CN115074792A - Preparation method of cobalt-based alloy film with special structure and product - Google Patents
Preparation method of cobalt-based alloy film with special structure and product Download PDFInfo
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- CN115074792A CN115074792A CN202210791961.3A CN202210791961A CN115074792A CN 115074792 A CN115074792 A CN 115074792A CN 202210791961 A CN202210791961 A CN 202210791961A CN 115074792 A CN115074792 A CN 115074792A
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- 229910000531 Co alloy Inorganic materials 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002131 composite material Substances 0.000 claims abstract description 89
- 239000000243 solution Substances 0.000 claims abstract description 65
- 238000007747 plating Methods 0.000 claims abstract description 49
- 238000004070 electrodeposition Methods 0.000 claims abstract description 46
- 230000002378 acidificating effect Effects 0.000 claims abstract description 44
- 239000002245 particle Substances 0.000 claims abstract description 41
- 239000000463 material Substances 0.000 claims abstract description 27
- 239000000758 substrate Substances 0.000 claims abstract description 23
- 230000007797 corrosion Effects 0.000 claims abstract description 15
- 238000005260 corrosion Methods 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 150000001868 cobalt Chemical class 0.000 claims abstract description 8
- 150000003657 tungsten Chemical class 0.000 claims abstract description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 6
- 239000012670 alkaline solution Substances 0.000 claims abstract description 5
- 238000002791 soaking Methods 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 239000008139 complexing agent Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 16
- KLOIYEQEVSIOOO-UHFFFAOYSA-N carbocromen Chemical group CC1=C(CCN(CC)CC)C(=O)OC2=CC(OCC(=O)OCC)=CC=C21 KLOIYEQEVSIOOO-UHFFFAOYSA-N 0.000 claims description 15
- 229940044175 cobalt sulfate Drugs 0.000 claims description 15
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 15
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical group [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 15
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical group [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 14
- 239000007772 electrode material Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 30
- 239000001257 hydrogen Substances 0.000 abstract description 30
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 239000007769 metal material Substances 0.000 abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 238000003756 stirring Methods 0.000 description 18
- 229910020515 Co—W Inorganic materials 0.000 description 13
- 238000012876 topography Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 238000001514 detection method Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000010494 dissociation reaction Methods 0.000 description 5
- 230000005593 dissociations Effects 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/089—Alloys
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/623—Porosity of the layers
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- Chemical Kinetics & Catalysis (AREA)
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention discloses a preparation method of a cobalt-based alloy film with a special structure and a product, belonging to the technical field of metal materials. The preparation method of the cobalt-based alloy film layer comprises the following steps: immersing a metal substrate material into an acidic composite plating solution for composite electrodeposition, and then immersing into an alkaline solution for soaking and corrosion to obtain the cobalt-based alloy film layer; the preparation of the acidic composite plating solution comprises the following steps: mixing cobalt salt, tungsten salt and Al 2 O 3 Adding the particles into a solvent, mixing, and adjusting the pH value to acidity to obtain the acidic composite plating solution. The cobalt-based alloy film has the advantages of improved wear resistance, reduced hydrogen evolution overpotential, improved hydrogen evolution performance and excellent catalytic performance.
Description
Technical Field
The invention relates to the technical field of metal materials, in particular to a preparation method and a product of a cobalt-based alloy film with a special structure.
Background
Among many clean energy sources, hydrogen energy is one of the most ideal energy carriers as an economic, efficient and sustainable green energy source, and is receiving more and more attention. Among the various hydrogen production technologies, hydro-electric dissociation hydrogen production is considered to be one of the most effective routes to "hydrogen economy". However, in practical application, hydrogen production by water and electricity dissociation usually needs to overcome a higher overpotential of hydrogen evolution, so that higher energy loss is caused, and in order to effectively solve the technical bottleneck that the overpotential of hydrogen evolution by water and electricity dissociation is too high, the application of the high-efficiency catalytic material is a technical key for breaking through the bottleneck. At present, noble metal platinum and alloy thereof are the most effective hydrogen evolution catalysts, but the scale application of the noble metal platinum and alloy thereof is limited by the defects of high price, rare resources, poor electrochemical stability and the like, and the powdery catalyst is limited by adhesives and electrochemical stability. Therefore, it is required to develop a non-noble metal electrode material having high mechanical strength and good catalytic activity.
