阅读说明：本技术 一种CeO2掺杂Cu/Mn复合膜/微晶界面层与金属基复合连接体及其制备方法 (CeO (CeO)2Cu/Mn-doped composite film/microcrystalline interface layer and metal-based composite connector and preparation method thereof ) 是由 郭平义 丁江涛 邵勇 黄铭瑞 毛胜勇 王宇鑫 何震 郭云霞 王冬朋 欧文祥 于 2020-11-16 设计创作，主要内容包括：本发明公开一种CeO2掺杂Cu/Mn复合膜/微晶界面层与金属基复合连接体及其制备方法,涉及固体氧化物燃料电池金属连接体复合材料领域,首先通过高能微弧合金技术沉积基体材料的微晶过渡层；再运用电化学沉积方法复合镀金属Cu结合纳米级CeO-2颗粒的复合膜；再电化学沉积金属Mn作为整个复合材料的外层。其中通过在电沉积Cu镀层时添加的一定量纳米级CeO-2来细化镀层晶粒,提高元素高温扩散性和复合层高温抗氧化性。有益效果为：制备的微晶界面层与金属基复合连接体,导电性强且具有优良的高温抗氧化性能,能够有效的阻止金属基材中Cr元素的外扩散,以提高固体氧化物燃料电池金属连接体的寿命与工作效率。(The invention discloses a CeO2 doped Cu/Mn composite membrane/microcrystalline interface layer and metal matrix composite connector and a preparation method thereof, relating to the field of solid oxide fuel cell metal connector composite materials, firstly depositing a microcrystalline transition layer of a base material by a high-energy micro-arc alloy technology; then the electrochemical deposition method is used to compound the metal Cu with the nanometer CeO 2 A composite film of particles; and electrochemically depositing metal Mn as an outer layer of the entire composite material. Wherein the Cu plating layer is electrodeposited with a certain amount of nano-scale CeO 2 To refineThe crystal grains of the coating improve the high-temperature diffusivity of elements and the high-temperature oxidation resistance of the composite layer. The beneficial effects are that: the prepared microcrystal interface layer and metal-based composite connector have strong conductivity and excellent high-temperature oxidation resistance, and can effectively prevent the outward diffusion of Cr element in a metal base material so as to improve the service life and the working efficiency of the metal connector of the solid oxide fuel cell.)

1. A CeO2 doped Cu/Mn composite film/microcrystalline interface layer and metal-based composite connector is characterized in that a substrate microcrystalline interface layer and Cu (CeO)₂) And the Mn composite coating is sequentially covered on the surface of a deposition base material, and the deposition base material is ferrite stainless steel.

2. The CeO2 doped Cu/Mn composite film/microcrystalline interface layer and metal matrix composite interconnect of claim 1, wherein Cu (CeO)₂) And a Mn composite coating, the sum of the thicknesses of the two is not more than 20 um, and Cu (CeO)₂) The thickness ratio of the layer to the Mn layer is between 1:1 and 1: 2.

3. The CeO2 doped Cu/Mn composite film/microcrystalline interface layer and metal matrix composite interconnect according to claim 2, wherein Cu (CeO)₂) The layer is formed by adding nano-scale CeO into a Cu plating layer₂So as to achieve the purpose of refining the crystal grains of the plating layer.

4. The CeO2 doped Cu/Mn composite film/microcrystalline interface layer and metal matrix composite interconnect according to claim 1, wherein the microcrystalline interface layer is made of a corresponding substrate material, and is a metallurgically bonded microcrystalline interface layer formed by depositing a layer of the same material on the surface of the substrate material by a high energy micro-arc alloying technique.

5. The CeO2 doped Cu/Mn composite film/microcrystalline interface layer and metal matrix composite connector according to claim 1, wherein the thickness of the microcrystalline interface layer is about 10-50 μm.

