CN106011958B - A kind of cupromanganese plating solution and its application for being used to prepare copper galaxite coating - Google Patents

Abstract

The invention provides a copper-manganese alloy plating solution for preparing copper-manganese spinel coatings, which comprises the following components: copper ion source 0.025mol/L～0.1mol/L; manganese ion source 0.25mol/L L～1.0mol/L; chelating agent 0.03mol/L～0.1mol/L; buffering agent 20g/L～200g/L; stabilizer 10g/L～50g/L; the balance is solvent. The invention also provides a method for preparing the copper-manganese spinel coating by using the plating solution, which comprises the following steps: 1. degreasing and activating; 2. electroplating; 3. post-treatment. The invention has the advantages of simple process, controllable conditions, uniform and dense coating, and good adhesion to metal substrates, and is suitable for depositing on the surface of solid oxide metal connectors, which can be converted into copper-manganese spinel coatings after oxidation treatment, improving the Solid Oxide Fuel Cell Service Life.

Description

A kind of copper-manganese alloy plating solution for preparing copper-manganese spinel coating and its application

technical field

The invention belongs to the technical field of electrochemistry, and in particular relates to a copper-manganese alloy plating solution for preparing copper-manganese spinel coatings and an application thereof.

Background technique

The solid oxide fuel cell is an all-solid-state chemical power generation device, which directly converts the chemical energy of the reactants into electrical energy at medium and high temperatures. It is a green energy source with little environmental pollution. However, its high operating cost hinders its popularization and use. The connector is a key component of solid oxide fuel cells and accounts for 30% to 70% of the total cost. Therefore, as long as the cost of the connector is greatly reduced, the solid oxide fuel cell can be greatly reduced. cost of fuel cells. Recently, as the operating temperature of solid oxide fuel cells has decreased from 1000°C to 600°C to 800°C, it has become possible to replace traditional ceramic materials with cheap ferritic stainless steel materials for connecting bodies. However, the oxidation products generated by the oxidation of ferritic stainless steel at higher temperatures can increase the contact resistance, and the volatilization of Cr in the stainless steel will cause "cathode poisoning", resulting in attenuation of battery pack performance. At present, the main method to solve this problem is to apply a conductive protective coating on the surface of the stainless steel connector. Among them, the copper-manganese spinel coating with good thermal stability, high electrical conductivity, and moderate thermal expansion coefficient has become one of the most effective protective coatings on the surface of stainless steel joints, and has attracted people's attention.

At present, the main preparation methods of copper-manganese spinel coatings are: electrodeposition, slurry coating, screen printing, plasma spraying and physical vapor deposition. Among them, the electrodeposition method is a method in which a copper-manganese alloy coating is deposited on the surface of stainless steel by electroplating, and then the alloy coating is oxidized at a high temperature and transformed into copper-manganese spinel. The method has the advantages of low cost, adjustable coating thickness, adapting to complex substrate shapes and the like. However, in the copper-manganese alloy electroplating system, the standard potential of Cu ²⁺ /Cu is 0.337V _H , and the standard potential of Mn ²⁺ /Mn is -1.18V _H . Among the metals that can be electroplated, the standard potential is the most negative, so it is very difficult to electroplate copper-manganese alloys. G. Zangari et al. found that Cu-Mn alloy can be electroplated on the surface of stainless steel when the pH of the simple sulfate system is 2.6-2.8 and 6.4-6.8. When the current density is low (<100mA·cm ^-2 ), the coating is spongy; when the current density is 150mA·cm ^-2 ~400mA·cm ^-2 , the coating is crystalline; when the current density is high, >400mA·cm ^- When ² , the coating tends to be amorphous. Among them, the Cu content of the better-quality coating is 2 at.% to 14 at.%. The thermal expansion coefficient and electrical conductivity of Mn _1.5 Cu _1.5 O ₄ in copper-manganese spinel meet the requirements of the connector coating, so the molar content of copper in the copper-manganese spinel coating cannot be lower than 30%, otherwise it is difficult to obtain performance requirements Copper-manganese spinel coating, so it is necessary to add a suitable complexing agent to close the copper-manganese alloy deposition potential, so that the manganese content in the copper-manganese alloy coating is moderate, and the coating quality is good, so it is necessary to invent a new copper-manganese alloy electroplating fluid to meet this need.

