Method for improving surface energy of nickel metal, and nickel-copper binary metal material and use thereof

Abstract

The present application provides a method for improving the surface energy of nickel metal, and a nickel-copper binary metal material and a use thereof. The method comprises: depositing a modified metal layer composed of second metal on the surface of a metal matrix composed of first metal, wherein one of the first metal and the second metal is nickel metal, and the first metal can form a solid solution with the second metal; then performing short-time heat treatment in a protective atmosphere, so that the atoms of the first metal and the atoms of the second metal are uniformly mixed without segregation and phase separation of elements, thereby obtaining a nickel-based binary metal material having surface energy ranging from 30 mJ / m2 to 80 mJ / m2. The method for improving the surface energy of a nickel metal matrix of the present application is simple and is easy to popularize; and the prepared nickel-based binary metal material has high surface energy and good hydrophilicity, and has wide prospects of application in the fields of hydrogen production by water electrolysis and the like.

Description

Method for improving nickel metal surface energy, nickel-copper binary metal material and application thereof

[0001] This application claims priority to the Chinese invention patent application with application number CN202311153662.8, application date September 7, 2023, and title “A nickel-copper alloy with high specific surface energy, its preparation method and application”, and application number CN202410319792.2, application date March 19, 2024, and title “Method for improving the surface energy of nickel metal, nickel-copper binary metal material and its application”. The above patent applications are incorporated herein by reference in their entirety. Technical Field

[0002] The present application belongs to the field of alloy technology, and specifically relates to a method for improving the surface energy of nickel metal, a nickel-copper binary metal material and its application. Background Art

[0003] Nickel metal is a silvery-white, hard, ductile and ferromagnetic metal, and is often used to make magnetic alloys and shape memory alloys. It is widely used in the electroplating industry and the manufacture of various alloys, and the alloys prepared from it have excellent corrosion resistance. Nickel is a metal that is not easily oxidized and can form a dense oxide film. It has strong corrosion resistance to most acid, alkali and salt media. Secondly, nickel alloys exhibit extremely high strength and toughness at high temperatures and can withstand high-temperature thermal expansion and mechanical stress. Therefore, they are widely used in chemical, petroleum, nuclear power, aviation and other fields. In addition, nickel alloys also have good mechanical properties and can be easily processed and welded. It is a metal material that is very easy to process. Due to the hydrogen evolution activity of nickel metal itself, nickel metal materials are also widely used in the field of hydrogen production by electrolysis of water. However, due to its low surface energy (<30mJ / m 2 ), making it less hydrophilic and unable to meet the needs of practical applications.

[0004] Surface atomic disorder, or the degree of surface atomic disorder, is positively correlated with surface entropy, which in turn is positively correlated with surface energy. Increasing surface atomic disorder can effectively increase surface energy, thereby increasing the hydrophilicity of the material surface. In recent years, numerous studies have demonstrated the significant benefits of hydrophilic surfaces in water electrolysis, leading to their widespread application in this field. Hydrophilic materials are known to favor the hydrogen evolution reaction, and increasing their hydrophilicity can effectively enhance hydrogen evolution activity.

[0005] Increasing the surface energy of nickel-based metal materials can effectively improve the hydrophilicity of nickel-based metal materials, but there is currently a lack of methods that can simply and easily increase the surface energy of the nickel metal matrix, which is also a difficult problem that the industry has been eager to solve.

[0006] Summary of the Invention

[0007] The main purpose of this application is to provide a method for improving the surface energy of nickel metal, a nickel-copper binary metal material and its application, so as to solve the problems of low surface energy and poor hydrophilicity of nickel-based metal materials in the prior art.

[0008] In order to achieve the above technical effects, this application provides the following technical solutions:

[0009] A first aspect of the present application provides a method for increasing the surface energy of nickel metal, comprising:

[0010] Depositing a modified metal layer on a pretreated surface of a metal substrate to form a composite metal material, wherein the metal substrate comprises a first metal, the modified metal layer comprises a second metal, one of the first metal and the second metal is nickel, and the first metal can form a solid solution with the second metal;

[0011] The composite metal material is heat treated in a protective atmosphere to uniformly mix the first metal atoms and the second metal atoms on the surface of the metal matrix, and the content of the second metal atoms on the surface of the metal matrix is ​​at least 1 to 10 at%, thereby obtaining a surface energy of 30 mJ / m 2 The above nickel-based binary metal materials.

[0012] The second aspect of the present application provides a high surface energy nickel-based binary metal material, the surface of which has uniformly mixed nickel atoms and modified metal atoms, and the content of modified metal atoms on the surface of the metal material is 1 to 10 at%, so that the surface energy of the metal material is 30 mJ / m 2 Above, wherein the modified metal can form a solid solution with metallic nickel.

[0013] The high surface energy nickel-based binary metal material can be prepared by utilizing the method for increasing the surface energy of nickel metal.

[0014] The third aspect of the present application provides the use of the high surface energy nickel-based binary metal material in the field of water electrolysis, such as hydrogen production by water electrolysis.

[0015] Compared with the prior art, the beneficial effects of this application are at least:

[0016] (1) In a method for improving the surface energy of a nickel metal substrate provided in the present application, a modified metal element that can form a solid solution with nickel metal is selected, and a small amount of modified metal is deposited on the surface of the nickel metal substrate. Then, a short-time heat treatment is performed, so that the modified metal atoms can diffuse on the surface of the nickel metal substrate and mix evenly with the nickel atoms, instead of entering the interior of the nickel metal substrate and forming an ordered alloy structure. This can effectively improve the atomic disorder on the surface of the nickel metal substrate, greatly increase the surface entropy of the nickel metal substrate, and enable it to obtain a higher surface energy. The process is simple, the required amount of modified metal is small, the cost is low, and it is suitable for large-scale production.

[0017] (2) Surface energy is derived from the free energy caused by the unsaturated bonds of surface molecules. The molecules at the surface will try to reduce this free energy by contacting with adjacent phase molecules. Water molecules have a strong bonding ability, so materials with large surface energy (i.e., high bonding potential) interact more strongly with water, and the material has a strong hydrophilicity. The surface energy of the high surface energy nickel-based binary metal material provided in this application is 30mJ / m 2 More than 30mJ / m 2 Less than or equal to 80mJ / m 2 , has good hydrophilicity, and the electrode with good hydrophilicity can effectively improve the contact between the electrode and water during the electrolysis of water, thereby improving the reaction activity of the electrode. Compared with the nickel metal electrode, it reaches 200mA / cm -2 The voltage of the current density can be reduced by 0.2 V, which indicates that it has broad application prospects in fields such as water electrolysis. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments recorded in this application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0019] FIG1 is an XRD diffraction pattern of the nickel-copper binary metal material prepared in Example 9.

[0020] FIG2 is one of the SEM morphology images of the nickel-copper binary metal material prepared in Example 9.

[0021] FIG3 is a second SEM morphology image of the nickel-copper binary metal material prepared in Example 9.

[0022] FIG4 is a diagram showing the distribution and content of Ni in the nickel-copper binary metal material prepared in Example 9.

[0023] FIG5 is a second diagram showing the distribution and content of Ni in the nickel-copper binary metal material prepared in Example 9.

[0024] FIG6 is a diagram showing the distribution and content of Cu in the nickel-copper binary metal material prepared in Example 9.

[0025] FIG7 is a second diagram showing the distribution and content of Cu elements in the nickel-copper binary metal material prepared in Example 9.

[0026] FIG8 is an AC-HADDF-STEM Fourier transform image, atomic image, and element distribution map of the nickel-copper binary metal material prepared in Example 9.

[0027] FIG9 is a three-dimensional atomic reconstruction of the nickel-copper binary metal material prepared in Example 9.

[0028] FIG10 is a high-resolution atomic distribution diagram of the nickel-copper binary metal material prepared in Example 9.

[0029] Figure 11 is an SEM morphology of the nickel-copper binary metal material prepared in Comparative Example 3.

[0030] Figure 12 is a nickel element distribution diagram of the nickel-copper binary metal material prepared in Comparative Example 3.

[0031] Figure 13 is a copper element distribution diagram of the nickel-copper binary metal material prepared in Comparative Example 3.

[0032] Figure 14 is an oxygen element distribution diagram of the nickel-copper binary metal material prepared in Comparative Example 3.