6. A preparation method of a CeO2 doped Cu/Mn composite film/microcrystalline interface layer and metal-based composite connector is characterized by comprising the following five steps:

step one, pretreating the surface of a metal substrate: polishing, cleaning and airing the metal base material, and sealing and storing;

depositing a metallurgical bonding microcrystalline interface layer which is the same as the base material on the surface of the base ferrite stainless steel by a high-energy micro-arc alloying technology, and adjusting parameters to keep the interface layer smooth and uniform; respectively preparing electrolyte solutions of impact Ni, Cu and Mn, applying the impact Ni to increase the binding force between the coating and the substrate, and simultaneously adding 0.01-0.08 mol/l of nano-scale CeO into the electrolyte solution for depositing Cu₂Powder, and uniformly stirring the deposition solution by using an ultrasonic or magnetic stirrer; depositing a layer of impact nickel by a direct current power supply, and then respectively depositing the impact nickel containing Cu (CeO) by adopting an electrochemical layered deposition technology₂) The layer and the metal Mn layer are successively deposited on a sample on which a refined crystal grain transition layer is deposited by a high-energy micro-arc alloying technology, and the test parameters are adjusted to ensure that the thickness ratio of the Cu/Mn coating is between 1:1 and 1: 2;

and fifthly, finally, carrying out high-temperature heat treatment to obtain the ultrathin Cr interface oxide combined CuMnCe-based high-temperature corrosion-resistant conductive layer/metal-based connector, wherein the heat treatment atmosphere is oxidizing atmosphere, the heat treatment temperature is 700-900 ℃, and the heat treatment time is 20-500 h.

7. According to claim 6The preparation method of the CeO2 doped Cu/Mn composite film/microcrystalline interface layer and metal-based composite connector is characterized in that in the fourth step, the current density of deposited nickel is 40-60 mA/cm²The deposition time is 1-2 min; cu (CeO)₂) The deposition parameters of the layers were: the current density of the deposition is 50-200 mA/cm²(ii) a The deposition parameters of the Mn layer were: the current density of the deposition is 100-300 mA/cm²(ii) a The whole deposition process is continuously stirred by a magnetic stirrer, the stirring speed is 650-700 rpm, and the temperature is controlled at 40 ℃.

8. The method for preparing a CeO 2-doped Cu/Mn composite film/microcrystalline interface layer and metal-based composite connector according to claim 6, wherein in the third step, the impact nickel solution is NiCl₂And HCl to deposit Cu electrolyte solution as CuSO₄·5H₂O and H₃BO₃And adding 0.01 to 0.08 mol/l of CeO₂(ii) a The electrolyte solution for depositing Mn is (NH)₄)₂SO₄And MnSO₄·H₂O preparation, no addition of CeO during Mn deposition₂。

9. The method for preparing a CeO 2-doped Cu/Mn composite film/microcrystalline interface layer and metal matrix composite connector according to claim 6, wherein in the second step, the maximum output power of the high-energy micro-arc alloying equipment is 2000W, the electrode rod is a 2-3 mm-diameter rod prepared from a matrix ferritic stainless steel, and the voltage range during interface layer deposition is 180-220V.

Technical Field

The invention relates to a composite material of a metal connector of a solid oxide fuel cell, in particular to a preparation method of a CeO2 doped Cu/Mn composite membrane/microcrystalline interface layer and a metal-based composite connector, which is applied to a solid oxide fuel cell or other high-temperature cells.

Background

The Solid Oxide Fuel Cell (SOFC) has the advantages of wide Fuel adaptability, high energy conversion efficiency, all-Solid-state, modular assembly, zero pollution and the like, and can directly use various hydrocarbon fuels such as hydrogen, carbon monoxide, natural gas, liquefied gas, coal gas, biomass gas and the like. The solid oxide fuel cell has a wide application range, and almost all the conventional electric power markets are covered, including residential, commercial, industrial, and utility power plants, and even portable power sources, power sources for remote areas, high-quality power sources, and the like, and the solid oxide fuel cell can be used as a power source for ships, a power source for transportation vehicles, and the like. Among them, a stationary commercial power supply, an industrial cogeneration system, and a small power supply are preferred.

