Electroplating cobalt additives and methods of use
By using electroplating cobalt additives containing grain refining agents, leveling agents and movers during the electroplating process, the problems of high strength of cobalt plating but poor ductility and large internal tension stress are solved, and the high refinement of the plating is achieved , uniformity and strong bonding force.
Patent Information
- Application Number
- CN202411443527.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-16
- Publication Date
- 2025-02-18
AI Technical Summary
In the prior art, the cobalt plating layer without additives has high strength but poor ductility, and has a large internal tension stress, which affects the uniformity of the plating layer and its binding force with the substrate.
Use electroplating cobalt additives, including grain refining agents (such as alkynol compounds), leveling agents (such as benzenesulfonamide compounds) and positioning agents (such as unsaturated sodium sulfonate) to improve grain fineness of the coating degree of transformation, leveling and bonding.
The grain refinement degree of the coating cobalt is significantly improved, the leveling of the low-zone coating is improved, and the bonding force between the coating is enhanced and the substrate is enhanced, and the uniformity and wear resistance of the coating are improved.
Smart Images
Figure CN119465317A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the field of electrochemical technology, and in particular to an electroplating cobalt additive and a use method thereof. Background Art
[0002] Cobalt can maintain high strength at high temperatures, and has high thermal conductivity, electrical conductivity and strong ferromagnetism. It is an important raw material for the production of heat-resistant alloys, hard alloys, corrosion-resistant alloys, magnetic alloys and various cobalt salts. The amount of electroplated cobalt accounts for about 1% to 3% of the total amount of cobalt. Electroplating refers to the process of forming a uniform and dense metal layer on the pre-plated metal surface by electrochemical methods in an electrolyte solution containing metal salts, with the plated metal or insoluble metal as the anode. Electroplating cobalt can not only improve the chemical stability of the metal surface, but also improve the hardness, wear resistance and electrical conductivity of the metal surface. Therefore, compared with other metal coatings, it is more suitable for the manufacture of mechanical parts, electronic equipment, solar cells, etc. For example, when preparing solar cell electrode materials, the high thermal conductivity of cobalt can be used to improve the thermal conduction efficiency of solar cells and improve the photoelectric conversion efficiency. In addition, the high thermal conductivity of cobalt can also improve the thermal stability of solar cells and reduce their failure risk in high temperature environments.
[0003] The electroplating process of metals can generally be divided into three steps. First, the particles of the electroactive material migrate to the outer Helmholtz layer near the cathode for electrosorption; then the cathode charge is transferred to the partially desolvated ions or simple ions adsorbed on the electrode to form adsorbed atoms; finally, the adsorbed atoms migrate on the electrode surface until they are incorporated into the lattice. The first process mentioned above will produce a certain overpotential. Only under the appropriate overpotential can the electrodeposition process of the metal have a sufficiently high grain nucleation rate, a medium charge migration rate and a sufficiently high crystallization overpotential, thereby ensuring that the coating is flat, dense and shiny, and firmly bonded to the base material. In order to ensure the quality of the coating, in addition to the basic components of the electroplating solution, the metal salt to be plated (main salt) and the complexing agent, conductive salt, pH adjustment salt, etc., a complete electroplating formula must also have various newly added ingredients. The amount of these ingredients is very small, but the effect is very large. If many electroplating solutions do not have these ingredients added, it is impossible to plate qualified and valuable coatings. These various chemical substances added to the plating tank are collectively referred to as electroplating additives.
[0004] Electroplating additives can be roughly divided into two categories: inorganic additives and organic additives. Now, organic additives are basically the main ones. They can be subdivided into brighteners, auxiliary brighteners, crystal refiners, softeners, and displacement agents. Additives with different functions generally have different structural characteristics and mechanisms of action, but multifunctional additives are also common. For example, saccharin can be used as a nickel plating brightener and a commonly used stress reliever; and additives with different functions may also follow the same mechanism of action. Appropriate electroplating additives can increase the overpotential of metal electrodeposition and provide a strong guarantee for the quality of the coating.
