CN115051009A - Y-doped Co-Mn spinel coating, and preparation method and application thereof - Google Patents
Y-doped Co-Mn spinel coating, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a Y-doped Co-Mn spinel coating, and a preparation method and application thereof, and belongs to the technical field of surface coating material preparation. The preparation method of the Y-doped Co-Mn spinel coating comprises the following steps: step 1: pre-treating; step 2: preparation of Co-Y 2 O 3 ‑Mn 3 O 4 A composite precursor coating; and step 3: preparing the Y-doped Co-Mn spinel coating. The invention also discloses the Y-doped Co-Mn spinel coating prepared by the preparation method and application thereof. By adopting the method, the prepared ferrite stainless steel surface protective coating is smoother and more compact, is more firmly combined with a matrix, has better plating winding performance, and has excellent Cr resistance and good conductivity.
Description
Technical Field
The invention relates to a Y-doped Co-Mn spinel coating, a preparation method and application thereof, belonging to the technical field of surface coating material preparation.
Background
The solid oxide fuel cell has the advantages of high cleanliness, modularization, high energy conversion efficiency, high specific power and power density and the like, and has wide application prospects. The single Solid Oxide Fuel Cell (SOFC) mainly comprises a cathode, an anode and an electrolyte, and the connecting body mainly plays roles of supporting and connecting single cells, conducting current, isolating Fuel gas and the like in a Cell stack. With the development of SOFC working temperature towards middle temperature (600-800 ℃), Ferritic Stainless Steel (FSS for short) has become one of the most ideal SOFC connector materials due to the advantages of good electrical and thermal conductivity, low cost, good processability and the like. However, in the SOFC working environment, the FSS surface is very easy to oxidize, and the generated oxide film can increase the contact resistance of the cell stack; meanwhile, Cr compounds generated by the reaction of Cr in the matrix and oxygen can migrate and deposit to the cathode, so that the electrical property of the cell is seriously attenuated, even the cell stack is failed, and the commercial development and application of the SOFC are seriously restricted. In order to solve the problem, the most effective method is to coat a spinel protective coating on the FSS surface so as to solve the problems of insufficient oxidation resistance, Cr volatilization and the like in FSS work and improve the service performance of the SOFC battery.
The common preparation method of the spinel coating on the FSS surface has the defects of expensive equipment, complex process, poor plating winding performance, difficult and uneven coating thickness, easy generation of air holes and cracks on the surface and the like, is difficult to adapt to the shape of a complex connector, has high cost, and needs to further improve the bonding strength of the prepared coating and a matrix.
In view of the above, there is a need to provide a new method for preparing a protective coating on the surface of ferritic stainless steel, so as to overcome the deficiencies of the prior art.
Disclosure of Invention
One of the purposes of the invention is to provide a preparation method of a Y-doped Co-Mn spinel coating.
The technical scheme for solving the technical problems is as follows: a preparation method of a Y-doped Co-Mn spinel coating comprises the following steps:
step 1: pretreatment of
Providing a ferritic stainless steel substrate, polishing, soaking in NaOH solution, taking out, cleaning, and soakingAt H 2 SO 4 Taking out the solution, cleaning, and then carrying out electrolytic corrosion treatment to obtain a pretreated matrix;
step 2: preparation of Co-Y 2 O 3 -Mn 3 O 4 Composite precursor coating
Taking the pretreated substrate obtained in the step 1 as a cathode, taking a double cobalt plate as a double anode, putting the substrate into a deposition solution, introducing direct current, and depositing to obtain Co-Y 2 O 3 -Mn 3 O 4 A composite precursor coating; wherein the deposition solution contains 80g/L-160g/L of Mn 3 O 4 5g/L-15g/L of Y 2 O 3 300g/L CoSO 4 ·7H 2 O, 50g/L CoCl 2 ·6H 2 O, 15g/L of H 3 BO 3 10g/L of sodium gluconate and 0.03g/L of lauryl sodium sulfate, wherein the pH value is 3-5;
and step 3: preparation of Y-doped Co-Mn spinel coatings
The Co-Y obtained in the step 2 2 O 3 -Mn 3 O 4 The composite precursor coating is converted into a Y-doped Co-Mn spinel coating through heat treatment.
