CN112593273A - Metal/sulfur-nickel-containing composite material and preparation method and application thereof - Google Patents
Metal/sulfur-nickel-containing composite material and preparation method and application thereof Download PDFInfo
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- CN112593273A CN112593273A CN202011435477.4A CN202011435477A CN112593273A CN 112593273 A CN112593273 A CN 112593273A CN 202011435477 A CN202011435477 A CN 202011435477A CN 112593273 A CN112593273 A CN 112593273A
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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Abstract
The invention discloses a metal/sulfur-nickel-containing composite material and a preparation method and application thereof. The preparation method comprises the following steps: at least enabling an anode, a cathode and an electroplating solution to jointly construct an electrochemical reaction system, wherein the cathode adopts metal wires and/or metal sheets, and the electroplating solution is a mixed solution at least containing nickel salt, a sulfur carrying agent, a buffering agent and water; electrifying the electrochemical reaction system for electroplating to obtain the metal/sulfur-containing nickel composite material with the inner layer being metal and the outer layer being sulfur-containing nickel material. The invention adopts the metal wire or the metal sheet as the cathode, saves the labor cost, simultaneously the product is a sulfur-containing nickel short rod or a block product, and the potential difference between the metal wire or the metal sheet and the sulfur-containing nickel on the outer layer leads the metal wire or the metal sheet to have better solubility, can be used as a high-solubility nickel anode, is used in the fields of diamond wire electroplating, nickel sulfamate electroplating, electronic product electroplating and the like, improves the limit current density, and improves the production efficiency.
Description
Technical Field
The invention relates to a metal/sulfur-containing nickel composite material, in particular to a metal/sulfur-containing nickel composite material for a high-activity anode used in nickel electroplating, a preparation method and application thereof, belonging to the technical field of electroplating.
Background
Nickel is an important national resource, wherein the nickel used for the nickel anode electroplating accounts for about 8 percent of the nickel dosage in China. Although the reserves of nickel in the crust are abundant and reach over 8900 ten thousand tons, China is a nickel-poor country, the reserves are only about 280 ten thousand tons, and the consumption of nickel is about 120 ten thousand tons every year. One of the most important nickel resources is electroplating. The common nickel has low solubility due to high passivation, and has the defects of relatively low utilization rate, sludge generation, easy bridging phenomenon, incapability of being used for high-speed electroplating and the like when being used for electroplating anodes. When common nickel is used for anode dissolution, the anode can be oxidized by separated oxygen atoms due to strong passivation property of the nickel, insoluble nickel oxide is generated, and anode sludge is finally formed; in addition, due to the formation of oxides, the nickel anode is locally and selectively dissolved to form a low-strength sponge-like porous structure, which leads to the increase of the cell voltage. The addition of chloride ions to the nickel plating bath can accelerate the dissolution of the nickel anode, but some problems remain. The chlorine ions can slow down the generation of oxygen atoms of the anode, reduce the oxidation of the nickel of the anode and improve the solubility. However, the addition of chloride ions has the following disadvantages: (1) the stress of the plating layer is increased, so that the bonding force between the plating layer and the substrate is reduced; (2) the hardness and stress are large, so that the post processing is difficult; (3) the obtained coating has much lower corrosion resistance than that of the chloride ion-free plating solution; (4) the solubility of the alloy is still insufficient when the alloy is used for high-speed electroplating of diamond wires and the like.
Due to the high activity of sulfur-containing nickel, there has been an increasing domestic demand for sulfur-containing nickel in recent years. The sulfur-containing nickel products from INCO and Falcon are the major products on the market. The sulfur element in the sulfur-containing nickel is doped into the nickel by reducing the sulfur-containing compounds (sulfur carrying agents) such as saccharin, benzene sulfinic acid, amide sulfonate or derivatives thereof and the like together with nickel ions in the deposition process; the internal structure is a typical island structure, and the sulfur content is about 0.015-0.027%; in the range of-1V to 1V, almost no passivation phenomenon occurs.
At present, the production of the sulfur-containing nickel product needs to use a cathode substrate, including a stainless steel plate, a titanium alloy plate and the like. Insulating shielding layers such as epoxy, organic silicon and the like are selectively coated or adhered on the cathode substrates, and uncoated or adhered parts are in a regularly-arranged circular structure. The diameter of the circle is 10-15mm, and sulfur-containing nickel grows in the circular structures to finally form a sulfur-containing nickel cake.
This process presents several problems, for example: the problems of the growth area of the circular sulfur-containing nickel and the product binding force; the product is very time-consuming and labor-consuming to pick; the shielding layer can be damaged when the product is picked, so that the repeated use of the matrix is influenced; at the junction of the insulating layer and the circular growth region, hydrogen is easy to evolve due to an interface effect, so that the product has many air holes, the quality is influenced, and the like.
Disclosure of Invention
The invention mainly aims to provide a metal/sulfur-nickel-containing composite material and a preparation method thereof, thereby overcoming the defects of the prior art.
The invention also aims to provide application of the metal/sulfur-nickel-containing composite material.