[0033] FIG15 is a contact angle diagram of the nickel-copper binary metal material prepared in Example 9 and water.

[0034] FIG16 is a diagram showing the contact angle between nickel mesh and water.

[0035] FIG17 is a graph showing the hydrogen evolution performance of the nickel-copper binary metal material prepared in Example 9 during electrolysis of water.

[0036] Figure 18 is a performance diagram of hydrogen evolution during electrolysis of water by the nickel-copper binary metal material prepared in Example 20 of the present application.

[0037] Figure 19 is a performance diagram of hydrogen evolution during electrolysis of water by the nickel-copper binary metal material prepared in Example 28 of the present application.

[0038] Figure 20 is a performance diagram of hydrogen evolution during electrolysis of water by the nickel-copper binary metal material prepared in Comparative Example 1 of the present application. DETAILED DESCRIPTION

[0039] The technical solution of this application will be explained in more detail below.

[0040] Some embodiments of the present application provide a method for increasing the surface energy of nickel metal, including:

[0041] Depositing a modified metal layer on a pretreated surface of a metal substrate to form a composite metal material, wherein the metal substrate comprises a first metal, the modified metal layer comprises a second metal, one of the first metal and the second metal is nickel, and the first metal can form a solid solution with the second metal;

[0042] The composite metal material is heat treated in a protective atmosphere to uniformly mix the first metal atoms and the second metal atoms on the surface of the metal matrix, and the content of the second metal atoms on the surface of the metal matrix is ​​at least 1 to 10 at%, thereby obtaining a surface energy of 30 mJ / m 2 The above nickel-based binary metal materials.

[0043] The second metal atom content on the surface of the metal substrate is preferably 2 to 10 at %, more preferably 2 to 5 at %.

[0044] Preferably, the surface energy of the nickel-based binary metal material is greater than 30 mJ / m 2 Less than or equal to 80mJ / m 2 .

[0045] In one embodiment, the second metal includes but is not limited to at least one of copper, iron, cobalt, and manganese, preferably copper, which can infinitely dissolve with nickel, thereby better increasing the disorder of the nickel-based binary metal material and further increasing its surface energy.

[0046] In one embodiment, the method for improving the surface energy of nickel metal specifically includes: depositing a modified metal layer on the surface of a pretreated metal substrate by at least electroplating or chemical plating to form a composite metal material.

[0047] In one embodiment, the electroplating process conditions include: temperature of 20 to 50° C., voltage of -0.1 to -1.5 V, time of 5 to 30 min, metal source concentration of 0.01 to 1 mol / L in the electroplating solution, and complexing agent concentration of 0.01 to 1 mol / L.

[0048] Preferably, the electroplating process conditions include: a temperature of 20-40°C, a voltage of -0.3-1V, a time of 5-15 minutes, a metal source concentration of 0.1-1 mol / L in the electroplating solution, and a complexing agent concentration of 0.1-1 mol / L. These process conditions can produce a metal coating of appropriate thickness while avoiding the formation of an ordered structure.

[0049] In one embodiment, the conditions of the chemical plating process include: the chemical plating solution contains 0.01-1 mol / L of metal source, 0.01-1 mol / L of complexing agent and 0.01-1 mol / L of reducing agent, and the chemical plating time is 5-30 minutes.

[0050] Preferably, the electroless plating process comprises a plating solution containing 0.1-1 mol / L of a metal source, 0.1-1 mol / L of a complexing agent, and 0.1-1 mol / L of a reducing agent, and a plating time of 5-15 minutes. These process conditions can produce a metal coating of suitable thickness while avoiding the formation of an ordered structure.

[0051] In one embodiment, the metal source includes at least one of sulfate, nitrate, and chloride containing the second metal element, but is not limited thereto.

[0052] In one embodiment, the complexing agent includes at least one of sodium tartrate, sodium citrate, ethylenediaminetetraacetic acid, and sodium pyrophosphate, but is not limited thereto.

[0053] In one embodiment, the reducing agent includes at least one of sodium hypophosphite, sodium borohydride, and borane, but is not limited thereto.

[0054] More preferably, in the electroplating process, the metal source is a sulfate containing a second metal element, and the complexing agent is sodium citrate, so as to obtain a more uniform metal coating.

[0055] More preferably, in the chemical plating process, the metal source is a metal chloride containing a second metal element, the complexing agent is sodium citrate, and the reducing agent is sodium borohydride, so as to obtain a more uniform metal coating.

[0056] In one embodiment, the heat treatment comprises: heating the composite metal material to 100-1100° C. at a heating rate of 2-10° C. / min in a protective atmosphere, and keeping the temperature for 20-480 minutes.

[0057] In one embodiment, the protective atmosphere includes a hydrogen and argon mixed atmosphere or a nitrogen atmosphere. For example, the hydrogen and argon mixed atmosphere contains 95 v / v% argon and 5 v / v% hydrogen.

[0058] In one embodiment, the metal substrate is a nickel substrate or a copper substrate with a purity higher than 99%.

[0059] Furthermore, the nickel substrate includes but is not limited to at least one of a nickel sheet, a nickel mesh, and nickel foam, and the copper substrate includes but is not limited to at least one of a copper sheet, a copper mesh, and copper foam.

[0060] In one embodiment, the pretreatment includes: removing pollutants on the surface of the metal substrate using at least an organic solvent and / or an alkaline solution; and removing an oxide layer on the surface of the metal substrate using at least an acidic agent. The pollutants are mainly oil stains.

[0061] In one embodiment, the alkali solution includes at least one of sodium hydroxide and potassium hydroxide, but is not limited thereto.

[0062] In some cases, the concentration of the alkali solution is 0.5 mol / L to 5 mol / L.

[0063] In some cases, the acidic reagent includes any one of sulfuric acid and hydrochloric acid, with a concentration of 0.5 mol / L to 5 mol / L.

[0064] In one embodiment, the organic solvent includes at least one of anhydrous ethanol and anhydrous acetone, but is not limited thereto.

[0065] Some embodiments of the present application provide a high surface energy nickel-based binary metal material prepared by the method for increasing the surface energy of nickel metal.

[0066] Some embodiments of the present application provide a high surface energy nickel-based binary metal material having a surface having uniformly mixed nickel atoms and modified metal atoms, and the content of modified metal atoms on the surface of the metal material is 1 to 10 at%, so that the surface energy of the metal material is 30 mJ / m 2 More than 30mJ / m 2 Less than or equal to 80mJ / m 2 , in which the modified metal can form a solid solution with metallic nickel.

[0067] In one embodiment, the modified metal includes but is not limited to at least one of copper, iron, cobalt, and manganese.

[0068] In one embodiment, the high surface energy nickel-based binary metal material includes 1 to 5 at % of modified metal atoms and 95 to 99 at % of nickel atoms.

[0069] Some embodiments of the present application provide a nickel-copper binary metal material, wherein nickel atoms and copper atoms are uniformly mixed on the surface of the metal material, and the copper atom content on the surface of the metal material is 1 to 10 at%, so that the surface energy of the metal material is 30 mJ / m 2 More than 30mJ / m 2 Less than or equal to 80mJ / m 2 .

[0070] In one embodiment, the nickel-copper binary metal material includes 1 to 5 at % copper atoms and 95 to 99 at % nickel atoms.

[0071] Some embodiments of the present application provide uses of the high surface energy nickel-based binary metal material or the nickel-copper binary metal material in the field of water electrolysis, such as hydrogen production by water electrolysis.

[0072] Some embodiments of the present application provide an electrode for producing hydrogen by electrolysis of water, which comprises the high surface energy nickel-based binary metal material or the nickel-copper binary metal material.

[0073] Some embodiments of the present application provide a water electrolysis hydrogen production system, comprising a hydrogen evolution electrode and an oxygen evolution electrode, at least one of the hydrogen evolution electrode and the oxygen evolution electrode comprising the high surface energy nickel-based binary metal material or the nickel-copper binary metal material.

[0074] The present application will be more fully understood through the following detailed description, which should be read in conjunction with the accompanying drawings. Detailed embodiments of the present application are disclosed herein; however, it should be understood that the disclosed embodiments are merely exemplary of the present application, and that the present application may be embodied in various forms. Therefore, the specific functional details disclosed herein should not be construed as limiting, but rather as a basis for the claims and as a representative basis for teaching those skilled in the art to employ the present application in various ways in virtually any appropriately detailed embodiment.