The principle of the invention is as follows:
the method comprises the steps of pretreating a ferritic stainless steel substrate to increase the binding force between a subsequent coating and the ferritic stainless steel substrate; then preparing Co-Y on the surface of the pretreated substrate by adopting a composite electrodeposition method 2 O 3 -Mn 3 O 4 The composite precursor coating enables Mn element and rare earth element Y to be embedded into the deposited Co matrix under the multi-field coupling effect; and finally, uniformly converting the composite precursor layer by adopting a heat treatment method to obtain the Y-doped Co-Mn spinel coating.
The preparation method of the Y-doped Co-Mn spinel coating combines the composite electrodeposition and the heat treatment conversion, has the advantages of simple process, low cost, firm and compact and uniform coating, good plating property and the like, solves the defects of long process, difficult adaptation to complex connector shapes, poor coating performance, high manufacturing cost and the like of the existing preparation method, and has important significance for developing and preparing spinel protective coatings on the surfaces of ferritic stainless steel.
The invention has the beneficial effects that:
1. by adopting the method, the prepared ferrite stainless steel surface protective coating is smoother and more compact, is more firmly combined with a matrix, has better plating winding performance, and has excellent Cr resistance and good conductivity.
2. The preparation method only needs 1-5V of voltage, has the advantages of simple equipment, short process flow, simple and convenient operation, low cost and wide market prospect, and is suitable for large-scale popularization and application.
On the basis of the technical scheme, the invention can be improved as follows.
Further, in step 1, the ferritic stainless steel is any one of SUS430, E-brite and Crofer 22.
The adoption of the further beneficial effects is as follows: the ferritic stainless steel has good electric conduction and heat conduction performance, heat fatigue resistance, excellent oxidation resistance and cold processing performance, and is suitable for being used as a matrix for the subsequent preparation of a Y-doped Co-Mn spinel coating.
Further, in step 1, the grinding refers to grinding the ferritic stainless steel substrate by using 200-mesh, 400-mesh and 800-mesh sandpaper in sequence.
The adoption of the further beneficial effects is as follows: impurities and stains on the surface of the substrate can be removed.
Further, in step 1, the soaking time is 10min, and the NaOH solution and the H solution are 2 SO 4 The concentration of the solution is 1mol/L, and deionized water is adopted for cleaning.
The adoption of the further beneficial effects is as follows: the matrix is prevented from being passivated and activated.
Further, in step 1, the electrolytic etching treatment refers to placing the cleaned substrate in an electrolytic etching solution, and etching for 5min at room temperature, wherein the electrolytic etching solution contains 50g/L of CoCl 2 ·6H 2 O and 1mol/L HCl with a pH value of 5.
The adoption of the further beneficial effects is as follows: by adopting the operation, the electrolytic corrosion of the matrix can be realized, and the binding force between the subsequent coating and the matrix is enhanced.
Further, in the step 2, the distance between the cathode and the double anode in the deposition solution is 35mm, and the cathode and the double anode are arranged in an equilateral triangle.
The adoption of the further beneficial effects is as follows: the efficiency of composite electrodeposition can be ensured, and the influence of stirring on the uniformity of the coating is reduced.
Further, in step 2, the current density of the direct current is 10mA/cm 2 -30mA/cm 2 The applied voltage is 1V-5V.
The adoption of the further beneficial effects is as follows: by adopting the parameters, the required equipment has low cost and better deposition effect.
Further, in the step 2, the electromagnetic stirring speed adopted by the deposition is 700r/min-900r/min, and the time is 10min-20 min.
Adopt above-mentioned further beneficial effect to be: by adopting the parameters, the coating is more uniform, the thickness is moderate, and the Mn content is high.
Further, in the step 3, the heat treatment conversion temperature is 800 ℃, the heating rate is 1 ℃/min-5 ℃/min, and the heat treatment conversion time is 60 min.
The adoption of the further beneficial effects is as follows: by adopting the parameters, the composite precursor layer can be completely converted into a single-phase spinel coating, and the coating is not easy to crack and peel.
The second object of the present invention is to provide a Y-doped Co-Mn spinel protective coating.
