CN115074792A - Preparation method of cobalt-based alloy film with special structure and product - Google Patents

Abstract

The invention discloses a preparation method and a product of a cobalt-based alloy film layer with a special structure, and belongs to the technical field of metal materials. The preparation method of a cobalt-based alloy film layer includes the following steps: immersing a metal base material in an acidic composite plating solution for composite electrodeposition, and then immersing it in an alkaline solution for immersion and corrosion to obtain the cobalt-based alloy film layer; the acidic composite plating solution The preparation of the composite plating solution includes: adding cobalt salt, tungsten salt and Al ₂ O ₃ particles into a solvent and mixing, and then adjusting the pH value to be acidic to obtain the acidic composite plating solution. The cobalt-based alloy film layer has improved wear resistance, reduced hydrogen evolution overpotential, improved hydrogen evolution performance, and has excellent catalytic performance.

Description

A kind of preparation method and product of special structure cobalt-based alloy film

technical field

The invention relates to the technical field of metal materials, in particular to a preparation method and product of a cobalt-based alloy film layer with a special structure.

Background technique

Among many clean energy sources, hydrogen energy, as an economical, efficient and sustainable green energy, is one of the most ideal energy carriers, and it has received more and more attention. Among various hydrogen production technologies, electrolysis of water is considered to be one of the most effective ways to the "hydrogen economy". However, in practical applications, water electrolysis for hydrogen production often needs to overcome a high hydrogen evolution overpotential, resulting in high energy loss. The key to breaking through this bottleneck is the technology. At present, precious metal platinum and its alloys are the most effective catalysts for hydrogen evolution, but the high price, scarcity of resources, and poor electrochemical stability limit their large-scale applications. Powdered catalysts are limited by binders and electrochemical stability. Therefore, there is an urgent need to develop a non-noble metal electrode material with high mechanical strength and good catalytic activity.

Among many non-precious metal electrocatalytic materials, transition metal phosphide is one of the electrocatalytic materials for hydrogen evolution with high catalytic activity, good stability and cost-effectiveness due to its unique electronic structure and metal-like properties. The potential of electrocatalytic materials. At present, most of the phosphide catalytic materials used for the hydrogen evolution of water electrolysis are prepared by the solution hydrothermal synthesis process and the high-temperature solid-phase reduction process. Most of their forms are powders, which need to be fully dispersed in the solvent, and then the Nafion solution and polyvinylidene fluoride are used. Binders such as organic solutions are used to fix it on the conductive carrier, so that the catalyst loading of the catalytic electrode is limited, and the binder will reduce the electrical conductivity of the electrode material, and there are also parts where the binder will coat and shield the catalyst. In addition, during the long-term electrolysis process, the active catalytic material is easy to fall off the surface of the electrode, resulting in poor stability of the catalytic electrode for hydrogen evolution in water electrolysis. However, how to prepare a non-precious metal electrode material with good catalytic activity and wear resistance has become a technical problem to be solved urgently by those skilled in the art.

SUMMARY OF THE INVENTION

The purpose of the present invention is to provide a preparation method and product _of a cobalt _- based alloy film with a special structure, so as to solve the problems existing in the prior art. It is deposited and then etched by NaOH solution to remove Al ₂ O ₃ particles with a special structure (compare Figures 1 to 2 with Figure 8, it can be seen that the special structure and the original structure, after the removal of the alumina particles, the surface remains porous ) cobalt-based alloy film, which has both wear resistance and high hydrogen evolution performance.

To achieve the above object, the present invention provides the following solutions

One of the technical solutions of the present invention:

The metal base material is immersed in an acidic composite plating solution for composite electrodeposition, and then immersed in an alkaline solution for immersion and corrosion to obtain the cobalt-based alloy film layer;

The preparation of the acidic composite plating solution includes: adding cobalt salt, tungsten salt and Al ₂ O ₃ particles into a solvent and mixing, and then adjusting the pH value to be acidic to obtain the acidic composite plating solution.

Co-W alloy film has compact structure, high hardness, good heat resistance, and excellent wear and corrosion resistance.

Removing the alumina particles by etching can form a porous structure on the surface, effectively increase the surface area, and improve its electrocatalytic performance.