In order to achieve the purpose, the invention adopts the following technical scheme:
the embodiment of the invention provides a preparation method of a metal/sulfur-nickel-containing composite material, which comprises the following steps:
at least an anode, a cathode and an electroplating solution are used for constructing an electrochemical reaction system together, wherein the cathode adopts metal wires and/or metal sheets, and the electroplating solution is a mixed solution at least containing nickel salt, a sulfur carrying agent, a buffering agent and water;
electrifying the electrochemical reaction system for electroplating to obtain the metal/sulfur-containing nickel composite material with the inner layer being metal and the outer layer being sulfur-containing nickel material.
In some preferred embodiments, the material of the metal wire or the metal sheet includes any one or a combination of two or more of nickel, nickel alloy, stainless steel, titanium alloy, and the like, but is not limited thereto.
In some preferred embodiments, the sulfur-carrying agent is a sulfur-containing organic compound having reducibility, and preferably includes any one or a combination of two or more of sodium benzene sulfinate, benzenesulfonic acid, thioethylene, benzoylsulfonimide, and the like.
In some preferred embodiments, the surfactant is selected from organic compounds capable of reducing the surface tension of water to 50mN/m or less, preferably any one or a combination of two or more of sodium 2-ethylhexyl sulfate, sodium dodecyl sulfate, sodium polyoxyethylene alkylphenol ether sulfate, and the like.
In some preferred embodiments, the electroplating is performed under process conditions including: the pH value of the electroplating solution is 3-6, the temperature of the electroplating solution is 40-70 ℃, the electroplating time is 5-7 days, and the relationship between the current density of the cathode and the electroplating time meets the following requirements: a is t.70 mA/dm2Wherein A is the current density and t is the plating time.
The embodiment of the invention also provides the metal/sulfur-containing nickel composite material prepared by the method, which comprises a metal layer serving as an inner layer and a sulfur-containing nickel material coated on the surface of the metal layer.
The embodiment of the invention also provides application of the metal/sulfur-containing nickel composite material in preparation of an electroplated nickel anode.
Correspondingly, the embodiment of the invention also provides an electroplated nickel anode which comprises the metal/sulfur-containing nickel composite material.
Furthermore, the embodiment of the invention also provides the application of the nickel electroplating anode in the fields of diamond wire electroplating, nickel sulfamate electroplating or electronic product electroplating and the like.
Compared with the prior art, the invention has the beneficial effects that:
1) the invention adopts the metal wire or the metal sheet as the cathode, greatly saves the equipment cost and the labor cost in the electroplating process, simultaneously the product is in a rod-shaped or block-shaped structure, a sulfur-containing nickel short rod or block product can be obtained by stamping, the product can be used as a high-solubility nickel anode and used as an anode in the fields of diamond wire electroplating, nickel sulfamate electroplating, electronic product electroplating and the like, the limit current density is improved, and the production efficiency is improved. Because of the potential difference between the metal wire or the metal sheet in the product and the sulfur-containing nickel on the outer layer, the sulfur-containing nickel short rod or block has better solubility than the existing sulfur-containing nickel, and has good market application prospect and research value;
2) the cathode substrate and the sediment are integrated into a whole, and the cathode substrate and the sediment are used as a final product, so that two complicated steps of cathode regional coating and finished product removal from the cathode are eliminated, the manufacturing process is shortened, and the efficiency is improved. The obtained product is a composite material with a certain potential difference between the inner layer and the outer layer, and the dissolubility of the product is superior to that of common sulfur-containing nickel;
3) the preparation method of the metal/sulfur-nickel-containing composite material with low cost, convenience and high efficiency, which is provided by the invention, adopts the metal wire or the metal sheet to replace the existing stainless steel plate or titanium alloy plate as the cathode; this cathode need not be covered with an insulating layer and the growth of sulfur-containing nickel is seen in all areas. After growth is finished, the product consists of the metal of the inner layer and the sulfur-containing nickel of the outer layer. The material and the preparation method thereof have the following advantages: the product does not need to be taken out from the substrate, but the substrate is taken as a part of the product, so that the step of selectively coating or adhering insulating shielding layers such as epoxy, organic silicon and the like on the substrate area can be eliminated, the existing sulfur-containing nickel cake can be replaced, the labor cost can be greatly reduced, and the generation time can be shortened; plates such as stainless steel, titanium alloy and the like are not needed, the equipment is light, and the energy consumption and the equipment cost are greatly reduced; the growing and forming double-layer composite bar or plate can be punched into various shapes, so that the use convenience of the material is improved; the finished product is a metal/sulfur-nickel-containing composite material, and the dissolution speed of the product can be effectively improved due to the potential difference between the inner layer metal and the sulfur-nickel-containing composite material.
Detailed Description
In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and extensive practices to provide a method for preparing a metal/sulfur-containing nickel composite material with low cost, convenience and high efficiency, wherein a metal filament or a metal sheet is used as a cathode, and a sulfur-containing nickel material is plated on the metal filament or the metal sheet. The method is carried out in an aqueous solution consisting of a nickel salt, a buffer, a sulfur-carrying agent, a surfactant and water. The obtained sulfur-containing nickel material contains a certain amount of sulfur elements introduced by the sulfur carrying agent besides the nickel elements.