The technical scheme for solving the technical problems is as follows: a Y-doped Co-Mn spinel coating prepared by the above preparation method.
The beneficial effects of the Y-doped Co-Mn spinel coating of the invention are as follows:
the Y-doped Co-Mn spinel coating is prepared by the preparation method, and the spinel coating is firmly combined with a matrix, and has good electric conduction and heat conduction performance and strong Cr resistance.
The invention also aims to provide application of the Y-doped Co-Mn spinel coating.
The technical scheme for solving the technical problems is as follows: the Y-doped Co-Mn spinel coating prepared by the preparation method is applied to a protective coating of an SOFC connector material.
The application of the invention has the beneficial effects that:
the Y-doped Co-Mn spinel coating can be used as a protective coating of an SOFC connector material, greatly improves the Cr resistance and the conductivity of the FSS connector material, is easy to realize batch production, and has wide application prospect.
Drawings
FIG. 1 shows Co-Y in example 1 of the present invention 2 O 3 -Mn 3 O 4 SEM image of composite primer surface.
FIG. 2 is a surface SEM image of a Y-doped Co-Mn spinel coating in example 1 of the present invention.
FIG. 3 is the EDS composition distribution on the surface of the Y-doped Co-Mn spinel coating in example 1 of the present invention.
FIG. 4 is a surface SEM image of a Y-doped Co-Mn spinel coating oxidized at 800 ℃ for 7 days in example 1 of the invention.
FIG. 5 is the EDS composition distribution on the surface of the Y-doped Co-Mn spinel coating oxidized at 800 ℃ for 7 days in example 1 of the invention.
FIG. 6 is an SEM image of the surface of an SUS430 substrate oxidized at 800 ℃ for 7 days in example 1 of the present invention.
FIG. 7 is an EDS composition distribution on a surface of SUS430 substrate oxidized at 800 ℃ for 7 days in example 1 of the present invention.
FIG. 8 is a cross-sectional SEM image of a Y-doped Co-Mn spinel coating oxidized at 800 ℃ for 7 days in example 1 of the present invention.
Detailed Description
The principles and features of this invention are described below in conjunction with the following detailed drawings, which are given by way of illustration only and are not intended to limit the scope of the invention.
Example 1:
the preparation method of the Y-doped Co-Mn spinel coating of the embodiment comprises the following steps:
step 1: pretreatment of
Providing an SUS430 ferritic stainless steel matrix with the specification of 20mm multiplied by 15mm multiplied by 2mm, polishing the ferritic stainless steel matrix by using 200-mesh, 400-mesh and 800-mesh sand papers in sequence, soaking the ferritic stainless steel matrix in NaOH solution with the concentration of 1mol/L for 10min, taking out the ferritic stainless steel matrix, ultrasonically cleaning the ferritic stainless steel matrix by using deionized water, and soaking the ferritic stainless steel matrix in H solution with the concentration of 1mol/L 2 SO 4 Taking out the solution for 10min, ultrasonically cleaning the solution by using deionized water, then placing the solution into an electrolytic corrosion solution, and carrying out electrolytic corrosion treatment for 5min at room temperature, wherein the electrolytic corrosion solution contains 50g/L of CoCl 2 ·6H 2 O and 1mol/L HCl with the pH value of 5 to obtain the pretreated matrix.
Step 2: preparation of Co-Y 2 O 3 -Mn 3 O 4 Composite precursor coating
And (2) placing the pretreated substrate obtained in the step (1) as a cathode and a double cobalt plate as a double anode in the deposition solution, wherein the distance between the cathode and the double anode in the deposition solution is 35mm, and the cathode and the double anode are arranged in an equilateral triangle. The deposition solution contains 120g/L of Mn 3 O 4 10g/L of Y 2 O 3 300g/L CoSO 4 ·7H 2 O, 50g/L CoCl 2 ·6H 2 O, 15g/L H 3 BO 3 10g/L of sodium gluconate and 0.03g/L of sodium dodecyl sulfate, and the pH value is 5.
Direct current is introduced, and the current density is 20mA/cm 2 Voltage of<2V; the electromagnetic stirring speed is 900r/min, the deposition time is 15min, and Co-Y is obtained 2 O 3 -Mn 3 O 4 And (3) compounding a precursor coating.
