CN111515385B - Copper-nickel core-shell type nano powder and conductive film, and preparation method and application thereof - Google Patents
Copper-nickel core-shell type nano powder and conductive film, and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of application of electronic materials and metal powder, and relates to copper-nickel core-shell nano powder and a conductive film, and a preparation method and application thereof. The preparation method of the copper-nickel core-shell nano powder comprises the following steps: and (2) simultaneously injecting the polyalcohol solution dissolved with the copper precursor and the ascorbic acid into the polyalcohol solution of the high-molecular coating agent, carrying out heat preservation reaction to form a copper core, then respectively injecting the polyalcohol solution dissolved with the nickel precursor and the reducing agent into the solution containing the copper core, carrying out heat preservation reaction, and carrying out epitaxial growth on a copper crystal face on a nickel shell layer under the induction action of the copper core to obtain the copper-nickel core-shell type nano powder with the completely closed shell layer. The copper-nickel core-shell nano powder obtained by the method provided by the invention has good oxidation resistance, and can be applied to a plurality of fields such as conductive slurry, conductive films, metal electrodes, magnetic shielding materials or catalysts.
Description
Technical Field
The invention belongs to the field of electronic materials and metal powder application, and particularly relates to copper-nickel core-shell nano powder and a conductive film, and a preparation method and application thereof.
Background
With the rapid development of the electronic and information industries, the research and development of high-performance electronic components have made higher requirements on metal conductive materials. At present, the electrode materials are mainly prepared from precious metals such as gold, silver and palladium and base metal materials such as copper, nickel and aluminum. Because of the high cost of precious metals, it is currently more desirable to replace precious metals with base metals to reduce production costs. Copper, as a relatively inexpensive base metal, has been widely used to prepare metal electrodes for use in electronic components. However, copper has limited applications due to its poor stability and susceptibility to oxidation. The surface of the copper powder particles is coated with a layer of nickel to form a core-shell structure, so that the stability of copper can be improved, the conductivity of the copper can not be obviously influenced, and the metal electrode prepared from the copper powder particles also has better oxidation resistance.
The chemical liquid phase method is one of the important methods for preparing nickel-coated copper powder. Kim et al reported (ACS appl. mater. interfaces 2018,10,1059-1066) the preparation of copper-nickel core-shell nanoparticles using a solvothermal reduction process. The method comprises the steps of dissolving synthesized copper seeds and nickel acetylacetonate into oleylamine, and reducing nickel salt by using aniline as a reducing agent to enable nickel to be independently nucleated and coated on the surface of copper particles. However, the nickel-coated copper particles prepared by the method have poor size uniformity, and nickel is coated with copper in a granular form and cannot form a closed core-shell structure. In addition, the organic reagents used in the method, namely oleylamine and aniline, have relatively high cost and are not friendly to the environment. CN1988973A uses palladium chloride solution to activate the surface of copper powder, uses hydrazine (hydrazine) as a reducing agent, and can obtain 0.5-1 micron nickel-plated copper powder with the mass fraction of 0.1-10% at 30-70 ℃. However, in the method, hydrazine (hydrazine) is used as a reducing agent, and the hydrazine has strong toxicity and causes certain pollution to the environment. In addition, the raw material contains noble metal palladium, which increases the production cost.
From the reported literature, the preparation of copper-nickel core-shell powders has the following problems. Firstly, the size of the powder is generally in micron and submicron level, and few reports are available for preparing nano powder with the size of about 100 nanometers, and the nano powder is beneficial to preparing an electrode layer with thinner thickness so as to meet the requirements of high-performance electronic elements. Secondly, the uniformity of the powder size is poor, which is not favorable for forming a uniform thin film electrode layer. In addition, nickel often has difficulty in tightly coating copper cores, and an effective heterogeneous bonding interface is not formed between copper and nickel, which may cause the oxidation resistance of the powder and the layered electrode to be reduced.
Disclosure of Invention
The invention aims to solve the problems and aims to provide a copper-nickel core-shell nano powder and a conductive film as well as a preparation method and application thereof. The copper-nickel core-shell nano powder prepared by the method provided by the invention has an adjustable size range (the particle size is 65-200 nanometers), the size is uniform, nickel and copper have a heteroepitaxial interface to form a tight coating, the thickness of a nickel layer can be adjusted, and the copper-nickel core-shell nano powder can be applied to a plurality of fields such as conductive slurry, a conductive film, a metal electrode, a magnetic shielding material, a catalyst and the like.
