Method for increasing surface energy of nickel metal, nickel-copper binary metal material and its application

Abstract

The present invention provides a method for increasing the surface energy of nickel metal, a nickel-copper binary metal material and its applications. The method includes: depositing a modified metal layer composed of a second metal on the surface of a metal substrate composed of a first metal, one of the first metal and the second metal being nickel metal, and the first metal being capable of forming a solid solution with the second metal, and then performing short-time heat treatment in a protective atmosphere to uniformly mix the first metal atoms and the second metal atoms without element segregation and phase separation, thereby obtaining a nickel-based binary metal material with a surface energy between 30 mJ / m<supgt;2< / supgt> and 80 mJ / m<supgt;2< / supgt>. The method for increasing the surface energy of the nickel metal substrate in the present invention is simple and easy to promote. The obtained nickel-based binary metal material has a high surface energy and good hydrophilicity, and has broad application prospects in fields such as electrolytic water hydrogen production.

Description

[0001] This invention claims the priority of a Chinese invention patent application with the application number CN202311153662.8, the application date of September 7, 2023, and the title "A Nickel-Copper Alloy with High Specific Surface Energy, Its Preparation Method and Application". The above patent application is incorporated herein by reference in its entirety. Technical Field

[0002] This invention belongs to the technical field of alloys, and specifically relates to a method for increasing the surface energy of nickel metal, a nickel-copper binary metal material, and its application. Background Art

[0003] Nickel metal is a nearly silver-white, hard, malleable, and ferromagnetic metal, 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, showing strong corrosion resistance to most acid, alkali, and salt media. Secondly, nickel alloys exhibit extremely high strength and toughness at high temperatures, capable of withstanding high-temperature thermal expansion and mechanical stress, so they are widely used in fields such as chemical engineering, petroleum, nuclear power, and aviation. In addition, nickel alloys also have good mechanical properties and can be easily processed and welded, making them a very easy-to-process metal material. Due to the hydrogen evolution activity inherent in nickel metal itself, nickel metal materials are also widely used in the field of electrolytic water hydrogen production. However, due to its low surface energy (<30 mJ / m 2 ), its hydrophilicity is poor, unable to meet the requirements of practical applications.

[0004] The surface atomic disorder, that is, the surface atomic chaos degree is positively correlated with the surface entropy, and the surface entropy is also positively correlated with the surface energy. Increasing the surface atomic disorder can effectively increase the surface energy, thereby increasing the hydrophilicity of the material surface. In recent years, a large number of studies have shown that hydrophilic surfaces have a huge promoting effect in electrolytic water and have been widely applied in the field of electrolytic water. Hydrophilic materials are beneficial to the hydrogen evolution reaction, and increasing hydrophilicity can effectively increase the hydrogen evolution activity.

[0005] Increasing the surface energy of nickel-based metal materials can effectively improve the hydrophilicity of nickel-based metal materials, but currently, there is a lack of a method 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. Summary of the Invention

[0006] The main purpose of this invention is to provide a method for increasing 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.

[0007] To achieve the above technical effects, this invention provides the following technical solutions:

[0008] The first aspect of the present invention provides a method for increasing the surface energy of a nickel metal, which includes:

[0009] Depositing a modified metal layer on the surface of a pretreated metal substrate to form a composite metal material, where the metal substrate contains a first metal, the modified metal layer contains 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;

[0010] Performing heat treatment on the composite metal material in a protective atmosphere to at least uniformly mix the first metal atoms and the second metal atoms on the surface of the metal substrate, and at least make the content of the second metal atoms on the surface of the metal substrate be 1-10 at%, so as to obtain a nickel-based binary metal material with a surface energy above 30 mJ / m 2 above.

[0011] The second aspect of the present invention provides a high surface energy nickel-based binary metal material, whose surface 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 1-10 at%, making the surface energy of the metal material above 30 mJ / m 2 above, where the modified metal can form a solid solution with metallic nickel.

[0012] The high surface energy nickel-based binary metal material can be prepared by using the method for increasing the surface energy of a nickel metal.

[0013] The third aspect of the present invention provides the use of the high surface energy nickel-based binary metal material in the field of electrolytic water, such as hydrogen production by electrolytic water.

[0014] Compared with the prior art, the beneficial effects of the present invention are at least:

[0015] (1) In the method for increasing the surface energy of a nickel metal substrate provided by the present invention, by selecting a modified metal element that can form a solid solution with the nickel metal, depositing a small amount of the modified metal on the surface of the nickel metal substrate, and then performing short-time heat treatment, the modified metal atoms can diffuse on the surface of the nickel metal substrate and be uniformly mixed with the nickel atoms, rather than entering the interior of the nickel metal substrate, nor forming an ordered alloy structure. Thus, the atomic disorder degree on the surface of the nickel metal substrate can be effectively increased, the surface entropy on the surface of the nickel metal substrate is greatly increased, enabling it to obtain a high surface energy. The process is simple, the amount of the modified metal required is small, the cost is low, and it is suitable for large-scale production.