And step 3: preparation of Y-doped Co-Mn spinel coatings
The Co-Y obtained in the step 2 2 O 3 -Mn 3 O 4 And carrying out heat treatment on the composite precursor coating at the temperature of 800 ℃, at the heating rate of 1 ℃/min and for 60min, and converting to obtain the Y-doped Co-Mn spinel coating.
The embodiment also provides the Y-doped Co-Mn spinel coating prepared by the preparation method.
The embodiment also provides application of the Y-doped Co-Mn spinel coating prepared by the preparation method in serving as a protective coating of an SOFC connector material.
FIG. 1 shows Co-Y in example 1 of the present invention 2 O 3 -Mn 3 O 4 SEM image of composite primer surface. As can be seen from the figure, Y is the same for the given process parameters of example 1 2 O 3 And Mn 3 O 4 The particles are uniformly embedded and spread in the Co matrix to form Co-Y 2 O 3 -Mn 3 O 4 And (3) compounding a precursor layer.
Fig. 2 is a SEM image of the surface of the Y-doped Co — Mn spinel coating in example 1 of the present invention, and fig. 3 is an EDS composition analysis of the surface of the Y-doped Co — Mn spinel coating in example 1 of the present invention. As can be seen from the figures 2 and 3, the Y-doped Co-Mn spinel coating prepared by the method has uniform and compact surface and no obvious defect, and can effectively inhibit the outward volatilization of Cr compounds. And experiments show that all surface coatings of the matrix are uniform and compact, which shows that the method has better plating winding performance.
FIG. 4 is an SEM image of the 800 ℃ oxidized 7-day surface of the Y-doped Co-Mn spinel coating in example 1 of the present invention, and FIG. 5 is the EDS composition distribution of the 800 ℃ oxidized 7-day surface of the Y-doped Co-Mn spinel coating in example 1 of the present invention. As can be seen from FIGS. 4 and 5, after the coating is oxidized at 800 ℃ for 7 days, the surface crystal grains of the Y-doped Co-Mn spinel coating are relatively uniform, flat and compact, the structure is favorable for keeping the coating in good contact with an electrode and maintaining the stability of the performance of the SOFC, and the surface of the coating is not detected to have the Cr element, which shows that the coating still has good performance of preventing the volatilization of Cr after being oxidized at high temperature for a long time.
FIG. 6 is an SEM image of a surface of an SUS430 substrate oxidized at 800 ℃ for 7 days in example 1 of the present invention, and FIG. 7 is an EDS component distribution of a surface of an SUS430 substrate oxidized at 800 ℃ for 7 days in example 1 of the present invention. As can be seen from fig. 6 and 7, after being oxidized at 800 ℃ for 7 days, the surface grains of the SUS430 ferritic stainless steel substrate are agglomerated, have uneven sizes and distributions, extremely uneven surface, loose inter-grain bonding, high oxidation rate and high surface Cr element content, which indicates that the SOFC connector and the cell stack have reduced conductivity due to severe volatilization of Cr element.
FIG. 8 is a cross-sectional SEM image of a Y-doped Co-Mn spinel coating prepared in example 1 of the invention oxidized at 800 ℃ for 7 days. As can be seen from the figure, the spinel coating is well combined with the matrix, and phenomena such as cracking, peeling and the like are avoided. The thickness of the Cr oxide layer at the junction of the matrix and the spinel coating is about 2 mu m, and the thickness of the coating is about 20 mu m, which shows that the oxidation rate of the matrix coated with the Y-doped Co-Mn spinel coating is low, and the prepared coating has excellent oxidation resistance.
The sample coated with the Y-doped Co-Mn spinel coating layer prepared in example 1 was oxidized at 800 ℃ for 7 days, and tested by the four-probe method to obtain a sample having an area specific resistance of 13.07 m.OMEGA.cm 2 Much smaller than the substrate surface specific resistance of 32.15m omega cm 2 And experimental results show that the thickness and the area specific resistance of the oxide layer tend to be stable at the moment, and the prepared protective coating has good Cr resistance, oxidation resistance and conductivity and can meet the use requirements of the SOFC connector.