Specifically, the invention provides copper-nickel core-shell type nano powder which is characterized in that a copper core in the copper-nickel core-shell type nano powder is a polyhedron, and external nickel is epitaxially grown on an exposed copper crystal face to form a closed shell layer with a smooth surface.
Preferably, the copper-nickel core-shell nano powder is in the shape of a polyhedron with the particle size of 65-200 nanometers.
Preferably, the thickness of the nickel shell layer is 1-20 nanometers, and the mole fraction of nickel is 0.5-50%.
The invention also provides a preparation method of the copper-nickel core-shell nano powder, which comprises the following steps:
(1) respectively dissolving a copper precursor, a nickel precursor, ascorbic acid and a high-molecular coating agent in a polyalcohol solution to form respective polyalcohol solutions;
(2) heating the polyalcohol solution of the high molecular coating agent to 110-170 ℃, then respectively injecting the polyalcohol solution of the copper precursor and the polyalcohol solution of the ascorbic acid into the polyalcohol solution of the high molecular coating agent at injection rates of V1 and V2 under the protection of inert gas, and then carrying out heat preservation reaction for 0.1-60 minutes;
(3) and (3) after the heat preservation reaction is finished, heating the system to 175-220 ℃, injecting the polyalcohol solution of the nickel precursor and the polyalcohol solution of the ascorbic acid into the reaction system in the step (2) at injection rates of V3 and V4 respectively, then preserving the heat for reaction for 1-120 minutes, naturally cooling the obtained reaction solution to room temperature, washing with ethanol, carrying out magnetic field separation, and drying to obtain the copper-nickel core-shell type nano powder. Wherein the number of times of ethanol washing can be 1-3. The magnetic field separation is used for separating the copper-nickel core-shell nano powder from the solution by precipitation. The drying conditions include a temperature of 50-70 ℃ and a time of 0.5-12 hours.
Preferably, the copper precursor is selected from at least one of copper formate, copper acetate and copper sulfate.
Preferably, the nickel precursor is selected from nickel acetate and/or nickel acetylacetonate.
Preferably, the polymer coating agent is selected from polyvinylpyrrolidone and/or polyethylene glycol.
Preferably, the polyol is selected from ethylene glycol and/or diethylene glycol.
Preferably, the concentration of the copper precursor in the polyalcohol solution is 0.001 g/mL-0.05 g/mL.
Preferably, the concentration of the nickel precursor in the polyalcohol solution is 0.001 g/mL-0.04 g/mL.
Preferably, the concentration of the ascorbic acid in the polyalcohol solution is 0.005 g/mL-0.1 g/mL.
Preferably, the concentration of the polymer coating agent in the polyalcohol solution is 0.001 g/mL-0.5 g/mL.
Preferably, in the step (1), the injection rate V1 is 0.1-5 mL/min, V2 is 0.1-5 mL/min, and the ratio of V1 to V2 is 1 (1-4).
Preferably, in the step (3), the injection rate V3 is 0.1-5 mL/min, V4 is 0.1-5 mL/min, and the ratio of V3 to V4 is 1 (1-4).
The invention also provides application of the copper-nickel core-shell nano powder in the fields of conductive slurry, conductive films, metal electrodes, magnetic shielding materials or catalysts.
The invention also provides a preparation method of the conductive film, which comprises the steps of dispersing the copper-nickel core-shell type nano powder in a solvent to form conductive slurry, coating the conductive slurry on a substrate to form the film, and roasting the film for 0.5 to 2 hours at the temperature of 300 to 400 ℃ in a reducing atmosphere to obtain the conductive film.
In addition, the invention also provides the conductive film prepared by the method.