Contents of the invention

The technical problem to be solved by the present invention is to provide a copper-manganese alloy plating solution that has stable chemical properties, does not volatilize harmful gases, and uses chemicals that are harmless to the environment. The preparation process of the plating solution is simple and the cost is low; the molar content of copper in the copper-manganese spinel coating prepared by using the plating solution is not less than 30%.

In order to solve the above-mentioned technical problems, the technical scheme adopted in the present invention is: a kind of copper-manganese alloy plating solution for preparing copper-manganese spinel coating, it is characterized in that, comprises each component of following concentration:

Copper ion source 0.025mol/L～0.1mol/L;

Manganese ion source 0.25mol/L～1.0mol/L;

Chelating agent 0.03mol/L～0.1mol/L;

Buffer 20g/L～200g/L;

Stabilizer 10g/L～50g/L;

The balance is solvent.

Above-mentioned a kind of copper-manganese alloy plating solution for preparing copper-manganese spinel coating is characterized in that, comprises each component of following concentration:

Copper ion source 0.05mol/L;

Manganese ion source 0.5mol/L;

Chelating agent 0.05mol/L;

Buffer 30g/L;

Stabilizer 20g/L;

The balance is solvent.

The above-mentioned copper-manganese alloy plating solution for preparing copper-manganese spinel coating is characterized in that the copper ion source is copper chloride.

The above-mentioned copper-manganese alloy plating solution for preparing copper-manganese spinel coatings is characterized in that the source of manganese ions is manganese chloride.

The above-mentioned copper-manganese alloy plating solution for preparing copper-manganese spinel coatings is characterized in that the chelating agent is disodium edetate.

The above-mentioned copper-manganese alloy plating solution for preparing copper-manganese spinel coatings is characterized in that the buffer is ammonium chloride or boric acid.

The above-mentioned copper-manganese alloy plating solution for preparing copper-manganese spinel coatings is characterized in that the stabilizer is ammonium bromide.

The above-mentioned copper-manganese alloy plating solution for preparing copper-manganese spinel coatings is characterized in that the solvent is deionized water.

The above-mentioned copper-manganese alloy plating solution for preparing copper-manganese spinel coating is characterized in that the pH value of the copper-manganese alloy plating solution is 3-7.

In addition, the present invention also provides a kind of method that utilizes above-mentioned copper-manganese alloy plating solution to prepare copper-manganese spinel coating, it is characterized in that, this method comprises the following steps:

Step 1, pre-plating treatment, including degreasing treatment and activation treatment, the specific process is:

Step 101, degreasing treatment: heat the alkaline degreasing agent to 80°C, then soak the metal piece to be plated in the heated alkaline degreasing agent for 30 minutes, take it out, clean it and dry it; the alkaline The degreaser includes the following components: trisodium phosphate 30g/L~40g/L, sodium carbonate 40g/L~50g/L, sodium hydroxide 50g/L~60g/L, sodium silicate 5g/L~ 6g/L, the balance is deionized water;

Step 102, activation treatment: soak the metal parts to be plated after the degreasing treatment in step 101 in hydrochloric acid-nitric acid composite acid solution for 60 seconds, and then soak them in dilute sulfuric acid with a mass percentage concentration of 10% to 20% for 60 seconds, Take it out and clean it up; the mass percent concentration of HCl in the hydrochloric acid-nitric acid compound acid solution is 20% to 30%, and the mass percent concentration of _HNO3 is 5% to 10%;

Step 2, electroplating treatment: place the metal piece to be plated after the activation treatment in step 102 in a plating tank filled with a copper-manganese alloy plating solution, take the metal piece to be plated as the cathode, and use the graphite plate as the anode. Electroplating at 20°C to 25°C and current density of 200mA·cm ^-2 to 700mA·cm ^-2 for 10min to 30min, then take out the metal parts after electroplating, clean them with deionized water and dry them, and place them on the metal parts Copper-manganese alloy coating is obtained on the surface;

Step 3, post-treatment: place the copper-manganese alloy coating described in step 2 in a tube furnace, first protect it in an argon atmosphere, and dehydrogenate it for 2 hours at a temperature of 800°C, and then dehydrogenate the dehydrogenated copper The manganese alloy coating is oxidized for 2 hours at a temperature of 800°C in the atmosphere, and finally a copper-manganese spinel coating is obtained on the surface of the metal piece.