Example 2:
the preparation method of the Y-doped Co-Mn spinel coating of the embodiment comprises the following steps:
step 1: pretreatment of
Providing an E-brite ferritic stainless steel matrix with the specification of 20mm multiplied by 15mm multiplied by 2mm, polishing the ferritic stainless steel matrix by using 200-mesh, 400-mesh and 800-mesh abrasive paper in sequence, soaking the ferritic stainless steel matrix in NaOH solution with the concentration of 1mol/L for 10min, taking out the ferritic stainless steel matrix, ultrasonically cleaning the ferritic stainless steel matrix by using deionized water, and soaking the ferritic stainless steel matrix in H solution with the concentration of 1mol/L 2 SO 4 Taking out the solution for 10min, ultrasonically cleaning the solution by using deionized water, then placing the solution into an electrolytic corrosion solution, and carrying out electrolytic corrosion treatment for 5min at room temperature, wherein the electrolytic corrosion solution contains 50g/L of CoCl 2 ·6H 2 O and 1mol/L HCl with the pH value of 5 to obtain the pretreated matrix.
Step 2: preparation of Co-Y 2 O 3 -Mn 3 O 4 Composite precursor coating
Taking the pretreated substrate obtained in the step 1 as a cathode, taking a double cobalt plate as a double anode, and placing the substrate and the double anode in a deposition solution, wherein the cathode and the double anode are depositedThe distance between the accumulated liquid is 35mm and is arranged in an equilateral triangle. The deposition solution contains 120g/L of Mn 3 O 4 15g/L of Y 2 O 3 300g/L CoSO 4 ·7H 2 O, 50g/L CoCl 2 ·6H 2 O, 15g/L H 3 BO 3 10g/L of sodium gluconate and 0.03g/L of sodium dodecyl sulfate, and the pH value is 4.
The direct current is introduced, and the current density of the direct current is 30mA/cm 2 Voltage of<5V, and (5); the electromagnetic stirring speed is 700r/min, the deposition time is 5min, and Co-Y is obtained 2 O 3 -Mn 3 O 4 And (3) compounding a precursor coating.
And step 3: preparation of Y-doped Co-Mn spinel coatings
The Co-Y obtained in the step 2 2 O 3 -Mn 3 O 4 And carrying out heat treatment on the composite precursor coating at the temperature of 800 ℃, at the heating rate of 5 ℃/min and for 60min, and converting to obtain the Y-doped Co-Mn spinel coating.
Compared with the embodiment 1, the Y-doped Co-Mn spinel coating with good combination with the matrix and good performance can be obtained by adopting the embodiment. Only when the deposition is carried out in the step 2 and the stirring speed is lower, the uniformity and the flatness of the surface of the coating are slightly reduced; the deposition time is short and the coating is slightly thin.
The embodiment also provides the Y-doped Co-Mn spinel coating prepared by the preparation method.
The embodiment also provides application of the Y-doped Co-Mn spinel coating prepared by the preparation method in serving as a protective coating of an SOFC connector material.
Example 3:
the preparation method of the Y-doped Co-Mn spinel coating of the present embodiment includes the following steps:
step 1: pretreatment of
Providing a Crofer22 ferritic stainless steel matrix with the specification of 20mm multiplied by 15mm multiplied by 2mm, polishing the ferritic stainless steel matrix by using 200-mesh, 400-mesh and 800-mesh sandpaper in sequence, soaking the ferritic stainless steel matrix in NaOH solution with the concentration of 1mol/L for 10min, taking out the ferritic stainless steel matrix, and then adopting a stripping methodUltrasonically cleaning with sub-water, and soaking in H with concentration of 1mol/L 2 SO 4 Taking out the solution for 10min, ultrasonically cleaning the solution by using deionized water, then placing the solution into an electrolytic corrosion solution, and carrying out electrolytic corrosion treatment for 5min at room temperature, wherein the electrolytic corrosion solution contains 50g/L of CoCl 2 ·6H 2 O and 1mol/L HCl with the pH value of 5 to obtain the pretreated matrix.