The preparation principle of the invention mainly lies in that: replacing the existing stainless steel plate or titanium alloy plate with a metal wire or a metal sheet as a cathode; this cathode need not be covered with an insulating layer and the growth of sulfur-containing nickel is seen in all areas. After growth is finished, the product consists of the metal of the inner layer and the sulfur-containing nickel of the outer layer. The material and the preparation method thereof have the following advantages: the product does not need to be taken out of the substrate, but the substrate is taken as a part of the product, so that the step of selectively coating or adhering insulating shielding layers such as epoxy, organic silicon and the like on the substrate area can be eliminated, the labor cost is greatly reduced, and the generation time is shortened; plates such as stainless steel, titanium alloy and the like are not needed, the equipment is light, and the energy consumption and the equipment cost are greatly reduced; the growing and forming double-layer composite bar or plate can be punched into various shapes, so that the use convenience of the material is improved; the finished product is a metal/sulfur-nickel-containing composite material, and the dissolution speed of the product can be effectively improved due to the potential difference between the inner layer metal and the sulfur-nickel-containing composite material.
The technical solution, its implementation and principles, etc. will be further explained as follows.
One aspect of the embodiments of the present invention provides a method for preparing a metal/sulfur-containing nickel composite material, which includes:
at least an anode, a cathode and an electroplating solution are used for constructing an electrochemical reaction system together, wherein the cathode adopts metal wires and/or metal sheets, and the electroplating solution is a mixed solution at least containing nickel salt, a sulfur carrying agent, a buffering agent and water;
electrifying the electrochemical reaction system for electroplating to obtain the metal/sulfur-containing nickel composite material with the inner layer being metal and the outer layer being sulfur-containing nickel material.
In some preferred embodiments, the preparation method is: and electroplating in a nickel ion-containing solution by using a metal wire or a metal sheet as a cathode to obtain a product of the metal/nickel-sulfur-containing composite material with the inner layer made of the metal and the outer layer made of a nickel-sulfur-containing material.
In some preferred embodiments, the material of the metal wire or the metal sheet includes any one or a combination of two or more of nickel, nickel alloy, stainless steel, titanium alloy, and the like, preferably nickel, nickel alloy, and the like, but is not limited thereto.
Further, the metal wire is a nickel wire, a nickel alloy wire, a stainless steel wire, a titanium alloy wire, a nickel-plated metal wire, etc., wherein the nickel wire and the nickel alloy wire are preferable, but not limited thereto.
In some preferred embodiments, the wire is an elongated wire, and the wire has an aspect ratio of 1: 1-200: 1, preferably 20: 1-100: 1.
in some preferred embodiments, the cross-sectional shape of the wire includes a circle, a square, a triangle, or any other planar shape, wherein the cross-section is preferably circular, but not limited thereto.
In some preferred embodiments, the foil has a thickness of 0.1mm to 3mm, preferably 0.1mm to 0.5mm, particularly preferably 0.3mm to 0.5 mm.
Further, the diameter of the metal wire is 0.1 mm-1 mm.
In some preferred embodiments, the area to thickness ratio of the foil is 10: 1-10000000: 1, preferably 1000: 1-10000000: 1.
in some preferred embodiments, the nickel salt includes nickel sulfate, nickel chloride, and the like, but is not limited thereto.
In some preferred embodiments, the sulfur-carrying agent is a sulfur-containing organic compound with reducibility, and preferably includes any one or a combination of two or more of sodium benzene sulfinate, benzene sulfonyl acid, benzene sulfonic acid, ethylene thiourea, benzoyl sulfonyl imide, and the like, but is not limited thereto.
Further, the buffer includes boric acid, sodium borate, etc., but is not limited thereto.
In some preferred embodiments, the electroplating solution further includes a surfactant selected from organic compounds capable of reducing the surface tension of water to 50mN/m or less, preferably any one or a combination of two or more of sodium 2-ethylhexyl sulfate, sodium dodecyl sulfate, sodium polyoxyethylene alkylphenol ether sulfate, behenyl trimethyl ammonium chloride, disodium lauryl sulfosuccinate monoester, and the like, but is not limited thereto.
In some more specific embodiments, the concentration of the nickel sulfate in the electroplating solution is 200-400 g/L, preferably 250-300 g/L, the concentration of the nickel chloride is 20-50 g/L, preferably 30-45 g/L, and particularly preferably 30-40 g/L, the concentration of the sulfur carrying agent is 5 mg/L-50 g/L, the concentration of the buffer agent is 20-40 g/L, and the concentration of the surfactant is 0.05-2 g/L.
In some more specific embodiments, the nickel ion-containing electroplating solution is composed of the following raw materials in percentage by weight: 150-300 g/L of nickel sulfate, 30-45 g/L of nickel chloride, 5-100 g/L of sulfur carrying agent, 20-30 g/L of buffering agent and 0.05-0.2 g/L of surfactant. In some preferred embodiments, the electroplating process uses process conditions including: the pH value of the electroplating solution is 3-6, preferably 4-4.5, particularly preferably 4-4.2, the temperature of the electroplating solution is 40-70 ℃, preferably 40-65 ℃, particularly preferably 60-65 ℃, the electroplating time is 5-7 days, and the relationship between the current density of the cathode and the electroplating time satisfies: a is t.70 mA/dm2Wherein A is the current density, t is the plating time, and t is the unit of hour.