With the development of SOFC technology, the working temperature of SOFC is reduced from 1000 ℃ to 650-800 ℃, so that the connector can be manufactured by using metal materials to replace the traditional perovskite ceramics. Compared with ceramic materials, metal materials have the advantages of high electronic conductivity and thermal conductivity, low cost, easy processing, high mechanical strength and the like, and are widely concerned. In the range of medium temperature SOFC operating temperatures, metallic materials still face high temperature oxidation problems. With Al formed only on the surface₂O₃、SiO₂Or Cr₂O₃The alloy of the oxide film has high temperature oxidation resistance. However, due to Al₂O₃And SiO₂Too low conductivity to form Al₂O₃And SiO₂The alloy of the film is not suitable for use as a tie material, only forming Cr₂O₃The alloys of the oxide films are most promising for use as solid oxide fuel cell interconnect materials. At present, the ferritic stainless steel metal substrate is one of the best choices as the SOFC connector material, and has the advantages of better corrosion resistance, matched thermal expansion coefficient, low cost and the like. But due to Cr formed after oxidation of Cr during operation of SOFC₂O₃Or Cr₂(OH)₂The vapor diffuses to the cathode to cause cathode poisoning, and the service life of the SOFC is shortened.

In order to prolong the service life of the SOFC, a protective coating is deposited on the surface of a metal connector of the solid oxide fuel cell, and the coating can improve the oxidation resistance of the metal connector and prevent Cr from volatilizing. In recent years, the coating materials applicable to the SOFC metal connector are widely researched, and at present, the coating materials are mainly classified into the following four types: active element oxide, rare earth perovskite oxide, MAlCrYO high-temperature-resistant alloy material and high-temperature corrosion-resistant conductive spinel. The more studied high temperature corrosion resistant conductive spinel coatings have high electronic conductivity and low ionic conductivity, and have a coefficient of thermal expansion and chemical compatibility similar to that of adjacent fuel cell components.

According to the current research situation, the spinel film layer materials can be divided into Cr-containing spinel and Cr-free spinelAnd (4) class. Cr-containing spinel film MgCr₂O₄、Mn_1.2Cr_1.8O₄、NiCr₂O₄、CuCr₂O₄、ZnCr₂O₄、CoCr₂O₄Equal conductivity is poor (except CoCr)₂O₄Outside the membrane layer, the other conductivities are all 0.01-0.4S-cm^-1About) and a thermal expansion coefficient of 7X 10^-6K^-1(TEC of stainless Steel plate at 11X 10^-6K^-1About) and has serious problems of Cr volatilization and the like, and has poor commercialization prospect, so that the Cr-free film material is the key point of research. Of all Cr-free spinel films, the spinel containing Fe element is most matched with the TEC of ferritic stainless steel, and the better conductive property is Cu_1.3Mn_1.7O₄（225S·cm-1，750℃）、MnCo₂O₄（60S·cm^-1800 ℃ C. spinel structure. Combining the two factors, the spinel film material suitable for the SOFC stainless steel metal connecting plate is CuFe₂O₄、Co₃O₄、MnxCo_3-xO_4（x = 0-3), and the like, wherein the Cu-Mn film layer has excellent performance and low cost, and is considered as the most effective and reasonable spinel film layer material for the SOFC stainless steel metal connecting plate.

Disclosure of Invention

In order to improve the high-temperature oxidation resistance of the metal connecting material of the solid oxide fuel cell and prevent the cathode poisoning phenomenon caused by volatilization of a chromide at high temperature, the invention aims to provide a preparation method of a composite film/microcrystalline interface layer and metal-based composite connector, which can make up for the defects of insufficient high-temperature oxidation resistance and the like of the metal connecting material. Wherein the CuMn-based spinel oxide has excellent thermal and electrical properties, and the electrical conductivity thereof is about 100-200 Scm at 800 DEG C^-1And has a thermal expansion coefficient similar to that of the metal ferrite stainless steel. In addition, the CuMn-based spinel has a special crystal structure, so that the CuMn-based spinel has good stability and high-temperature oxidation resistance at the temperature of 200-1600 ℃, is suitable for being applied to a surface protective coating of a metal connector, and can improve the high-temperature oxidation resistance of a metal connecting material of a solid oxide fuel cell and prevent chromizingThe dual purpose of material volatilization has good application prospect.

The invention also aims to provide a preparation method of the CeO2 doped Cu/Mn composite film/microcrystalline interface layer and metal-based composite connector, which comprises the steps of depositing a fine-grained transition layer by a high-energy micro-arc alloying technology, and adding CeO₂The Cu and the Mn are deposited on the surface of the fine-grain transition layer in sequence, and finally the ultrathin Cr interface oxide is combined with the CuMnCe-based high-temperature corrosion-resistant conducting layer/metal-based connector material is obtained through high-temperature heat treatment.