[0005] Generally, the strength of the cobalt coating obtained without additives is greater than that of the nickel coating, but the ductility is worse than that of the nickel coating, and the cobalt coating obtained by the plating tank without additives has internal tensile stress, and the internal tensile stress value under certain conditions may be very large. Therefore, the development of electroplating cobalt additives to obtain a certain thickness and uniform and fine coating, while improving the bonding strength between the coating and the substrate, is of great significance in the development and application of functional materials and structural materials with high wear resistance and high corrosion resistance.
[0006] The defects of the prior art are:
[0007] 1. The strength of the cobalt coating obtained without additives is greater than that of the nickel coating, but the ductility is worse than that of the nickel coating.
[0008] 2. The cobalt coating obtained by the plating tank without additives has internal tensile stress, and the value of internal tensile stress under certain conditions may be very large. Summary of the invention
[0009] In view of the above problems, the present invention provides an electroplating cobalt additive and a method of using the same, the purpose of which is to significantly improve the grain refinement of the cobalt in the coating, improve the flatness of the low area of the coating, and improve the bonding strength between the coating and the substrate while obtaining a uniform and fine coating of a certain thickness.
[0010] To solve the above problems, the technical solution provided by the present invention is:
[0011] An electroplating cobalt additive, comprising a grain refiner, a leveler and a displacement agent; the electroplating cobalt additive is used for electroplating cobalt;
[0012] The grain refiner is an acetylene alcohol compound; the leveler is a benzenesulfonamide compound or a benzenesulfonic acid compound; and the displacement agent is an unsaturated sodium sulfonate.
[0013] Preferably, the grain refiner is 1,4-butynediol, or diethoxybutynediol, or propoxybutynediol, or ethoxypropynyl alcohol, or propoxypropynyl alcohol.
[0014] Preferably, the leveler is benzenesulfinic acid, or 1,3,6-naphthalenetrisulfonic acid, or p-toluenesulfonamide, or o-sulfonylbenzeneimide, or bis-benzenesulfonimide.
[0015] Preferably, the displacement agent is sodium allyl sulfonate, sodium propynyl sulfonate, or sodium vinyl sulfonate.
[0016] A method for using the electroplating cobalt additive comprises the following steps:
[0017] S100. Prepare basic cobalt electroplating solution;
[0018] S200. Adding the compounded cobalt electroplating additive;
[0019] S300. Placing the electroplating cobalt solution containing the electroplating cobalt additive in an electroplating tank; then using an insoluble titanium mesh and a soluble cobalt plate as an anode and a plated object as a cathode, turning on a power source, and performing electroplating.
[0020] Preferably, the basic cobalt electroplating solution in step S100 contains a soluble cobalt salt and boric acid; and the pH value of the basic cobalt electroplating solution is adjusted within a range of 3 to 4.
[0021] Preferably, the soluble cobalt salt is anhydrous cobalt chloride.
[0022] Preferably, the content of the anhydrous cobalt chloride is between 40 g / L and 60 g / L; the content of the boric acid is between 10 g / L and 40 g / L.
[0023] Preferably, the content of the grain refiner in the electroplating cobalt additive compounded in step S200 is in the range of 0.02 g / L to 0.05 g / L, the content of the leveler is in the range of 0.02 g / L to 0.1 g / L, and the content of the moving agent is in the range of 2 g / L to 5 g / L.
[0024] Preferably, the temperature range of electroplating is 55°C to 60°C.
[0025] Compared with the prior art, the present invention has the following advantages:
[0026] 1. Since the present invention uses an electroplating cobalt additive, the grain refinement of the cobalt in the coating is significantly improved, and the leveling of the low area of the coating is improved.