Further, the concentration of cobalt salt in the acidic composite plating solution is 0.05-0.1 mol/L, the concentration of tungsten salt is 0.05-0.1 mol/L, and the concentration of Al ₂ O ₃ particles is 10-30 g/L; The pH value of the acidic composite plating solution is 4.5 to 6.0.

The coating thickness of the composite high-concentration alumina particles is lower than that of the low-concentration coating. The complexing agent can play the role of lightening, leveling and buffering.

Further, the cobalt salt is cobalt sulfate; the tungsten salt is sodium tungstate.

Further, the acidic composite plating solution also contains a complexing agent.

Further, the concentration of the complexing agent in the acidic composite plating solution is 0.2-0.4 mol/L; the complexing agent is diammonium hydrogen citrate.

Further, the conditions of the composite electrodeposition are: constant current density, the current density is 10-50mA/cm ² , the electrodeposition time is 30-60min, and the electrodeposition temperature is 40-70°C.

Further, the alkaline solution includes a NaOH solution; the concentration of the NaOH solution is 5-7 mol/L.

Further, the temperature of the soaking corrosion is 60-80°C.

The second technical solution of the present invention: a cobalt-based alloy film prepared by the above preparation method.

The third technical solution of the present invention: an application of the above-mentioned cobalt-based alloy film layer in the preparation of electrode materials.

The present invention discloses the following technical effects:

(1) Using the acidic composite plating solution of the present invention to perform composite electrodeposition on the base material, a Co-W alloy film layer with excellent mechanical properties can be formed, which is further immersed in a NaOH solution for corrosion, and finally formed on the surface of the substrate with a thickness of Cobalt-based alloy film with a special structure of 10-13μm, the composite film has a smooth surface, a special structure, and a friction coefficient of 0.5-0.8. When corroded at a current density of 10-100mA/cm ² , its hydrogen evolution overpotential is reduced (with Compared with 572mV of Co-W coating), the catalytic performance is improved.

(2) The special-structured cobalt-based alloy film prepared by the present invention has both wear resistance and high hydrogen evolution performance.

(3) The present invention adds Al ₂ O ₃ particles on the basis of the existing co-deposition of cobalt salt and tungsten salt, and the three substances are compound and co-deposited under the action of the complexing agent diammonium hydrogen citrate, which can make The Co-W-Al ₂ O ₃ composite film can be obtained, which can improve the wear resistance of the film. Then, the Al ₂ O ₃ particles are removed by etching in NaOH solution to obtain a cobalt-based alloy film with a special structure. The cobalt-based film layer itself has excellent performance, and the degranulation method used in the present invention prepares a special-structured cobalt-based alloy film layer, so that the film layer has larger porosity, specific surface area and chemical activity, and further improves the film layer. Mechanical and catalytic properties. In addition, the present invention adopts the method of composite electrodeposition and corrosion and degranulation, and the obtained film has the advantages of wear resistance, large specific surface area (with porous structure, large specific surface area) and high hydrogen evolution performance.

(4) The method of the present invention is suitable for preparing various electrode materials in electrocatalysis (which need to have excellent hydrogen evolution performance and wear resistance requirements).

(5) The present invention adopts composite electrodeposition and corrosion degranulation technology to improve its hydrogen evolution performance and mechanical performance.

(6) The preparation method of the present invention is simple to operate, clean and environmentally friendly, suitable for metal materials with complex shapes and blind holes, and is easy to industrialize.

Description of drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the accompanying drawings required in the embodiments will be briefly introduced below. Obviously, the drawings in the following description are only some of the present invention. In the embodiments, for those of ordinary skill in the art, other drawings can also be obtained according to these drawings without any creative effort.

