growing the medium entropy alloy coating in a high-temperature high-oxygen pressure environment, setting the temperature to 750 ℃ and the oxygen partial pressure to 10 4 And (3) performing oxidation for 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 Cu-rich oxide, the middle layer is CoFe oxide, and the inner side is Ni-rich oxide. At 800 DEG CThe high-temperature conductivity of the high-temperature chromium-free composite material is lower than 100S/cm, and the high-temperature chromium-free composite material has excellent high-temperature oxidation resistance and can effectively prevent volatilization of chromium compounds at high temperature.
Example 2
The surface of the ferrite stainless steel 430SS substrate is pretreated, polished to 1500# by water-abrasive paper, then cleaned and dried by distilled water and acetone, and stored in a sealed bag. The entropy alloy in CuNiCoFe was arc melted, pre-weighed blocks of pure metal Cu, ni, co, fe, in proportions 25 at%, 25 at%, 25 at% and 25 at%, respectively. And smelting the entropy alloy in the CuNiCoFe by adopting a vacuum induction furnace, and electrifying and heating the diffusion pump electric furnace, feeding in a hot chamber and starting a heating switch when the vacuum degree reaches 5 Pa. Processing and pre-grinding the smelted CuNiCoFe medium-entropy alloy to prepare an alloy electrode, depositing a CuNiCoFe medium-entropy alloy coating on the surface of a substrate by adopting an electric spark technology, continuously introducing argon as a shielding gas at a deposition voltage of about 200V to obtain an ultrafine-grain medium-entropy alloy coating, and metallurgically combining the ultrafine-grain medium-entropy alloy coating with the substrate to prepare a medium-coating with a thickness of about 15 mu m. And then thermally growing the medium entropy alloy coating in a high-temperature high-oxygen pressure environment, setting the temperature to 750 ℃ and the oxygen partial pressure to 10 4 And (3) performing oxidation for 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 Cu-rich oxide, the middle layer is CoFe oxide, and the inner side is Ni-rich oxide. The high-temperature conductivity of the high-temperature chromium-free alloy is lower than 100S/cm at 800 ℃, has excellent high-temperature oxidation resistance, and can effectively prevent the volatilization of chromium compounds at high temperature.
Example 3
The surface of the ferrite stainless steel 430SS substrate is pretreated, polished to 2000# by water-abrasive paper, then cleaned and dried by distilled water and acetone, and stored in a sealed bag. The entropy alloy in CuNiCoFe was arc melted, pre-weighed blocks of pure metal Cu, ni, co, fe, in proportions 25 at%, 25 at%, 25 at% and 25 at%, respectively. And smelting the entropy alloy in the CuNiCoFe by adopting a vacuum induction furnace, and electrifying and heating the diffusion pump electric furnace, feeding the materials in a hot chamber and starting a heating switch when the vacuum degree reaches 2 Pa. Processing and premilling the smelted CuNiCoFe medium entropy alloy to prepare an alloy electrode, depositing a CuNiCoFe medium entropy alloy coating on the surface of a substrate by adopting an electric spark technology, wherein the deposition voltage is about 200V, and the substrate is maintainedArgon is continuously introduced as shielding gas to obtain the superfine grain medium-entropy alloy coating, the superfine grain medium-entropy alloy coating is metallurgically bonded with the substrate, and the thickness of the coating is controlled to be about 20 mu m in preparation. And then thermally growing the medium entropy alloy coating in a high-temperature high-oxygen pressure environment, setting the temperature to 950 ℃ and the oxygen partial pressure to 10 5 And (3) performing oxidation for 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 Cu-rich oxide, the middle layer is CoFe oxide, and the inner side is Ni-rich oxide. The high-temperature conductivity of the high-temperature chromium-free alloy is lower than 100S/cm at 800 ℃, has excellent high-temperature oxidation resistance, and can effectively prevent the volatilization of chromium compounds at high temperature.
