CN115074792B - 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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- CN115074792B CN115074792B CN202210791961.3A CN202210791961A CN115074792B CN 115074792 B CN115074792 B CN 115074792B CN 202210791961 A CN202210791961 A CN 202210791961A CN 115074792 B CN115074792 B CN 115074792B
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- 229910000531 Co alloy Inorganic materials 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002131 composite material Substances 0.000 claims abstract description 87
- 239000000243 solution Substances 0.000 claims abstract description 64
- 238000007747 plating Methods 0.000 claims abstract description 52
- 230000002378 acidificating effect Effects 0.000 claims abstract description 46
- 238000004070 electrodeposition Methods 0.000 claims abstract description 45
- 239000002245 particle Substances 0.000 claims abstract description 42
- 239000000463 material Substances 0.000 claims abstract description 28
- 239000000758 substrate Substances 0.000 claims abstract description 17
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 12
- 239000000956 alloy Substances 0.000 claims abstract description 12
- 230000007797 corrosion Effects 0.000 claims abstract description 11
- 238000005260 corrosion Methods 0.000 claims abstract description 11
- 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
- 238000002156 mixing Methods 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 5
- 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 42
- 239000008139 complexing agent Substances 0.000 claims description 20
- 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
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000007772 electrode material Substances 0.000 claims description 6
- 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 15
- 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 24
- 238000003756 stirring Methods 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 229910020515 Co—W Inorganic materials 0.000 description 13
- 238000012876 topography Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000001514 detection method Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 238000005868 electrolysis reaction Methods 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
- 238000005406 washing Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 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
- 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
- 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
- 239000002659 electrodeposit Substances 0.000 description 1
- 238000001027 hydrothermal synthesis 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
- 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
Classifications
-
- 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 & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- 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 layer with a special structure and a product thereof, 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 corrosion to obtain the cobalt-base alloy film layer; the preparation of the acidic composite plating solution comprises the following steps: cobalt salt, tungsten salt and Al 2 O 3 And adding the particles into a solvent, mixing, and then adjusting the pH value to be acidic to obtain the acidic composite plating solution. The cobalt-based alloy film layer 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 layer with a special structure.
Background
Among the many clean energy sources, hydrogen energy is one of the most ideal energy carriers as an economical, efficient, sustainable green energy source, and has received increasing attention. Among the various hydrogen production technologies, water-electrolytic hydrogen production is considered one of the most efficient routes to "hydrogen economy". However, in practical application, the hydrogen production by water electrolysis often needs to overcome higher hydrogen evolution overpotential, thereby causing higher energy loss, and the application of the high-efficiency catalytic material is a technical key for breaking through the bottleneck in order to effectively solve the technical bottleneck of the too high hydrogen evolution overpotential by water electrolysis. At present, noble metal platinum and the alloy thereof are the most effective hydrogen evolution catalysts, but the defects of high price, rare resources, poor electrochemical stability and the like limit the large-scale application of the noble metal platinum and the alloy thereof, and the powdery catalyst is limited by the adhesive and the electrochemical stability. Therefore, there is a need to develop a non-noble metal electrode material having high mechanical strength and good catalytic activity.
Among the numerous non-noble metal electrocatalytic materials, transition metal phosphide is one of the hydrogen evolution electrocatalytic materials with high catalytic activity, good stability and good cost effectiveness due to the unique electronic structure and metalloid characteristics thereof, and has the potential to replace Pt-based electrocatalytic materials. At present, most phosphide catalytic materials used for water electrolysis hydrogen evolution are prepared by adopting a solution hydrothermal synthesis process and a high-temperature solid-phase reduction process, most of the phosphide catalytic materials are powder, the phosphide catalytic materials are required to be fully dispersed in a solvent, and then the phosphide catalytic materials are fixed on a conductive carrier by utilizing binders such as Nafion solution, polyvinylidene fluoride organic solution and the like, so that the catalyst loading capacity of a catalytic electrode is limited, the electric conductivity of the electrode material is reduced by the binders, and meanwhile, partial active sites of the catalyst are covered and shielded by the binders, so that the catalytic performance of the catalyst is 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 water electrolysis hydrogen evolution catalytic electrode 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 technicians in the field.