In order to achieve the purpose of the invention, the invention adopts the following technical scheme:

firstly, depositing a microcrystal (or nanocrystalline) transition layer of a base material (ferrite) by a high-energy micro-arc alloy technology; then the electrochemical deposition method is used to compound the metal Cu with the nanometer CeO₂A composite film of particles; and electrochemically depositing metal Mn as an outer layer of the entire composite material. Wherein the Cu plating layer is electrodeposited with a certain amount of nano-scale CeO₂To refine the crystal grains of the coating and improve the high-temperature diffusivity of elements and the high-temperature oxidation resistance of the composite layer. The thickness of the Cu and Mn composite coating is not more than 20 um, and the thickness ratio of the Cu layer to the Mn layer is between 1:1 and 1: 2. The preparation method comprises the following steps:

step one, pretreating the surface of a metal substrate: polishing, cleaning and airing the metal base material, and sealing and storing;

and secondly, depositing a metallurgical bonding microcrystalline interface layer which is the same as the base material on the surface of the base ferrite stainless steel by a high-energy micro-arc alloying technology, and adjusting parameters to keep the interface layer smooth and uniform. The maximum output power of the high-energy micro-arc alloying equipment is 2000W, the used electrode bar is a bar material with the diameter of 2-3mm and prepared by using matrix ferrite stainless steel, and the voltage range is 180-220V when an interface layer is deposited.

Step three, respectively preparing electrolyte solutions of Ni, Cu and Mn, wherein the impact nickel solution is NiCl₂And HCl; simultaneously adding 0.01-0.08 mol/l of nano-scale CeO into electrolyte solution for depositing Cu₂Powder, and uniformly stirring the deposition solution by an ultrasonic wave or a magnetic stirrer. Depositing Cu electrolyteThe solution is CuSO₄·5H₂O and H₃BO₃And adding 0.01 to 0.08 mol/l of CeO₂(ii) a The electrolyte solution for depositing Mn is (NH)₄)₂SO₄And MnSO₄·H₂O preparation, no addition of CeO during Mn deposition₂。

Depositing a layer of impact nickel by a direct current power supply, and then respectively depositing CeO by adopting an electrochemical layered deposition technology₂The Cu layer and the metal Mn layer are deposited on a sample on which a refined crystal grain transition layer is deposited by a high-energy micro-arc alloying technology in sequence, and test parameters are adjusted to enable the thickness ratio of the Cu/Mn coating to be 1:1 and 1: 2. The nickel solution is NiCl₂And HCl with a current density of 40-60 mA/cm²The deposition time is 1-2 min. The deposition parameters of Cu are: the current density of the deposition is 50-200 mA/cm²(ii) a The deposition parameters of Mn are: the current density of the deposition is 100-300 mA/cm²(ii) a The whole deposition process is continuously stirred by a magnetic stirrer, the stirring speed is 650-700 rpm, and the temperature is controlled at 40 ℃.

And fifthly, finally, carrying out high-temperature heat treatment to obtain the ultrathin Cr interface oxide combined CuMnCe-based high-temperature corrosion-resistant conductive layer/metal-based connector. The heat treatment atmosphere is oxidizing atmosphere, the heat treatment temperature is 700-900 ℃, and the heat treatment time is 20-500 h. The specific surface resistance of the prepared composite layer connector can be measured and measured by a specific surface resistance testing system so as to judge the conductivity of the composite layer connector.

The method has the beneficial effects that (1) a transition layer of refined crystal grain base material is deposited on the base stainless steel by the high-energy micro-arc alloying technology, and the rapid outer diffusion of Cr and the rapid inner diffusion of O are promoted by the microcrystalline structure₂In combination, promote rapid growth of the Cr-rich interfacial oxide layer. Thus, the diffusion and exchange of elements between the matrix and the composite layer are inhibited, a condition is created for the growth of the CuMn spinel coating, the rapid growth of the thin continuous Cr interface oxide reduces the surface specific resistance caused by the composite material interface. (2) The middle layer is added with nano CeO₂Can obtain a Cu layer with fine and uniform grain size, is beneficial to the rapid internal diffusion of oxygen during high-temperature heat treatment and the rapid interdiffusion between Cu and MnThe continuous growth of single-phase CuMn spinel is promoted, and the reaction stabilization time is shortened, so that the high-temperature conductivity of the composite layer is increased, the thickness of the total oxide layer is controlled, and the oxidation resistance of the composite layer is greatly improved. At the same time, CeO₂Doping also plays an active element effect, influences the growth of the oxide and promotes the interface combination of each layer. (3) The prepared composite coating has a thickness less than 20 μm, high conductivity and good high-temperature oxidation resistance, and can effectively prevent cathode poisoning caused by diffusion of Cr from the outside of the matrix. After high-temperature oxidation, spinel plating with better high-temperature conductivity and high-temperature oxidation resistance is obtained, and Cr at the interface of the coating/substrate is obviously reduced₂O₃The growth of the connecting body improves the high-temperature performance and the electric conductivity of the connecting body, and also improves the working efficiency of the fuel cell.