Compared with the prior art, the present invention has the following advantages:

1. The copper-manganese alloy plating solution of the present invention has stable chemical properties, does not volatilize harmful gases, and the medicines used are harmless to the environment.

2. The preparation process of the copper-manganese alloy plating solution of the present invention is simple and low in cost, and the copper molar content in the copper-manganese spinel coating prepared by using the plating solution is not less than 30%.

3. After the copper-manganese alloy plating solution of the present invention is subjected to electroplating treatment, a copper-manganese spinel coating is obtained, and the coating has excellent adhesion performance to the metal part substrate.

4. The invention has simple process, controllable conditions, uniform and dense coating, and good adhesion to the metal substrate. It is suitable for depositing on the surface of solid oxide metal connectors, and can be converted into copper-manganese spinel coating after oxidation treatment. . The copper-manganese spinel coating can improve the oxidation resistance of the metal connector, reduce its surface specific resistance, and improve the service life of the solid oxide fuel cell.

The present invention will be described in further detail below in conjunction with the accompanying drawings and embodiments.

Description of drawings

Fig. 1 is the SEM photo of the surface of the copper-manganese alloy coating prepared by using the copper-manganese alloy plating solution of Example 1 of the present invention.

Fig. 2 is a SEM photo of the surface of the copper-manganese spinel coating prepared by using the copper-manganese alloy plating solution of Example 1 of the present invention.

Fig. 3 is a cross-sectional SEM photo of the copper-manganese spinel coating prepared by using the copper-manganese alloy plating solution of Example 1 of the present invention.

detailed description

Example 1

The copper-manganese alloy plating solution that present embodiment is used for preparing copper-manganese spinel coating comprises each component of following concentration:

Copper ion source 0.05mol/L; The copper ion source is copper chloride;

Manganese ion source 0.5mol/L; Described manganese ion source is manganese chloride;

Chelating agent 0.05mol/L; The chelating agent is disodium edetate;

Buffer 30g/L; Described buffer is ammonium chloride or boric acid;

Stabilizer 20g/L; Described stabilizer is ammonium bromide;

Surplus is solvent; Described solvent is deionized water;

The pH value of the copper-manganese alloy plating solution is 5.

The preparation method of plating solution described in the present embodiment is:

Step 1. Add the chelating agent to deionized water, mix evenly, add copper ion source to the solution in which the chelating agent is dissolved while stirring, and stir evenly to obtain solution A;

Step 2, dissolving the manganese ion source in deionized water, then adding a buffer and a stabilizer in turn, and stirring evenly to obtain solution B;

Step 3: After stirring solution A for 1 hour, mix it with solution B evenly, stir for 2 hours, adjust the pH value with dilute hydrochloric acid, and finally add water to make the volume to 1 L to obtain a copper-manganese alloy plating solution.

The method that present embodiment utilizes above-mentioned copper-manganese alloy plating solution to prepare copper-manganese spinel coating comprises the following steps:

Step 1, pre-plating treatment, including degreasing treatment and activation treatment, the specific process is:

Step 101, degreasing treatment: heat the alkaline degreasing agent to 80°C, then soak the metal piece to be plated in the heated alkaline degreasing agent for 30 minutes, take it out, clean it and dry it; the alkaline The degreaser includes the following components: trisodium phosphate 35g/L, sodium carbonate 45g/L, sodium hydroxide 55g/L, sodium silicate 5.5g/L, and the balance is deionized water;

Step 102, activation treatment: soak the metal parts to be plated after the degreasing treatment in step 101 in hydrochloric acid-nitric acid compound acid solution for 60 seconds, then soak them in dilute sulfuric acid with a concentration of 15% by mass for 60 seconds, take them out and wash them Clean; the hydrochloric acid-nitric acid composite acid solution is prepared by adding water to commercially available concentrated hydrochloric acid and commercially available concentrated nitric acid, and the mass percent concentration of HCl in the prepared composite acid solution is 25%, and the mass percent concentration of _HNO3 is 8%. ;