Fig. 1 is the surface topography diagram of the special structure cobalt-based alloy film prepared in Example 1 of the present invention;

Fig. 2 is the surface topography of the special structure cobalt-based alloy film prepared in Example 2 of the present invention;

Fig. 3 is the surface topography of the special structure cobalt-based alloy film prepared in Example 3 of the present invention;

4 is a surface topography diagram of a special-structure cobalt-based alloy film prepared in Example 4 of the present invention;

Fig. 5 is the surface topography diagram of the special structure cobalt-based alloy film prepared in Example 5 of the present invention;

6 is a surface topography diagram of a special-structure cobalt-based alloy film prepared in Example 6 of the present invention;

Fig. 7 is the surface topography diagram of the film layer prepared by Comparative Example 1 of the present invention;

Fig. 8 is the surface topography diagram of the film layer prepared by Comparative Example 2 of the present invention;

Fig. 9 is the surface topography diagram of the film layer prepared by Comparative Example 3 of the present invention;

Fig. 10 is the surface topography of the film layer prepared by Comparative Example 4 of the present invention;

FIG. 11 is a surface topography diagram of the film prepared in Comparative Example 5 of the present invention.

Detailed ways

Various exemplary embodiments of the present invention will now be described in detail, which detailed description should not be construed as a limitation of the invention, but rather as a more detailed description of certain aspects, features, and embodiments of the invention.

It should be understood that the terms described in the present invention are only used to describe particular embodiments, and are not used to limit the present invention. Additionally, for numerical ranges in the present disclosure, it should be understood that each intervening value between the upper and lower limits of the range is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated value or intervening value in that stated range is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention relates. Although only the preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and materials in connection with which the documents are referred. In the event of conflict with any incorporated document, the content of this specification controls.

It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present invention without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from the description of the present invention. The description and examples of the present application are only exemplary.

As used herein, "comprising," "including," "having," "containing," and the like, are open-ended terms, meaning including but not limited to.

Example 1

A preparation method of a cobalt-based alloy film with a special structure:

(1) Preparation of acidic composite plating solution: add cobalt sulfate, sodium tungstate, complexing agent (diammonium hydrogen citrate), and alumina particles (particle size: 1 μm) into solvent water and mix, dissolve, and stir evenly to obtain acidic Composite plating solution.

The concentrations of the components are: cobalt sulfate 0.1 mol/L, sodium tungstate 0.1 mol/L, complexing agent (diammonium hydrogen citrate) 0.2 mol/L, and alumina particles 20 g/L. The temperature of the acidic composite plating solution was a constant temperature of 60°C, and the pH value was 5.0.

(2) Immerse the metal base material in an acidic composite plating solution to carry out composite electrodeposition (the composite electrodeposition is carried out under the condition of air stirring, a constant current density is used, the current density is 20mA/cm ² , the electrodeposition time is 60min, and the electrodeposition time is 60min. The temperature is 60 ℃), after the electrodeposition is finished, take out, wash with water, and dry with cold air; then immerse in a constant temperature (80 ℃) reactor containing NaOH solution (concentration is 5mol/L), and corrode for 60min under air stirring to remove alumina The particles are taken out, washed with water, and dried in cold air to obtain a cobalt-based alloy film layer with a special structure (a base material with a composite film layer).

The prepared cobalt-based alloy film with special structure was placed under a scanning electron microscope to observe its surface morphology. The results are shown in Figure 1. It can be seen from the figure that the obtained composite film has a smooth surface and a uniform special structure. After testing, the thickness of the obtained special-structure cobalt-based alloy film is 13 μm, the friction coefficient is 0.54, and it is corroded at a current density of 10 mA/cm ² . 40mV.

Example 2

A preparation method of a cobalt-based alloy film with a special structure:

(1) Preparation of acidic composite plating solution: add cobalt sulfate, sodium tungstate, complexing agent (diammonium hydrogen citrate), and alumina particles (particle size: 1 μm) into solvent water and mix, dissolve, and stir evenly to obtain acidic Composite plating solution.

The concentrations of each component are: cobalt sulfate 0.1 mol/L, sodium tungstate 0.1 mol/L, complexing agent (diammonium hydrogen citrate) 0.2 mol/L, and alumina particles 10 g/L. The temperature of the acidic composite plating solution was a constant temperature of 60°C, and the pH value was 5.0.

(2) Immerse the metal base material in an acidic composite plating solution to carry out composite electrodeposition (the composite electrodeposition is carried out under the condition of air stirring, a constant current density is used, the current density is 20mA/cm ² , the electrodeposition time is 60min, and the electrodeposition time is 60min. The temperature is 60 ℃), after the electrodeposition is finished, take out, wash with water, and dry with cold air; then immerse in a constant temperature (80 ℃) reactor containing NaOH solution (concentration is 5mol/L), and corrode for 60min under air stirring to remove alumina The particles are taken out, washed with water, and dried in cold air to obtain a cobalt-based alloy film layer with a special structure (a base material with a composite film layer).