Step 2: preparation of Co-Y 2 O 3 -Mn 3 O 4 Composite precursor coating
And (2) placing the pretreated substrate obtained in the step (1) as a cathode and a double cobalt plate as a double anode in the deposition solution, wherein the distance between the cathode and the double anode in the deposition solution is 35mm, and the cathode and the double anode are arranged in an equilateral triangle. The deposition solution contains 120g/L of Mn 3 O 4 15g/L of Y 2 O 3 300g/L CoSO 4 ·7H 2 O, 50g/L CoCl 2 ·6H 2 O, 15g/L H 3 BO 3 10g/L of sodium gluconate and 0.03g/L of sodium dodecyl sulfate, and the pH value is 4.
The direct current is introduced, and the current density of the direct current is 10mA/cm 2 Voltage of<2V, the adopted electromagnetic stirring speed is 800r/min, the deposition time is 15min, and Co-Y is obtained 2 O 3 -Mn 3 O 4 And (3) compounding a precursor coating.
And step 3: preparation of Y-doped Co-Mn spinel coatings
The Co-Y obtained in the step 2 2 O 3 -Mn 3 O 4 And carrying out heat treatment on the composite precursor coating at the temperature of 800 ℃, at the heating rate of 5 ℃/min and for 60min, and converting to obtain the Y-doped Co-Mn spinel coating.
With this example, a Y-doped Co — Mn spinel coating with good bonding to the matrix and good performance was also obtained compared to example 1. Only the heating rate of the heat treatment in the step 3 is higher, and the cracking tendency of the coating surface is increased, so the heating rate is not more than 5 ℃/min.
The embodiment also provides the Y-doped Co-Mn spinel coating prepared by the preparation method.
The embodiment also provides application of the Y-doped Co-Mn spinel coating prepared by the preparation method in serving as a protective coating of an SOFC connector material.
Comparative example 1
The materials and process parameters of the comparative example are the same as those of example 1, except that the substrate is not pretreated, the obtained composite precursor coating is poorly combined with the substrate, the content of Mn in the coating is low, and the coating is uneven.
Comparative example 2
The materials and test procedure of this comparative example were the same as those of example 1 except that the current densities in step 2 were 5mA/cm, respectively 2 And 40mA/cm 2 When the current density is 5mA/cm 2 In the process, the obtained composite precursor coating is not uniform and cannot well cover the surface of the substrate; when the current density is 40mA/cm 2 When the current is overlarge, the composite precursor coating is not uniformly distributed, and the deposition efficiency is low.
Comparative example 3
The materials and test procedures of this comparative example are the same as those of example 1, except that the pH values of the chinese deposit solution in step 2 are 2 and 6, and when the pH is 2, the composite precursor coating is not uniform and cannot cover the substrate surface well; when the pH is 6, the coating has more bubbles and the deposition efficiency is low.
Comparative example 4
The materials and test steps of the comparative example are the same as those of example 1, except that the stirring speed in step 2 is 500r/min and 1000r/min, when the stirring speed is 500r/min, the magnetons are difficult to rotate, and the composite precursor coating is not uniform; when the speed is 1000r/min, the coating is not uniform, the deposition efficiency is low, and the Mn content is low.
Comparative example 5
The materials and test procedures of this comparative example were the same as those of example 1 except that the deposition time in step 2 was 30min, and the Y-doped Co — Mn spinel coating was too thick, which easily resulted in oxidation exfoliation and reduced conductivity.
Comparative example 6
The materials and test procedures of this comparative example were the same as example 1 except that the heat treatment conversion temperature was 600 ℃ and 700 ℃ in no 3, at which time the composite precursor coating could not be completely converted to a single phase spinel coating, the Cr-blocking properties of the coating were poor and non-uniform.
Comparative example 7
The materials and test procedures of this comparative example were the same as those of example 1, except that the heat treatment conversion time in step 3 was 30min, at which time the composite precursor coating did not fully convert to a single-phase Y-doped Co-Mn spinel coating, affecting the Cr-rejection and conductivity properties of the coating.
Comparative example 8
The materials and test steps of the comparative example are the same as those of example 1, except that the temperature rise rate of heat treatment conversion in step 3 is 10 ℃/min, and then the composite precursor coating is easy to crack and fall off when being converted into a spinel coating.