Step 2, electroplating treatment: place the metal piece to be plated after the activation treatment in step 102 in a plating tank filled with a copper-manganese alloy plating solution, take the metal piece to be plated as the cathode, and use the graphite plate as the anode. Electroplating for 20 minutes at 22°C with a current density of 500mA·cm ^-2 , then take out the electroplated metal parts, clean them with deionized water and dry them, and obtain a copper-manganese alloy coating on the surface of the metal parts;

Step 3, post-treatment: place the copper-manganese alloy coating described in step 2 in a tube furnace, protect it in an argon atmosphere, and treat it with dehydrogenation at 800°C for 2 hours, and then dehydrogenate the copper-manganese alloy after dehydrogenation treatment The alloy coating is oxidized for 2 hours at 800°C in the atmosphere, and finally a copper-manganese spinel coating is obtained on the surface of the metal piece.

Fig. 1 is the SEM photograph of the surface of the copper-manganese alloy coating prepared by utilizing the copper-manganese alloy plating solution of this embodiment. It can be seen from Figure 1 that the coating is uniform and dense with good quality. Fig. 2 is the surface SEM photograph of the copper-manganese spinel coating prepared by using the copper-manganese alloy plating solution of this embodiment. 3 is a cross-sectional SEM photo of the copper-manganese spinel coating prepared by using the copper-manganese alloy plating solution of this embodiment, wherein layer I is a metal substrate, and layer II is a copper-manganese spinel coating. Combining Figures 2 and 3, it can be seen that after the copper-manganese alloy coating is oxidized, a uniform layer of Cu ₂ MnO ₄ spinel coating is formed on the surface of the metal piece, where the atomic percentage [Cu]/[Mn]=2, which meets the design requirements.

The chemical properties of the copper-manganese alloy plating solution in this embodiment are stable, no harmful gas is volatilized, and the medicines used are harmless to the environment. The preparation process of the plating solution is simple and the cost is low. After the copper-manganese alloy plating solution is used for electroplating, a copper-manganese spinel coating is obtained. The coating has excellent adhesion to the metal substrate and is suitable for deposition on solid oxidation The surface of the object metal connector can be transformed into a copper-manganese spinel coating after oxidation treatment. The copper-manganese spinel coating can improve the oxidation resistance of the metal connector, reduce its surface specific resistance, and improve the service life of the solid oxide fuel cell.

Example 2

The copper-manganese alloy plating solution that present embodiment is used for preparing copper-manganese spinel coating comprises each component of following concentration:

Copper ion source 0.075mol/L; The copper ion source is copper chloride;

Manganese ion source 0.8mol/L; Described manganese ion source is manganese chloride;

Chelating agent 0.05mol/L; The chelating agent is disodium edetate;

Buffer 100g/L; Described buffer is ammonium chloride or boric acid;

Stabilizer 40g/L; Described stabilizer is ammonium bromide;

Surplus is solvent; Described solvent is deionized water;

The pH value of the copper-manganese alloy plating solution is 6.

The preparation method of plating solution described in the present embodiment is:

Step 1. Add the chelating agent to deionized water, mix evenly, add copper ion source to the solution in which the chelating agent is dissolved while stirring, and stir evenly to obtain solution A;

Step 2, dissolving the manganese ion source in deionized water, then adding a buffer and a stabilizer in turn, and stirring evenly to obtain solution B;

Step 3: After stirring solution A for 1 hour, mix it with solution B evenly, stir for 2 hours, adjust the pH value with dilute ammonia water, and finally add water to make the volume to 1 L to obtain a copper-manganese alloy plating solution.

The method that present embodiment utilizes above-mentioned copper-manganese alloy plating solution to prepare copper-manganese spinel coating comprises the following steps:

Step 1, pre-plating treatment, including degreasing treatment and activation treatment, the specific process is:

Step 101, degreasing treatment: heat the alkaline degreasing agent to 80°C, then soak the metal piece to be plated in the heated alkaline degreasing agent for 30 minutes, take it out, clean it and dry it; the alkaline The degreaser includes the following components: trisodium phosphate 32g/L, sodium carbonate 48g/L, sodium hydroxide 56g/L, sodium silicate 5.7g/L, and the balance is deionized water;