[0027] 2. Since the present invention uses electroplating cobalt additives, a uniform and fine coating of a certain thickness is obtained, and the bonding force between the coating and the substrate is improved, which is of great significance in the development and application of functional materials and structural materials with high wear resistance and high corrosion resistance. BRIEF DESCRIPTION OF THE DRAWINGS
[0028] Figure 1A schematic diagram of a scanning electron microscope image of a cobalt coating obtained by using a basic cobalt electroplating solution according to a specific embodiment of the present invention;
[0029] Figure 2 It is a schematic diagram of a scanning electron microscope image of a cobalt coating obtained after adding a grain refiner to a basic cobalt electroplating solution of a specific embodiment of the present invention;
[0030] Figure 3 It is a schematic diagram of a scanning electron microscope image of a cobalt coating obtained after adding a grain refiner and a displacement agent to a basic cobalt electroplating solution of a specific embodiment of the present invention;
[0031] Figure 4 A schematic diagram of a scanning electron microscope image of a cobalt coating obtained by adding a grain refiner and a leveler to a basic cobalt electroplating solution according to a specific embodiment of the present invention;
[0032] Figure 5 This is a schematic diagram of a scanning electron microscope image of a cobalt coating obtained after a grain refiner, a leveler and a displacement agent are added to a basic cobalt electroplating solution according to a specific embodiment of the present invention. DETAILED DESCRIPTION
[0033] The present invention is further explained below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not used to limit the scope of the present invention. After reading the present invention, various equivalent forms of modifications to the present invention by those skilled in the art all fall within the scope defined by the claims attached to this application.
[0034] Embodiment 1:
[0035] Electroplating cobalt additives include grain refiners, levelers and moving agents; electroplating cobalt additives are used for electroplating cobalt.
[0036] The grain refiner is an acetylene alcohol compound; the leveler is a benzenesulfonamide compound or a benzenesulfonic acid compound; and the displacement agent is an unsaturated sodium sulfonate.
[0037] It should be noted that the grain refiner is 1,4-butynediol, or diethoxybutynediol, or propoxybutynediol, or ethoxypropynyl alcohol, or propoxypropynyl alcohol.
[0038] It should be noted that the leveling agent is benzenesulfinic acid, or 1,3,6-naphthalenetrisulfonic acid, or p-toluenesulfonamide, or o-sulfonylbenzeneimide, or bisbenzenesulfonimide.
[0039] It should be noted that the displacement agent is sodium allyl sulfonate, sodium propynyl sulfonate, or sodium vinyl sulfonate.
[0040] A method for using a cobalt electroplating additive comprises the following steps:
[0041] S100. Prepare basic cobalt electroplating solution.
[0042] S200. Add compounded cobalt electroplating additive.
[0043] S300. Placing a cobalt electroplating solution containing a cobalt electroplating additive in an electroplating tank; then using an insoluble titanium mesh and a soluble cobalt plate as an anode and a plated object as a cathode, turning on a power source, and performing electroplating.
[0044] In this specific embodiment, the basic electroplating cobalt solution in step S100 contains soluble cobalt salt and boric acid; the pH value of the basic electroplating cobalt solution is adjusted in the range of 3 to 4.
[0045] It should be noted that the soluble cobalt salt is anhydrous cobalt chloride.
[0046] In this specific embodiment, the content of anhydrous cobalt chloride is in the range of 40 g / L to 60 g / L; the content of boric acid is in the range of 10 g / L to 40 g / L.
[0047] In this specific embodiment, the content of the grain refiner in the compounded cobalt electroplating additive in step S200 is in the range of 0.02 g / L to 0.05 g / L, the content of the leveler is in the range of 0.02 g / L to 0.1 g / L, and the content of the moving agent is in the range of 2 g / L to 5 g / L.
[0048] In this specific embodiment, the temperature range of electroplating is 55° C. to 60° C. The current density is adjusted as needed.
[0049] The components, contents and pH values of the cobalt electroplating solution of this embodiment are as follows:
[0050] Basic cobalt electroplating solution: CoCl2, 60g / L; Boric acid: 10g / L
[0051] pH value: pH = 4
[0052] Specific steps: first weigh CoCl2·6H2O and add it to water, stir it, and add boric acid after it is fully dissolved. Then adjust the pH to 4 with hydrochloric acid and sodium hydroxide to obtain an electroplating solution.
[0053] Electroplating is carried out with the cobalt sheet as the anode and the stainless steel plate as the cathode.
[0054] The electroplating conditions are: current density 1ASD, electroplating temperature 55°C, and electroplating time 2min.
[0055] The coating was peeled off and observed by scanning electron microscope. The results are as follows: Figure 1 As shown, the particle size is relatively large and is convex.
