CN111501071A - Nickel electrodeposition layer and workpiece comprising same - Google Patents
Nickel electrodeposition layer and workpiece comprising same Download PDFInfo
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- CN111501071A CN111501071A CN202010457744.1A CN202010457744A CN111501071A CN 111501071 A CN111501071 A CN 111501071A CN 202010457744 A CN202010457744 A CN 202010457744A CN 111501071 A CN111501071 A CN 111501071A
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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
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
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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
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
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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
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/10—Electrodes, e.g. composition, counter electrode
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/531—Electrode connections inside a battery casing
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention provides a nickel electrodeposition layer and a workpiece comprising the same, wherein the nickel electrodeposition layer comprises nickel metal particles, the particle size of the nickel metal particles is 10-250 nm, and the nickel electrodeposition layer is prepared by adopting a nickel electrodeposition solution through an electrodeposition method. The nickel electrodeposition solution is a solution of an ammonia system, compared with the solution of an acidic system for electrodeposition, the ammonia system is an alkaline system, acid mist is not generated in the electrodeposition process, and the anode reaction is a nitrogen separation reaction, so that the nickel electrodeposition solution has no corrosion pollution to the environment; free H in ammoniacal systems+No hydrogen evolution side reaction is generated on the ions and the cathode, the current efficiency is high, the deposition of the nickel on the cathode plate is more stable and uniform, and the obtained nickel electrodeposition layerHas good uniformity and high density, thereby greatly improving the wear resistance, the corrosion resistance and the like of the nickel-plated plate.
Description
Technical Field
The invention belongs to the field of metal surface treatment, relates to a method for electrodepositing a metal coating on the surface of a metal substrate, and particularly relates to a nickel electrodeposition layer and a workpiece comprising the nickel electrodeposition layer.
Background
Nickel is a silver white metal, has good corrosion resistance and extremely high wear resistance, and is widely used for preparing corrosion-resistant alloys and wear-resistant alloys, such as nickel-plated copper tabs for lithium batteries; are also commonly used in hydrogenation catalysts, ceramic articles, electronic circuitry, and nickel compound production, among others.
At present, the electrodeposition of nickel usually adopts an acidic system, namely nickel sulfate or nickel chloride and the like are used as main salts, boric acid or other weak acids are used as buffering agents, other additives are added, and the nickel is prepared by deposition according to certain electrodeposition process parameters after uniform mixing. However, the method is easy to generate a large amount of acid mist, and brings great pollution to the working environment; meanwhile, hydrogen ions existing in an acidic system easily obtain electrons on a cathode plate so as to generate a side reaction of hydrogen evolution, so that the current efficiency is lower than 95%; the separation of hydrogen gas easily causes the nickel deposition layer to be loose and porous, the structure compactness is poor, the corrosion resistance is poor and the like; in addition, chlorine gas formed by the reaction of the chloride ions on the anode plate may further deteriorate the production environment and bring great physical harm to operators.
Disclosure of Invention
In order to solve the defects in the conventional nickel electrodeposition process by an acid system, the invention provides a nickel electrodeposition layer and a workpiece comprising the nickel electrodeposition layer.
The purpose of the invention is realized by the following technical scheme:
a nickel electrodeposition layer, wherein the nickel electrodeposition layer comprises nickel metal particles, and the particle size of the nickel metal particles is 10-250 nm.
According to the invention, the wear of the nickel electrodeposition layer is 6 to 10 mg/h.
According to the invention, the hardness of the nickel electrodeposition layer is more than or equal to 110HV, such as 110-200 HV.
The invention also provides a preparation method of the nickel electrodeposition layer, wherein the method comprises the following steps:
electrodepositing nickel electrodeposition liquid to prepare the nickel electrodeposition layer;
wherein the nickel electrodeposition bath comprises ammonia, a nickel salt, a first additive and a second additive; wherein the first additive is selected from animal glue; the second additive is selected from ammonium salts.
According to the invention, the first additive is selected from animal glue, the animal glue is selected from one, two or three of bone glue, skin glue and gelatin, and the adding amount of the first additive is 0.5-5 g/L.
According to the invention, the ammonium salt is selected from one of the following compounds of formula (I):
in the formula (I), R1、R2、R3And R4Identical or different, independently from each other, from alkyl and aryl-substituted alkyl; x is selected from halogen.
According to the invention, the ammonium salt is selected from one, two or more of cetyl trimethyl ammonium bromide, benzyl triethyl ammonium chloride, tetrabutyl ammonium bromide and tetrabutyl ammonium chloride.