The method is mainly characterized in that a double-injection method, namely a method of simultaneously injecting a metal precursor and a reducing agent, is used for controlling the nucleation and growth of copper core particles, so that copper cores with uniform size are obtained, and the nucleation and growth of nickel on the surface of copper are induced by the copper cores, so that core-shell structure powder with uniform size is formed. In the specific preparation process, polyalcohol which is relatively friendly to environment and relatively low in cost is used as a reaction solvent, ascorbic acid which is non-toxic to people is used as a reducing agent, the addition amount of a metal precursor and the reducing agent is controlled by a double injection method, so that a copper core with uniform size is obtained, nickel salt can be reduced at a lower temperature under the induction action of the copper core, a closed heterogeneous shell layer is formed on the surface of the copper core in an epitaxial growth mode instead of forming nickel nanoparticles by single nucleation, and the copper-nickel core-shell type nanopowder with uniform size is finally obtained. Compared with the existing one-step reaction method (also called as 'one-pot method') or the method of singly injecting the reducing agent and the metal precursor, the double-injection method provided by the invention can conveniently adjust the dynamic process of metal particle nucleation, solve the problem of non-uniform size of the nano powder and simultaneously obtain the adjustable size and the adjustable thickness of the nickel shell layer. More importantly, the nickel is used for hermetically coating the copper core in the form of a heterogeneous shell layer with a smooth surface, the characteristic greatly improves the oxidation resistance of the copper core and the conductive slurry, the conductive film, the metal electrode, the magnetic shielding material or the catalyst prepared from the copper core, and the nickel can be applied to occasions with harsh requirements on oxidation resistance.
Drawings
FIG. 1 is a scanning electron micrograph of the copper core nanopowder prepared in example 1 with a scale of 1 μm.
Fig. 2 is a scanning electron micrograph of the copper-nickel core-shell nanopowder prepared in example 1 with a 1 μm scale.
Fig. 3 is an electron diffraction pattern of the copper-nickel core-shell type nanopowder prepared in example 1.
Fig. 4 is a surface scanning analysis diagram of the copper-nickel core-shell type nanopowder prepared in example 1.
FIG. 5 is a scanning electron micrograph of the copper-nickel core-shell nanopowder prepared in example 2, with a scale of 400 nm.
FIG. 6 is a scanning electron micrograph of the copper-nickel core-shell nanopowder prepared in example 3, with a scale of 400 nm.
FIG. 7 is a scanning electron micrograph of the copper-nickel core-shell nanopowder prepared in example 4, with a scale of 200 nm.
FIG. 8 is a scanning electron micrograph of the copper-nickel core-shell nanopowder prepared in example 5 with a scale of 400 nm.
FIG. 9 is a scanning electron micrograph of the copper-nickel core-shell nanopowder prepared in example 6, with a scale of 400 nm.
FIG. 10 is a scanning electron micrograph of the copper-nickel core-shell type nanopowder prepared in example 7, with a 500 nm scale.
Detailed Description
The following detailed description of embodiments of the invention is intended to be illustrative of the invention and is not to be construed as limiting the invention. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
(1) Separately dissolving copper acetate monohydrate, nickel acetate tetrahydrate, ascorbic acid and polyvinylpyrrolidone PVP (K30) in ethylene glycol solutions to form respective ethylene glycol solutions;
(2) adding 10mL of PVP (K30) glycol solution with the concentration of 0.037g/mL into a flask, introducing argon for protection, heating to 140 ℃, simultaneously injecting 4mL of ethylene glycol solution of copper acetate monohydrate with the concentration of 0.015g/mL and 4mL of ethylene glycol solution of ascorbic acid with the concentration of 0.032g/mL into the flask by using an injection pump at the injection rate of 0.5mL/min, and after the injection is finished, keeping the temperature at 140 ℃ for reaction for 30 minutes to form a copper core;
(3) after the heat preservation reaction is finished, heating to 195 ℃, injecting 4mL of ethylene glycol solution of nickel acetate tetrahydrate with the concentration of 0.01g/mL and 4mL of ethylene glycol solution of ascorbic acid with the concentration of 0.011g/mL into the flask at the injection rate of 0.5mL/min by using an injection pump, preserving the temperature at 195 ℃ after the injection is finished, reacting for 30 minutes, naturally cooling the obtained reaction solution to room temperature, washing twice by using ethanol, separating the product by using a magnet, drying in a vacuum drying oven at 50 ℃ for 4 hours to obtain the copper-nickel core-shell type nano powder, wherein the copper core in the copper-nickel core type nano powder is a polyhedron, and the nickel outside is epitaxially grown by using an exposed copper crystal face to form a closed shell layer with a smooth surface.