[0075] Example 1 This example provides a nickel-copper binary metal material, the preparation method of which includes:

[0076] First, a nickel sheet was used as a substrate and pretreated, including: immersing the nickel substrate in anhydrous ethanol and anhydrous acetone in turn and ultrasonicating for 5 minutes respectively to remove surface oil stains, and immersing the nickel substrate in 0.5 mol / L sulfuric acid solution and ultrasonicating for 5 minutes to remove surface oxides.

[0077] Then, copper nitrate solution was used as the plating solution, citric acid was used as the complexing agent, the copper nitrate concentration in the plating solution was 0.01 mol / L, and the citric acid concentration was 0.01 mol / L. Electroplating was carried out at a voltage of -0.3 V for 5 minutes to obtain a nickel substrate with a copper layer plated on the surface. The electroplating was carried out at 25°C.

[0078] Afterwards, heat treatment was carried out in a reducing mixed gas atmosphere of 5% hydrogen and 95% argon, with a heat treatment temperature of 100°C, a heating rate of 10°C / min, and a heat treatment time of 20 minutes. The material was then cooled in the furnace to obtain the nickel-copper binary metal material Ni-Cu@1.

[0079] Example 2 The only difference between this example and Example 1 is that the concentration of the sulfuric acid solution in Example 2 is 5 mol / L, the concentration of copper nitrate in the electroplating solution is 0.1 mol / L, and the concentration of citric acid is 0.1 mol / L. The heat treatment temperature is 1100°C, the heat treatment time is 480 minutes, and the heating rate is 2°C / min. The other conditions remain the same as in Example 1.

[0080] In this embodiment, a nickel-copper binary metal material Ni-Cu@11 is prepared.

[0081] Example 3 This example provides a nickel-copper binary metal material, the preparation method of which includes:

[0082] First, a nickel sheet was used as a substrate and pretreated, including: immersing the nickel substrate in anhydrous ethanol and anhydrous acetone in turn and ultrasonicating for 5 minutes respectively to remove surface oil stains, and immersing the nickel substrate in a 2 mol / L sulfuric acid solution and ultrasonicating for 5 minutes to remove surface oxides.

[0083] Subsequently, copper sulfate solution was used as the electroplating solution, sodium pyrophosphate was used as the chelating agent, the copper sulfate concentration in the electroplating solution was 0.01 mol / L, and the sodium pyrophosphate concentration was 0.01 mol / L. Electroplating was carried out at a voltage of -0.3 V for 5 minutes to obtain a nickel substrate with a copper layer plated on the surface. The electroplating was carried out at 25°C.

[0084] Then, heat treatment was carried out in an inert atmosphere of nitrogen at a heat treatment temperature of 100° C., a heating rate of 10° C. / min, and a heat treatment time of 20 minutes, followed by furnace cooling.

[0085] In this embodiment, a nickel-copper binary metal material Ni-Cu@2 is prepared.

[0086] Example 4 This example provides a nickel-copper binary metal material, the preparation method of which includes:

[0087] The only difference between this embodiment and embodiment 3 is that the concentration of the sulfuric acid solution in embodiment 4 is 5 mol / L, the concentration of copper sulfate in the electroplating solution is 0.1 mol / L, and the concentration of sodium pyrophosphate is 0.1 mol / L. The heat treatment temperature is 1100°C, the heat treatment time is 480 minutes, and the heating rate is 2°C / min. The remaining conditions remain the same as those in embodiment 3.

[0088] In this embodiment, a nickel-copper binary metal material Ni-Cu@22 is prepared.

[0089] Example 5 This example provides a nickel-copper binary metal material, the preparation method of which includes:

[0090] First, a nickel sheet was used as a substrate and pretreated, including: immersing the nickel substrate in a 2 mol / L sodium hydroxide solution and ultrasonicating for 5 minutes to remove surface oil stains, and then immersing the nickel substrate in a 2 mol / L hydrochloric acid solution and ultrasonicating for 5 minutes to remove surface oxides.

[0091] Subsequently, copper chloride solution was used as the plating solution, ethylenediaminetetraacetic acid (EDTA) was used as the complexing agent, the copper chloride concentration in the plating solution was 0.01 mol / L, and the EDTA concentration was 0.01 mol / L. Electroplating was carried out at a voltage of -0.3 V for 5 minutes to obtain a nickel substrate with a copper layer plated on the surface. The electroplating was carried out at 25°C.

[0092] Then, heat treatment was performed in a reducing atmosphere of 5% hydrogen and 95% argon at a temperature of 100° C. for 20 minutes.

[0093] In this embodiment, a nickel-copper binary metal material Ni-Cu@3 is obtained.

[0094] Example 6 This example provides a nickel-copper binary metal material, the preparation method of which includes:

[0095] The only difference between Example 6 and Example 5 is that the concentration of the sodium hydroxide solution in Example 6 is 5 mol / L, the concentration of the hydrochloric acid solution is 5 mol / L, the concentration of the copper chloride in the electroplating solution is 0.1 mol / L, and the concentration of EDTA is 0.1 mol / L. The heat treatment temperature is 1100°C, the heat treatment time is 480 minutes, and the heating rate is 2°C / min. The other conditions remain the same as in Example 5.

[0096] In this embodiment, a nickel-copper binary metal material Ni-Cu@33 is prepared.

[0097] Example 7 This example provides a nickel-copper binary metal material, the preparation method of which includes:

[0098] First, a nickel mesh was pretreated as a substrate, including: immersing the nickel substrate in anhydrous ethanol and anhydrous acetone in turn and ultrasonicating for 5 minutes respectively to remove surface oil stains, and then immersing the nickel substrate in a 2 mol / L sulfuric acid solution and ultrasonicating for 5 minutes to remove surface oxides.

[0099] Subsequently, copper nitrate solution was used as the plating solution, citric acid was used as the chelating agent, the copper nitrate concentration in the plating solution was 0.01 mol / L, and the citric acid concentration was 0.01 mol / L. Electroplating was carried out at a voltage of -0.3 V for 5 minutes to obtain a nickel substrate with a copper layer plated on the surface. The electroplating was carried out at 25°C.

[0100] Afterwards, heat treatment was carried out in a reducing mixed gas atmosphere of 5% hydrogen and 95% argon, with a heat treatment temperature of 100°C, a heating rate of 10°C / min, and a heat treatment time of 20 minutes. The material was cooled in the furnace to obtain the nickel-copper binary metal material Ni-Cu@4.

[0101] Example 8 This example provides a nickel-copper binary metal material, the preparation method of which includes:

[0102] The only difference between this embodiment and embodiment 7 is that the concentration of the sulfuric acid solution in embodiment 8 is 5 mol / L, the concentration of copper nitrate in the electroplating solution is 0.1 mol / L, and the concentration of citric acid is 0.1 mol / L. The heat treatment temperature is 1100°C, the heat treatment time is 480 minutes, and the heating rate is 2°C / min. The remaining conditions remain the same as those in embodiment 7.

[0103] In this embodiment, a nickel-copper binary metal material Ni-Cu@44 is prepared.

[0104] Example 9 This example provides a nickel-copper binary metal material, the preparation method of which includes:

[0105] First, a nickel mesh was pretreated as a substrate, including: immersing the nickel substrate in anhydrous ethanol and anhydrous acetone in turn and ultrasonicating for 5 minutes respectively to remove surface oil stains, and then immersing the nickel substrate in a 2 mol / L sulfuric acid solution and ultrasonicating for 5 minutes to remove surface oxides.

[0106] Subsequently, copper sulfate solution was used as the plating solution, sodium pyrophosphate was used as the chelating agent, the copper sulfate concentration in the plating solution was 0.01 mol / L, and the sodium pyrophosphate concentration was 0.01 mol / L. Electroplating was carried out at a voltage of -0.3 V for 5 minutes to obtain a nickel substrate with a copper layer plated on the surface. The electroplating was carried out at 25°C.

[0107] Afterwards, heat treatment was carried out in a nitrogen atmosphere at a temperature of 100°C, a heating rate of 10°C / min, and a heat treatment time of 20 minutes. The material was cooled in the furnace to obtain a nickel-copper binary metal material Ni-Cu@5.