Drawings

FIG. 1 is a schematic view of a composite membrane/microcrystalline interface layer and a metal matrix composite interconnect structure;

FIG. 2 is a summary table of the processes and properties of examples 1-5.

Having the embodiments

The technical solution of the present invention will be described with reference to the following specific examples:

example 1

And (2) polishing the 430SS substrate by 400-2000 # water abrasive paper, then cleaning by using distilled water and acetone, airing or blow-drying, and sealing and storing.

And (2) depositing a smooth 430SS refined crystal grain transition layer on the surface of the substrate by using an electrode bar rod with the diameter of 2mm through a high-temperature micro-arc alloying technology, adjusting the voltage to 180V, preparing the 430SS refined crystal grain layer on the surface of the substrate, and then repairing and flattening the prepared refined crystal grain layer.

Step (3) preparing 400ml of electrolyte solution in a beaker for impact Ni plating, pouring 200ml of distilled water in the beaker, and adding 1M NiCl₂After stirring until no precipitate was formed, 128mL of HCl was added and distilled water was gradually added to 400 mL. Preparing 400ml of electrolyte solution for electrodepositing Cu, pouring 300ml of distilled water into a beaker, and adding 0.32M CuSO₄·5H₂O, stirring until no precipitate is formed, adding 0.13M boric acid and adding sulfuric acidAdjusting the pH = 3-3.5, and gradually adding distilled water to 400 ml. Addition of 0.01M CeO₂Stirring the mixture for 2 hours at a speed of 650rpm by a magnetic stirrer so that CeO is obtained₂Are uniformly distributed in the plating solution. Meanwhile, electrolyte solution for electro-deposition of Mn is prepared, 600ml of distilled water is added into a 1L beaker, and 0.9M (NH) is added₄)₂SO₄Fully stirring until the components are completely dissolved, and adding 1.2M MnSO₄·H₂O, stirring for 2h until the solution is completely dissolved, and gradually adding distilled water to 1L.

Step (4) placing the sample into mixed acid for 1min to remove oxide skin, taking out the sample, cleaning the sample in distilled water, and placing 15% of H₂SO₄And activating for 2min, and meanwhile, putting the solution for depositing the Cu and the Mn into a water bath kettle and heating to 40 ℃. The nickel plate is used as an anode, the sample is used as a cathode, and the current density is set to be 40mA/cm²And depositing for improving the bonding force between the plating layer and the transition layer. The graphite plate is used as an anode, the matrix is used as a cathode, and the current density of the direct current power supply is adjusted to be 50mA/cm²And adjusting the current according to the above to start depositing metal Cu for 2min, and cleaning the cathode and anode plates with deionized water after deposition. The graphite plate is used as an anode, the matrix is used as a cathode, and the current density of the direct current power supply is adjusted to be 100mA/cm²And the current is adjusted accordingly to start the deposition of the metal Mn for 1 min. The thickness ratio of the deposited Cu layer to the Mn layer is 1:1, and the total thickness is 8.4 um. The entire deposition process required stirring by a magnetic stirrer at a speed of 650 pm.

Step (5) oxidizing the prepared sample for 20 hours at 700 ℃ in air atmosphere to obtain the CeO-containing sample₂The thickness of the Cu-Mn spinel composite coating is 16 mu m, and the resistance of the Cu-Mn spinel composite coating is 50.1m omega/cm through the test of a surface specific resistance test system²(direct high temperature contact with platinum sheet test without platinum slurry). Finally, the metal matrix composite connector material is prepared and can be applied to solid oxide fuel cells.