FIG. 1 is a scanning electron micrograph of copper nuclei having a relatively uniform size distribution. FIG. 2 is a scanning electron micrograph of the copper-nickel core-shell nanopowder, which is polyhedral in shape, has an average particle size of about 130 nm, and has smooth and continuous particle surface without defects such as pores and cracks. Fig. 3 is an electron diffraction pattern of the copper-nickel core-shell type nanopowder, confirming that nickel coats the copper core in an epitaxial growth manner, thus having a compact heterojunction surface. Fig. 4 (from left to right) is a high angle annular dark field image, a copper power plane scan, and a nickel power plane scan of a copper-nickel core-shell nanoparticle, confirming the core-shell structure of nickel-coated copper.
Example 2
(1) Separately dissolving copper acetate monohydrate, nickel acetate tetrahydrate, ascorbic acid and polyvinylpyrrolidone PVP (K30) in ethylene glycol solutions to form respective ethylene glycol solutions;
(2) adding 10mL of PVP (K30) glycol solution with the concentration of 0.037g/mL into a flask, introducing argon for protection, heating to 140 ℃, simultaneously injecting 4mL of ethylene glycol solution of copper acetate monohydrate with the concentration of 0.015g/mL and 4mL of ethylene glycol solution of ascorbic acid with the concentration of 0.032g/mL into the flask by using an injection pump at the injection rate of 0.5mL/min, and after the injection is finished, keeping the temperature at 140 ℃ for reaction for 30 minutes to form a copper core;
(3) after the heat preservation reaction is finished, heating to 195 ℃, injecting 4mL of ethylene glycol solution of nickel acetate tetrahydrate with the concentration of 0.005g/mL and 4mL of ethylene glycol solution of ascorbic acid with the concentration of 0.006g/mL into the flask at the injection rate of 0.5mL/min by using an injection pump, preserving the temperature and reacting for 30 minutes at 195 ℃ after the injection is finished, naturally cooling the obtained reaction solution to room temperature, washing twice by using ethanol, separating the product by using a magnet, drying in a vacuum drying oven at 50 ℃ for 4 hours to obtain the copper-nickel core-shell type nano powder, wherein the copper core in the copper-nickel core type nano powder is a polyhedron, and the nickel on the outside is epitaxially grown by using an exposed copper crystal face to form a closed shell layer with a smooth surface. Compared with example 1, the obtained copper-nickel core-shell nanopowder has a thinner nickel shell layer.
FIG. 5 is a scanning electron micrograph of the copper-nickel core-shell nanopowder, which is polyhedral in shape, has an average particle size of about 115 nm, and has smooth and continuous particle surface without defects such as pores and cracks.
Example 3
(1) Separately dissolving copper acetate monohydrate, nickel acetate tetrahydrate, ascorbic acid and polyvinylpyrrolidone PVP (K30) in ethylene glycol solutions to form respective ethylene glycol solutions;
(2) adding 10mL of PVP (K30) glycol solution with the concentration of 0.037g/mL into a flask, introducing argon for protection, heating to 140 ℃, simultaneously injecting 4mL of ethylene glycol solution of copper acetate monohydrate with the concentration of 0.015g/mL and 4mL of ethylene glycol solution of ascorbic acid with the concentration of 0.032g/mL into the flask by using an injection pump at the injection rate of 0.5mL/min, and after the injection is finished, keeping the temperature at 140 ℃ for reaction for 30 minutes to form a copper core;
(3) after the heat preservation reaction is finished, heating to 195 ℃, injecting 2mL of ethylene glycol solution of nickel acetate tetrahydrate with the concentration of 0.0025g/mL and 2mL of ethylene glycol solution of ascorbic acid with the concentration of 0.003g/mL into the flask at the injection rate of 0.5mL/min by using an injection pump, preserving the temperature and reacting for 30 minutes at 195 ℃ after the injection is finished, naturally cooling the obtained reaction solution to room temperature, washing twice by using ethanol, separating the product by using a magnet, and drying in a vacuum drying oven at 50 ℃ for 4 hours to obtain the copper-nickel core-shell nano powder. Compared with the example 2, the obtained copper-nickel core-shell type nano powder has a thinner nickel shell layer.
FIG. 6 is a scanning electron micrograph of the copper-nickel core-shell nanopowder, which is polyhedral in shape, has an average particle size of about 110 nm, and has smooth and continuous particle surface without defects such as pores and cracks.