According to the invention, the second additive is added in an amount of 0.2 to 1.0 g/L.
According to the invention, the aqueous ammonia (NH)3·H2O) concentration of 2.0-5.0 mol/L.
According to the invention, the nickel salt is selected from nickel chloride, or a combination of nickel chloride and nickel oxide.
According to the present invention, Ni is contained in the nickel electrodeposition bath2+The amount of (B) is 25-100 g/L.
According to the invention, the temperature of the electrodeposition is 35-65 ℃; the time of the electrodeposition is 0.5-8h, the electrodeposition adopts a direct current electrodeposition mode, and the current density is 250-600A/m2。
According to the invention, the electrodeposited cathode plate is made of a steel substrate, a titanium substrate, a copper substrate, an aluminum substrate or the like. For example, carbon steel or alloy steel, or oxygen-free copper for the copper tab of the lithium battery.
According to the invention, the electrodeposited anode plate is a graphite plate.
According to the invention, the distance between the cathode plate and the anode plate is 3-5 cm.
The workpiece comprises a workpiece substrate and a nickel layer on the surface of the workpiece substrate, wherein the nickel layer is the nickel electrodeposition layer.
According to the invention, the substrate is, for example, a steel substrate, a titanium substrate, a copper substrate, an aluminum substrate or the like. Specifically, for example, carbon steel or alloy steel, or oxygen-free copper for a copper tab of a lithium battery.
According to the invention, the workpiece is a tab for a lithium battery, which comprises oxygen-free copper of a substrate and a nickel layer on the surface of the substrate, wherein the nickel layer is the nickel electrodeposition layer.
The invention has the beneficial effects that:
the invention provides a nickel electrodeposition layer and a workpiece comprising the same, wherein the nickel electrodeposition layer is prepared by a method for electrodepositing nickel electrodeposition liquid, and the nickel electrodeposition liquid is a solution of an ammoniacal system. The nickel electrodeposition solution comprises ammonia water, nickel salt, a first additive and a second additive, and the high-wear-resistant and corrosion-resistant nickel electrodeposition layer is prepared by an electrodeposition method. Compared with the solution of an acidic system for electrodeposition, the electrodeposition liquid is an alkaline system, particularly an ammonia system, acid mist is not generated in the electrodeposition process, and the anodic reaction is a nitrogen separation reaction, so that the electrodeposition liquid has no corrosion pollution to the environment; free H in ammoniacal systems+The ion and cathode do not generate hydrogen evolution side reaction, the current efficiency is high, the nickel can be ensured to be deposited on the cathode plate more stably and uniformly, and the obtained nickel electrodeposition layer has good uniformity and high density, thereby greatly improving the wear resistance, the corrosion resistance and the like of the nickel-plated plate.
Specifically, the electrodeposition method is used for nickel plating of the tab of the lithium ion battery, the nickel layer of the prepared nickel-plated tab is good in uniformity and high in density, and the wear resistance and corrosion resistance of the tab are improved, so that the service life of the tab is greatly prolonged.
Detailed Description
< Nickel electrodeposition liquid >
As described above, the present invention provides a nickel electrodeposition bath including aqueous ammonia, a nickel salt, a first additive and a second additive; wherein the first additive is selected from animal glue; the second additive is selected from ammonium salts.
In a preferred embodiment of the present invention, the first additive is selected from animal glue, for example, one, two or three selected from bone glue, hide glue, gelatin. The addition of the first additive can enhance the cathode polarization, improve the deposition reduction overpotential of nickel and achieve the effect of refining grains.
In a preferred embodiment of the present invention, the first additive is added in an amount of 0.5-5 g/L, for example, 0.5 g/L, 0.6 g/L0, 0.7 g/L1, 0.8 g/L2, 0.9 g/L3, 1 g/L4, 1.5 g/L, 2 g/L, 2.5 g/L, 3 g/L, 3.5 g/L, 4 g/L, 4.5 g/L, 5 g/L.
In a preferred embodiment of the invention, the second additive is selected from ammonium salts. Illustratively, the ammonium salt is selected from one of the following compounds of formula (I):
in the formula (I), R1、R2、R3And R4Identical or different, independently from each other, from alkyl and aryl-substituted alkyl; x is selected from halogen (such as fluorine, chlorine, bromine, iodine, etc.).
For example, R1、R2、R3And R4One of them is selected from long-chain alkyl or aryl substituted alkyl, and the other three are the same and selected from C1-C6 alkyl.