Further, the electroplating conditions are as follows: the pH value is 3-6, the temperature of the plating solution is 40-65 ℃, the cathode current density is increased along with the time, the electroplating time is 5-7 days, and the surfactant and the sulfur carrying agent are added according to the ampere product of the electroplating time.
In some preferred embodiments, the preparation method further comprises: the wire and/or foil is pre-treated prior to electroplating.
Further, the pre-processing comprises:
providing a mixed solution containing an alkaline solution and a surfactant;
and (2) placing the metal wire and/or the metal sheet into the mixed solution, and cleaning for 3-10 min at 40-70 ℃, preferably 60-70 ℃.
Further, the surfactant includes sodium lauryl sulfate, but is not limited thereto.
Furthermore, the concentration of the surfactant in the mixed solution is 0.5 g/L-2 g/L.
Further, the alkaline solution includes a sodium hydroxide/potassium hydroxide solution and the like, but is not limited thereto.
In some preferred embodiments, the preparation method further comprises: after the pretreatment is completed, the resulting wire and/or foil is placed in an acidic solution at least to remove the oxide film from the surface.
Further, the acidic solution includes a sulfuric acid solution, but is not limited thereto.
Further, the anode may be made of titanium alloy, nickel, graphite, or the like, but is not limited thereto.
In some more specific embodiments, the preparation method of the metal/sulfur-containing nickel composite material specifically comprises the following steps:
step 1, preparing an electroplating solution:
dissolving nickel salt, sulfur carrying agent, buffering agent and surfactant in deionized water according to mass concentration, and adjusting ionic strength and pH value to proper values.
Step 2, pretreatment of the metal wire or the metal sheet:
adding a proper amount of sodium dodecyl sulfate into NaOH solution with the mass percent concentration of 10-20% or KOH solution with the mass percent concentration of 5-20% to obtain mixed solution, putting the metal wire or the metal sheet into the mixed solution, and cleaning for 3-10 minutes at the cleaning temperature of 40-70 ℃;
wherein, the concentration of the sodium dodecyl sulfate in the mixed solution is preferably 0.5g/l to 10g/l, and more preferably 2 g/l; the cleaning temperature is preferably 60-70 ℃;
step 3, surface oxidation film removal treatment of the metal substrate:
removing the surface oxidation film in a sulfuric acid solution with the mass percentage concentration of 10%;
step 4, preparing the metal/sulfur-containing nickel composite material:
and (3) putting the metal substrate treated in the step (3) into the electroplating solution prepared in the step (1) for electroplating preparation. The conditions are as follows: a pure nickel plate is arranged in the titanium basket as an anode, a nickel wire with the diameter of 0.1 mm-1 mm or a nickel sheet with the diameter of 0.1 mm-0.5 mm is arranged as a cathode, and the relation between the current density of the cathode and the time is that A is t.70 mA/dm2T is time (taking hours as unit), the pH of the plating solution is adjusted by sulfuric acid to be 4-4.5, the temperature of the plating solution is 60-65 ℃, and deposition is carried outThe time is 8 days, and the whole solution needs to be circularly filtered.
Step 5, cutting or punch forming:
taking out the grown finished product, and stamping or cutting to form. The product made by using the metal wire as the cathode is punched into a short rod with the length of 3-5cm, and the product made by using the metal sheet as the cathode is cut into square blocks with the length and the width of 4 cm.
Further, the preparation method also comprises the step of cutting and stamping the high-solubility metal/sulfur-containing nickel composite material product used as the electroplated nickel anode to obtain a rod-shaped or block-shaped product. Wherein the rod-shaped product has excellent fluidity when used as an anode for nickel electroplating.
In another aspect of the embodiments of the present invention, there is also provided a metal/sulfur-containing nickel composite material prepared by the foregoing method, including a metal layer as an inner layer, and a sulfur-containing nickel material overlaying a surface of the metal layer.
Further, the mass content of sulfur in the sulfur-containing nickel material is 0.005 wt% -0.5 wt%, preferably 0.010 wt% -0.05 wt%.
Further, the content of the metal wire and/or the metal sheet in the metal/sulfur-nickel-containing composite material is 0.01 wt% to 20 wt%, preferably 0.01 wt% to 1 wt%, that is, the mass of the metal wire or the metal sheet accounts for 0.01 wt% to 20 wt% of the total mass of the product.
Further, the metal/sulfur-nickel-containing composite material is in a rod-shaped or block-shaped structure.
In another aspect of the embodiment of the invention, the application of the metal/sulfur-containing nickel composite material in preparing an electroplated nickel anode is also provided.
Accordingly, another aspect of an embodiment of the present invention also provides an electroplated nickel anode comprising the aforementioned metal/sulfur-containing nickel composite material.
Further, when the high-solubility metal/sulfur-containing nickel composite material product is used as an anode for nickel electroplating, the maximum limiting current density is 2-5 times greater than that of the common sulfur-free nickel.
Furthermore, when the high-solubility metal/sulfur-containing nickel composite material product is used as an anode for nickel electroplating, chlorine ions do not need to be added into the electroplating solution, and the electroplating solution is preferably a nickel sulfamate nickel plating system.