Disclosure of Invention
The invention aims to provide a preparation method and a product of a cobalt-base alloy film layer with a special structure, which solve the problems in the prior art 2 O 3 Particle composite electrodeposition, and removing Al by NaOH solution corrosion 2 O 3 The cobalt-based alloy film layer with a special structure (comparing fig. 1-2 with fig. 8, the special structure and the original structure can be seen, and the surface of the aluminum oxide particles is left to be porous after being removed) is formed by the particles, and the film layer has wear resistance and higher hydrogen evolution performance.
In order to achieve the above object, the present invention provides the following scheme
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 corrosion to obtain the cobalt-base alloy film layer;
the preparation of the acidic composite plating solution comprises the following steps: cobalt salt, tungsten salt and Al 2 O 3 And adding the particles into a solvent, mixing, and then 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 alumina particles 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 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 thickness of the coating 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, flattening 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 of 10-50 mA/cm 2 The electrodeposition 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 soaking corrosion temperature is 60-80 ℃.
The second technical scheme of the invention is as follows: the cobalt-based alloy film prepared by the preparation method.
The third technical scheme of the invention: an application of the cobalt-based alloy film layer in preparing electrode materials.
The invention discloses the following technical effects:
(1) The acidic composite plating solution is adopted to carry out composite electrodeposition on a substrate material, a Co-W alloy film layer with excellent mechanical property can be formed, the Co-W alloy film layer is further immersed into NaOH solution for corrosion, and finally, a cobalt-base alloy film layer with a special structure and a thickness of 10-13 mu m is formed on the surface of the substrate, and the surface of the composite film is flat and specialUniform structure, friction coefficient of 0.5-0.8, 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 wear resistance and higher hydrogen evolution performance.
(3) The invention adds Al based on the existing cobalt salt and tungsten salt composite codeposition 2 O 3 The particles and the three substances are compositely Co-deposited under the action of the complexing agent diammonium hydrogen citrate, so that Co-W-Al can be prepared 2 O 3 The wear resistance of the film layer can be improved by the composite film layer. Then corrosion-removing Al in NaOH solution 2 O 3 And (3) obtaining the cobalt-based alloy film with a special structure through the particles. The cobalt-based film layer has excellent performance, and the cobalt-based alloy film layer with a special structure is prepared by the particle removal method, so that the film layer has larger porosity, specific surface area and chemical activity, and the mechanical property and catalytic property of the film layer are further improved. In addition, the invention adopts a mode of composite electrodeposition and corrosion degranulation, and the obtained film layer has the advantages of wear resistance, large specific surface area (porous structure, large specific surface area), high hydrogen evolution performance and the like.
(4) The method is suitable for preparing various electrode materials in electrocatalysis (with excellent hydrogen evolution performance and wear resistance requirements).
(5) The invention adopts the composite electrodeposition and corrosion degranulation 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 that are 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 other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a surface topography of a cobalt-based alloy film layer of a specific structure prepared in example 1 of the present invention;
FIG. 2 is a surface topography of a cobalt-based alloy film layer of a specific structure prepared in example 2 of the present invention;
FIG. 3 is a surface topography of a cobalt-based alloy film layer of a particular structure prepared in example 3 of the present invention;
FIG. 4 is a surface topography of a cobalt-based alloy film layer of a particular structure prepared in example 4 of the present invention;
FIG. 5 is a surface topography of a cobalt-based alloy film layer of a particular structure prepared in example 5 of the present invention;
FIG. 6 is a surface topography of a cobalt-based alloy film layer of a particular structure prepared in example 6 of the present invention;
FIG. 7 is a surface topography of a film layer prepared in comparative example 1 of the present invention;
FIG. 8 is a surface topography of a film layer prepared in comparative example 2 of the present invention;
FIG. 9 is a surface topography of a film layer prepared in comparative example 3 of the present invention;
FIG. 10 is a surface topography of a film layer prepared in comparative example 4 of the present invention;
FIG. 11 is a surface topography of a film prepared in comparative example 5 of the present invention.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions 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. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the 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 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 for the purpose of disclosing and describing the methods and materials associated with the documents. 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 invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
Example 1
A preparation method of a cobalt-based alloy film layer with a special structure comprises the following steps:
(1) Preparing an acidic composite plating solution: sequentially adding cobalt sulfate, sodium tungstate, complexing agent (diammonium hydrogen citrate) and alumina particles (particle size of 1 μm) into solvent water, mixing, dissolving, and stirring uniformly to obtain the acidic composite plating solution.