Step 102, activation treatment: soak the metal parts to be plated after the degreasing treatment in step 101 in hydrochloric acid-nitric acid compound acid solution for 60 seconds, then soak them in dilute sulfuric acid with a concentration of 18% by mass for 60 seconds, take them out and wash them Clean; the hydrochloric acid-nitric acid composite acid solution is prepared by adding water to commercially available concentrated hydrochloric acid and commercially available concentrated nitric acid, and the mass percent concentration of HCl in the prepared composite acid solution is 20%, and the mass percent concentration of _HNO3 is 8%. ;

Step 2, electroplating treatment: place the metal piece to be plated after the activation treatment in step 102 in a plating tank filled with a copper-manganese alloy plating solution, take the metal piece to be plated as the cathode, and use the graphite plate as the anode. Electroplating for 18 minutes at 24°C with a current density of 250mA cm ^-2 , then take out the electroplated metal parts, clean them with deionized water and dry them, and obtain a copper-manganese alloy coating on the surface of the metal parts;

Step 3, post-treatment: place the copper-manganese alloy coating described in step 2 in a tube furnace, protect it in an argon atmosphere, and treat it with dehydrogenation at 800°C for 2 hours, and then dehydrogenate the copper-manganese alloy after dehydrogenation treatment The alloy coating is oxidized for 2 hours at 800°C in the atmosphere, and finally a copper-manganese spinel coating is obtained on the surface of the metal piece.

The chemical properties of the copper-manganese alloy plating solution in this embodiment are stable, no harmful gas is volatilized, and the medicines used are harmless to the environment. The preparation process of the plating solution is simple and the cost is low. After the copper-manganese alloy plating solution is used for electroplating, a copper-manganese spinel coating is obtained. The coating has excellent adhesion to the metal substrate and is suitable for deposition on solid oxidation The surface of the object metal connector can be transformed into a copper-manganese spinel coating after oxidation treatment. The copper-manganese spinel coating can improve the oxidation resistance of the metal connector, reduce its surface specific resistance, and improve the service life of the solid oxide fuel cell.

Example 3

The copper-manganese alloy plating solution that present embodiment is used for preparing copper-manganese spinel coating comprises each component of following concentration:

Copper ion source 0.025mol/L; The copper ion source is copper chloride;

Manganese ion source 1.0mol/L; Described manganese ion source is manganese chloride;

Chelating agent 0.03mol/L; The chelating agent is disodium edetate;

Buffer 200g/L; Described buffer is ammonium chloride or boric acid;

Stabilizer 10g/L; Described stabilizer is ammonium bromide;

Surplus is solvent; Described solvent is deionized water;

The pH value of the copper-manganese alloy plating solution is 3.

The preparation method of plating solution described in the present embodiment is:

Step 1. Add the chelating agent to deionized water, mix evenly, add copper ion source to the solution in which the chelating agent is dissolved while stirring, and stir evenly to obtain solution A;

Step 2, dissolving the manganese ion source in deionized water, then adding a buffer and a stabilizer in turn, and stirring evenly to obtain solution B;

Step 3: After stirring solution A for 1 hour, mix it with solution B evenly, stir for 2 hours, adjust the pH value with dilute hydrochloric acid, and finally add water to make the volume to 1 L to obtain a copper-manganese alloy plating solution.

The method that present embodiment utilizes above-mentioned copper-manganese alloy plating solution to prepare copper-manganese spinel coating comprises the following steps:

Step 1, pre-plating treatment, including degreasing treatment and activation treatment, the specific process is:

Step 101, degreasing treatment: heat the alkaline degreasing agent to 80°C, then soak the metal piece to be plated in the heated alkaline degreasing agent for 30 minutes, take it out, clean it and dry it; the alkaline The degreaser includes the following components: trisodium phosphate 30g/L, sodium carbonate 50g/L, sodium hydroxide 50g/L, sodium silicate 6g/L, and the balance is deionized water;

Step 102, activation treatment: soak the metal parts to be plated after the degreasing treatment in step 101 in hydrochloric acid-nitric acid compound acid solution for 60 seconds, then soak them in dilute sulfuric acid with a concentration of 10% by mass for 60 seconds, take them out and wash them Clean; the hydrochloric acid-nitric acid composite acid solution is prepared by adding water to commercially available concentrated hydrochloric acid and commercially available concentrated nitric acid, the mass percent concentration of HCl in the prepared composite acid solution is 30%, and the mass percent concentration of _HNO3 is 5% ;