The invention also provides application of the nickel electroplating anode in the fields of diamond wire electroplating, nickel sulfamate electroplating or electronic product electroplating and the like.
In conclusion, according to the technical scheme, the metal wire or the metal sheet is used as the cathode, so that the equipment cost and the labor cost in the electroplating process are greatly saved, meanwhile, the product is in a rod-shaped or block-shaped structure, a sulfur-containing nickel short rod or block-shaped product can be obtained through stamping, the product can be used as a high-solubility nickel anode and used as an anode in the fields of diamond wire electroplating, nickel sulfamate electroplating, electronic product electroplating and the like, the limiting current density is improved, and the production efficiency is improved. Because of the potential difference between the metal wire or the metal sheet in the product and the sulfur-containing nickel on the outer layer, the sulfur-containing nickel short rod or block has better solubility than the existing sulfur-containing nickel, and has good market application prospect and research value.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention are described in detail below with reference to several preferred embodiments, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. The test methods in the following examples are carried out under conventional conditions without specifying the specific conditions. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The reagents used in the following examples were all of analytical purity.
Example 1
The formula of the product preparation solution in the embodiment is as follows: the solvent is deionized water, 300g/L of nickel sulfate, 40g/L of nickel chloride, 30g/L of boric acid, 0.15g/L of sodium dodecyl sulfate and 0.25g/L of sodium benzene sulfinate are taken, and the pH value is controlled to be 4-4.2; the temperature is 50-55 ℃.
The metal cathode is nickel wire with the diameter of 0.5mm and the length of 100mm, 50 wires are arranged, the distance between each wire and each wire is 20mm, the metal cathode shuttles in the plastic basket frame and is positioned on the same plane, and two rows of anodes are respectively arranged at the positions 30mm away from the two sides of the metal cathode. Adding a proper amount of sodium dodecyl sulfate into a KOH solution with the mass percentage concentration of 5-20% and the concentration of 0.5g/L to obtain a mixed solution, putting the nickel wire into the mixed solution, and cleaning for 10 minutes at the temperature of 40 ℃. Removing the surface oxidation film in a sulfuric acid solution with the mass percentage concentration of 10%; the preparation of the material was carried out in the prepared solution. The cathode current density changes along with the change of time, and is specifically proportional to the cathode current density and the time or proportional to the square of the cathode current density and the time. Adjusting the pH value of the plating solution to 4-4.5 by using sulfuric acid, keeping the temperature of the plating solution at 60-65 ℃, settling for 7 days, circularly filtering the whole solution, analyzing the surface tension and the content of the sulfur-carrying agent once every 4 hours, and supplementing and adding a proper amount of the sulfur-carrying agent.
Taking out the grown finished product, wherein the diameter of the finished product is a bar with the diameter of 10-15mm, the inner layer of the finished product is pure nickel wire, the outer layer of the finished product is sulfur-containing nickel, and the component ratio of the sulfur-containing nickel is more than 99%. And (5) stamping into short rods of 3-5cm to finally obtain the finished product.
When the finished metal/sulfur-nickel-containing composite material prepared by the embodiment is used as a nickel anode, the available limiting current density is more than 30A/dm2I.e. when the current density is 30A/dm2The anodic dissolution efficiency is greater than 95%.
Example 2
The formula of the product preparation solution in the embodiment is as follows: the solvent is deionized water, 250g/L of nickel sulfate, 30g/L of nickel chloride, 35g/L of boric acid, 0.25g/L of 2-ethylhexyl sodium sulfate and 0.25g/L of ethylene thiourea are taken, and the pH value is controlled to be 4-4.2; the temperature is 50-55 ℃.
The metal cathode is a nickel sheet with the thickness of 0.1mm, the length and the width are 700mm and 500mm respectively, the position 2mm away from the edge at the periphery is fixed by a plastic basket, and two rows of anodes are arranged at the positions 20mm away from the two sides of the metal cathode respectively. Adding a proper amount of sodium dodecyl sulfate into a KOH solution with the mass percentage concentration of 5-20 percent, wherein the concentration is 5g/L to obtain a mixed solution,the nickel flakes were put into the mixed solution and washed at a temperature of 60 ℃ for 5 minutes. Removing the surface oxidation film in a sulfuric acid solution with the mass percentage concentration of 10%; the preparation of the material was carried out in the prepared solution. The cathode current density changes with time, and concretely, the relation between the cathode current density and the time is that A is t.70 mA/dm2And t is time (taking hours as a unit), the pH value of the plating solution is adjusted by sulfuric acid to be kept at 4-4.5, the temperature of the plating solution is 60-65 ℃, the deposition time is 6 days, the whole solution needs to be circularly filtered, the surface tension and the content of the sulfur carrying agent are analyzed every 4 hours, and the solution is supplemented and added into a proper amount.
Taking out the grown finished product, wherein the diameter of the finished product is 5-10mm, the inner layer of the finished product is a pure nickel sheet, and the outer layer of the finished product is sulfur-containing nickel, wherein the component ratio of the sulfur-containing nickel is more than 98%. Cutting into square blocks with length and width of 4cm to obtain final product.