The prepared cobalt-based alloy film with special structure was placed under a scanning electron microscope to observe its surface morphology. The results are shown in Figure 2. It can be seen from the figure that the obtained composite film has a smooth surface and a uniform special structure. After testing, the thickness of the obtained special-structure cobalt-based alloy film is 11 μm, the friction coefficient is 0.53, and it is corroded at a current density of 10 mA/cm ² . 5mV.

Example 3

A preparation method of a cobalt-based alloy film with a special structure:

(1) Preparation of acidic composite plating solution: add cobalt sulfate, sodium tungstate, complexing agent (diammonium hydrogen citrate), and alumina particles (particle size: 1 μm) into solvent water and mix, dissolve, and stir evenly to obtain acidic Composite plating solution.

The concentrations of the components are: cobalt sulfate 0.1 mol/L, sodium tungstate 0.1 mol/L, complexing agent (diammonium hydrogen citrate) 0.2 mol/L, and alumina particles 30 g/L. The temperature of the acidic composite plating solution was a constant temperature of 60°C, and the pH value was 5.0.

(2) Immerse the metal base material in an acidic composite plating solution to carry out composite electrodeposition (the composite electrodeposition is carried out under the condition of air stirring, a constant current density is used, the current density is 20mA/cm ² , the electrodeposition time is 60min, and the electrodeposition time is 60min. The temperature is 60 ℃), after the electrodeposition is finished, take out, wash with water, and dry with cold air; then immerse in a constant temperature (80 ℃) reactor containing NaOH solution (concentration is 5mol/L), and corrode for 60min under air stirring to remove alumina The particles are taken out, washed with water, and dried in cold air to obtain a cobalt-based alloy film layer with a special structure (a base material with a composite film layer).

The prepared cobalt-based alloy film with special structure was placed under a scanning electron microscope to observe its surface morphology. The results are shown in Figure 3. It can be seen from the figure that the obtained composite film has a smooth surface and a uniform special structure. After testing, the thickness of the obtained special-structure cobalt-based alloy film is 10 μm, the friction coefficient is 0.68, and it is corroded at a current density of 10 mA/cm ² . 29mV.

Example 4

A preparation method of a cobalt-based alloy film with a special structure:

(1) Preparation of acidic composite plating solution: Add cobalt sulfate, sodium tungstate, complexing agent (diammonium hydrogen citrate), and alumina particles (particle size: 80 nm) into solvent water and mix, dissolve, and stir evenly to obtain acidic Composite plating solution.

The concentrations of each component are: cobalt sulfate 0.1 mol/L, sodium tungstate 0.1 mol/L, complexing agent (diammonium hydrogen citrate) 0.2 mol/L, and alumina particles 10 g/L. The temperature of the acidic composite plating solution was a constant temperature of 60°C, and the pH value was 5.0.

(2) Immerse the metal base material in an acidic composite plating solution to carry out composite electrodeposition (the composite electrodeposition is carried out under the condition of air stirring, a constant current density is used, the current density is 20mA/cm ² , the electrodeposition time is 60min, and the electrodeposition time is 60min. The temperature is 60 ℃), after the electrodeposition is finished, take out, wash with water, and dry with cold air; then immerse in a constant temperature (80 ℃) reactor containing NaOH solution (concentration is 5mol/L), and corrode for 60min under air stirring to remove alumina The particles are taken out, washed with water, and dried in cold air to obtain a cobalt-based alloy film layer with a special structure (a base material with a composite film layer).

The prepared cobalt-based alloy film with special structure was placed under a scanning electron microscope to observe its surface morphology. The results are shown in Figure 4. It can be seen from the figure that the obtained composite film has a smooth surface and a uniform special structure. After testing, the thickness of the obtained special-structure cobalt-based alloy film is 12 μm, the friction coefficient is 0.69, and it is corroded at a current density of 10 mA/cm ² . 11mV.