Example 4
(1) Separately dissolving copper acetate monohydrate, nickel acetate tetrahydrate, ascorbic acid and polyvinylpyrrolidone PVP (K30) in diethylene glycol solutions to form respective diethylene glycol solutions;
(2) adding 10mL of a diethylene glycol solution of PVP (K30) with the concentration of 0.037g/mL into a flask, introducing argon for protection, heating to 140 ℃, simultaneously injecting 4mL of a diethylene glycol solution of copper acetate monohydrate with the concentration of 0.015g/mL and 4mL of a diethylene glycol solution of ascorbic acid with the concentration of 0.032g/mL into the flask by using a syringe pump at the injection rate of 0.5mL/min, and after the injection is finished, keeping the temperature at 140 ℃ for reaction for 30 minutes to form a copper core;
(3) after the heat preservation reaction is finished, heating to 195 ℃, injecting 4mL of ethylene glycol solution of nickel acetate tetrahydrate with the concentration of 0.01g/mL and 4mL of diethylene glycol solution of ascorbic acid with the concentration of 0.011g/mL into the flask at the injection rate of 0.5mL/min by using an injection pump, preserving the heat at 210 ℃ for 20 minutes after the injection is finished, naturally cooling the reaction liquid to room temperature, washing twice by using ethanol, separating the product by using a magnet, drying in a vacuum drying oven at 50 ℃ for 4 hours to obtain the copper-nickel core-shell type nano powder, wherein the copper core in the copper-nickel core-shell type nano powder is a polyhedron, and the nickel on the outside is subjected to epitaxial growth by using the exposed copper crystal face to form a closed shell layer with a smooth surface. Compared with the example 2, the obtained copper-nickel core-shell type nano powder has a thinner nickel shell layer.
FIG. 7 is a scanning electron micrograph of the copper-nickel core-shell nanopowder, which is polyhedral in shape, has an average particle size of about 135 nm, and has smooth and continuous particle surface without defects such as pores and cracks.
Example 5
(1) Separately dissolving copper acetate monohydrate, nickel acetate tetrahydrate, ascorbic acid and polyvinylpyrrolidone PVP (K30) in ethylene glycol solutions to form respective ethylene glycol solutions;
(2) adding 10mL of PVP (K30) glycol solution with the concentration of 0.037g/mL into a flask, introducing argon for protection, heating to 140 ℃, injecting 4mL of copper acetate monohydrate glycol solution with the concentration of 0.015g/mL by using a syringe pump at the injection rate of 0.25mL/min, simultaneously injecting 4mL of ascorbic acid glycol solution with the concentration of 0.032g/mL at the injection rate of 0.5mL/min, and after the injection is finished, keeping the temperature at 140 ℃ for reaction for 15 minutes to form a copper core;
(3) after the heat preservation reaction is finished, heating to 200 ℃, injecting 4mL of ethylene glycol solution of nickel acetate tetrahydrate with the concentration of 0.01g/mL and 4mL of ethylene glycol solution of ascorbic acid with the concentration of 0.011g/mL into a flask at the injection rate of 0.5mL/min by using an injection pump, preserving the heat at 200 ℃ for reaction for 30 minutes after the injection is finished, naturally cooling the obtained reaction liquid to room temperature, washing twice by using ethanol, separating the product by using a magnet, drying in a vacuum drying oven at 50 ℃ for 4 hours to obtain the copper-nickel core-shell type nano powder, wherein the copper core in the copper-nickel core-shell type nano powder is a polyhedron, and the nickel on the outside is epitaxially grown by using the exposed copper crystal face to form a closed shell layer with a smooth surface. Compared with example 1, the obtained copper-nickel core-shell nanopowder has a thinner nickel shell layer.
FIG. 8 is a scanning electron micrograph of the copper-nickel core-shell nanopowder, which is polyhedral in shape, has an average particle size of about 70 nm, and has smooth and continuous particle surface without defects such as pores and cracks.