[0056] Embodiment 2:
[0057] The components, contents and pH values of the cobalt electroplating solution of this embodiment are as follows:
[0058] Basic cobalt electroplating solution: CoCl2, 60g / L; Boric acid: 10g / L
[0059] pH value: pH = 4
[0060] Electroplating cobalt additive: 0.02g / L grain refiner
[0061] Specific steps: first weigh CoCl2·6H2O and add it to water, stir it, and add boric acid after it is fully dissolved. Then adjust the pH to 4 with hydrochloric acid and sodium hydroxide to obtain a basic electroplating solution, then add the electroplating cobalt additive and stir it evenly. The electroplating cobalt additive is a grain refiner, specifically butynediol diethoxy ether.
[0062] Electroplating is carried out with the cobalt sheet as the anode and the stainless steel plate as the cathode.
[0063] The electroplating conditions are: current density 1ASD, electroplating temperature 55°C, and electroplating time 2min.
[0064] The coating was peeled off and observed by scanning electron microscope. The results are as follows: Figure 2 As shown, compared with the cobalt coating without additives, the grains are obviously refined.
[0065] Embodiment 3:
[0066] The components, contents and pH values of the cobalt electroplating solution of this embodiment are as follows:
[0067] Basic cobalt electroplating solution: CoCl2, 60g / L; Boric acid: 10g / L
[0068] pH value: pH = 4
[0069] Electroplating cobalt additives: 0.02g / L grain refiner and 5g / L displacement agent
[0070] Specific steps: first weigh CoCl2·6H2O and add it to water, stir it, and add boric acid after it is fully dissolved. Then adjust the pH to 4 with hydrochloric acid and sodium hydroxide to obtain a basic electroplating solution, then add the electroplating cobalt additive and stir evenly. The grain refiner is specifically butynediol diethoxy ether, and the displacement agent is specifically sodium allyl sulfonate.
[0071] Electroplating is carried out with the cobalt sheet as the anode and the stainless steel plate as the cathode.
[0072] The electroplating conditions are: current density 1ASD, electroplating temperature 55°C, and electroplating time 2min.
[0073] The coating was peeled off and observed by scanning electron microscope. The results are as follows: Figure 3 As shown in the figure, after adding grain refiner and displacement agent, the coating presents a wire mesh structure.
[0074] Example 4
[0075] The components, contents and pH values of the cobalt electroplating solution of this embodiment are as follows:
[0076] Basic cobalt electroplating solution: CoCl2, 60g / L; Boric acid: 10g / L
[0077] pH value: pH = 4
[0078] Electroplating cobalt additives: 0.02g / L grain refiner and 0.02g / L leveler
[0079] Specific steps: first weigh CoCl2·6H2O and add it to water, stir it, and add boric acid after it is fully dissolved. Then adjust the pH to 4 with hydrochloric acid and sodium hydroxide to obtain a basic electroplating solution, then add the electroplating cobalt additive and stir evenly. The grain refiner is specifically butynediol diethoxy ether, and the leveler is specifically bisbenzenesulfonimide.
[0080] Electroplating is carried out with the cobalt sheet as the anode and the stainless steel plate as the cathode.
[0081] The electroplating conditions are: current density 1ASD, electroplating temperature 55°C, and electroplating time 2min.
[0082] The coating was peeled off and observed by scanning electron microscope. The results are as follows: Figure 4 As shown, the plating is fine and dense.
[0083] Example 5
[0084] The components, contents and pH values of the cobalt electroplating solution of this embodiment are as follows:
[0085] Basic cobalt electroplating solution: CoCl2, 60g / L; Boric acid: 10g / L
[0086] pH value: pH = 4
[0087] Electroplating cobalt additives: 0.02g / L grain refiner, 0.02g / L leveler and 5g / L moving agent
[0088] Specific steps: first weigh CoCl2·6H2O and add it to water, stir it, and add boric acid after it is fully dissolved. The pH is adjusted to 4 by hydrochloric acid and sodium hydroxide to obtain a basic electroplating solution, and then the electroplating cobalt additive is added and stirred evenly. The grain refiner is specifically butynediol diethoxy ether, the leveler is specifically bisbenzenesulfonimide, and the positioning agent is specifically sodium allyl sulfonate.
[0089] Electroplating is carried out with the cobalt sheet as the anode and the stainless steel plate as the cathode.
[0090] The electroplating conditions are: current density 1ASD, electroplating temperature 55°C, and electroplating time 2min.