Among numerous non-noble metal electrocatalytic materials, transition metal phosphide is one of hydrogen evolution electrocatalytic materials with high catalytic reaction activity, good stability and good cost effectiveness due to the unique electronic structure and metalloid characteristics thereof, and has the potential of replacing a Pt-based electrocatalytic material. At present, most phosphide catalytic materials for hydrogen evolution through water-electricity dissociation are prepared through a solution hydrothermal synthesis process and a high-temperature solid-phase reduction process, most phosphide catalytic materials are in powder form, and need to be fully dispersed in a solvent, and then binders such as a Nafion solution and a polyvinylidene fluoride organic solution are used for fixing the phosphide catalytic materials on a conductive carrier, so that the catalyst loading capacity of a catalytic electrode is limited, the electrical conductivity of the electrode material can be reduced through the binders, and meanwhile, partial active point positions of the catalyst can be coated and shielded through the binders, so that the catalytic performance of the electrode material can be reduced; in addition, in the long-time electrolysis process, the active catalytic material is easy to fall off from the surface of the electrode, so that the stability of the catalytic electrode for hydrogen evolution through water-electricity dissociation is poor. How to prepare a non-noble metal electrode material with good catalytic activity and wear resistance becomes a technical problem to be solved by the technical personnel in the field.
Disclosure of Invention
The invention aims to provide a method for preparing a cobalt-based alloy film with a special structure and a product, which are used for solving the problems in the prior art 2 O 3 The particles are subjected to composite electrodeposition and are corroded by NaOH solutionEtching to remove Al 2 O 3 The cobalt-based alloy film layer is formed by particles and has a special structure (the special structure and the original structure can be seen by comparing fig. 1-2 and fig. 8, and the surface of the aluminum oxide particles is left with a plurality of pores after being removed), and the film layer 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 schemes of the invention is as follows:
immersing a metal substrate material into an acidic composite plating solution for composite electrodeposition, and then immersing into an alkaline solution for soaking and corrosion to obtain the cobalt-based alloy film layer;
the preparation of the acidic composite plating solution comprises the following steps: mixing cobalt salt, tungsten salt and Al 2 O 3 And adding the particles into a solvent, mixing, and adjusting the pH value to be acidic to obtain the acidic composite plating solution.
The Co-W alloy film layer has compact structure, high hardness, good heat resistance and excellent wear resistance and corrosion resistance.
The alumina particles are removed by a corrosion method, so that a porous structure can be formed on the surface, the surface area is effectively increased, and the electrocatalytic performance of the catalyst is improved.
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 Al is 2 O 3 The concentration of the particles is 10-30 g/L; the pH value of the acidic composite plating solution is 4.5-6.0.
The coating thickness of the composite high-concentration alumina particles is lower than that of the low-concentration coating. The complexing agent can play a role in brightening, 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 as follows: constant current density of 10-50 mA/cm 2 Electrodeposition ofThe time is 30-60 min, and the electrodeposition temperature is 40-70 ℃.
Further, the alkaline solution comprises a NaOH solution; the concentration of the NaOH solution is 5-7 mol/L.
Further, the temperature of soaking corrosion is 60-80 ℃.
The second technical scheme of the invention is as follows: a cobalt-based alloy film layer prepared by the preparation method.
The third technical scheme of the invention is as follows: an application of the cobalt-based alloy film layer in preparing an electrode material.