Comparative example 9
The process parameters and test procedure of this comparative example were the same as in example 1, except that the deposition bath Mn in step 2 was used 3 O 4 The content was 60g/L and 200 g/L. When Mn is present 3 O 4 When the content is 60g/L, the Mn content in the composite precursor coating and the spinel coating is less; mn 3 O 4 When the content is 200g/L, the Mn content and the conductivity do not change much.
Comparative example 10
The process parameters and test procedure of this comparative example were the same as those of example 1 except that the deposition solution Y was used in step 2 2 O 3 The content was 2g/L and 20 g/L. When Y is 2 O 3 When the content is 2g/L, the combination of the coating and the matrix is not firm; when Y is 2 O 3 When the content is 20g/L, the Mn content in the coating layer is small and the conductivity is lowered.
The above-described embodiments are merely preferred embodiments of the present invention, which should not be construed as limiting the invention, and any modifications, equivalents, improvements, etc. made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A preparation method of a Y-doped Co-Mn spinel coating is characterized by comprising the following steps:
step 1: pretreatment of
Providing a ferritic stainless steel substrate, polishing, soaking in NaOH solution, taking out, cleaning, and soaking in H 2 SO 4 Taking out the solution, cleaning, and then carrying out electrolytic corrosion treatment to obtain a pretreated matrix;
step 2: preparation of Co-Y 2 O 3 -Mn 3 O 4 Composite precursor coating
Taking the pretreated substrate obtained in the step 1 as a cathode, taking a double cobalt plate as a double anode, putting the substrate into a deposition solution, introducing direct current, and depositing to obtain Co-Y 2 O 3 -Mn 3 O 4 A composite precursor coating; wherein the deposition solution contains 80g/L-160g/L of Mn 3 O 4 5g/L-15g/L of Y 2 O 3 300g/L CoSO 4 ·7H 2 O, 50g/L CoCl 2 ·6H 2 O, 15g/L of H 3 BO 3 10g/L of sodium gluconate and 0.03g/L of sodium dodecyl sulfate, and the pH value is 3-5;
and step 3: preparation of Y-doped Co-Mn spinel coatings
The Co-Y obtained in the step 2 2 O 3 -Mn 3 O 4 The composite precursor coating is converted into a Y-doped Co-Mn spinel coating through heat treatment.
2. The method of preparing a Y-doped Co-Mn spinel coating according to claim 1, wherein in step 1, the ferritic stainless steel is any one of SUS430, E-brite, and Crofer 22; the grinding refers to grinding the ferritic stainless steel substrate by using 200-mesh, 400-mesh and 800-mesh sandpaper in sequence.
3. The method of claim 1, wherein the soaking time is 10min, the NaOH solution and the H solution in step 1 are all 10min 2 SO 4 The concentration of the solution is 1mol/L, and the deionized water is adopted for cleaning.
4. The method for preparing Y-doped Co-Mn spinel coating according to claim 1, wherein in the step 1, the electrolytic etching treatment is to place the cleaned substrate in an electrolytic etching solution and etch the substrate for 5min at room temperature, wherein the electrolytic etching solution contains 50g/L of CoCl 2 ·6H 2 O and 1mol/L HCl, and the pH value is 5.
5. The method of claim 1, wherein in step 2, the cathode and the bi-anode are both spaced 35mm apart in the deposition solution and arranged in an equilateral triangle.
6. The method of preparing a Y-doped Co-Mn spinel coating according to claim 1, wherein in step 2, the current density of the direct current is 10mA/cm 2 -30mA/cm 2 The applied voltage is 1V-5V.
7. The method for preparing a Y-doped Co-Mn spinel coating according to claim 1, wherein in step 2, the deposition is performed with an electromagnetic stirring rate of 700r/min to 900r/min for a time of 10min to 20 min.
8. The method for preparing a Y-doped Co-Mn spinel coating according to claim 1, wherein in step 3, the heat treatment conversion temperature is 800 ℃, the heating rate is 1 ℃/min to 5 ℃/min, and the heat treatment conversion time is 60 min.
9. A Y-doped Co-Mn spinel coating produced by the method of any one of claims 1 to 8.
10. Use of a Y-doped Co-Mn spinel coating prepared by a method according to any one of claims 1 to 8 as a protective coating for SOFC interconnect materials.
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