For example, the ammonium salt is selected from one, two or more of cetyltrimethylammonium bromide, benzyltriethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride. The addition of the second additive can inhibit the reduction of impurities at the cathode in the electrodeposition process, improve the current efficiency and improve the flatness and the brightness of the nickel electrodeposition layer.
In a preferred embodiment of the present invention, the second additive is added in an amount of 0.2-1.0 g/L, for example 0.2 g/L, 0.3 g/L, 0.4 g/L, 0.5 g/L, 0.6 g/L, 0.7 g/L, 0.8 g/L, 0.9 g/L, 1 g/L.
In a preferred embodiment of the present invention, the aqueous ammonia (NH)3·H2O) is 2.0-5.0 mol/L, such as 2 mol/L, 2.5 mol/L, 3 mol/L, 3.5 mol/L, 4 mol/L, 4.5 mol/L and 5 mol/L, and the addition of the ammonia water can enable the nickel electrodeposition solution to form an ammonia system, thereby avoiding H+The ions are separated out at the cathode, and the nitrogen separation reaction of the anode is promoted, so that the generation of an acid mist phenomenon is avoided, and the current efficiency is improved.
In a preferred embodiment of the invention, the nickel salt is selected from nickel chloride, or a combination of nickel chloride and nickel oxide.
In a preferred embodiment of the present invention, Ni is contained in the nickel electrodeposition bath2+The amount of (B) is 25-100 g/L, for example 25 g/L, 30 g/L0, 35 g/L1, 40 g/L2, 45 g/L3, 50 g/L4, 55 g/L5, 60 g/L6, 65 g/L, 70 g/L, 75 g/L, 80 g/L, 85 g/L, 90 g/L, 95 g/L, 100 g/L.
In a preferred embodiment of the present invention, the pH of the nickel electrodeposition bath is 10 to 14.
< preparation method of Nickel electrodeposition liquid >
As described above, the present invention provides a method for preparing a nickel electrodeposition bath, the method comprising:
and mixing ammonia water, nickel salt, a first additive and a second additive to prepare the nickel electrodeposition solution.
For example, the mixing is performed in the order of addition of ammonia water, nickel salt, first additive and second additive.
< Nickel electrodeposition layer >
The invention also provides a nickel electrodeposition layer, wherein the nickel electrodeposition layer comprises nickel metal particles, and the particle size of the nickel metal particles is 10-250 nm, such as 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, 120nm, 150nm, 200nm and 250 nm.
In a preferred embodiment of the present invention, the nickel electrodeposition layer is prepared by the above-mentioned nickel electrodeposition bath.
In a preferred embodiment of the present invention, the nickel electrodeposition layer is prepared by electrodeposition of the above-mentioned nickel electrodeposition bath.
In a preferred embodiment of the invention, the electrodeposition temperature is 35 to 65 ℃, for example 40 to 50 ℃, such as 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃; the electrodeposition time is 0.5-8h, such as 0.5h, 1h, 3h, 4h, 5h, 6h, 7h, and 8 h.
In a preferred embodiment of the present invention, the electrodeposition is performed by direct current electrodeposition with a current density of 250-600A/m2E.g. 250A/m2、300A/m2、350A/m2、400A/m2、450A/m2、500A/m2、550A/m2、600A/m2。
In a preferred embodiment of the present invention, the electrodeposited cathode plate is made of a steel substrate, a titanium substrate, a copper substrate, an aluminum substrate, or the like, such as carbon steel or alloy steel, and also such as oxygen-free copper for a copper tab of a lithium battery.
In a preferred embodiment of the present invention, the electrodeposited anode plate is a graphite plate.
In a preferred embodiment of the present invention, the distance between the cathode plate and the anode plate is 3 to 5 cm.
In a preferred embodiment of the present invention, the electrodeposition is performed by stirring, and for example, the electrodeposition may be performed by one, two or more mixing and stirring methods of mechanical stirring, ultrasonic stirring or magnetic stirring. Preferably, the stirring mode is a combination of mechanical stirring and ultrasonic stirring, wherein the rotating speed of the mechanical stirring is 150-250r/min, and the frequency of the ultrasonic stirring is 55-75 Hz.
In a preferred embodiment of the present invention, the thickness of the nickel electrodeposition layer is 2cm or less.
In a preferred embodiment of the present invention, the hardness of the nickel electrodeposition layer is 110HV or more, such as 110HV and 200 HV.