Example 2

And (2) polishing the 430SS substrate by 400-2000 # water abrasive paper, then cleaning by using distilled water and acetone, airing or blow-drying, and sealing and storing.

And (2) depositing a smooth 430SS refined crystal grain transition layer on the surface of the substrate by using an electrode bar rod with the diameter of 2mm through a high-temperature micro-arc alloying technology, adjusting the voltage to 190V, preparing the 430SS refined crystal grain layer on the surface of the substrate, and repairing and flattening the prepared refined crystal grain layer.

Step (3) preparing 400ml of electrolyte solution in a beaker for impact Ni plating, pouring 200ml of distilled water in the beaker, and adding 1M NiCl₂After stirring until no precipitate was formed, 128mL of HCl was added and distilled water was gradually added to 400 mL. Preparing 400ml of electrolyte solution for electrodepositing Cu, pouring 300ml of distilled water into a beaker, and adding 0.32M CuSO₄·5H₂And O, stirring until no precipitate exists, adding 0.13M boric acid, adding sulfuric acid to adjust the pH = 3-3.5, and gradually adding distilled water to 350 ml. Addition of 0.02M CeO₂Stirring the mixture for 2 hours at 660rpm by a magnetic stirrer so that CeO is obtained₂Are uniformly distributed in the plating solution. Meanwhile, electrolyte solution for electro-deposition of Mn is prepared, 600ml of distilled water is added into a 1L beaker, and 0.9M (NH) is added₄）₂SO₄Fully stirring until the components are completely dissolved, and adding 1.2M MnSO₄·H₂O, stirring for 2h until the solution is completely dissolved, and gradually adding distilled water to 1L.

Step (4) placing the sample into mixed acid for 1min to remove oxide skin, taking out the sample, cleaning the sample in distilled water, and placing 15% of H₂SO₄Activating for 1min, and simultaneously heating the Cu and Mn deposits in a water bath to 40 ℃. Before depositing Cu, depositing a layer of impact nickel on the surface of a transition layer, taking a nickel plate as an anode and a sample as a cathode, and setting the current density to be 50mA/cm²And depositing for improving the bonding force between the plating layer and the transition layer. The graphite plate is used as an anode, the sample is used as a cathode, and the current density of the direct current power supply is adjusted to be 60mA/cm²And adjusting the current according to the above to start depositing metal Cu for 2min, and cleaning the cathode and anode plates with deionized water after deposition. And using graphite plate as anode and sample as cathode, regulating current density of DC power supply to 150mA/cm²And the current is adjusted accordingly to start the deposition of the metal Mn for 1 min. After depositionThe thickness ratio of the Cu layer to the Mn layer is 1:1.2, and the total thickness is 10.2 um. The whole deposition process required stirring by a magnetic stirrer at 660 rpm.

Step (5) oxidizing the prepared sample for 100h at 750 ℃ in air atmosphere to obtain the CeO-containing sample₂The Cu-Mn spinel composite coating is tested to have the resistance of 62.3m omega/cm through a surface specific resistance testing system²(direct high temperature contact with platinum sheet test without platinum slurry). Finally, the metal matrix composite connector material is obtained and can be applied to solid oxide fuel cells.

Example 3

And (2) polishing the 430SS substrate by 400-2000 # water abrasive paper, then cleaning by using distilled water and acetone, airing or blow-drying, and sealing and storing.

And (2) depositing a smooth 430SS refined crystal grain transition layer on the surface of the substrate by using an electrode bar with the diameter of 2.5mm through a high-temperature micro-arc alloying technology, adjusting the voltage to 200V, preparing the 430SS refined crystal grain layer on the surface of the substrate, and repairing and flattening the prepared refined crystal grain layer.

Step (3) preparing 400ml of electrolyte solution in a beaker for impact Ni plating, pouring 200ml of distilled water in the beaker, and adding 1M NiCl₂After stirring until no precipitate was formed, 128mL of HCl was added and distilled water was gradually added to 400 mL. Preparing 400ml of electrolyte solution for electrodepositing Cu, pouring 300ml of distilled water into a beaker, and adding 0.32M CuSO₄·5H₂And O, stirring until no precipitate exists, adding 0.13M boric acid, adding sulfuric acid to adjust the pH = 3-3.5, and gradually adding distilled water to 400 ml. Addition of 0.04M CeO₂Stirring the mixture for 2 hours at 670rpm by a magnetic stirrer so that CeO is obtained₂Are uniformly distributed in the plating solution. Meanwhile, electrolyte solution for electro-deposition of Mn is prepared, 600ml of distilled water is added into a 1L beaker, and 0.9M (NH) is added₄)₂SO₄Fully stirring until the components are completely dissolved, and adding 1.2M MnSO₄·H₂O, stirring for 2h until the solution is completely dissolved, and gradually adding distilled water to 1L.