[0108] Example 10 This example provides a nickel-copper binary metal material, the preparation method of which includes:

[0109] The only difference between this embodiment and embodiment 9 is that the concentration of the sulfuric acid solution in embodiment 10 is 5 mol / L, the concentration of copper sulfate in the electroplating solution is 0.1 mol / L, and the concentration of sodium pyrophosphate is 0.1 mol / L. The heat treatment temperature is 1100°C, the heat treatment time is 480 minutes, and the heating rate is 2°C / min. The other conditions remain the same as those in embodiment 9.

[0110] In this embodiment, a nickel-copper binary metal material Ni-Cu@55 is prepared.

[0111] Example 11 This example provides a nickel-copper binary metal material, the preparation method of which includes:

[0112] First, a nickel mesh was used as a substrate and pretreated, including: immersing the nickel substrate in a 2 mol / L sodium hydroxide solution and ultrasonically treating it for 5 minutes to remove surface oil stains, and then immersing the nickel substrate in a 2 mol / L hydrochloric acid solution and ultrasonically treating it for 5 minutes to remove surface oxides.

[0113] Subsequently, copper chloride solution was used as the plating solution, EDTA was used as the complexing agent, the copper chloride concentration in the plating solution was 0.01 mol / L, and the EDTA concentration was 0.01 mol / L. Electroplating was carried out at a voltage of -0.3 V for 5 minutes to obtain a nickel substrate with a copper layer plated on the surface. The electroplating was carried out at 25°C.

[0114] Afterwards, heat treatment was performed in a reducing atmosphere of 5% hydrogen and 95% argon at a temperature of 100° C. for 20 minutes to obtain a nickel-copper binary metal material Ni-Cu@6.

[0115] Example 12 This example provides a nickel-copper binary metal material, the preparation method of which includes:

[0116] The only difference between this embodiment and embodiment 11 is that in embodiment 12, the concentration of the sodium hydroxide solution is 5 mol / L, the concentration of the hydrochloric acid solution is 5 mol / L, the concentration of the copper chloride in the electroplating solution is 0.1 mol / L, and the concentration of the EDTA is 0.1 mol / L. The heat treatment temperature is 1100°C, the heat treatment time is 480 minutes, and the heating rate is 2°C / min. The remaining conditions remain the same as those in embodiment 11.

[0117] In this embodiment, a nickel-copper binary metal material Ni-Cu@66 is prepared.

[0118] Example 13 This example provides a nickel-copper binary metal material, the preparation method of which includes:

[0119] First, nickel foam was used as a substrate and pretreated, including: immersing the substrate in anhydrous ethanol and anhydrous acetone in sequence and ultrasonically treating them for 5 minutes respectively to remove surface oil stains, and then immersing the substrate in a 2 mol / L sulfuric acid solution and ultrasonically treating them for 5 minutes to remove surface oxides.

[0120] Afterwards, copper nitrate was used as the plating solution and citric acid was used as the complexing agent. The copper nitrate concentration in the plating solution was 0.01 mol / L and the citric acid concentration was 0.01 mol / L. Electroplating was carried out at a voltage of -0.3 V for 5 minutes to obtain a nickel substrate with a copper layer plated on the surface. The electroplating was carried out at 25°C.

[0121] Then, heat treatment was carried out in a reducing mixed gas atmosphere of 5% hydrogen and 95% argon, with a heat treatment temperature of 100°C, a heating rate of 10°C / min, cooling with the furnace, and a heat treatment time of 20 minutes to obtain the nickel-copper binary metal material Ni-Cu@7.

[0122] Example 14 This example provides a nickel-copper binary metal material, the preparation method of which includes:

[0123] The only difference between this example and Example 13 is that in Example 14, the concentration of the sulfuric acid solution is 5 mol / L, the concentration of copper nitrate in the electroplating solution is 0.1 mol / L, and the concentration of citric acid is 0.1 mol / L. The heat treatment temperature is 1100°C, the heat treatment time is 480 minutes, and the heating rate is 2°C / min. The remaining conditions remain the same as in Example 13.

[0124] In this embodiment, a nickel-copper binary metal material Ni-Cu@77 is prepared.

[0125] Example 15 This example provides a nickel-copper binary metal material, the preparation method of which includes:

[0126] First, nickel foam was used as a substrate and pretreated, including: immersing the substrate in anhydrous ethanol and anhydrous acetone in sequence and ultrasonically treating them for 5 minutes respectively to remove surface oil stains, and then immersing the substrate in 2 mol / L sulfuric acid solution and ultrasonically treating it for 5 minutes to remove surface oxides.

[0127] Then, copper sulfate was used as the plating solution and sodium pyrophosphate was used as the complexing agent. The concentration of copper sulfate in the plating solution was 0.01 mol / L and the concentration of sodium pyrophosphate was 0.01 mol / L. Electroplating was carried out at a voltage of -0.3 V for 5 minutes to obtain a nickel substrate with a copper layer plated on the surface. The electroplating was carried out at 25°C.

[0128] Thereafter, heat treatment was carried out in an inert atmosphere of nitrogen at a heat treatment temperature of 100°C, a heating rate of 10°C / min, followed by furnace cooling, and a heat treatment time of 20 minutes to obtain a nickel-copper binary metal material Ni-Cu@8.

[0129] Example 16 This example provides a nickel-copper binary metal material, the preparation method of which includes:

[0130] The only difference between this example and Example 15 is that in Example 16, the concentration of the sulfuric acid solution is 5 mol / L, the concentration of copper sulfate in the electroplating solution is 0.1 mol / L, and the concentration of sodium pyrophosphate is 0.1 mol / L. The heat treatment temperature is 1100°C, the heat treatment time is 480 minutes, and the heating rate is 2°C / min. All other conditions remain the same as in Example 15.

[0131] In this embodiment, a nickel-copper binary metal material Ni-Cu@88 is prepared.

[0132] Example 17 This example provides a nickel-copper binary metal material, the preparation method of which includes:

[0133] First, nickel foam was used as a substrate and pretreated, including: immersing the substrate in a 2 mol / L sodium hydroxide solution and ultrasonicating for 5 minutes to remove surface oil stains, and then immersing the substrate in a 2 mol / L hydrochloric acid solution and ultrasonicating for 5 minutes to remove surface oxides.

[0134] Subsequently, copper chloride was used as the plating solution and EDTA was used as the complexing agent. The copper chloride concentration in the plating solution was 0.01 mol / L and the EDTA concentration was 0.01 mol / L. Electroplating was carried out at a voltage of -0.3 V for 5 minutes to obtain a nickel substrate with a copper layer plated on the surface. The electroplating was carried out at 25°C.

[0135] Then, a heat treatment was performed in a reducing atmosphere of 5% hydrogen and 95% argon at a temperature of 100° C. for 20 minutes to obtain a nickel-copper binary metal material Ni-Cu@9.

[0136] Example 18 This example provides a nickel-copper binary metal material, the preparation method of which includes:

[0137] The only difference between this example and Example 17 is that in Example 18, the concentration of the sodium hydroxide solution is 5 mol / L, the concentration of the hydrochloric acid solution is 5 mol / L, the concentration of the copper chloride in the electroplating solution is 0.1 mol / L, and the concentration of EDTA is 0.1 mol / L. The heat treatment temperature is 1100°C, the heat treatment time is 480 minutes, and the heating rate is 2°C / min. The remaining conditions remain the same as in Example 17.

[0138] In this embodiment, a nickel-copper binary metal material Ni-Cu@99 is prepared.

[0139] Example 19 This example provides a nickel-copper binary metal material, the preparation method of which includes:

[0140] First, a copper sheet was used as a substrate and pretreated, including: immersing the substrate in anhydrous ethanol and anhydrous acetone in sequence and ultrasonically treating each for 5 minutes to remove surface oil stains, and then immersing the substrate in a 2 mol / L sulfuric acid solution and ultrasonically treating each for 5 minutes to remove surface oxides.

[0141] Subsequently, nickel nitrate was used as the plating solution and citric acid was used as the complexing agent. The nickel nitrate concentration in the plating solution was 0.01 mol / L and the citric acid concentration was 0.01 mol / L. Electroplating was carried out at a voltage of -0.3 V for 5 minutes to obtain a copper substrate with a nickel layer plated on the surface. The electroplating was carried out at 25°C.