Wherein the concentration of each component is respectively as follows: cobalt sulfate 0.1mol/L, sodium tungstate 0.1mol/L, complexing agent (diammonium hydrogen citrate) 0.2mol/L, and alumina particles 20g/L. 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 constant current density is adopted, wherein the current density is 20 mA/cm) 2 The electrodeposition time is 60min, the electrodeposition temperature is 60 ℃, and the product is taken out, washed and dried by cold air after the electrodeposition is finished; then is immersed in a solution containing NaAnd (3) in a constant-temperature (80 ℃) reactor with the concentration of OH solution being 5mol/L, corroding for 60min under air stirring to remove alumina particles, taking out, washing with water, and drying with cold air to obtain the cobalt-base alloy film layer (substrate material with composite film layer) with a special structure.
The prepared cobalt-based alloy film layer with the special structure is placed under a scanning electron microscope to observe the surface morphology, the result is shown in figure 1, and the obtained composite film layer has flat surface and uniform special structure as can be seen from the figure. Through detection, the thickness of the cobalt-based alloy film layer with the special structure is 13 mu m, the friction coefficient is 0.54, and the thickness is 10mA/cm 2 The hydrogen evolution overpotential was 532mV, which was 40mV lower than 572mV of the Co-W plating.
Example 2
A preparation method of a cobalt-based alloy film layer with a special structure comprises the following steps:
(1) Preparing an acidic composite plating solution: sequentially adding cobalt sulfate, sodium tungstate, complexing agent (diammonium hydrogen citrate) and alumina particles (particle size of 1 μm) into solvent water, mixing, dissolving, and stirring uniformly to obtain the acidic composite plating solution.
Wherein the concentration of each component is respectively as follows: cobalt sulfate 0.1mol/L, sodium tungstate 0.1mol/L, complexing agent (diammonium hydrogen citrate) 0.2mol/L, and alumina particles 10g/L. 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 constant current density is adopted, wherein the current density is 20 mA/cm) 2 The electrodeposition time is 60min, the electrodeposition temperature is 60 ℃, and the product is taken out, washed and dried by cold air after the electrodeposition is finished; then immersing the mixture into a constant-temperature (80 ℃) reactor containing NaOH solution (the concentration is 5 mol/L), corroding for 60 minutes under air stirring to remove alumina particles, taking out, washing with water, and drying with cold air to obtain the cobalt-based alloy film layer (the substrate material with the composite film layer) with the special structure.
The prepared cobalt-based alloy film with special structure is placed under a scanning electron microscope to observe the surface morphology, the result is shown in figure 2, and the obtained composite film has flat surface and special structure as can be seen from the figureAnd (5) uniformity. Through detection, the thickness of the cobalt-based alloy film layer with the special structure is 11 mu m, the friction coefficient is 0.53, and the thickness is 10mA/cm 2 The hydrogen evolution overpotential was 567mV, which was reduced by 5mV compared to 572mV of the Co-W plating.
Example 3
A preparation method of a cobalt-based alloy film layer with a special structure comprises the following steps:
(1) Preparing an acidic composite plating solution: sequentially adding cobalt sulfate, sodium tungstate, complexing agent (diammonium hydrogen citrate) and alumina particles (particle size of 1 μm) into solvent water, mixing, dissolving, and stirring uniformly to obtain the acidic composite plating solution.
Wherein the concentration of each component is respectively as follows: cobalt sulfate 0.1mol/L, sodium tungstate 0.1mol/L, complexing agent (diammonium hydrogen citrate) 0.2mol/L, and alumina particles 30g/L. 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 constant current density is adopted, wherein the current density is 20 mA/cm) 2 The electrodeposition time is 60min, the electrodeposition temperature is 60 ℃, and the product is taken out, washed and dried by cold air after the electrodeposition is finished; then immersing the mixture into a constant-temperature (80 ℃) reactor containing NaOH solution (the concentration is 5 mol/L), corroding for 60 minutes under air stirring to remove alumina particles, taking out, washing with water, and drying with cold air to obtain the cobalt-based alloy film layer (the substrate material with the composite film layer) 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 morphology, the result is shown in figure 3, and the obtained composite film layer has flat surface and uniform special structure as can be seen from the figure. Through detection, the thickness of the cobalt-based alloy film layer with the special structure is 10 mu m, the friction coefficient is 0.68, and the thickness is 10mA/cm 2 The hydrogen evolution overpotential was 543mV, which was reduced by 29mV compared to 572mV of the Co-W plating.