Step 2, electroplating treatment: place the metal piece to be plated after the activation treatment in step 102 in a plating tank filled with a copper-manganese alloy plating solution, take the metal piece to be plated as the cathode, and use the graphite plate as the anode. Electroplating for 30 minutes at 20°C with a current density of 700mA·cm ^-2 , then take out the electroplated metal parts, clean them with deionized water and dry them, and obtain a copper-manganese alloy coating on the surface of the metal parts;

Step 3, post-treatment: place the copper-manganese alloy coating described in step 2 in a tube furnace, protect it in an argon atmosphere, and treat it with dehydrogenation at 800°C for 2 hours, and then dehydrogenate the copper-manganese alloy after dehydrogenation treatment The alloy coating is oxidized for 2 hours at 800°C in the atmosphere, and finally a copper-manganese spinel coating is obtained on the surface of the metal piece.

The chemical properties of the copper-manganese alloy plating solution in this embodiment are stable, no harmful gas is volatilized, and the medicines used are harmless to the environment. The preparation process of the plating solution is simple and the cost is low. After the copper-manganese alloy plating solution is used for electroplating, a copper-manganese spinel coating is obtained. The coating has excellent adhesion to the metal substrate and is suitable for deposition on solid oxidation The surface of the object metal connector can be transformed into a copper-manganese spinel coating after oxidation treatment. The copper-manganese spinel coating can improve the oxidation resistance of the metal connector, reduce its surface specific resistance, and improve the service life of the solid oxide fuel cell.

Example 4

The copper-manganese alloy plating solution that present embodiment is used for preparing copper-manganese spinel coating comprises each component of following concentration:

Copper ion source 0.1mol/L; The copper ion source is copper chloride;

Manganese ion source 0.25mol/L; The manganese ion source is manganese chloride;

Chelating agent 0.1mol/L; The chelating agent is disodium edetate;

Buffer 20g/L; Described buffer is ammonium chloride or boric acid;

Stabilizer 50g/L; Described stabilizer is ammonium bromide;

Surplus is solvent; Described solvent is deionized water;

The pH value of the copper-manganese alloy plating solution is 7.

The preparation method of plating solution described in the present embodiment is:

Step 1. Add the chelating agent to deionized water, mix evenly, add copper ion source to the solution in which the chelating agent is dissolved while stirring, and stir evenly to obtain solution A;

Step 2, dissolving the manganese ion source in deionized water, then adding a buffer and a stabilizer in turn, and stirring evenly to obtain solution B;

Step 3: After stirring solution A for 1 hour, mix it with solution B evenly, stir for 2 hours, adjust the pH value with dilute ammonia water, and finally add water to make the volume to 1 L to obtain a copper-manganese alloy plating solution.

The method that present embodiment utilizes above-mentioned copper-manganese alloy plating solution to prepare copper-manganese spinel coating comprises the following steps:

Step 1, pre-plating treatment, including degreasing treatment and activation treatment, the specific process is:

Step 101, degreasing treatment: heat the alkaline degreasing agent to 80°C, then soak the metal piece to be plated in the heated alkaline degreasing agent for 30 minutes, take it out, clean it and dry it; the alkaline The degreaser includes the following components: 40g/L trisodium phosphate, 40g/L sodium carbonate, 60g/L sodium hydroxide, 5g/L sodium silicate, and the balance is deionized water;

Step 102, activation treatment: soak the metal parts to be plated after the degreasing treatment in step 101 in hydrochloric acid-nitric acid compound acid solution for 60 seconds, then soak them in dilute sulfuric acid with a concentration of 20% by mass for 60 seconds, take them out and wash them Clean; the hydrochloric acid-nitric acid composite acid solution is prepared by adding water to commercially available concentrated hydrochloric acid and commercially available concentrated nitric acid, the mass percent concentration of HCl in the prepared composite acid solution is 20%, and the mass percent concentration of _HNO3 is 10% ;

Step 2, electroplating treatment: place the metal piece to be plated after the activation treatment in step 102 in a plating tank filled with a copper-manganese alloy plating solution, take the metal piece to be plated as the cathode, and use the graphite plate as the anode. Electroplating at 25°C, current density 200mA·cm ^-2 , and voltage 20V for 10 minutes, then take out the metal parts after electroplating, clean them with deionized water and dry them, and obtain a copper-manganese alloy coating on the surface of the metal parts;

Step 3, post-treatment: place the copper-manganese alloy coating described in step 2 in a tube furnace, protect it in an argon atmosphere, and treat it with dehydrogenation at 800°C for 2 hours, and then dehydrogenate the copper-manganese alloy after dehydrogenation treatment The alloy coating is oxidized for 2 hours at 800°C in the atmosphere, and finally a copper-manganese spinel coating is obtained on the surface of the metal piece.