The invention discloses the following technical effects:
(1) the acid composite plating solution is adopted to carry out composite electrodeposition on a substrate material, a Co-W alloy film layer with excellent mechanical performance can be formed, the Co-W alloy film layer is further immersed into a NaOH solution to be corroded, and finally a special structure cobalt-based alloy film layer with the thickness of 10-13 mu m is formed on the surface of the substrate, the surface of the composite film is smooth, the special structure is uniform, the friction coefficient is 0.5-0.8, and the thickness of the composite film is 10-100mA/cm 2 The hydrogen evolution overpotential is reduced (compared with 572mV of Co-W plating), and the catalytic performance is improved.
(2) The cobalt-based alloy film layer with the special structure prepared by the invention has the advantages of wear resistance and high hydrogen evolution performance.
(3) The invention adds Al on the basis of the prior cobalt salt and tungsten salt composite codeposition 2 O 3 The particles and the three substances are compositely Co-deposited under the action of complexing agent diammonium hydrogen citrate to prepare Co-W-Al 2 O 3 The composite film layer can improve the wear resistance of the film layer. Then corroding in NaOH solution to remove Al 2 O 3 And (4) granulating to obtain the cobalt-based alloy film with a special structure. The cobalt-based film layer has excellent performance, and the cobalt-based alloy film layer with a special structure is prepared by a degranulation method, so that the film layer has larger porosity, specific surface area and chemical activity, and the mechanical property and the catalytic property of the film layer are further improved. In addition, the invention adopts a composite electrodeposition and corrosion particle removal mode, and the obtained film layer has wear resistance and large specific surface area (has the advantages of wear resistance and large specific surface areaPorous structure, large specific surface area) and high hydrogen evolution performance.
(4) The method of the invention is suitable for preparing various electrode materials in electrocatalysis (which needs to have excellent hydrogen evolution performance and wear resistance).
(5) The invention adopts the composite electrodeposition and corrosion particle removal technology, and improves the hydrogen evolution performance and the mechanical property.
(6) The preparation method disclosed by the invention is simple to operate, clean and environment-friendly, is suitable for metal materials with complex shapes and blind holes, and is easy to industrialize.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a surface topography of a cobalt-based alloy film with a special structure prepared in example 1 of the present invention;
FIG. 2 is a surface topography of a cobalt-based alloy film with a special structure prepared in example 2 of the present invention;
FIG. 3 is a surface topography of a cobalt-based alloy film with a special structure prepared in example 3 of the present invention;
FIG. 4 is a surface topography of a cobalt-based alloy film with a special structure prepared in example 4 of the present invention;
FIG. 5 is a surface topography of a cobalt-based alloy film with a special structure prepared in example 5 of the present invention;
FIG. 6 is a surface topography of a cobalt-based alloy film with a special structure prepared in example 6 of the present invention;
FIG. 7 is a surface topography of a film prepared in comparative example 1 of the present invention;
FIG. 8 is a surface topography of a film prepared according to comparative example 2 of the present invention;
FIG. 9 is a surface topography of a film prepared in comparative example 3 of the present invention;
FIG. 10 is a surface topography of a film prepared in comparative example 4 of the present invention;
fig. 11 is a surface topography of a film layer prepared in comparative example 5 of the present invention.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, 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 belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and materials in connection with which they pertain. In case of conflict with any incorporated document, the present specification will control.
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 disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
Example 1
A preparation method of a cobalt-based alloy film with a special structure comprises the following steps:
(1) preparing an acidic composite plating solution: and sequentially adding cobalt sulfate, sodium tungstate, a complexing agent (diammonium hydrogen citrate) and alumina particles (the particle size is 1 mu m) into solvent water, mixing, dissolving and uniformly stirring to obtain the acidic composite plating solution.