[0091] The coating was peeled off and observed by scanning electron microscope. The results are as follows: Figure 5 As shown, the coating is finer and denser than that in Example 4.
[0092] In the above detailed description, various features are grouped together in a single embodiment to simplify the disclosure. This method of disclosure should not be interpreted as reflecting an intention that the embodiments of the claimed subject matter require more features than are clearly stated in each claim. On the contrary, as reflected in the appended claims, the invention is in a state of having less than all the features of the disclosed individual embodiments. Therefore, the appended claims are hereby expressly incorporated into the detailed description, with each claim standing on its own as a separate preferred embodiment of the invention.
[0093] The disclosed embodiments are described above to enable any person skilled in the art to implement or use the present invention. Various modifications of these embodiments are obvious to those skilled in the art, and the general principles defined herein may also be applied to other embodiments without departing from the spirit and scope of the present disclosure. Therefore, the present disclosure is not limited to the embodiments given herein, but is consistent with the broadest scope of the principles and novel features disclosed in this application.
[0094] The above description includes examples of one or more embodiments. Of course, it is not possible to describe all possible combinations of components or methods for the purpose of describing the above embodiments, but it should be recognized by those skilled in the art that the various embodiments may be further combined and arranged. Therefore, the embodiments described herein are intended to cover all such changes, modifications and variations that fall within the scope of protection of the appended claims. In addition, with respect to the term "comprising" used in the specification or claims, the word is covered in a manner similar to the term "including", just as "including," is explained as a transitional word in the claims. In addition, any term "or" used in the specification of the claims is intended to mean "non-exclusive or".
[0095] The specific implementation methods described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific implementation method of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.
Claims
1. A cobalt electroplating additive, characterized in that: It contains a grain refiner, a leveler and a displacement agent; the electroplating cobalt additive is used for electroplating cobalt; The grain refiner is an acetylene alcohol compound; the leveler is a benzenesulfonamide compound or a benzenesulfonic acid compound; and the displacement agent is an unsaturated sodium sulfonate.
2. The cobalt electroplating additive according to claim 1, characterized in that: The grain refiner is 1,4-butynediol, or diethoxybutynediol, or propoxybutynediol, or ethoxypropynyl alcohol, or propoxypropynyl alcohol.
3. The cobalt electroplating additive according to claim 2, characterized in that: The leveling agent is benzenesulfinic acid, or 1,3,6-naphthalenetrisulfonic acid, or p-toluenesulfonamide, or o-sulfonylbenzeneimide, or bis-benzenesulfonimide.
4. The cobalt electroplating additive according to claim 3, characterized in that: The displacement agent is sodium allyl sulfonate, sodium propynyl sulfonate, or sodium vinyl sulfonate.
5. A method for using the electroplating cobalt additive according to claim 4, characterized in that: The following steps are involved: S100. Prepare basic cobalt electroplating solution; S200. Adding the compounded cobalt electroplating additive; S300. Placing the electroplating cobalt solution containing the electroplating cobalt additive in an electroplating tank; then using an insoluble titanium mesh and a soluble cobalt plate as an anode and a plated object as a cathode, turning on a power source, and performing electroplating.
6. The method for using the cobalt electroplating additive according to claim 5, characterized in that: The basic electroplating cobalt solution in step S100 contains soluble cobalt salt and boric acid; the pH value of the basic electroplating cobalt solution is adjusted to a range of 3 to 4.
7. The method for using the cobalt electroplating additive according to claim 6, characterized in that: The soluble cobalt salt is anhydrous cobalt chloride.
8. The method for using the cobalt electroplating additive according to claim 7, characterized in that: The content range of the anhydrous cobalt chloride is 40g / L to 60g / L; the content range of the boric acid is 10g / L to 40g / L.
9. The method for using the cobalt electroplating additive according to claim 8, characterized in that: The content of the grain refiner in the electroplating cobalt additive compounded in step S200 is in the range of 0.02 g / L to 0.05 g / L, the content of the leveler is in the range of 0.02 g / L to 0.1 g / L, and the content of the moving agent is in the range of 2 g / L to 5 g / L.
10. The method for using the cobalt electroplating additive according to claim 9, characterized in that: The temperature range of electroplating is 55℃~60℃.