In a preferred embodiment of the present invention, the wear amount of the nickel electrodeposition layer is 6 to 10 mg/h.
< method for producing Nickel electrodeposition layer >
The invention also provides a preparation method of the nickel electrodeposition layer, which comprises the following steps:
1) preparing the nickel electrodeposition solution;
2) electrodeposition is carried out using a steel substrate, a titanium substrate, a copper substrate or an aluminum substrate as a cathode plate and a graphite plate as an anode plate.
In a preferred embodiment of the invention, the electrodeposition temperature is 35 to 65 ℃, for example 40 to 50 ℃; the time of the electro-deposition is 0.5-8 h.
In a preferred embodiment of the present invention, the electrodeposition is performed by direct current electrodeposition with a current density of 250-600A/m2。
In a preferred embodiment of the invention, the steel or titanium substrate is, for example, carbon steel or alloy steel.
In a preferred embodiment of the present invention, the distance between the cathode plate and the anode plate is 3 to 5 cm.
In a preferred embodiment of the present invention, the electrodeposition is performed by stirring, for example, mechanical stirring, ultrasonic stirring, magnetic stirring, or a mixture of two or more stirring methods. Preferably, the stirring mode is a combination of mechanical stirring and ultrasonic stirring, wherein the rotating speed of the mechanical stirring is 150-250r/min, and the frequency of the ultrasonic stirring is 55-75 Hz.
In the invention, in the electrodeposition process, the ammonia system does not generate acid mist, and the anode reaction is a nitrogen separation reaction, so that the method has no corrosion pollution to the environment; free H in ammoniacal systems+The ion and cathode do not generate a diluted hydrogen side reaction, and the current efficiency is high; the nickel is stably and uniformly deposited on the cathode plate, and the obtained nickel electrodeposition layer has good uniformity, high density and the like.
< article >
The invention also provides a workpiece, which comprises a workpiece substrate and a nickel layer on the surface of the workpiece substrate, wherein the nickel layer is the nickel electrodeposition layer. Wherein, the part can be a winding needle or a tab.
In a preferred embodiment of the invention, the product is a tab for a lithium battery, which comprises oxygen-free copper of a substrate and a nickel layer on the surface of the substrate, wherein the nickel layer is the nickel electrodeposition layer. The nickel layer of the tab has good uniformity and high density, and the wear resistance and corrosion resistance of the tab are improved, so that the service life of the tab is greatly prolonged.
The preparation method of the present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Example 1
Preparing a nickel electrodeposition solution:
the nickel electrodeposition solution is prepared by uniformly dissolving ammonia water, nickel chloride, a first additive and a second additive at 55 ℃ by mixing and mechanical stirring (the stirring speed is 180r/min), wherein the nickel electrodeposition solution comprises the following components:
Ni2+25g/L，NH3·H2o2.5 mol/L, a first additive bone glue 0.5 g/L, a second additive cetyl trimethyl ammonium bromide 0.5 g/L;
the preparation process of the electrodeposited nickel comprises the following steps:
taking a 22cm long by 8cm wide graphite plate as an anode, a 20cm long by 6cm wide stainless steel plate as a cathode substrate, wherein the distance between the two electrodes is 3.0cm, and the current density is 300A/m2The electrodeposition temperature is 40 ℃, and the electrodeposition time is 6 h.
Example 2
Preparing a nickel electrodeposition solution:
the nickel electrodeposition solution is prepared by uniformly dissolving ammonia water, nickel chloride and nickel oxide in a mass ratio of 2:1, a first additive and a second additive at 60 ℃ by mixing and mechanically stirring (the stirring speed is 250r/min), wherein the nickel electrodeposition solution comprises the following components:
Ni2+25 g/L of nickel salt, NH3·H2O is 2.5 mol/L, the first additive gelatin is 2.5 g/L, and the second additive tetrabutylammonium bromide is 0.25 g/L;
the preparation process of the electrodeposited nickel comprises the following steps:
taking a 22cm long by 8cm wide graphite plate as an anode, a 20cm long by 6cm wide titanium plate as a cathode substrate, wherein the distance between the two electrodes is 4.0cm, and the current density is 450A/m2The electrodeposition temperature is 40 ℃, and the electrodeposition time is 8 h.