Example 6
(1) Separately dissolving copper acetate monohydrate, nickel acetate tetrahydrate, ascorbic acid and polyvinylpyrrolidone PVP (K30) in ethylene glycol solutions to form respective ethylene glycol solutions;
(2) adding 10mL of PVP (K30) glycol solution with the concentration of 0.037g/mL into a flask, introducing argon for protection, heating to 140 ℃, simultaneously injecting 4mL of ethylene glycol solution of copper acetate monohydrate with the concentration of 0.015g/mL and 4mL of ethylene glycol solution of ascorbic acid with the concentration of 0.032g/mL into the flask by using an injection pump at the injection rate of 0.5mL/min, and after the injection is finished, keeping the temperature at 140 ℃ for reaction for 30 minutes to form a copper core;
(3) after the heat preservation reaction is finished, heating to 180 ℃, injecting 4mL of ethylene glycol solution of nickel acetate tetrahydrate with the concentration of 0.01g/mL and 4mL of ethylene glycol solution of ascorbic acid with the concentration of 0.011g/mL into a flask at the injection rate of 0.5mL/min by using an injection pump, preserving the heat at 180 ℃ for reaction for 60 minutes after the injection is finished, naturally cooling the obtained reaction liquid to room temperature, washing twice by using ethanol, separating the product by using a magnet, drying in a vacuum drying oven at 50 ℃ for 4 hours to obtain the copper-nickel core-shell type nano powder, wherein the copper core in the copper-nickel core type nano powder is a polyhedron, and the nickel on the outside is epitaxially grown by using the exposed copper crystal face to form a closed shell layer with a smooth surface.
FIG. 9 is a scanning electron micrograph of the Cu-Ni core-shell nanopowder of this example, which is polyhedral in shape, has an average particle size of about 125 nm, and has smooth and continuous particle surface without defects such as voids and cracks.
Comparative example 1
(1) Separately dissolving copper acetate monohydrate, nickel acetate tetrahydrate, ascorbic acid and polyvinylpyrrolidone PVP (K30) in ethylene glycol solutions to form respective ethylene glycol solutions;
(2) adding 10mL of PVP (K30) glycol solution with the concentration of 0.037g/mL into a flask, introducing argon for protection, heating to 140 ℃, simultaneously injecting 4mL of ethylene glycol solution of copper acetate monohydrate with the concentration of 0.015g/mL and 4mL of ethylene glycol solution of ascorbic acid with the concentration of 0.064g/mL into the flask by using an injection pump at the injection rate of 0.5mL/min, and after the injection is finished, carrying out heat preservation reaction at 140 ℃ for 30 minutes to form a copper core;
(3) after the heat preservation reaction is finished, continuously heating to 195 ℃, injecting 2mL of ethylene glycol solution of nickel acetate tetrahydrate with the concentration of 0.0025g/mL into the flask by using an injection pump at the injection rate of 0.5mL/min, preserving the heat at 195 ℃ for reaction for 30 minutes after the injection is finished, naturally cooling the obtained reaction liquid to room temperature, washing the reaction liquid twice by using ethanol, separating the product by using a magnet, and drying the product in a 50 ℃ vacuum drying oven for 4 hours to obtain the copper-nickel core-shell type nano powder, wherein the copper core in the copper-nickel core-shell type nano powder is a polyhedron, and the nickel outside the copper core is epitaxially grown by using an exposed copper crystal face to form a closed shell layer with a smooth surface.
FIG. 10 is a scanning electron micrograph of the copper-nickel core-shell type nanopowder of this example. From the results of fig. 10, it can be seen that the average particle size was slightly smaller than that of the product of example 2, about 100 nm (near the size of the copper core), the size uniformity was poor, and nickel was only partially reduced, resulting in uneven distribution of the nickel shell. This illustrates that the metal precursor alone does not give the desired structure, and that the uniform particle size and nickel shell can be guaranteed only by the double injection (cf. example 2), i.e. by injecting the metal precursor and the reducing agent simultaneously.
Example 8
The copper core nano powder and the copper-nickel core shell type nano powder prepared in example 2 were respectively added to a mixed solution containing 50 vol% of ethylene glycol and 50 vol% of ethylene glycol methyl ether, and subjected to ultrasonic treatment and stirring to prepare a slurry having a solid content of 40 wt%, and then coated on a glass substrate with a coating rod to form a thin film, and then baked at 350 ℃ for 1 hour in a 5% hydrogen-argon mixed atmosphere to form a conductive thin film. After cooling to room temperature, the resistance of the conductive film was measured with a four-probe resistance meter. The resistance of the copper thin film was 8. mu. omega. cm, while that of the copper-nickel core-shell type thin film was 48. mu. omega. cm. Then, the film was heat-treated in a muffle furnace at 200 ℃ for 1 hour in an air atmosphere, and the electric resistance of the film was measured. The resistance of the copper thin film was too large to be measured by a resistance meter, while the resistance of the copper-nickel core-shell type thin film increased only to 92 μ Ω cm. After heat treatment, the color of the copper film changed to blue, indicating severe oxidation, while the color of the copper-nickel core-shell film did not change, showing good oxidation resistance.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made in the above embodiments by those of ordinary skill in the art without departing from the principle and spirit of the present invention.