Wherein the concentration of each component is respectively as follows: 0.1mol/L of cobalt sulfate, 0.1mol/L of sodium tungstate, 0.2mol/L of complexing agent (diammonium hydrogen citrate) and 20g/L of alumina particles. The temperature of the acidic composite plating solution is 60 ℃ constant temperature, and the pH value is 5.0.
(2) Immersing the metal substrate material into an acidic composite plating solution for composite electrodeposition (the composite electrodeposition is carried out under the condition of air stirring and adopts constant current density which is 20mA/cm 2 The electrodeposition time is 60min, the electrodeposition temperature is 60 ℃), and the film is taken out, washed by water and dried by cold air after the electrodeposition is finished; then immersing the substrate in a constant-temperature (80 ℃) reactor containing NaOH solution (with the concentration of 5mol/L), corroding for 60min under the stirring of air to remove alumina particles, taking out, washing with water, and drying with cold air to obtain the cobalt-based alloy film (the substrate material with the composite film) with the special structure.
The prepared cobalt-based alloy film layer with the special structure is placed under a scanning electron microscope to observe the surface appearance of the cobalt-based alloy film layer, and the result is shown in figure 1, and the obtained composite film layer is smooth in surface and uniform in special structure. The detection shows that the thickness of the obtained cobalt-based alloy film layer with the special structure is 13 mu m, the friction coefficient is 0.54 and is 10mA/cm 2 The hydrogen evolution overpotential of the corrosion is 532mV, which is reduced by 40mV compared with 572mV of the Co-W plating.
Example 2
A preparation method of a cobalt-based alloy film with a special structure comprises the following steps:
(1) preparing an acidic composite plating solution: and sequentially adding cobalt sulfate, sodium tungstate, a complexing agent (diammonium hydrogen citrate) and alumina particles (the particle size is 1 mu m) into solvent water, mixing, dissolving and uniformly stirring to obtain the acidic composite plating solution.
Wherein the concentration of each component is respectively as follows: 0.1mol/L of cobalt sulfate, 0.1mol/L of sodium tungstate, 0.2mol/L of complexing agent (diammonium hydrogen citrate) and 10g/L of alumina particles. The temperature of the acidic composite plating solution is 60 ℃ constant temperature, and the pH value is 5.0.
(2) Immersing the metal substrate material into an acidic composite plating solution for composite electrodeposition (the composite electrodeposition is carried out under the condition of air stirring and adopts constant current density which is 20mA/cm 2 The electrodeposition time is 60min, the electrodeposition temperature is 60 ℃), and the film is taken out, washed by water and dried by cold air after the electrodeposition is finished; then immersing the substrate in a constant-temperature (80 ℃) reactor containing NaOH solution (with the concentration of 5mol/L), corroding for 60min under the stirring of air to remove alumina particles, taking out, washing with water, and drying with cold air to obtain the cobalt-based alloy film (the substrate material with the composite film) with the special structure.
The prepared cobalt-based alloy film layer with the special structure is placed under a scanning electron microscope to observe the surface appearance of the cobalt-based alloy film layer, and the result is shown in figure 2, and the obtained composite film layer is smooth in surface and uniform in special structure. The detection shows that the thickness of the obtained cobalt-based alloy film layer with the special structure is 11 mu m, the friction coefficient is 0.53 and is 10mA/cm 2 The overpotential for hydrogen evolution is 567mV, which is reduced by 5mV compared to 572mV for the Co-W coating.
Example 3
A preparation method of a cobalt-based alloy film with a special structure comprises the following steps:
(1) preparing an acidic composite plating solution: and sequentially adding cobalt sulfate, sodium tungstate, a complexing agent (diammonium hydrogen citrate) and alumina particles (the particle size is 1 mu m) into solvent water, mixing, dissolving and uniformly stirring to obtain the acidic composite plating solution.
Wherein the concentration of each component is respectively as follows: 0.1mol/L of cobalt sulfate, 0.1mol/L of sodium tungstate, 0.2mol/L of complexing agent (diammonium hydrogen citrate) and 30g/L of alumina particles. The temperature of the acidic composite plating solution is 60 ℃ constant temperature, and the pH value is 5.0.