Example 4
The surface of the ferrite stainless steel 430SS substrate is pretreated, polished to 2000# by water-abrasive paper, then cleaned and dried by distilled water and acetone, and stored in a sealed bag. The entropy alloy in CuNiCoFe was arc melted, pre-weighed blocks of pure metal Cu, ni, co, fe, in proportions 25 at%, 25 at%, 25 at% and 25 at%, respectively. And smelting the entropy alloy in the CuNiCoFe by adopting a vacuum induction furnace, and electrifying and heating the diffusion pump electric furnace, feeding the materials in a hot chamber and starting a heating switch when the vacuum degree reaches 2 Pa. Processing and pre-grinding the smelted CuNiCoFe medium-entropy alloy to prepare an alloy electrode, depositing a CuNiCoFe medium-entropy alloy coating on the surface of a substrate by adopting an electric spark technology, continuously introducing argon as a shielding gas at a deposition voltage of about 200V to obtain an ultrafine-grain medium-entropy alloy coating, and metallurgically combining the ultrafine-grain medium-entropy alloy coating with the substrate to prepare a medium-coating with a thickness of about 18 mu m. And then thermally growing the medium entropy alloy coating in a high-temperature high-oxygen pressure environment, setting the temperature to 850 ℃ and the oxygen partial pressure to 10 5 And (3) performing oxidation for 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 Cu-rich oxide, the middle layer is CoFe oxide, and the inner side is Ni-rich oxide. The high-temperature conductivity of the high-temperature chromium-free alloy is lower than 100S/cm at 800 ℃, has excellent high-temperature oxidation resistance, and can effectively prevent the volatilization of chromium compounds at high temperature.
Example 5
The surface of the ferrite stainless steel 430SS substrate is pretreated, polished to 1800# by water-abrasive paper, then cleaned and dried by distilled water and acetone, and stored in a sealed bag. Electric powerThe entropy alloy in the arc smelting CuNiCoFe is pre-weighed into a pure metal Cu, ni, co, fe block, and the proportions are 25 at%, 25 at%, 25 at% and 25 at% respectively. And smelting the entropy alloy in the CuNiCoFe by adopting a vacuum induction furnace, and electrifying and heating the diffusion pump electric furnace, feeding the materials in a hot chamber and starting a heating switch when the vacuum degree reaches 2 Pa. Processing and pre-grinding the smelted CuNiCoFe medium-entropy alloy to prepare an alloy electrode, depositing a CuNiCoFe medium-entropy alloy coating on the surface of a substrate by adopting an electric spark technology, continuously introducing argon as a shielding gas at a deposition voltage of about 200V to obtain an ultrafine-grain medium-entropy alloy coating, and metallurgically combining the ultrafine-grain medium-entropy alloy coating with the substrate to prepare a medium-coating with a thickness of about 12 mu m. And then thermally growing the medium entropy alloy coating in a high-temperature high-oxygen pressure environment, setting the temperature to 800 ℃ and the oxygen partial pressure to 10 4 And (3) performing oxidation for 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 Cu-rich oxide, the middle layer is CoFe oxide, and the inner side is Ni-rich oxide. The high-temperature conductivity of the high-temperature chromium-free alloy is lower than 100S/cm at 800 ℃, has excellent high-temperature oxidation resistance, and can effectively prevent the volatilization of chromium compounds at high temperature.
The foregoing is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Any person skilled in the art will make any equivalent substitution or modification to the technical solution and technical content disclosed in the invention without departing from the scope of the technical solution of the invention, and the technical solution of the invention is not departing from the scope of the invention.

Claims (3)

1. The preparation method of the high-temperature-resistant medium-entropy alloy coating composite metal connector is characterized by comprising the following steps of:
(1) pretreatment of the surface of a ferrite stainless steel substrate: pre-grinding, cleaning with acetone, drying and sealing;
(2) arc melting the entropy alloy in CuNiCoFe, controlling Cu, ni, co, fe concentration, and respectively preparing 25 at%, 25 at%, 25 at% and 25 at%;
(3) processing and pre-grinding the smelted medium entropy alloy to prepare an alloy electrode, depositing a CuNiCoFe medium entropy alloy coating on the surface of a substrate by adopting an electric spark technology, wherein the deposition voltage is 200V, and argon is used for protection;
(4) pre-oxidizing CuNiCoFe medium entropy alloy coating in high temperature and high oxygen pressure environment at 750-950 deg.c and oxygen partial pressure of 10 4 ~10 5 And (3) Pa, the time is 50 h, and the high-temperature-resistant medium-entropy alloy coating composite metal connector is obtained, wherein the thickness of the CuNiCoFe medium-entropy alloy coating is 10-20 mu m.
2. The method for preparing a high temperature resistant medium entropy alloy coated composite metal connector according to claim 1, wherein the step (3) is performed by adopting an electric spark deposition technology to obtain an ultra-fine grain medium entropy alloy coating, and the ultra-fine grain medium entropy alloy coating is metallurgically bonded with a substrate.
3. The method for preparing a high temperature resistant medium entropy alloy coated composite metal connector according to claim 2, wherein the composite high temperature resistant corrosion resistant conductive coating is applicable to solid oxide fuel cell connector materials.
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