Example 3
The formula of the product preparation solution in the embodiment is as follows: the solvent is deionized water, 300g/L of nickel sulfate, 40g/L of nickel chloride, 30g/L of boric acid, 0.5g/L of sodium ethylhexyl sulfate and 2.5g/L of benzenesulfonic acid are taken, and the pH value is controlled to be 4-4.2; the temperature is 50-55 ℃.
The metal cathode is made of stainless steel wires with the diameter of 0.5mm and the length of 50mm, 50 stainless steel wires are arranged, the distance between each wire and each wire is 20mm, the metal cathode shuttles in the plastic basket frame and is positioned on the same plane, and two rows of anodes are respectively arranged at the positions 30mm away from the two sides of the metal cathode. Adding a proper amount of sodium dodecyl sulfate into a KOH solution with the mass percentage concentration of 5-20% to obtain a mixed solution with the concentration of 8g/L, putting the nickel wire into the mixed solution, and cleaning for 3 minutes at the temperature of 70 ℃. Removing the surface oxidation film in a sulfuric acid solution with the mass percentage concentration of 20%; the preparation of the material was carried out in the prepared solution. The cathode current density changes along with the change of time, and concretely, the relation between the cathode current density and the time is that A is t.60 mA/dm2And t is time (in hours), the plating solution is adjusted by sulfuric acid to maintain a pH value of 4-4.5, the plating solution temperature is 60 ℃, the deposition time is 5 days, the whole solution needs to be circularly filtered, the surface tension and the content of the sulfur carrying agent are analyzed every 4 hours, and the solution is supplemented and added into a proper amount.
Taking out the grown finished product, wherein the diameter of the finished product is a bar of 10-15mm, the inner layer of the finished product is a stainless steel wire, the outer layer of the finished product is sulfur-containing nickel, and the component ratio of the sulfur-containing nickel is more than 99%. And (5) stamping into short rods of 3-5cm to finally obtain the finished product.
Example 4
The formula of the product preparation solution in the embodiment is as follows: the solvent is deionized water, 400g/L of nickel sulfate, 30g/L of nickel chloride, 25g/L of boric acid, 0.05g/L of polyoxyethylene alkylphenol ether sodium sulfate and 5g/L of benzenesulfonic acid are taken as the solvents, and the pH value is controlled to be 4-4.2; the temperature is 50-55 ℃.
The metal cathode is a stainless steel sheet with the thickness of 0.1mm, the length and the width are 700mm and 500mm respectively, the position 2mm away from the edge at the periphery is fixed by a plastic basket, and two rows of anodes are arranged at the positions 20mm away from the two sides of the metal cathode respectively. Adding a proper amount of sodium dodecyl sulfate into a KOH solution with the mass percentage concentration of 5-20% to obtain a mixed solution with the concentration of 10g/L, putting the stainless steel sheet into the mixed solution, and cleaning for 4 minutes at the temperature of 65 ℃. Removing the surface oxidation film in a sulfuric acid solution with the mass percentage concentration of 20%; the preparation of the material was carried out in the prepared solution. The cathode current density changes with time, and concretely, the relation between the cathode current density and the time is that A is t.70 mA/dm2And t is time (in hours), the plating solution is adjusted by sulfuric acid to maintain a pH value of 4-4.5, the plating solution temperature is 65 ℃, the deposition time is 7 days, the whole solution needs to be circularly filtered, the surface tension and the content of the sulfur carrying agent are analyzed every 4 hours, and the solution is supplemented and added into a proper amount.
Taking out the grown finished product, wherein the diameter of the finished product is 5-10mm, the inner layer of the finished product is a stainless steel sheet, and the outer layer of the finished product is sulfur-containing nickel, wherein the component ratio of the sulfur-containing nickel is more than 98%. Cutting into square blocks with length and width of 4cm to obtain final product.
Example 5
The formula of the product preparation solution in the embodiment is as follows: the solvent is deionized water, 200g/L of nickel sulfate, 20g/L of nickel chloride, 20g/L of boric acid, 2g/L of behenyl trimethyl ammonium chloride and 0.005g/L of benzoyl sulfimide are taken, and the pH value is controlled to be 4-4.5.
The metal cathode is titanium with the thickness of 1mmThe length and width of the alloy sheet are respectively 800mm and 600mm, the position 2mm away from the edge at the periphery is fixed by a plastic basket, and two rows of anodes are respectively arranged at the positions 20mm away from the two sides of the alloy sheet. Adding a proper amount of sodium dodecyl sulfate into a KOH solution with the mass percentage concentration of 5-20% and the concentration of 1g/L to obtain a mixed solution, putting the titanium alloy sheet into the mixed solution, and cleaning for 6 minutes at the temperature of 50 ℃. Removing the surface oxidation film in a sulfuric acid solution with the mass percentage concentration of 20%; the preparation of the material was carried out in the prepared solution. The cathode current density changes with time, and concretely, the relation between the cathode current density and the time is that A is t.70 mA/dm2And t is time (in hours), the plating solution is adjusted by sulfuric acid to maintain a pH value of 4-4.5, the plating solution temperature is 70 ℃, the deposition time is 5 days, the whole solution needs to be circularly filtered, the surface tension and the content of the sulfur carrying agent are analyzed every 4 hours, and the solution is supplemented and added into a proper amount.