(2) Immersing the metal substrate material into an acidic composite plating solution for composite electrodeposition (the composite electrodeposition is carried out under the condition of air stirring and adopts constant current density which is 20mA/cm 2 The electro-deposition time is 60min, and the electro-deposition temperature is 60 DEG C) Taking out after the electrodeposition is finished, washing with water, and drying by cold air; then immersing the substrate in a constant-temperature (80 ℃) reactor containing NaOH solution (with the concentration of 5mol/L), corroding for 60min under the stirring of air to remove alumina particles, taking out, washing with water, and drying with cold air to obtain the cobalt-based alloy film (the substrate material with the composite film) with the special structure.
The prepared cobalt-based alloy film layer with the special structure is placed under a scanning electron microscope to observe the surface appearance of the cobalt-based alloy film layer, and the result is shown in figure 3, wherein the surface of the obtained composite film layer is flat and the special structure is uniform. The detection shows that the thickness of the obtained cobalt-based alloy film layer with the special structure is 10 mu m, the friction coefficient is 0.68 and is 10mA/cm 2 The overpotential for hydrogen evolution is 543mV, which is reduced by 29mV compared to 572mV for the Co-W coating.
Example 4
A preparation method of a cobalt-based alloy film with a special structure comprises the following steps:
(1) preparing an acidic composite plating solution: and sequentially adding cobalt sulfate, sodium tungstate, a complexing agent (diammonium hydrogen citrate) and alumina particles (with the particle size of 80nm) into solvent water, mixing, dissolving and uniformly stirring to obtain the acidic composite plating solution.
Wherein the concentration of each component is respectively as follows: 0.1mol/L of cobalt sulfate, 0.1mol/L of sodium tungstate, 0.2mol/L of complexing agent (diammonium hydrogen citrate) and 10g/L of alumina particles. The temperature of the acidic composite plating solution is 60 ℃ and the pH value is 5.0.
(2) Immersing the metal substrate material into an acidic composite plating solution for composite electrodeposition (the composite electrodeposition is carried out under the condition of air stirring and adopts constant current density which is 20mA/cm 2 The electrodeposition time is 60min, the electrodeposition temperature is 60 ℃), and the film is taken out, washed by water and dried by cold air after the electrodeposition is finished; then immersing the substrate in a constant-temperature (80 ℃) reactor containing NaOH solution (with the concentration of 5mol/L), corroding for 60min under the stirring of air to remove alumina particles, taking out, washing with water, and drying with cold air to obtain the cobalt-based alloy film (the substrate material with the composite film) with the special structure.
The prepared cobalt-based alloy film layer with the special structure is placed under a scanning electron microscope to observe the surface appearance of the cobalt-based alloy film layer, and the result is shown in figure 4As can be seen from the figure, the surface of the obtained composite film is flat and the special structure is uniform. The detection shows that the thickness of the obtained cobalt-based alloy film layer with the special structure is 12 mu m, the friction coefficient is 0.69 and is 10mA/cm 2 The overpotential for hydrogen evolution is 561mV, which is reduced by 11mV compared to 572mV for the Co-W coating.
Example 5
A preparation method of a cobalt-based alloy film with a special structure comprises the following steps:
(1) preparing an acidic composite plating solution: and sequentially adding cobalt sulfate, sodium tungstate, a complexing agent (diammonium hydrogen citrate) and alumina particles (with the particle size of 5 microns) into solvent water, mixing, dissolving and uniformly stirring to obtain the acidic composite plating solution.
Wherein the concentration of each component is respectively as follows: 0.1mol/L of cobalt sulfate, 0.1mol/L of sodium tungstate, 0.2mol/L of complexing agent (diammonium hydrogen citrate) and 20g/L of alumina particles. The temperature of the acidic composite plating solution is 60 ℃ constant temperature, and the pH value is 5.0.