Step (4) placing the sample into mixed acid for 1min to remove oxide skin, taking outThen washing in distilled water, adding 15% H₂SO₄Activating for 1min, and simultaneously heating the Cu and Mn deposits in a water bath to 40 ℃. Before depositing Cu, depositing a layer of impact nickel on the surface of a transition layer, taking a nickel plate as an anode and a sample as a cathode, and setting the current density to be 60mA/cm²And depositing for improving the bonding force between the plating layer and the substrate. The graphite plate is used as an anode, the sample is used as a cathode, and the current density of the direct current power supply is adjusted to be 150mA/cm²And adjusting the current according to the above to start depositing metal Cu for 2min, and cleaning the cathode and anode plates with deionized water after deposition. And using graphite plate as anode and sample as cathode, regulating current density of DC power supply to 200mA/cm²And the current is adjusted accordingly to start the deposition of the metal Mn for 1 min. The thickness ratio of the Cu layer to the Mn layer after deposition is 1:1.4, and the total thickness is 12.3 um. The whole deposition process required stirring by a magnetic stirrer at 670 rpm.

Step (5) oxidizing the prepared sample for 200h at 800 ℃ in the air atmosphere to obtain the CeO-containing sample₂The Cu-Mn spinel composite coating with the thickness of 24.6um passes through a surface specific resistance test system to test the resistance of 80.6m omega/cm²(direct high temperature contact with platinum sheet test without platinum slurry). Finally, the metal matrix composite connector material is obtained and can be applied to solid oxide fuel cells.

Example 4

And (2) polishing the 430SS substrate by 400-2000 # water abrasive paper, then cleaning by using distilled water and acetone, airing or blow-drying, and sealing and storing.

And (2) depositing a smooth 430SS refined crystal grain transition layer on the surface of the substrate by using an electrode bar with the diameter of 3mm through a high-temperature micro-arc alloying technology, adjusting the voltage to 210V, preparing the 430SS refined crystal grain layer on the surface of the substrate, and repairing and flattening the prepared refined crystal grain layer.

Step (3) preparing 400ml of electrolyte solution in a beaker for impact Ni plating, pouring 200ml of distilled water in the beaker, and adding 1M NiCl₂After stirring until no precipitate was formed, 128mL of HCl was added and distilled water was gradually added to 400 mL. Dispose 400ml of electricityThe electrolyte solution for depositing Cu is poured into a beaker with 300ml of distilled water and then 0.32M CuSO is added₄·5H₂And O, stirring until no precipitate exists, adding 0.13M boric acid, adjusting the pH = 3-3.5 by adding ammonia water and sulfuric acid, and gradually adding distilled water to 400 ml. Addition of 0.06M CeO₂Stirring the mixture for 2 hours at 700rpm by a magnetic stirrer so that CeO is obtained₂Are uniformly distributed in the plating solution. Meanwhile, electrolyte solution for electro-deposition of Mn is prepared, 600ml of distilled water is added into a 1L beaker, and 0.9M (NH) is added₄)₂SO₄Fully stirring until the components are completely dissolved, and adding 1.2M MnSO₄·H₂O, stirring for 2h until the solution is completely dissolved, and gradually adding distilled water to 1L.