Example 5

A preparation method of a cobalt-based alloy film with a special structure:

(1) Preparation of acidic composite plating solution: add cobalt sulfate, sodium tungstate, complexing agent (diammonium hydrogen citrate), and alumina particles (particle size: 5 μm) into solvent water and mix, dissolve, and stir evenly to obtain acidic Composite plating solution.

The concentrations of the components are: cobalt sulfate 0.1 mol/L, sodium tungstate 0.1 mol/L, complexing agent (diammonium hydrogen citrate) 0.2 mol/L, and alumina particles 20 g/L. The temperature of the acidic composite plating solution was a constant temperature of 60°C, and the pH value was 5.0.

(2) Immerse the metal base material in an acidic composite plating solution to carry out composite electrodeposition (the composite electrodeposition is carried out under the condition of air stirring, a constant current density is used, the current density is 20mA/cm ² , the electrodeposition time is 60min, and the electrodeposition time is 60min. The temperature is 60 ℃), after the electrodeposition is finished, take out, wash with water, and dry with cold air; then immerse in a constant temperature (80 ℃) reactor containing NaOH solution (concentration is 5mol/L), and corrode for 60min under air stirring to remove alumina The particles are taken out, washed with water, and dried in cold air to obtain a cobalt-based alloy film layer with a special structure (a base material with a composite film layer).

The prepared cobalt-based alloy film with special structure was placed under a scanning electron microscope to observe its surface morphology. The results are shown in Figure 5. It can be seen from the figure that the obtained composite film has a smooth surface and a uniform special structure. After testing, the thickness of the obtained special-structure cobalt-based alloy film is 12 μm, the friction coefficient is 0.78, and it corrodes at a current density of 10 mA/cm ² , and its hydrogen evolution overpotential is 559 mV, which is lower than the 572 mV of Co-W coating 13mV.

Example 6

A preparation method of a cobalt-based alloy film with a special structure:

(1) Preparation of acidic composite plating solution: add cobalt sulfate, sodium tungstate, complexing agent (diammonium hydrogen citrate), and alumina particles (particle size: 5 μm) into solvent water and mix, dissolve, and stir evenly to obtain acidic Composite plating solution.

The concentrations of the components are: cobalt sulfate 0.1 mol/L, sodium tungstate 0.1 mol/L, complexing agent (diammonium hydrogen citrate) 0.2 mol/L, and alumina particles 30 g/L. The temperature of the acidic composite plating solution was a constant temperature of 60°C, and the pH value was 5.0.

(2) Immerse the metal base material in an acidic composite plating solution to carry out composite electrodeposition (the composite electrodeposition is carried out under the condition of air stirring, a constant current density is used, the current density is 20mA/cm ² , the electrodeposition time is 60min, and the electrodeposition time is 60min. The temperature is 60 ℃), after the electrodeposition is finished, take out, wash with water, and dry with cold air; then immerse in a constant temperature (80 ℃) reactor containing NaOH solution (concentration is 5mol/L), and corrode for 60min under air stirring to remove alumina The particles are taken out, washed with water, and dried in cold air to obtain a cobalt-based alloy film layer with a special structure (a base material with a composite film layer).

The prepared cobalt-based alloy film with special structure was placed under a scanning electron microscope to observe its surface morphology. The results are shown in Figure 6. It can be seen from the figure that the obtained composite film has a smooth surface and a uniform special structure. After testing, the thickness of the obtained special-structure cobalt-based alloy film is 11 μm, the friction coefficient is 0.80, and it is corroded at a current density of 10 mA/cm ² . 10mV.

Comparative Example 1

Same as Example 1, the difference is that the composite electrodeposition is not immersed in NaOH solution for corrosion.

The prepared film layer was placed under a scanning electron microscope to observe its surface morphology. The results are shown in Figure 7. It can be seen from the figure that the surface of the obtained film layer is smooth, and composite alumina particles can be seen. After testing, the thickness of the obtained film layer was 13 μm, the friction coefficient was 0.58, and the hydrogen evolution overpotential was 568 mV.

Comparative Example 2

Same as Example 1, the difference is that the acidic composite plating solution in step (1) does not contain alumina particles, and is not immersed in NaOH solution for corrosion after composite electrodeposition.