[0142] Then, heat treatment was performed in a reducing mixed gas atmosphere of 5% hydrogen and 95% argon at a temperature of 100° C., a heating rate of 10° C. / min, and a heat treatment time of 20 minutes. The material was cooled in the furnace to obtain a nickel-copper binary metal material Ni@1-Cu.

[0143] Example 20 This example provides a nickel-copper binary metal material, the preparation method of which includes:

[0144] The only difference between this example and Example 19 is that in Example 20, the concentration of the sulfuric acid solution is 5 mol / L, the concentration of nickel nitrate in the electroplating solution is 0.1 mol / L, and the concentration of citric acid is 0.1 mol / L. The heat treatment temperature is 1100°C, the heat treatment time is 480 minutes, and the heating rate is 2°C / min. The remaining conditions remain the same as in Example 19.

[0145] In this embodiment, a nickel-copper binary metal material Ni@11-Cu is prepared.

[0146] Example 21 This example provides a nickel-copper binary metal material, the preparation method of which includes:

[0147] First, a copper sheet was used as a substrate and pretreated, including: immersing the substrate in anhydrous ethanol and anhydrous acetone in sequence and ultrasonically treating each for 5 minutes to remove surface oil stains, and then immersing the substrate in a 2 mol / L sulfuric acid solution and ultrasonically treating each for 5 minutes to remove surface oxides.

[0148] Subsequently, nickel sulfate was used as the plating solution and sodium pyrophosphate was used as the complexing agent. The nickel sulfate concentration in the plating solution was 0.01 mol / L and the sodium pyrophosphate concentration was 0.01 mol / L. Electroplating was carried out at a voltage of -0.3 V for 5 minutes to obtain a copper substrate with a nickel layer plated on the surface. The electroplating was carried out at 25°C.

[0149] Then, heat treatment was performed under an inert nitrogen atmosphere at a temperature of 100°C, a heating rate of 10°C / min, a heat treatment time of 20 minutes, and furnace cooling to obtain a nickel-copper binary metal material Ni@2-Cu.

[0150] Example 22 This example provides a nickel-copper binary metal material, the preparation method of which includes:

[0151] The only difference between this example and Example 21 is that in Example 22, the concentration of the sulfuric acid solution is 5 mol / L, the concentration of nickel sulfate in the electroplating solution is 0.1 mol / L, and the concentration of sodium pyrophosphate is 0.1 mol / L. The heat treatment temperature is 1100°C, the heat treatment time is 480 minutes, and the heating rate is 2°C / min. All other conditions remain the same as in Example 21.

[0152] In this embodiment, a nickel-copper binary metal material Ni@22-Cu is prepared.

[0153] Example 23 This example provides a nickel-copper binary metal material, the preparation method of which includes:

[0154] First, a copper sheet was used as a substrate and pretreated, including: immersing the substrate in 2 mol / L sodium hydroxide and ultrasonically treating for 5 minutes to remove surface oil stains, and then immersing the substrate in 2 mol / L hydrochloric acid and ultrasonically treating for 5 minutes to remove surface oxides.

[0155] Subsequently, nickel chloride was used as the plating solution and EDTA was used as the complexing agent. The nickel chloride concentration in the plating solution was 0.01 mol / L and the EDTA concentration was 0.01 mol / L. Electroplating was carried out at a voltage of -0.3 V for 5 minutes to obtain a copper substrate with a nickel layer plated on the surface. The electroplating was carried out at 25°C.

[0156] The heat treatment was carried out in a reducing atmosphere of 5% hydrogen and 95% argon at a temperature of 100° C. for 20 minutes to obtain a nickel-copper binary metal material Ni@3-Cu.

[0157] Example 24 This example provides a nickel-copper binary metal material, the preparation method of which includes:

[0158] The only difference between this example and Example 23 is that in Example 24, the concentration of the sodium hydroxide solution is 5 mol / L, the concentration of the hydrochloric acid solution is 5 mol / L, the concentration of nickel chloride in the electroplating solution is 0.1 mol / L, and the concentration of EDTA is 0.1 mol / L. The heat treatment temperature is 1100°C, the heat treatment time is 480 minutes, and the heating rate is 2°C / min. All other conditions remain the same as in Example 23.

[0159] In this embodiment, a nickel-copper binary metal material Ni@33-Cu is prepared.

[0160] Example 25 This example provides a nickel-copper binary metal material, the preparation method of which includes:

[0161] First, a copper mesh was used as a substrate and pretreated, including: immersing the substrate in anhydrous ethanol and anhydrous acetone in sequence and ultrasonically treating them for 5 minutes respectively to remove surface oil stains, and then immersing the substrate in a 2 mol / L sulfuric acid solution and ultrasonically treating them for 5 minutes to remove surface oxides.

[0162] Subsequently, nickel nitrate was used as the plating solution and citric acid was used as the complexing agent. The nickel nitrate concentration in the plating solution was 0.01 mol / L and the citric acid concentration was 0.01 mol / L. Electroplating was carried out at a voltage of -0.3 V for 5 minutes to obtain a copper substrate with a nickel layer plated on the surface. The electroplating was carried out at 25°C.

[0163] Then, heat treatment was carried out in a reducing mixed gas atmosphere of 5% hydrogen and 95% argon, with a heat treatment temperature of 100°C, a heating rate of 10°C / min, cooling with the furnace, and a heat treatment time of 20 minutes to obtain a nickel-copper binary metal material Ni@4-Cu.

[0164] Example 26 This example provides a nickel-copper binary metal material, the preparation method of which includes:

[0165] The only difference between this example and Example 25 is that in Example 26, the concentration of the sulfuric acid solution is 5 mol / L, the concentration of nickel nitrate in the electroplating solution is 0.1 mol / L, and the concentration of citric acid is 0.1 mol / L. The heat treatment temperature is 1100°C, the heat treatment time is 480 minutes, and the heating rate is 2°C / min. The remaining conditions remain the same as in Example 25.

[0166] In this embodiment, a nickel-copper binary metal material Ni@44-Cu is prepared.

[0167] Example 27 This example provides a nickel-copper binary metal material, the preparation method of which includes:

[0168] First, a copper mesh was used as a substrate and pretreated, including: immersing the substrate in anhydrous ethanol and anhydrous acetone in turn and ultrasonicating for 5 minutes respectively to remove surface oil stains, and then immersing the substrate in 2 mol / L sulfuric acid and ultrasonicating for 5 minutes to remove surface oxides.

[0169] Subsequently, copper sulfate was used as the plating solution and sodium pyrophosphate was used as the chelating agent. The copper sulfate concentration in the plating solution was 0.01 mol / L and the sodium pyrophosphate concentration was 0.01 mol / L. Electroplating was carried out at a voltage of -0.3 V for 5 minutes to obtain a nickel substrate with a copper layer plated on the surface. The electroplating was carried out at 25°C.

[0170] Then, heat treatment was performed under an inert nitrogen atmosphere at a temperature of 100°C, a heating rate of 10°C / min, followed by furnace cooling, for 20 minutes to obtain a nickel-copper binary metal material Ni-Cu@5.

[0171] Example 28 This example provides a nickel-copper binary metal material, the preparation method of which includes:

[0172] The only difference between this example and Example 27 is that in Example 28, the concentration of the sulfuric acid solution is 5 mol / L, the concentration of nickel sulfate in the electroplating solution is 0.1 mol / L, and the concentration of sodium pyrophosphate is 0.1 mol / L. The heat treatment temperature is 1100°C, the heat treatment time is 480 minutes, and the heating rate is 2°C / min. All other conditions remain the same as in Example 27.

[0173] In this embodiment, a nickel-copper binary metal material Ni-Cu@55 is prepared.

[0174] Example 29 This example provides a nickel-copper binary metal material, the preparation method of which includes:

[0175] First, a copper mesh was used as a substrate and pretreated, including immersing the substrate in a 2 mol / L sodium hydroxide solution and ultrasonicating for 5 minutes to remove surface oil stains, and then immersing the substrate in a 2 mol / L hydrochloric acid solution and ultrasonicating for 5 minutes to remove surface oxides.

[0176] Subsequently, nickel chloride was used as the plating solution and ethylenediaminetetraacetic acid (EDTA) was used as the complexing agent, and electroplating was carried out at a voltage of -0.3 V for 5 minutes to obtain a copper substrate with a nickel layer plated on the surface. The nickel chloride concentration in the plating solution was 0.01 mol / L and the ethylenediaminetetraacetic acid (EDTA) concentration was 0.01 mol / L, and the electroplating was carried out at 25°C.