Taking out the grown finished product, wherein the diameter of the finished product is 5-10mm, the inner layer of the finished product is a titanium alloy sheet, the outer layer of the finished product is sulfur-containing nickel, and the component ratio of the sulfur-containing nickel is more than 98%. Cutting into square blocks with length and width of 4cm to obtain final product.
Example 6
The formula of the product preparation solution in the embodiment is as follows: the solvent is deionized water, 280g/L of nickel sulfate, 50g/L of nickel chloride, 40g/L of sodium borate, 0.1g/L of disodium lauryl sulfosuccinate and 50g/L of sodium benzene sulfinate are taken, and the pH value is controlled to be 3-6; the temperature is 50-55 ℃.
The metal cathodes are nickel alloy wires with the diameter of 0.1mm and the length of 2mm, 50 nickel alloy wires are arranged, the distance between each wire and each wire is 20mm, the metal cathodes shuttle in the plastic basket frame and are positioned on the same plane, and two rows of anodes are respectively arranged at the positions 30mm away from the two sides of the metal cathodes. Adding a proper amount of sodium dodecyl sulfate into a NaOH solution with the mass percentage concentration of 5-20% to obtain a mixed solution with the concentration of 8g/L, putting the nickel alloy wire into the mixed solution, and cleaning for 3 minutes at the temperature of 70 ℃. Removing the surface oxidation film in a sulfuric acid solution with the mass percentage concentration of 20%; the preparation of the material was carried out in the prepared solution. The cathode current density changes with time, specifically the relation between the cathode current density and timeIs A ═ t.60 mA/dm2And t is time (in hours), the plating solution is adjusted by sulfuric acid to maintain a pH value of 4-4.5, the plating solution temperature is 60 ℃, the deposition time is 5 days, the whole solution needs to be circularly filtered, the surface tension and the content of the sulfur carrying agent are analyzed every 4 hours, and the solution is supplemented and added into a proper amount.
Taking out the grown finished product, wherein the diameter of the finished product is 10-15mm, the inner layer of the finished product is nickel alloy wire, the outer layer of the finished product is sulfur-containing nickel, and the component ratio of the sulfur-containing nickel is more than 99%. And (5) stamping into short rods of 3-5cm to finally obtain the finished product.
Comparative example
The inventors of the present invention compared with example 1 of the present invention, which uses a conventional stainless steel plate or titanium alloy plate as a cathode substrate, have found that the results are not satisfactory, for example: the problems of the growth area of the circular sulfur-containing nickel and the product binding force; the product is very time-consuming and labor-consuming to pick; the shielding layer can be damaged when the product is picked, so that the repeated use of the matrix is influenced; at the junction of the insulating layer and the circular growth region, hydrogen is easy to evolve due to an interface effect, so that the product has many air holes, the quality is influenced, and the like. The obtained product has low anode dissolution efficiency when used for nickel anode electroplating, and is obviously inferior to that of the product in the example 1.
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
Unless specifically stated otherwise, use of the terms "comprising", "including", "having" or "having" is generally to be understood as open-ended and not limiting.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.
Claims (10)
1. A preparation method of a metal/sulfur-nickel-containing composite material is characterized by comprising the following steps:
at least an anode, a cathode and an electroplating solution are used for constructing an electrochemical reaction system together, wherein the cathode adopts metal wires and/or metal sheets, and the electroplating solution is a mixed solution at least containing nickel salt, a sulfur carrying agent, a buffering agent and water;
electrifying the electrochemical reaction system for electroplating to obtain the metal/sulfur-containing nickel composite material with the inner layer being metal and the outer layer being sulfur-containing nickel material.
2. The method of claim 1, wherein: the material of the metal wire or the metal sheet comprises any one or the combination of more than two of nickel, nickel alloy, stainless steel and titanium alloy, and preferably nickel and/or nickel alloy;
and/or the metal wire is in a long strip shape, and the length-diameter ratio of the metal wire is 1: 1-200: 1, preferably 20: 1-100: 1;
and/or the cross-sectional shape of the wire comprises a circle, a square or a triangle, preferably a circle;
and/or the diameter of the metal wire is 0.1 mm-1 mm;
and/or the thickness of the metal sheet is 0.1 mm-3 mm, preferably 0.1 mm-0.5 mm, and particularly preferably 0.3 mm-0.5 mm;
and/or the area to thickness ratio of the metal sheet is 10: 1-10000000: 1, preferably 1000: 1-10000000: 1.
3. the method of claim 1, wherein: the nickel salt comprises nickel sulfate and/or nickel chloride;
and/or the sulfur carrying agent is a sulfur-containing organic compound with reducibility, and preferably comprises any one or the combination of more than two of sodium benzene sulfinate, benzene sulfonyl acid, benzene sulfonic acid, ethylene thiourea and benzoyl sulfonyl imide;
and/or, the buffering agent comprises boric acid and/or sodium borate;
and/or, the electroplating solution also comprises a surfactant which is selected from organic compounds capable of reducing the surface tension of water to below 50mN/m, preferably any one or a combination of more than two of 2-ethylhexyl sodium sulfate, lauryl sodium sulfate, polyoxyethylene alkylphenol ether sodium sulfate, behenyl trimethyl ammonium chloride and lauryl sulfonated succinic acid monoester disodium.