Example 4
A preparation method of a cobalt-based alloy film layer with a special structure comprises the following steps:
(1) Preparing an acidic composite plating solution: sequentially adding cobalt sulfate, sodium tungstate, complexing agent (diammonium hydrogen citrate) and alumina particles (with the particle size of 80 nm) into solvent water, mixing, dissolving and stirring uniformly to obtain the acidic composite plating solution.
Wherein the concentration of each component is respectively as follows: cobalt sulfate 0.1mol/L, sodium tungstate 0.1mol/L, complexing agent (diammonium hydrogen citrate) 0.2mol/L, and alumina particles 10g/L. 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 constant current density is adopted, wherein the current density is 20 mA/cm) 2 The electrodeposition time is 60min, the electrodeposition temperature is 60 ℃, and the product is taken out, washed and dried by cold air after the electrodeposition is finished; then immersing the mixture into a constant-temperature (80 ℃) reactor containing NaOH solution (the concentration is 5 mol/L), corroding for 60 minutes under air stirring to remove alumina particles, taking out, washing with water, and drying with cold air to obtain the cobalt-based alloy film layer (the substrate material with the composite film layer) 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 morphology, the result is shown in figure 4, and the obtained composite film layer has flat surface and uniform special structure as can be seen from the figure. Through detection, the thickness of the cobalt-based alloy film layer with the special structure is 12 mu m, the friction coefficient is 0.69, and the thickness is 10mA/cm 2 The hydrogen evolution overpotential was 561mV, which was reduced by 11mV compared to 572mV of the Co-W plating.
Example 5
A preparation method of a cobalt-based alloy film layer with a special structure comprises the following steps:
(1) Preparing an acidic composite plating solution: sequentially adding cobalt sulfate, sodium tungstate, complexing agent (diammonium hydrogen citrate) and alumina particles (particle size of 5 μm) into solvent water, mixing, dissolving, and stirring uniformly to obtain the acidic composite plating solution.
Wherein the concentration of each component is respectively as follows: cobalt sulfate 0.1mol/L, sodium tungstate 0.1mol/L, complexing agent (diammonium hydrogen citrate) 0.2mol/L, and alumina particles 20g/L. 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 constant current density is adopted, wherein the current density is 20 mA/cm) 2 The electrodeposition time is 60min, the electrodeposition temperature is 60 ℃, and the product is taken out, washed and dried by cold air after the electrodeposition is finished; then immersing the mixture into a constant-temperature (80 ℃) reactor containing NaOH solution (the concentration is 5 mol/L), corroding for 60 minutes under air stirring to remove alumina particles, taking out, washing with water, and drying with cold air to obtain the cobalt-based alloy film layer (the substrate material with the composite film layer) 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 morphology, the result is shown in figure 5, and the obtained composite film layer has flat surface and uniform special structure as can be seen from the figure. Through detection, the thickness of the cobalt-based alloy film layer with the special structure is 12 mu m, the friction coefficient is 0.78, and the thickness is 10mA/cm 2 The hydrogen evolution overpotential was 559mV, which was 13mV less than 572mV of the Co-W plating.
Example 6
A preparation method of a cobalt-based alloy film layer with a special structure comprises the following steps:
(1) Preparing an acidic composite plating solution: sequentially adding cobalt sulfate, sodium tungstate, complexing agent (diammonium hydrogen citrate) and alumina particles (particle size of 5 μm) into solvent water, mixing, dissolving, and stirring uniformly to obtain the acidic composite plating solution.
Wherein the concentration of each component is respectively as follows: cobalt sulfate 0.1mol/L, sodium tungstate 0.1mol/L, complexing agent (diammonium hydrogen citrate) 0.2mol/L, and alumina particles 30g/L. 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 constant current density is adopted, wherein the current density is 20 mA/cm) 2 The electrodeposition time is 60min, the electrodeposition temperature is 60 ℃, and the product is taken out, washed and dried by cold air after the electrodeposition is finished; then immersing in a constant temperature (80 ℃) reactor containing NaOH solution (the concentration is 5 mol/L), corroding for 60min under air stirring to remove alumina particles, taking out, and waterWashing and drying with cold air to obtain the cobalt-base alloy film layer (substrate material with composite film layer) with special structure.
The prepared cobalt-based alloy film layer with the special structure is placed under a scanning electron microscope to observe the surface morphology, the result is shown in figure 6, and the obtained composite film layer has flat surface and uniform special structure as can be seen from the figure. Through detection, the thickness of the cobalt-based alloy film layer with the special structure is 11 mu m, the friction coefficient is 0.80, and the thickness is 10mA/cm 2 The hydrogen evolution overpotential was 562mV, which was reduced by 10mV compared to 572mV of the Co-W plating.