[0177] Then, heat treatment was performed in a reducing atmosphere of 5% hydrogen and 95% argon at a temperature of 100° C. for 20 minutes to obtain a nickel-copper binary metal material Ni@6-Cu.

[0178] Example 30 This example provides a nickel-copper binary metal material, the preparation method of which includes:

[0179] The only difference between this example and Example 29 is that in Example 30, the concentration of the sodium hydroxide solution is 5 mol / L, the concentration of the hydrochloric acid solution is 5 mol / L, the concentration of nickel chloride in the electroplating solution is 0.1 mol / L, and the concentration of EDTA is 0.1 mol / L. The heat treatment temperature is 1100° C., the heat treatment time is 480 minutes, and the heating rate is 2° C. / min. The remaining conditions remain the same as in Example 29.

[0180] In this embodiment, a nickel-copper binary metal material Ni@66-Cu is prepared.

[0181] Example 31 This example provides a nickel-copper binary metal material, the preparation method of which includes:

[0182] First, the copper foam was used as a substrate and pretreated, including: immersing the substrate in anhydrous ethanol and anhydrous acetone in sequence and ultrasonically treating them for 5 minutes respectively to remove surface oil stains, and then immersing the substrate in 2 mol / L sulfuric acid and ultrasonically treating them for 5 minutes to remove surface oxides.

[0183] Subsequently, nickel nitrate was used as the electroplating solution, and citric acid was used as the complexing agent. The concentration of nickel nitrate and citric acid in the electroplating solution was 0.01 mol / L. Electroplating was carried out at a voltage of -0.3 V for 5 minutes to obtain a copper substrate with a nickel layer on the surface. The electroplating was carried out at 25°C.

[0184] Then, heat treatment was carried out in a reducing mixed gas atmosphere of 5% hydrogen and 95% argon, with a heat treatment temperature of 100°C, a heating rate of 10°C / min, and a heat treatment time of 20 minutes. The material was cooled in the furnace to obtain the nickel-copper binary metal material Ni@7-Cu.

[0185] Example 32 This example provides a nickel-copper binary metal material, the preparation method of which includes:

[0186] The only difference between this example and Example 31 is that in Example 32, the concentration of the sulfuric acid solution is 5 mol / L, the concentration of nickel nitrate in the electroplating solution is 0.1 mol / L, and the concentration of citric acid is 0.1 mol / L. The heat treatment temperature is 1100°C, the heat treatment time is 480 minutes, and the heating rate is 2°C / min. All other conditions remain the same as in Example 31.

[0187] In this embodiment, a nickel-copper binary metal material Ni@77-Cu is prepared.

[0188] Example 33 This example provides a nickel-copper binary metal material, the preparation method of which includes:

[0189] First, the copper foam was used as a substrate and pretreated, including: immersing the substrate in anhydrous ethanol and anhydrous acetone in sequence and ultrasonically treating them for 5 minutes respectively to remove surface oil stains, and then immersing the substrate in 2 mol / L sulfuric acid and ultrasonically treating them for 5 minutes to remove surface oxides.

[0190] Subsequently, nickel sulfate was used as the plating solution and sodium pyrophosphate was used as the complexing agent. The nickel sulfate concentration in the plating solution was 0.01 mol / L and the sodium pyrophosphate concentration was 0.01 mol / L. Electroplating was carried out at a voltage of -0.3 V for 5 minutes to obtain a copper substrate with a nickel layer plated on the surface. The electroplating was carried out at 25°C.

[0191] Then, heat treatment was carried out in an inert atmosphere of nitrogen at a heat treatment temperature of 100°C, a heating rate of 10°C / min, and a heat treatment time of 20 minutes. The material was cooled in the furnace to obtain a nickel-copper binary metal material Ni@8-Cu.

[0192] Example 34 This example provides a nickel-copper binary metal material, the preparation method of which includes:

[0193] The only difference between this example and Example 33 is that in Example 34, the concentration of sulfuric acid is 5 mol / L, the concentration of nickel sulfate in the electroplating solution is 0.1 mol / L, and the concentration of sodium pyrophosphate is 0.1 mol / L. The heat treatment temperature is 1100°C, the heat treatment time is 480 minutes, and the heating rate is 2°C / min. All other conditions remain the same as in Example 33.

[0194] In this embodiment, a nickel-copper binary metal material Ni@88-Cu is prepared.

[0195] Example 35 This example provides a nickel-copper binary metal material, the preparation method of which includes:

[0196] First, the copper foam was used as a substrate and pretreated, including immersing the substrate in a 2 mol / L sodium hydroxide solution and ultrasonicating for 5 minutes to remove surface oil stains, and then immersing the substrate in a 2 mol / L hydrochloric acid solution and ultrasonicating for 5 minutes to remove surface oxides.

[0197] Subsequently, nickel chloride was used as the plating solution and EDTA was used as the complexing agent. The nickel chloride concentration in the plating solution was 0.01 mol / L and the EDTA concentration was 0.01 mol / L. Electroplating was carried out at a voltage of -0.3 V for 5 minutes to obtain a copper substrate with a nickel layer plated on the surface. The electroplating was carried out at 25°C.

[0198] Then, a heat treatment was performed in a reducing atmosphere of 5% hydrogen and 95% argon at a temperature of 100° C. for 20 minutes to obtain a nickel-copper binary metal material Ni@9-Cu.

[0199] Example 36 This example provides a nickel-copper binary metal material, the preparation method of which includes:

[0200] The only difference between this example and Example 35 is that in Example 36, the concentration of the sodium hydroxide solution is 5 mol / L, the concentration of the hydrochloric acid solution is 5 mol / L, the concentration of nickel chloride in the electroplating solution is 0.1 mol / L, and the concentration of EDTA is 0.1 mol / L. The heat treatment temperature is 1100°C, the heat treatment time is 480 minutes, and the heating rate is 2°C / min. The remaining conditions remain the same as in Example 35.

[0201] In this embodiment, a nickel-copper binary metal material Ni@99-Cu is prepared.

[0202] Example 37 This example provides a nickel-copper binary metal material, the preparation method of which includes:

[0203] First, a nickel sheet was used as a substrate and pretreated, including: immersing the substrate in anhydrous ethanol and anhydrous acetone in sequence and ultrasonically treating each for 5 minutes to remove surface oil stains, and then immersing the substrate in 2 mol / L sulfuric acid and ultrasonically treating each for 5 minutes to remove surface oxides.

[0204] Subsequently, copper nitrate was used as a copper source, citric acid as a chelating agent, hypophosphite as a reducing agent, the concentration of copper nitrate in the chemical plating solution was 0.01 mol / L, the concentration of citric acid was 0.01 mol / L, and the concentration of hypophosphite was 0.01 mol / L, and the chemical plating was carried out for 5 minutes.

[0205] Then, heat treatment was carried out in a reducing atmosphere of 5% hydrogen and 95% argon at a temperature of 100° C. for 20 minutes to obtain a nickel-copper binary metal material Ni-Cu@@1.

[0206] Example 38 This example provides a nickel-iron binary metal material, the preparation method of which includes:

[0207] First, a nickel sheet was used as a substrate and pretreated, including: immersing the nickel substrate in anhydrous ethanol and anhydrous acetone in turn and ultrasonicating for 5 minutes respectively to remove surface oil stains, and immersing the nickel substrate in 0.5 mol / L sulfuric acid solution and ultrasonicating for 5 minutes to remove surface oxides.

[0208] Subsequently, ferric nitrate was used as the plating solution and sodium citrate was used as the chelating agent. The concentration of ferric nitrate in the plating solution was 0.01 mol / L and the concentration of sodium citrate was 0.01 mol / L. Electroplating was carried out at a voltage of -0.6 V for 5 minutes to obtain a nickel substrate with an iron layer plated on the surface. The electroplating was carried out at 25°C.

[0209] Then, heat treatment was carried out in a reducing mixed gas atmosphere of 5% hydrogen and 95% argon, with a heat treatment temperature of 100°C, a heating rate of 10°C / min, and a heat treatment time of 20 minutes. The material was cooled in the furnace to obtain nickel-iron metal material Ni-Fe@1.