The chemical properties of the copper-manganese alloy plating solution in this embodiment are stable, no harmful gas is volatilized, and the medicines used are harmless to the environment. The preparation process of the plating solution is simple and the cost is low. After the copper-manganese alloy plating solution is used for electroplating, a copper-manganese spinel coating is obtained. The coating has excellent adhesion to the metal substrate and is suitable for deposition on solid oxidation The surface of the object metal connector can be transformed into a copper-manganese spinel coating after oxidation treatment. The copper-manganese spinel coating can improve the oxidation resistance of the metal connector, reduce its surface specific resistance, and improve the service life of the solid oxide fuel cell.

In addition, in order to determine the optimal ratio of the copper-manganese alloy electroplating solution, the applicant of the present invention has carried out a large number of experimental verifications, optimized the dosage of the developed basic formula, and adjusted the main salt concentration, pH value, current The density and deposition time are as follows: In the test, 430 stainless steel substrates of the same size were used for electroplating, the electroplating temperature was 25 ^℃ , and the addition amount of NH ₄ Br and NH ₄ Cl was unchanged, 20g/L and 30g/L respectively . The morphology, cross-sectional morphology and composition of the obtained copper-manganese spinel coating were tested by SEM and EDS. Table 1 shows the test results of the influence of the selection of plating solution components and pH values on the appearance of copper-manganese spinel coatings.

Table 1 Effect of selection of plating solution components and pH value on appearance of copper-manganese spinel coating

It can be seen from Table 1 that the comparison test 1#, 2#, 3# and 4# shows that the optimization result of obtaining a more suitable copper-manganese spinel coating is 1#. SEM analysis of the coating surface shows that the coating is uniform and dense, with good quality, and a uniform layer of Cu ₂ MnO ₄ spinel coating is formed on the surface of the metal piece, wherein the atomic percentage [Cu]/[Mn]=2, Meet the design requirements and provide technical support for the development of protective coatings on the surface of SOFC connectors.

The above descriptions are only preferred embodiments of the present invention, and do not limit the present invention in any way. All simple modifications, changes and equivalent changes made to the above embodiments according to the technical essence of the invention still belong to the protection scope of the technical solution of the invention.

Claims (8)

1. a kind of cupromanganese plating solution for being used to prepare copper galaxite coating, it is characterised in that include each group of following concentration Point：

Copper ion source 0.025mol/L~0.1mol/L；

Manganese ion source 0.25mol/L~0.5mol/L；The manganese ion source is protochloride manganese；

Chelating agent 0.03mol/L~0.1mol/L；

Buffer 20g/L~200g/L；

Stabilizer 10g/L~50g/L；The stabilizer is ammonium bromide；

Surplus is solvent；

The method that copper galaxite coating is prepared using the cupromanganese plating solution is comprised the following steps：

Step 1: treatment before plating, including oil removal treatment and activation process, detailed process are：

Step 101, oil removal treatment：Alkaline degreaser is heated to 80 DEG C, the alkalescence that then plating metal part is placed in after heating 30min is soaked in degreaser, cleans up and dries after taking-up；The alkaline degreaser includes each component of following concentration：Phosphorus Sour trisodium 30g/L~40g/L, sodium carbonate 40g/L~50g/L, sodium hydroxide 50g/L~60g/L, sodium metasilicate 5g/L~6g/L, Surplus is deionized water；

Step 102, activation process：Plating metal part after oil removal treatment in step 101 is placed in the compound acid solution of hydrochloric acid-nitric acid 60s is soaked, is subsequently placed in the dilute sulfuric acid that mass percent concentration is 10%~20% and soaks 60s, cleaned up after taking-up；Institute The mass percent concentration for stating HCl in the compound acid solution of hydrochloric acid-nitric acid is 20%~30%, HNO₃Mass percent concentration be 5%~10%；