Example 3
Preparing a nickel electrodeposition solution:
the nickel electrodeposition solution is prepared by uniformly dissolving ammonia water, nickel chloride, a first additive and a second additive at 55 ℃ by mixing and mechanical stirring (the stirring speed is 180r/min), wherein the nickel electrodeposition solution comprises the following components:
Ni2+25g/L，NH3·H2o2.5 mol/L, a first additive bone glue 0.5 g/L, a second additive cetyl trimethyl ammonium bromide 0.5 g/L;
the preparation process of the electrodeposited nickel comprises the following steps:
taking a 22cm long by 8cm wide graphite plate as an anode, a 20cm long by 6cm wide stainless steel plate as a cathode substrate, with a distance of 5.0cm between the two electrodes and a current density of 300A/m2The electrodeposition temperature is 40 ℃, and the electrodeposition time is 6 h.
Example 4
Preparing a nickel electrodeposition solution:
the nickel electrodeposition solution is prepared by uniformly dissolving ammonia water, nickel chloride, a first additive and a second additive at 55 ℃ by mixing and mechanical stirring (the stirring speed is 180r/min), wherein the nickel electrodeposition solution comprises the following components:
Ni2+25g/L，NH3·H2o2.5 mol/L, a first additive bone glue 0.5 g/L, a second additive cetyl trimethyl ammonium bromide 0.5 g/L;
the preparation process of the electrodeposited nickel comprises the following steps:
taking a 22cm long by 8cm wide graphite plate as an anode, a 20cm long by 6cm wide stainless steel plate as a cathode substrate, wherein the distance between the two electrodes is 3.0cm, and the current density is 600A/m2The electrodeposition temperature is 40 ℃, and the electrodeposition time is 6 h.
Example 5
Preparing a nickel electrodeposition solution:
the nickel electrodeposition solution is prepared by uniformly dissolving ammonia water, nickel chloride, a first additive and a second additive at 55 ℃ by mixing and mechanical stirring (the stirring speed is 180r/min), wherein the nickel electrodeposition solution comprises the following components:
Ni2+100g/L，NH3·H2o2.5 mol/L, a first additive bone glue 0.5 g/L, a second additive cetyl trimethyl ammonium bromide 0.5 g/L;
the preparation process of the electrodeposited nickel comprises the following steps:
taking a 22cm long by 8cm wide graphite plate as an anode, a 20cm long by 6cm wide stainless steel plate as a cathode substrate, wherein the distance between the two electrodes is 3.0cm, and the current density is 300A/m2The electrodeposition temperature is 40 ℃, and the electrodeposition time is 6 h.
Example 6
Preparing a nickel electrodeposition solution:
the nickel electrodeposition solution is prepared by uniformly dissolving ammonia water, nickel chloride, a first additive and a second additive at 55 ℃ by mixing and mechanical stirring (the stirring speed is 180r/min), wherein the nickel electrodeposition solution comprises the following components:
Ni2+25g/L，NH3·H2o2.5 mol/L, a first additive bone glue 0.5 g/L, a second additive cetyl trimethyl ammonium bromide 0.5 g/L;
the preparation process of the electrodeposited nickel comprises the following steps:
taking a 22cm long by 8cm wide graphite plate as an anode, taking a C1020 oxygen-free copper matrix (size: 20cm long by 6cm wide) for a nickel-plated copper tab for a lithium battery as a cathode substrate, wherein the distance between the two electrodes is 3.0cm, and the current density is 300A/m2The electrodeposition temperature is 40 ℃, and the electrodeposition time is 0.5 h.
Comparative example 1
And taking a titanium plate with the length of 20cm and the width of 6cm as a cathode substrate, taking nickel sulfate as main salt, and carrying out electrodeposition according to a traditional sulfuric acid system to obtain a comparative nickel product.
Test example 1
The current efficiencies of the electrodeposition processes of examples 1 to 6 and comparative example 1 were calculated according to the formula η ═ m/(n × t × q × I).
Where η is the current efficiency, m is the mass of nickel electrodeposited over time t, I is the current through the cathode, t is the electrodeposition time, q is the electrochemical equivalent of nickel, n is the number of cells, the current efficiency results are shown in Table 1.
Test example 2
The nickel electrodeposition layers obtained in examples 1 to 6 and comparative example 1 were subjected to hardness test: the compactness of the nickel electrodeposition layer can be effectively reflected by hardness, the test mode adopts indentation hardness to measure the capability of the deposition layer for resisting a hard object to be indented into the surface of the deposition layer, Vickers hardness is used for expressing the hardness value HV, and a microhardness meter is used for measuring the Vickers hardness of the electrodeposition layer, wherein the Vickers hardness meter is a diamond regular rectangular pyramid pressure head with an included angle of 136 degrees on two surfaces, the load force is 100g, and the loading time is 30 s. The hardness test results are shown in table 1.