Depositing a smooth 430SS refined crystal grain transition layer on the surface of the substrate by a high-temperature micro-arc alloying technology, then putting the sample into mixed acid for 1min for descaling, taking out, cleaning in distilled water, and putting 15% of H₂SO₄Activating for 1min, and simultaneously heating the Cu and Mn deposits in a water bath to 40 ℃. Before depositing Cu, depositing a layer of impact nickel on the surface of the transition layer, taking a nickel plate as an anode and a matrix as a cathode, and setting the current density to be 50mA/cm²And depositing for improving the bonding force between the plating layer and the transition layer. Using a graphite plate as an anode and a sample as a cathode, and adjusting the current density of a direct current power supply to be 200mA/cm²And adjusting the current according to the above to start depositing metal Cu for 2min, and cleaning the cathode and anode plates with deionized water after deposition. And using graphite plate as anode and sample as cathode, regulating current density of DC power supply to 250mA/cm²And the current is adjusted accordingly to start the deposition of the metal Mn for 1 min. The thickness ratio of the Cu layer to the Mn layer after deposition is 1:1.6, and the total thickness is 14.5 um. The whole deposition process required stirring by a magnetic stirrer at a speed of 700 rpm.

Step (5) oxidizing the prepared sample for 300h at 850 ℃ in air atmosphere to obtain the CeO-containing sample₂The Cu-Mn spinel composite coating with the thickness of 29.0um passes through a surface specific resistance test system to test the resistance of 85.3m omega/cm²(with platinum sheet)Direct high temperature contact test without platinum paste). Finally, the metal matrix composite connector material is obtained and can be applied to solid oxide fuel cells.

Example 5

And (2) polishing the 430SS substrate by 400-2000 # water abrasive paper, then cleaning by using distilled water and acetone, airing or blow-drying, and sealing and storing.

And (2) depositing a smooth 430SS refined crystal grain transition layer on the surface of the substrate by using an electrode bar with the diameter of 3mm through a high-temperature micro-arc alloying technology, adjusting the voltage to 220V, preparing the 430SS refined crystal grain layer on the surface of the substrate, and repairing and flattening the prepared refined crystal grain layer.

Step (3) preparing 400ml of electrolyte solution in a beaker for impact Ni plating, pouring 200ml of distilled water in the beaker, and adding 1M NiCl₂After stirring until no precipitate was formed, 128mL of HCl was added and distilled water was gradually added to 400 mL. Preparing 400ml of electrolyte solution for electrodepositing Cu, pouring 300ml of distilled water into a beaker, and adding 0.32M CuSO₄·5H₂And O, stirring until no precipitate exists, adding 0.13M boric acid, adding sulfuric acid to adjust the pH = 3-3.5, and gradually adding distilled water to 400 ml. Addition of 0.08M CeO₂Stirring the mixture for 2 hours at 750rpm by a magnetic stirrer so that CeO is obtained₂Are uniformly distributed in the plating solution. Meanwhile, electrolyte solution for electro-deposition of Mn is prepared, 600ml of distilled water is added into a 1L beaker, and 0.9M (NH) is added₄)₂SO₄Fully stirring until the components are completely dissolved, and adding 1.2M MnSO₄·H₂O, stirring for 2h until the solution is completely dissolved, and gradually adding distilled water to 1L.

Step (4), putting the sample into mixed acid for 1min to remove oxide skin, taking out the sample, cleaning the sample in distilled water, and putting 15% of H into the sample₂SO₄Activating for 1min, and simultaneously heating the Cu and Mn deposits in a water bath to 40 ℃. Before depositing Cu, depositing a layer of impact nickel on the surface of a transition layer, taking a nickel plate as an anode and a sample as a cathode, and setting the current density to be 50mA/cm²And depositing for improving the bonding force between the plating layer and the transition layer. Graphite plate as anodeThe sample is a cathode, and the current density of the direct current power supply is adjusted to be 50mA/cm²And adjusting the current according to the above to start depositing metal Cu for 2min, and cleaning the cathode and anode plates with deionized water after deposition. And using graphite plate as anode and sample as cathode, regulating current density of DC power supply to 300mA/cm²And the current is adjusted accordingly to start the deposition of the metal Mn for 1 min. The thickness ratio of the deposited Cu layer to the Mn layer is 1:2, and the total thickness is 16.5 um. The whole deposition process required stirring by a magnetic stirrer at a speed of 750 rpm.

Step (5) oxidizing the prepared sample for 500h at 900 ℃ in air atmosphere to obtain the CeO-containing sample₂The thickness of the Cu-Mn spinel composite coating is 33.0 um. The resistance of the material is tested to 90.9m omega/cm by a surface specific resistance testing system²(direct high temperature contact with platinum sheet test without platinum slurry). Finally, the metal matrix composite connector material is obtained and can be applied to solid oxide fuel cells.