The obtained film (Co-W coating) was placed under a scanning electron microscope to observe its surface morphology. The results are shown in Figure 8. It can be seen from the figure that the surface of the obtained film is smooth, continuous and dense, and has no whisker-like morphology. After testing, the thickness of the obtained film layer was 8 μm, the friction coefficient was 0.63, and the hydrogen evolution overpotential was 572 mV.

Comparative Example 3

Same as Example 1, the difference is that the particle size of the alumina particles is 30 nm.

The obtained film was placed under a scanning electron microscope to observe its surface morphology. The results are shown in Figure 9. It can be seen from the figure that the surface of the obtained film is smooth, continuous and uniform, and the special structure is not obvious. After testing, the thickness of the obtained film was 11 μm, the friction coefficient was 0.71, and it was corroded at a current density of 10 mA/cm ² .

Comparative Example 4

Same as Example 1, the difference is that the current density of composite electrodeposition is 100 mA/cm ² .

The obtained composite film layer was placed under a scanning electron microscope to observe its surface morphology. The results are shown in Figure 10. It can be seen from the figure that the obtained composite film layer has a smooth surface and a uniform special structure. After testing, the obtained composite film has a thickness of 10 μm, a friction coefficient of 0.59, and is corroded at a current density of 100 mA/cm ² .

Comparative Example 5

Same as Example 1, the difference is that the concentration of cobalt sulfate is 0.15 mol/L.

The obtained film was placed under a scanning electron microscope to observe its surface morphology. The results are shown in Figure 11. It can be seen from the figure that the surface of the obtained film is smooth, continuous and uniform, and the special structure is not obvious. After testing, the thickness of the obtained film is 5 μm, the friction coefficient is 0.78, and it is corroded at a current density of 10 mA/cm ² .

The above-mentioned embodiments are only to describe the preferred modes of the present invention, but not to limit the scope of the present invention. Without departing from the design spirit of the present invention, those of ordinary skill in the art can make various modifications to the technical solutions of the present invention. Variations and improvements should fall within the protection scope determined by the claims of the present invention.

Claims (10)

1. a preparation method of a cobalt-based alloy film, is characterized in that, comprises the following steps: metal base material is immersed in acid composite plating solution to carry out composite electrodeposition, then immersed in alkaline solution for immersion corrosion, to obtain described cobalt base alloy film; The preparation of the acidic composite plating solution includes: adding cobalt salt, tungsten salt and Al ₂ O ₃ particles into a solvent and mixing, and then adjusting the pH value to be acidic to obtain the acidic composite plating solution. 2 . The method for preparing a cobalt-based alloy film layer according to claim 1 , wherein the concentration of the cobalt salt in the acidic composite plating solution is 0.05-0.1 mol/L, and the concentration of the tungsten salt is 0.05-0.1 mol. 3 . /L, the concentration of Al ₂ O ₃ particles is 10-30 g/L; the pH of the acidic composite plating solution is 4.5-6.0. 3 . The method for preparing a cobalt-based alloy film layer according to claim 1 , wherein the cobalt salt is cobalt sulfate; and the tungsten salt is sodium tungstate. 4 . 4 . The method for preparing a cobalt-based alloy film layer according to claim 1 , wherein the acidic composite plating solution further contains a complexing agent. 5 . 5. The method for preparing a cobalt-based alloy film layer according to claim 4, wherein the concentration of the complexing agent in the acidic composite plating solution is 0.2-0.4 mol/L; the complexing agent is lemon Diammonium hydrogen acid. 6 . The method for preparing a cobalt-based alloy film layer according to claim 1 , wherein the conditions for the composite electrodeposition are: constant current density, the current density is 10-50 mA/cm ² , and the electrodeposition time is 30 ~60min, the electrodeposition temperature is 40~70℃. 7 . The method for preparing a cobalt-based alloy film layer according to claim 1 , wherein the alkaline solution comprises a NaOH solution; the concentration of the NaOH solution is 5-7 mol/L. 8 . 8 . The method for preparing a cobalt-based alloy film layer according to claim 1 , wherein the temperature of the immersion corrosion is 60-80° C. 9 . 9. A cobalt-based alloy film prepared by the preparation method of any one of claims 1 to 8. 10. An application of the cobalt-based alloy film of claim 9 in the preparation of electrode materials.

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