Claims (10)
1. The copper-nickel core-shell type nano powder is characterized in that a copper core in the copper-nickel core-shell type nano powder is a polyhedron, external nickel is subjected to epitaxial growth by exposed copper crystal faces, and the copper core is hermetically coated in a heterogeneous shell layer form with a smooth surface.
2. The copper-nickel core-shell nanopowder of claim 1, wherein the copper-nickel core-shell nanopowder is polyhedral in shape and has a particle size of 65-200 nm; the thickness of the nickel shell layer is 1-20 nanometers, and the mole fraction of nickel is 0.5-50%.
3. The method for preparing the copper-nickel core-shell nanopowder of claim 1 or 2, comprising the steps of:
(1) respectively dissolving a copper precursor, a nickel precursor, ascorbic acid and a high-molecular coating agent in a polyalcohol solution to form respective polyalcohol solutions;
(2) heating the polyalcohol solution of the high molecular coating agent to 110-170 ℃, then respectively injecting the polyalcohol solution of the copper precursor and the polyalcohol solution of the ascorbic acid into the polyalcohol solution of the high molecular coating agent at injection rates of V1 and V2 under the protection of inert gas, and then carrying out heat preservation reaction for 0.1-60 minutes;
(3) and (3) after the heat preservation reaction is finished, heating the system to 175-220 ℃, injecting the polyalcohol solution of the nickel precursor and the polyalcohol solution of the ascorbic acid into the reaction system in the step (2) at injection rates of V3 and V4 respectively, then preserving the heat for reaction for 1-120 minutes, naturally cooling the obtained reaction solution to room temperature, washing with ethanol, carrying out magnetic field separation, and drying to obtain the copper-nickel core-shell type nano powder.
4. The method for preparing the copper-nickel core-shell nanopowder of claim 3, wherein in step (1), the copper precursor is selected from at least one of copper formate, copper acetate and copper sulfate; the nickel precursor is selected from nickel acetate and/or nickel acetylacetonate; the polymer coating agent is selected from polyvinylpyrrolidone and/or polyethylene glycol; the polyol is selected from ethylene glycol and/or diethylene glycol.
5. The method for preparing the copper-nickel core-shell nanopowder of claim 3, wherein in step (1), the concentration of the copper precursor in the polyol solution is 0.001-0.05 g/mL; the concentration of the nickel precursor in the polyalcohol solution is 0.001-0.04 g/mL; the concentration of the ascorbic acid in the polyalcohol solution is 0.005-0.1 g/mL; the concentration of the polymer coating agent in the polyalcohol solution is 0.001-0.5 g/mL.
6. The method for preparing the copper-nickel core-shell nanopowder of claim 3, wherein in the step (2), the injection rate V1 is 0.1-5 mL/min, the injection rate V2 is 0.1-5 mL/min, and the ratio of V1 to V2 is 1 (1-4).
7. The method for preparing the copper-nickel core-shell nanopowder of claim 3, wherein in the step (3), the injection rate V3 is 0.1-5 mL/min, the injection rate V4 is 0.1-5 mL/min, and the ratio of V3 to V4 is 1 (1-4).
8. The copper-nickel core-shell nano-powder of claim 1 or 2 is applied to the fields of conductive paste, conductive thin films, metal electrodes, magnetic shielding materials or catalysts.
9. A preparation method of a conductive film is characterized in that the method comprises the steps of dispersing the copper-nickel core-shell nano powder in a solvent to form conductive slurry, coating the conductive slurry on a substrate to form the film, and roasting at 300-400 ℃ for 0.5-2 hours in a reducing atmosphere to obtain the conductive film.
10. The conductive film prepared by the method of claim 9.
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| CN113457707B (en) * | 2021-06-29 | 2023-11-21 | 湖北航泰科技有限公司 | MOFs-based core-shell structure ZnCo@NPC nanomaterial and preparation method thereof |
| KR102694708B1 (en) * | 2021-08-20 | 2024-08-13 | 삼성전기주식회사 | Conductive paste and multilayer ceramic component using the same |
| JP7340727B1 (en) * | 2022-09-30 | 2023-09-07 | 三井金属鉱業株式会社 | Nickel particles and method for producing nickel particles |
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