[0210] Example 39 This example provides a nickel-cobalt binary metal material, the preparation method of which includes:

[0211] First, a nickel sheet was used as a substrate and pretreated, including: immersing the nickel substrate in anhydrous ethanol and anhydrous acetone in turn and ultrasonicating for 5 minutes respectively to remove surface oil stains, and immersing the nickel substrate in 0.5 mol / L sulfuric acid solution and ultrasonicating for 5 minutes to remove surface oxides.

[0212] Subsequently, cobalt nitrate was used as the plating solution, and sodium citrate was used as the complexing agent. The concentration of cobalt nitrate and sodium citrate in the plating solution was 0.01 mol / L. Electroplating was carried out at a voltage of -0.8 V for 5 minutes to obtain a nickel substrate with a cobalt layer on the surface. The electroplating was carried out at 25°C.

[0213] Then, heat treatment was carried out in a reducing mixed gas atmosphere of 5% hydrogen and 95% argon, with a heat treatment temperature of 100°C, a heating rate of 10°C / min, and a heat treatment time of 20 minutes. The material was cooled in the furnace to obtain a nickel-cobalt metal material Ni-Co@1.

[0214] Example 40 This example provides a nickel-manganese binary metal material, the preparation method of which includes:

[0215] First, a nickel sheet was used as a substrate and pretreated, including: immersing the nickel substrate in anhydrous ethanol and anhydrous acetone in turn and ultrasonicating for 5 minutes respectively to remove surface oil stains, and immersing the nickel substrate in 0.5 mol / L sulfuric acid solution and ultrasonicating for 5 minutes to remove surface oxides.

[0216] Subsequently, manganese nitrate was used as the plating solution and sodium citrate was used as the complexing agent. The concentration of manganese nitrate in the plating solution was 0.01 mol / L and the concentration of sodium citrate was 0.01 mol / L. Electroplating was carried out at a voltage of -1.0 V for 5 minutes to obtain a nickel substrate with a manganese layer plated on the surface. The electroplating was carried out at 25°C.

[0217] Then, heat treatment was carried out in a reducing mixed gas atmosphere of 5% hydrogen and 95% argon, with a heat treatment temperature of 100°C, a heating rate of 10°C / min, cooling with the furnace, and a heat treatment time of 20 minutes to obtain a nickel-manganese metal material Ni-Mn@1.

[0218] Comparative Example 1 The only difference between this comparative example and Example 9 is that no heat treatment is performed in Comparative Example 1, and the other conditions remain the same as in Example 9.

[0219] Comparative Example 2 The only difference between this comparative example and Example 9 is that the concentration of copper sulfate in the electroplating solution in Comparative Example 2 is 0.2 mol / L, and the other conditions remain the same as those in Example 9.

[0220] Comparative Example 3 The only difference between this comparative example and Example 9 is that the heat treatment in Comparative Example 3 is carried out in air, and the other conditions are consistent with Example 9.

[0221] Comparative Example 4 The only difference between this comparative example and Example 9 is that the heat treatment time in Comparative Example 4 is 5 minutes, and the other conditions are consistent with Example 9.

[0222] Comparative Example 5 The only difference between this comparative example and Example 9 is that the heat treatment time in Comparative Example 5 is 600 minutes, and the other conditions remain the same as in Example 9.

[0223] The surface energy of the binary metal materials obtained in Examples 1-40 and Comparative Examples 1-5 was measured and calculated using a contact angle tester in combination with the Owens equation. The test results are shown in Table 1 below.

[0224] Owens formula: γ SL =γ S +γ L -2(γ SD γ LD ) 1 / 2 -2(γ SP γ LP ) 1 / 2

[0225] Among them, γ SL is the solid-liquid interfacial tension; γ S is the solid surface energy; γ L is the surface tension of the liquid; γ SD is the solid dispersion force; γ LD is the liquid dispersion force; γ SP is the solid polar force; γ LP is the liquid polarity force.

[0226] Table 1 Comparison of contact angles and surface energies of alloys obtained in Examples 1-40 and Comparative Examples 1-5

[0227] As shown in Table 1 above, after copper plating on a pretreated nickel metal substrate or nickel plating on a pretreated copper metal substrate, a short-term heat treatment in a reducing atmosphere or an inert atmosphere is performed to obtain a nickel-copper binary metal material with uniform surface atomic mixing, no element segregation and phase separation, and high surface energy. The materials all exhibit large surface energy and good hydrophilicity, and their surface energy is significantly improved relative to the nickel metal substrate. The samples in the comparative examples have different degrees of decrease in surface energy relative to the nickel metal substrate because the nickel and copper atoms are not uniformly mixed and the surface energy of the copper metal is less than that of the nickel metal.

[0228] Similarly, binary metal materials with high surface energy can be produced by plating iron, cobalt or manganese on a pretreated nickel metal substrate and then performing a short-term heat treatment in a reducing atmosphere or an inert atmosphere.

[0229] Further, please refer to Figure 1, which is an XRD diffraction pattern of the nickel-copper binary metal material prepared in Example 9. The characteristic peak of nickel appears, and the characteristic peak of copper does not appear, indicating that the copper doping amount is low and no nickel-copper alloy is formed. At the same time, the nickel and copper in this nickel-copper binary metal material do not form an ordered structure possessed by an alloy. Therefore, the description of "nickel-copper alloy" in the domestic priority text (i.e., CN202311153662.8) has been corrected in this application.

[0230] Figures 2 and 3 are SEM morphologies of the nickel-copper binary metal material prepared in Example 9, which has no obvious difference from the pure nickel mesh.

[0231] 4 to 7 are element distribution and content diagrams of the nickel-copper binary metal material prepared in Example 9. It can be seen that the copper element is evenly distributed on the surface of the nickel metal substrate, and the content is less than 5 at %.

[0232] Figure 8 is the AC-HADDF-STEM Fourier transform image, atomic image and element distribution map of the nickel-copper binary metal material prepared in Example 9. It can be seen that copper atoms are uniformly dispersed in the nickel metal matrix, and nickel atoms and copper atoms are uniformly mixed without element segregation and phase separation.

[0233] Figures 9 and 10 are respectively the three-dimensional atomic reconstruction image and the high-resolution atomic distribution image obtained by detecting the nickel-copper binary metal material prepared in Example 9 using the three-dimensional atom probe technology. It can be seen that the copper atoms are uniformly dispersed in the nickel metal matrix, and the nickel atoms and copper atoms are uniformly mixed without element segregation and phase separation.

[0234] The metal material prepared in Comparative Example 1 has a small surface energy and poor hydrophilicity, indicating that copper atoms need to be evenly dispersed on the surface of the nickel matrix and cannot separate from the nickel metal. The atomic disorder has a great influence on the surface properties of the metal material.

[0235] The metal material prepared in Comparative Example 2 has a small surface energy and poor hydrophilicity, indicating that the copper element should not be too much. Too much copper element will cause uneven dispersion of copper atoms and form a nickel-copper alloy with the nickel matrix. The element content has a great influence on the surface properties of the metal material.

[0236] Figure 11 is an SEM morphology of the nickel-copper binary metal material prepared in Comparative Example 3, and Figures 12-14 are distribution diagrams of nickel, copper, and oxygen elements in the nickel-copper binary metal material prepared in Comparative Example 3, respectively. It can be seen that after heat treatment in air, an oxide film appears on the surface of the metal material, and the nickel and copper elements are unevenly distributed, which results in the metal material prepared in Comparative Example 3 having a smaller surface energy and poorer hydrophilicity, as shown in Table 1.

[0237] The metal materials prepared in Comparative Examples 4 and 5 have low surface energy and poor hydrophilicity, indicating that the heat treatment time cannot be too long or too short, and that heat treatment has a significant impact on the surface properties of the metal materials.

[0238] Figure 15 is a contact angle diagram of the nickel-copper binary metal material prepared in Example 9 and water. It can be seen that the contact angle of the Ni-Cu@5 metal material with water is 0°, and the surface energy of the metal material can reach 77.58 mJ / m 2 Figure 16 shows the contact angle of nickel mesh with water. It can be seen that the contact angle of nickel mesh with water is 108-109°, and its surface energy is less than 31.86 mJ / m 2 .