4. The production method according to claim 3, characterized in that: the concentration of the nickel sulfate in the electroplating solution is 200-400 g/L, preferably 250-300 g/L, the concentration of the nickel chloride is 20-50 g/L, preferably 30-40 g/L, the concentration of the sulfur carrying agent is 5 mg/L-50 g/L, the concentration of the buffering agent is 20-40 g/L, and the concentration of the surfactant is 0.05-2 g/L.
5. The method according to claim 1, wherein the plating is performed under process conditions including: the pH value of the electroplating solution is 3-6, preferably 4-4.5, particularly preferably 4-4.2, the temperature of the electroplating solution is 40-70 ℃, preferably 40-65 ℃, particularly preferably 60-65 ℃, the electroplating time is 5-7 days, and the relationship between the current density of the cathode and the electroplating time satisfies: a is t.70 mA/dm2Wherein A is the current density and t is the plating time.
6. The method of claim 1, further comprising: pre-treating the wire and/or foil prior to electroplating;
preferably, the pretreatment comprises:
providing a mixed solution containing an alkaline solution and a surfactant;
placing the metal wire and/or the metal sheet in the mixed solution, and cleaning for 3-10 min at 40-70 ℃, preferably 60-70 ℃;
preferably, the surfactant comprises sodium lauryl sulfate; preferably, the concentration of the surfactant in the mixed solution is 0.5g/l to 10 g/l; preferably, the alkaline solution comprises a sodium hydroxide/or potassium hydroxide solution;
preferably, the preparation method further comprises: after the pretreatment is completed, the obtained metal wire and/or metal sheet is placed in an acidic solution at least for removing an oxide film on the surface; preferably, the acidic solution comprises a sulfuric acid solution.
7. A metal/sulfur-nickel-containing composite material produced by the method of any one of claims 1 to 6, comprising a metal layer as an inner layer, and a sulfur-nickel-containing material overlaying a surface of the metal layer;
preferably, the content of sulfur in the sulfur-containing nickel material is 0.005 wt% -0.5 wt%, preferably 0.010 wt% -0.05 wt%;
preferably, the content of the metal wires and/or the metal sheets in the metal/sulfur-nickel-containing composite material is 0.01 wt% -20 wt%, and preferably 0.01 wt% -1 wt%;
preferably, the metal/sulfur-containing nickel composite material has a rod-like or block-like structure.
8. Use of the metal/sulfur-containing nickel composite material of claim 7 for the preparation of an electroplated nickel anode.
9. An electroplated nickel anode comprising the metal/sulfur-containing nickel composite material of claim 7.
10. Use of the nickel electroplated anode of claim 9 in the field of diamond wire plating, nickel sulfamate plating or electronic product plating.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113248840A (en) * | 2021-05-10 | 2021-08-13 | 宁波晶美科技有限公司 | Automobile door handle and electroplating process thereof |
| CN115430597A (en) * | 2022-11-03 | 2022-12-06 | 中国科学院宁波材料技术与工程研究所 | Super-hydrophilic nickel-based multilayer composite film material and preparation method and application thereof |
| CN115449876A (en) * | 2022-11-11 | 2022-12-09 | 中国科学院宁波材料技术与工程研究所 | Gradient wetting copper-nickel multilayer composite material and preparation method and application thereof |
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| CN110067011A (en) * | 2019-03-28 | 2019-07-30 | 上海大学 | Prepare the method and electric deposition device of bulk nano-crystalline nickel |
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| US4087339A (en) * | 1976-07-02 | 1978-05-02 | The International Nickel Company, Inc. | Electrowinning of sulfur-containing nickel |
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| CN110067011A (en) * | 2019-03-28 | 2019-07-30 | 上海大学 | Prepare the method and electric deposition device of bulk nano-crystalline nickel |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113248840A (en) * | 2021-05-10 | 2021-08-13 | 宁波晶美科技有限公司 | Automobile door handle and electroplating process thereof |
| CN113248840B (en) * | 2021-05-10 | 2022-04-15 | 宁波晶美科技有限公司 | Automobile door handle and electroplating process thereof |
| CN115430597A (en) * | 2022-11-03 | 2022-12-06 | 中国科学院宁波材料技术与工程研究所 | Super-hydrophilic nickel-based multilayer composite film material and preparation method and application thereof |
| CN115430597B (en) * | 2022-11-03 | 2023-03-07 | 中国科学院宁波材料技术与工程研究所 | Super-hydrophilic nickel-based multilayer composite film material and preparation method and application thereof |
| CN115449876A (en) * | 2022-11-11 | 2022-12-09 | 中国科学院宁波材料技术与工程研究所 | Gradient wetting copper-nickel multilayer composite material and preparation method and application thereof |
| CN115449876B (en) * | 2022-11-11 | 2023-02-28 | 中国科学院宁波材料技术与工程研究所 | Gradient wetting copper-nickel multilayer composite material and preparation method and application thereof |
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