Comparative example 1
The difference from example 1 is that the composite electrodeposit is not immersed in NaOH solution for etching.
The surface morphology of the prepared film layer is observed under a scanning electron microscope, the result is shown in figure 7, and the surface of the film layer is flat and the composite alumina particles are visible. The thickness of the obtained film layer was measured to be 13 μm, the friction coefficient was 0.58, and the hydrogen evolution overpotential was 568mV.
Comparative example 2
The difference from example 1 is that the acidic composite plating solution in step (1) does not contain alumina particles, and the composite electrodeposition is not immersed in NaOH solution for etching.
The surface morphology of the obtained film layer (Co-W coating) is observed under a scanning electron microscope, the result is shown in figure 8, and the obtained film layer has a flat surface, is continuous and compact, and does not need a shape morphology. The thickness of the obtained film was 8 μm, the coefficient of friction was 0.63, and the hydrogen evolution overpotential was 572mV.
Comparative example 3
The difference from example 1 is that the particle size of the alumina particles is 30nm.
The surface morphology of the obtained film layer is observed under a scanning electron microscope, the result is shown in figure 9, and the obtained film layer has flat, continuous and uniform surface and unobvious special structure as can be seen from the figure. The film layer obtained by the detection has a thickness of 11 μm and a friction coefficient of 0.71 at 10mA/cm 2 Is corroded at a current density of 560mV hydrogen evolution overpotential and CThe o-W coating was reduced by 12mV compared to 572mV.
Comparative example 4
As in example 1, the difference is that the current density of the composite electrodeposition is 100mA/cm 2 。
The surface morphology of the obtained composite film layer is observed under a scanning electron microscope, and the result is shown in figure 10, and the obtained composite film layer has flat surface and uniform special structure as can be seen from the figure. The thickness of the obtained composite film layer is 10 mu m, the friction coefficient is 0.59, and the film layer is 100mA/cm 2 The hydrogen evolution overpotential was 550mV, which was reduced by 22mV compared to 572mV of the Co-W plating.
Comparative example 5
The difference is that the concentration of cobalt sulfate is 0.15mol/L as in example 1.
The surface morphology of the obtained film layer is observed under a scanning electron microscope, the result is shown in figure 11, and the obtained film layer has flat, continuous and uniform surface and unobvious special structure as can be seen from the figure. The film layer obtained by detection has a thickness of 5 μm and a friction coefficient of 0.78 at 10mA/cm 2 The hydrogen evolution overpotential was 575mV, which was increased by 3mV compared to 572mV of the Co-W plating.
The above embodiments are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the protection scope defined by the claims of the present invention without departing from the design spirit of the present invention.
Claims (9)
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 corrosion to obtain the cobalt-base alloy film layer;
the preparation of the acidic composite plating solution comprises the following steps: cobalt salt, tungsten salt and Al 2 O 3 Adding the particles into a solvent, mixing, and then adjusting the pH value to be acidic to obtain the acidic composite plating solution;
the concentration of cobalt salt in the acidic composite plating solution is 0.1mol/L, the concentration of tungsten salt is 0.1mol/L, and Al 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.
2. The method for producing a cobalt-based alloy film according to claim 1, wherein the cobalt salt is cobalt sulfate; the tungsten salt is sodium tungstate.
3. The method for producing a cobalt-based alloy film according to claim 1, wherein the acidic composite plating solution further contains a complexing agent.
4. The method for producing a cobalt-based alloy film according to claim 3, wherein the concentration of the complexing agent in the acidic composite plating solution is 0.2 to 0.4mol/L; the complexing agent is diammonium hydrogen citrate.
5. The method for preparing a cobalt-based alloy film according to 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 ℃.
6. The method for producing 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.
7. The method for producing a cobalt-based alloy film according to claim 1, wherein the soaking corrosion temperature is 60 to 80 ℃.
8. A cobalt-based alloy film layer produced by the production method according to any one of claims 1 to 7.
9. Use of the cobalt-based alloy film layer of claim 8 in the preparation of an electrode material.
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| CN102605386A (en) * | 2012-02-29 | 2012-07-25 | 华侨大学 | Method for preparing Ni/NiCo2O4 porous composite electrode for alkaline medium oxygen evolution |
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