Step 2: electroplating processes：Plating metal part after activation process in step 102 is placed in and is loaded with cupromanganese plating solution In coating bath, using the plating metal part after activation process as negative electrode, using graphite cake as anode, in 20 DEG C~25 DEG C of bath temperature, electricity Current density is 200mAcm^-2~700mAcm^-2Under conditions of electroplate 10min~30min, afterwards by the metalwork after plating Take out, dried up after being cleaned up with deionized water, cupromanganese coating is obtained on metalwork surface；

Step 3: post processing：The plating of cupromanganese described in step 2 is placed in tube furnace, first protected in argon gas atmosphere, temperature Spend for dehydrogenation 2h under conditions of 800 DEG C, be then in air atmosphere, temperature by the cupromanganese coating after dehydrogenation Oxidation processes 2h under conditions of 800 DEG C, copper galaxite coating is finally obtained on metalwork surface.

2. a kind of cupromanganese plating solution for being used to prepare cupromanganese spinelle coating according to claim 1, its feature It is, includes each component of following concentration：

Copper ion source 0.05mol/L；

Manganese ion source 0.5mol/L；

Chelating agent 0.05mol/L；

Buffer 30g/L；

Stabilizer 20g/L；

Surplus is solvent.

3. a kind of cupromanganese plating solution for being used to prepare copper galaxite coating according to claim 1 or 2, its feature exist In the copper ion source is copper chloride.

4. a kind of cupromanganese plating solution for being used to prepare copper galaxite coating according to claim 1 or 2, its feature exist In the chelating agent is disodium ethylene diamine tetraacetate.

5. a kind of cupromanganese plating solution for being used to prepare copper galaxite coating according to claim 1 or 2, its feature exist In the buffer is ammonium chloride or boric acid.

6. a kind of cupromanganese plating solution for being used to prepare copper galaxite coating according to claim 1 or 2, its feature exist In the solvent is deionized water.

7. a kind of cupromanganese plating solution for being used to prepare copper galaxite coating according to claim 1 or 2, its feature exist In the pH value of the cupromanganese plating solution is 3~7.

8. a kind of method for preparing copper galaxite coating using cupromanganese plating solution as claimed in claim 1 or 2, its feature exist In this method comprises the following steps：

Step 1: treatment before plating, including oil removal treatment and activation process, detailed process are：

Step 101, oil removal treatment：Alkaline degreaser is heated to 80 DEG C, the alkalescence that then plating metal part is placed in after heating 30min is soaked in degreaser, cleans up and dries after taking-up；The alkaline degreaser includes each component of following concentration：Phosphorus Sour trisodium 30g/L~40g/L, sodium carbonate 40g/L~50g/L, sodium hydroxide 50g/L~60g/L, sodium metasilicate 5g/L~6g/L, Surplus is deionized water；

Step 102, activation process：Plating metal part after oil removal treatment in step 101 is placed in the compound acid solution of hydrochloric acid-nitric acid 60s is soaked, is subsequently placed in the dilute sulfuric acid that mass percent concentration is 10%~20% and soaks 60s, cleaned up after taking-up；Institute The mass percent concentration for stating HCl in the compound acid solution of hydrochloric acid-nitric acid is 20%~30%, HNO₃Mass percent concentration be 5%~10%；

Step 2: electroplating processes：Plating metal part after activation process in step 102 is placed in and is loaded with cupromanganese plating solution In coating bath, using the plating metal part after activation process as negative electrode, using graphite cake as anode, in 20 DEG C~25 DEG C of bath temperature, electricity Current density is 200mAcm^-2~700mAcm^-2Under conditions of electroplate 10min~30min, afterwards by the metalwork after plating Take out, dried up after being cleaned up with deionized water, cupromanganese coating is obtained on metalwork surface；

Step 3: post processing：The plating of cupromanganese described in step 2 is placed in tube furnace, first protected in argon gas atmosphere, temperature Spend for dehydrogenation 2h under conditions of 800 DEG C, be then in air atmosphere, temperature by the cupromanganese coating after dehydrogenation Oxidation processes 2h under conditions of 800 DEG C, copper galaxite coating is finally obtained on metalwork surface.