(2) Immersing the metal substrate material into an acidic composite plating solution for composite electrodeposition (the composite electrodeposition is carried out under the condition of air stirring and adopts constant current density which is 20mA/cm 2 The electrodeposition time is 60min, the electrodeposition temperature is 60 ℃), and the film is taken out, washed by water and dried by cold air after the electrodeposition is finished; then immersing the substrate in a constant-temperature (80 ℃) reactor containing NaOH solution (with the concentration of 5mol/L), corroding for 60min under the stirring of air to remove alumina particles, taking out, washing with water, and drying with cold air to obtain the cobalt-based alloy film (the substrate material with the composite film) with the special structure.
The prepared cobalt-based alloy film layer with the special structure is placed under a scanning electron microscope to observe the surface appearance of the cobalt-based alloy film layer, and the result is shown in figure 5, and the obtained composite film layer is smooth in surface and uniform in special structure. The detection shows that the thickness of the obtained cobalt-based alloy film layer with the special structure is 12 mu m, the friction coefficient is 0.78 and is 10mA/cm 2 The hydrogen evolution overpotential of the corrosion is 559mV, which is reduced by 13mV compared with 572mV of the Co-W plating.
Example 6
A preparation method of a cobalt-based alloy film with a special structure comprises the following steps:
(1) preparing an acidic composite plating solution: and sequentially adding cobalt sulfate, sodium tungstate, a complexing agent (diammonium hydrogen citrate) and alumina particles (with the particle size of 5 microns) into solvent water, mixing, dissolving and uniformly stirring to obtain the acidic composite plating solution.
Wherein the concentration of each component is respectively as follows: 0.1mol/L of cobalt sulfate, 0.1mol/L of sodium tungstate, 0.2mol/L of complexing agent (diammonium hydrogen citrate) and 30g/L of alumina particles. The temperature of the acidic composite plating solution is 60 ℃ constant temperature, and the pH value is 5.0.
(2) Immersing the metal substrate material into an acidic composite plating solution for composite electrodeposition (the composite electrodeposition is carried out under the condition of air stirring and adopts constant current density which is 20mA/cm 2 The electrodeposition time is 60min, the electrodeposition temperature is 60 ℃), and the film is taken out, washed by water and dried by cold air after the electrodeposition is finished; then immersing the substrate in a constant-temperature (80 ℃) reactor containing NaOH solution (with the concentration of 5mol/L), corroding for 60min under the stirring of air to remove alumina particles, taking out, washing with water, and drying with cold air to obtain the cobalt-based alloy film (the substrate material with the composite film) with the special structure.
The prepared cobalt-based alloy film layer with the special structure is placed under a scanning electron microscope to observe the surface appearance of the cobalt-based alloy film layer, and the result is shown in figure 6, wherein the surface of the obtained composite film layer is flat and the special structure is uniform. The detection shows that the thickness of the obtained cobalt-based alloy film layer with the special structure is 11 mu m, the friction coefficient is 0.80 and is 10mA/cm 2 The hydrogen evolution overpotential of the corrosion is 562mV, which is reduced by 10mV compared with 572mV for the Co-W plating.
Comparative example 1
The difference from example 1 is that the composite electrodeposition was not carried out by etching by immersion in NaOH solution.
The prepared film layer is placed under a scanning electron microscope to observe the surface appearance of the film layer, and the result is shown in figure 7, wherein the surface of the obtained film layer is flat and the composite alumina particles can be seen. The thickness of the obtained film layer is 13 μm, the friction coefficient is 0.58, and the hydrogen evolution overpotential is 568 mV.
Comparative example 2
The difference from example 1 is that the acidic composite plating solution in step (1) does not contain alumina particles, and is not immersed in a NaOH solution for corrosion after composite electrodeposition.