Test example 3
The electrodeposited nickel obtained in examples 1 to 6 and comparative example 1 was subjected to an abrasion loss test: the densification of an electrodeposited layer can be expressed in terms of the wear resistance of the deposited layer, with greater wear yielding poorer densification and conversely better densification. The wear resistance of the electrodeposited layer is quantitatively characterized by adopting a wear measuring instrument, under the condition of a steel ball with the load of 500g (the steel ball meeting the GB4208-2008 standard requirement), a back-and-forth friction test is carried out on the surface of a final product for 30min at the speed of 100r/min, and the wear amount is represented by calculating the weight difference before and after wear. The results of the wear measurements are shown in table 1.
Test example 4
The electrodeposited nickel obtained in examples 1 to 6 and comparative example 1 was subjected to XRD testing and calculated the particle size of the corresponding nickel metal particles in combination with the scherrer equation.
TABLE 1
From the comparison of the results of the above-mentioned respective specific examples 1 to 6 with the results of comparative example 1, it can be seen that: an electrodeposition method of nickel, in particular to a method for electrodepositing nickel by an ammoniacal system, the current efficiency of the electrodeposited nickel is higher than that of the electrodeposited nickel by a conventional acidic system; the prepared cathode nickel plate has good compactness, high hardness and high wear resistance; the overall particle size of the cathode nickel particles obtained by the ammonia electrodeposition is slightly smaller; in addition, the electrodeposition mixed liquid used for electrodepositing nickel in an ammonia system is non-acidic, acid mist is not formed in the electrodeposition process, harmful gas is not generated in the reaction of a cathode and an anode, the method is relatively friendly to the electrodeposition environment, and the pollution degree is low.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A nickel electrodeposition layer, wherein the nickel electrodeposition layer comprises nickel metal particles, and the particle size of the nickel metal particles is 10-250 nm.
2. The nickel electrodeposition layer according to claim 1, wherein the wear amount of the nickel electrodeposition layer is 6 to 10 mg/h.
3. The nickel electrodeposition layer according to claim 1 or 2, wherein the hardness of the nickel electrodeposition layer is 110HV or more.
4. The method of preparing a nickel electrodeposition layer according to any one of claims 1 to 3, wherein the method comprises the steps of:
electrodepositing nickel electrodeposition liquid to prepare the nickel deposition layer;
wherein the nickel electrodeposition bath comprises ammonia, a nickel salt, a first additive and a second additive; wherein the first additive is selected from animal glue; the second additive is selected from ammonium salts.
5. The preparation method according to claim 4, wherein the first additive is selected from animal glue, the animal glue is selected from one, two or three of bone glue, skin glue and gelatin, and the adding amount of the first additive is 0.5-5 g/L.
6. The production method according to claim 4 or 5, wherein the ammonium salt is one selected from the following compounds represented by the formula (I):
in the formula (I), R1、R2、R3And R4Identical or different, independently from each other, from alkyl and aryl-substituted alkyl; x is selected from halogen.
7. The method according to any one of claims 4 to 6, wherein the ammonium salt is one or two or more selected from cetyltrimethylammonium bromide, benzyltriethylammonium chloride, tetrabutylammonium bromide and tetrabutylammonium chloride, and the second additive is added in an amount of 0.2 to 1.0 g/L.
8. The production method according to any one of claims 4 to 7, wherein the aqueous ammonia (NH)3·H2O) concentration of 2.0-5.0 mol/L;
the nickel salt is selected from nickel chloride or the combination of nickel chloride and nickel oxide, and Ni in the nickel electrodeposition solution2+The amount of (B) is 25-100 g/L.
9. The production method according to any one of claims 4 to 8Wherein the temperature of the electrodeposition is 35-65 ℃; the time of the electrodeposition is 0.5-8h, the electrodeposition adopts a direct current electrodeposition mode, and the current density is 250-600A/m2。
10. An article comprising an article substrate and a nickel layer on the surface of the article substrate, wherein the nickel layer is the nickel electrodeposition layer as defined in any one of claims 1 to 3.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010457744.1A CN111501071A (en) | 2020-05-26 | 2020-05-26 | Nickel electrodeposition layer and workpiece comprising same |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010457744.1A CN111501071A (en) | 2020-05-26 | 2020-05-26 | Nickel electrodeposition layer and workpiece comprising same |
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| CN111501071A true CN111501071A (en) | 2020-08-07 |
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