[0239] FIG17 is a graph showing the electrolysis and hydrogen evolution performance of the nickel-copper binary metal material prepared in Example 9. Compared with pure nickel metal, the current density at -0.46 V can reach 200 mA / cm due to its increased hydrophilicity. 2 , much lower than the -0.75V of pure nickel.

[0240] FIG18 is a graph showing the electrolytic water hydrogen evolution performance of the nickel-copper binary metal material prepared in Example 20. Compared with pure nickel metal, the current density at -0.55 V can reach 200 mA / cm due to its increased hydrophilicity. 2 , much lower than the -0.75V of pure nickel.

[0241] FIG19 is a graph showing the electrolytic water hydrogen evolution performance of the nickel-copper binary metal material prepared in Example 28. Compared with pure nickel metal, the current density at -0.50 V can reach 200 mA / cm due to its increased hydrophilicity. 2 , much lower than the -0.75V of pure nickel.

[0242] Figure 20 is a graph showing the electrolysis and hydrogen evolution performance of the nickel-copper binary metal material prepared in Comparative Example 1. Compared with pure nickel metal, the current density at -0.95V reaches 200mA / cm due to the reduction of its hydrophilicity. 2 , much higher than the -0.75V of pure nickel.

[0243] In summary, the present application provides a method for increasing the surface energy of a nickel metal substrate, wherein another metal capable of forming a solid solution with the nickel metal is deposited on the surface of the nickel metal substrate, and then a short-term heat treatment is performed in a reducing atmosphere or an inert atmosphere, thereby effectively increasing the surface energy of the nickel metal substrate, so that the surface energy of the obtained binary metal material is between 30 mJ / m 2 Up to 80mJ / m 2 between them, thereby obtaining high hydrophilicity, which enables it to play a greater application advantage as a hydrogen / oxygen evolution electrode in the field of water electrolysis.

[0244] The various aspects, embodiments, features and examples of the present application should be considered as illustrative in all respects and are not intended to limit the present application, the scope of which is defined solely 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 present application as claimed.

Claims

1. A method for increasing the surface energy of nickel metal, characterized in that: include: Depositing a modified metal layer on the surface of a pretreated metal substrate to form a composite metal material, wherein the metal substrate comprises a first metal, and the modified metal layer comprises a second metal, one of the first metal and the second metal is nickel, and the first metal can form a solid solution with the second metal; The composite metal material is heat treated in a protective atmosphere to at least uniformly mix the first metal atoms and the second metal atoms on the surface of the metal matrix, and at least the second metal atom content on the surface of the metal matrix is ​​1 to 10 at%, thereby obtaining a surface energy of 30 mJ / m 2 The above nickel-based binary metal materials.

2. The method for improving the surface energy of nickel metal according to claim 1, characterized in that: The surface energy of the nickel-based binary metal material is greater than 30 mJ / m 2 Less than or equal to 80mJ / m 2 ; And / or, the second metal includes at least one of copper, iron, cobalt and manganese, preferably, the second metal is copper; And / or, the method for improving the surface energy of nickel metal specifically includes: at least using electroplating or chemical plating process to deposit a modified metal layer on the surface of a pretreated metal substrate to form a composite metal material.

3. The method for improving the surface energy of nickel metal according to claim 2, characterized in that: The conditions of the electroplating process include: temperature of 20 to 50°C, voltage of -0.1 to -1.5V, time of 5 to 30min, metal source concentration of 0.01 to 1mol / L in the electroplating solution, and complexing agent concentration of 0.01 to 1mol / L; Preferably, the conditions of the electroplating process include: temperature of 20 to 40°C, voltage of -0.3 to -1V, time of 5 to 15min, metal source concentration of 0.1 to 1mol / L in the electroplating solution, and complexing agent concentration of 0.1 to 1mol / L.

4. The method for improving the surface energy of nickel metal according to claim 2, characterized in that: The conditions of the chemical plating process include: the chemical plating solution contains 0.01-1 mol / L of metal source, 0.01-1 mol / L of complexing agent and 0.01-1 mol / L of reducing agent, and the chemical plating time is 5-30 min; Preferably, the conditions of the chemical plating process include: the chemical plating solution contains 0.1-1 mol / L of metal source, 0.1-1 mol / L of complexing agent and 0.1-1 mol / L of reducing agent, and the chemical plating time is 5-15 min.

5. The method for increasing the surface energy of nickel metal according to any one of claims 3-4, characterized in that: The metal source includes at least one of a sulfate, a nitrate, and a chloride containing a second metal element; And / or, the complexing agent includes at least one of sodium tartrate, sodium citrate, ethylenediaminetetraacetic acid, and sodium pyrophosphate; Preferably, the metal source is a sulfate containing a second metal element, and the complexing agent is sodium citrate.

6. The method for increasing the surface energy of nickel metal according to claim 4, characterized in that: The reducing agent includes at least one of sodium hypophosphite, sodium borohydride and borane; And / or, the metal source is a metal chloride containing a second metal element, the complexing agent is sodium citrate, and the reducing agent is sodium borohydride.

7. The method for improving the surface energy of nickel metal according to claim 1, characterized in that: The heat treatment comprises: heating the composite metal material to 100-1100° C. at a heating rate of 2-10° C. / min in a protective atmosphere, and keeping the temperature for 20-480 min; Preferably, the protective atmosphere comprises a mixed atmosphere of hydrogen and argon or a nitrogen atmosphere; wherein the mixed atmosphere of hydrogen and argon comprises 95 v / v% argon and 5 v / v% hydrogen; And / or, the metal substrate is a nickel substrate or a copper substrate with a purity higher than 99%; preferably, the nickel substrate comprises at least one of a nickel sheet, a nickel mesh, and nickel foam, and the copper substrate comprises at least one of a copper sheet, a copper mesh, and copper foam; And / or, the pretreatment includes: using at least an organic solvent and / or an alkaline solution to remove pollutants on the surface of the metal substrate; and using at least an acidic reagent to remove an oxide layer on the surface of the metal substrate; preferably, the alkaline solution includes at least one of sodium hydroxide and potassium hydroxide; and the organic solvent includes at least one of anhydrous ethanol and anhydrous acetone.

8. A high surface energy nickel-based binary metal material, characterized in that: The high surface energy nickel-based binary metal material is prepared by the method described in any one of claims 1-7.

9. A high surface energy nickel-based binary metal material, characterized in that: The surface of the metal material has uniformly mixed nickel atoms and modified metal atoms, and the content of the modified metal atoms on the surface of the metal material is 1 to 10 at%, so that the surface energy of the metal material is 30 mJ / m 2 In the above, the modified metal can form a solid solution with metallic nickel.

10. The high surface energy nickel-based binary metal material according to claim 9, characterized in that: The modified metal includes at least one of copper, iron, cobalt, and manganese; and / or the surface material of the high surface energy nickel-based binary metal material includes 1 to 5 at% modified metal atoms and 95 to 99 at% nickel atoms; and / or the surface energy of the nickel-based binary metal material is greater than 30 mJ / m 2 Less than or equal to 80mJ / m 2 .

11. A nickel-copper binary metal material, characterized in that: Nickel atoms and copper atoms are uniformly mixed on the surface of the metal material, and the copper atom content on the surface of the metal material is 1 to 10 at%, so that the surface energy of the metal material is 30 mJ / m 2 above.

12. The nickel-copper binary metal material according to claim 11, characterized in that: The surface material of the nickel-copper binary metal material comprises 1 to 5 at% copper atoms and 95 to 99 at% nickel atoms; and / or the surface energy of the nickel-copper binary metal material is greater than 30 mJ / m 2 Less than or equal to 80mJ / m 2 .

13. Use of the high surface energy nickel-based binary metal material according to any one of claims 8 to 10 or the nickel-copper binary metal material according to any one of claims 11 to 12 in hydrogen production by electrolysis of water.

14. An electrode for producing hydrogen by electrolysis of water, characterized in that: The electrode comprises the high surface energy nickel-based binary metal material according to any one of claims 8 to 10 or the nickel-copper binary metal material according to any one of claims 11 to 12.

15. A system for producing hydrogen by electrolysis of water, comprising a hydrogen evolution electrode and an oxygen evolution electrode, characterized in that: At least one of the hydrogen evolution electrode and the oxygen evolution electrode comprises the high surface energy nickel-based binary metal material according to any one of claims 8 to 10 or the nickel-copper binary metal material according to any one of claims 11 to 12.

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