The obtained film (Co-W coating) was observed under a scanning electron microscope to obtain a surface morphology, and the result is shown in FIG. 8, from which it can be seen that the obtained film has a smooth surface, is continuous and compact, and has no morphology. The thickness of the obtained film layer is 8 μm, the friction coefficient is 0.63, and the hydrogen evolution overpotential is 572 mV.
Comparative example 3
The difference from example 1 is that the alumina particles have a particle size of 30 nm.
The obtained film layer is placed under a scanning electron microscope to observe the surface appearance of the film layer, and the result is shown in figure 9, which shows that the obtained film layer has a smooth, continuous and uniform surface and an unobvious special structure. The obtained film layer has a thickness of 11 μm, a friction coefficient of 0.71 at 10mA/cm 2 The hydrogen evolution overpotential of 560mV compared to 572mV for the Co-W coating is reduced by 12 mV.
Comparative example 4
The difference from example 1 is that the current density of the composite electrodeposition is 100mA/cm 2 。
The surface morphology of the obtained composite film layer was observed under a scanning electron microscope, and the result is shown in fig. 10, which shows that the surface of the obtained composite film layer is flat and the special structure is uniform. The detection shows that the thickness of the obtained composite film layer is 10 mu m, the friction coefficient is 0.59 and the friction coefficient is 100mA/cm 2 The hydrogen evolution overpotential of the corrosion is 550mV, which is reduced by 22mV compared to 572mV for the Co-W coating.
Comparative example 5
The difference from example 1 is that the concentration of cobalt sulfate was 0.15 mol/L.
The obtained film layer was observed under a scanning electron microscope for surface morphology, and the result is shown in fig. 11, which shows that the obtained film layer has a smooth, continuous and uniform surface and an unobvious special structure. The obtained film layer has a thickness of 5 μm, a friction coefficient of 0.78 at 10mA/cm 2 Corrosion at a hydrogen evolution overpotential of 575mV, and CThe 572mV of the o-W plating layer is increased by 3 mV.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (10)
1. The preparation method of the cobalt-based alloy film layer is characterized by comprising the following steps of: immersing a metal substrate material into an acidic composite plating solution for composite electrodeposition, and then immersing into an alkaline solution for soaking and corrosion to obtain the cobalt-based alloy film layer;
the preparation of the acidic composite plating solution comprises the following steps: mixing cobalt salt, tungsten salt and Al 2 O 3 Adding the particles into a solvent, mixing, and adjusting the pH value to acidity to obtain the acidic composite plating solution.
2. The method for preparing the cobalt-based alloy film layer according to claim 1, wherein 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 Al is present in the acidic composite plating solution 2 O 3 The concentration of the particles is 10-30 g/L; the pH value of the acidic composite plating solution is 4.5-6.0.
3. The method of preparing a cobalt-based alloy film according to claim 1, wherein the cobalt salt is cobalt sulfate; the tungsten salt is sodium tungstate.
4. The method for preparing a cobalt-based alloy film according to claim 1, wherein the acidic composite plating solution further contains a complexing agent.
5. The method for preparing the 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 diammonium hydrogen citrate.
6. The method of preparing a cobalt-based alloy film layer of claim 1, wherein the conditions of the composite electrodeposition are: constant current density of 10-50 mA/cm 2 The electrodeposition time is 30-60 min, and the electrodeposition temperature is 40-70 ℃.
7. The method of preparing a cobalt-based alloy film layer of claim 1, wherein the alkaline solution comprises a NaOH solution; the concentration of the NaOH solution is 5-7 mol/L.
8. The method for preparing the cobalt-based alloy film layer according to claim 1, wherein the temperature of the soaking corrosion is 60-80 ℃.
9. A cobalt-based alloy film layer produced by the production method according to any one of claims 1 to 8.
10. Use of a cobalt-based alloy film layer according to claim 9 for the preparation of an electrode material.
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