[0016] (2) The surface energy stems from the free energy caused by the unsaturated bonds of surface molecules. The molecules at the surface will attempt to reduce this free energy by contacting the molecules of the adjacent phase. Water molecules have a strong bonding ability. Therefore, materials with high surface energy (i.e., high bonding potential) interact more strongly with water, and the hydrophilicity of the materials is strong. The surface energy of the high-surface-energy nickel-based binary metal material provided by the present invention is above 30 mJ / m 2 Above, preferably greater than 30 mJ / m 2 And less than or equal to 80 mJ / m 2 , having good hydrophilicity. Electrodes with good hydrophilicity can effectively improve the contact between the electrode and water during the electrolysis of water, thereby enhancing the reaction activity of the electrode. Compared with nickel metal electrodes, the voltage required to reach a current density of 200 mA / cm -2 Can be reduced by ~0.2 V, indicating that it has broad application prospects in fields such as electrolysis of water. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for use in the description of the embodiments or the prior art. Obviously, the drawings in the following description are only some embodiments recorded in the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0018] Figure 1 XRD diffraction pattern of the nickel-copper binary metal material prepared in Example 9.

[0019] Figure 2 One of the SEM morphology diagrams of the nickel-copper binary metal material prepared in Example 9.

[0020] Figure 3 Another SEM morphology diagram of the nickel-copper binary metal material prepared in Example 9.

[0021] Figure 4 One of the diagrams of the distribution and content of Ni element in the nickel-copper binary metal material prepared in Example 9.

[0022] Figure 5 Another diagram of the distribution and content of Ni element in the nickel-copper binary metal material prepared in Example 9.

[0023] Figure 6 One of the diagrams of the distribution and content of Cu element in the nickel-copper binary metal material prepared in Example 9.

[0024] Figure 7 Another diagram of the distribution and content of Cu element in the nickel-copper binary metal material prepared in Example 9.

[0025] Figure 8AC-HADDF-STEM Fourier transform diagram, atomic image and elemental distribution map of the nickel-copper binary metal material prepared in Example 9.

[0026] Figure 9 Three-dimensional atomic reconstruction diagram of the nickel-copper binary metal material prepared in Example 9.

[0027] Figure 10 High-resolution atomic distribution map of the nickel-copper binary metal material prepared in Example 9.

[0028] Figure 11 SEM morphology diagram of the nickel-copper binary metal material prepared in Comparative Example 3.

[0029] Figure 12 Nickel elemental distribution map of the nickel-copper binary metal material prepared in Comparative Example 3.

[0030] Figure 13 Copper elemental distribution map of the nickel-copper binary metal material prepared in Comparative Example 3.

[0031] Figure 14 Oxygen elemental distribution map of the nickel-copper binary metal material prepared in Comparative Example 3.

[0032] Figure 15 Contact angle diagram of the nickel-copper binary metal material prepared in Example 9 with water.

[0033] Figure 16 Contact angle diagram of nickel mesh with water.

[0034] Figure 17 Electrolytic water hydrogen evolution performance diagram of the nickel-copper binary metal material prepared in Example 9.

[0035] Figure 18 Electrolytic water hydrogen evolution performance diagram of the nickel-copper binary metal material prepared in Example 20 of the present invention.

[0036] Figure 19 Electrolytic water hydrogen evolution performance diagram of the nickel-copper binary metal material prepared in Example 28 of the present invention.

[0037] Figure 20 Electrolytic water hydrogen evolution performance diagram of the nickel-copper binary metal material prepared in Comparative Example 1 of the present invention. Detailed Description of the Invention

[0038] The technical solution of the present invention will be explained and described in more detail as follows.

[0039] A method for increasing the surface energy of nickel metal provided by some embodiments of the present invention includes:

[0040] A modified metal layer is deposited on the surface of a pretreated metal substrate to form a composite metal material. The metal substrate contains a first metal, and the modified metal layer contains 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;

[0041] 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 substrate, and at least make the content of the second metal atoms on the surface of the metal substrate be 1-10 at%, so as to obtain a nickel-based binary metal material with a surface energy of more than 30 mJ / m 2 above.

[0042] Among them, the content of the second metal atoms on the surface of the metal substrate is preferably 2-10 at%, more preferably 2-5 at%.

[0043] Preferably, the surface energy of the nickel-based binary metal material is greater than 30 mJ / m 2 and less than or equal to 80 mJ / m 2 .

[0044] 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 be infinitely solid-solved with nickel, so as to better increase the disorder degree of the nickel-based binary metal material, and further increase its surface energy.

[0045] In one embodiment, the method for increasing the surface energy of nickel metal specifically includes: at least using electroplating or electroless plating process to deposit a modified metal layer on the surface of a pretreated metal substrate to form a composite metal material.

[0046] In one embodiment, the conditions of the electroplating process include: the temperature is 20-50 °C, the voltage is -0.1 to -1.5 V, the time is 5-30 min, the concentration of the metal source contained in the electroplating solution is 0.01-1 mol / L, and the concentration of the complexing agent is 0.01-1 mol / L.

[0047] More preferably, the conditions of the electroplating process include: the temperature is 20-40 °C, the voltage is -0.3 to -1 V, the time is 5-15 min, the concentration of the metal source contained in the electroplating solution is 0.1-1 mol / L, and the concentration of the complexing agent is 0.1-1 mol / L. Using these process conditions can obtain a metal coating with a suitable thickness and avoid the appearance of an ordered structure.

[0048] In one embodiment, the conditions of the electroless plating process include: the electroless 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 electroless plating time is 5-30 min.

[0049] More preferably, the conditions of the electroless plating process include: the electroless plating solution contains 0.1 - 1 mol / L metal source, 0.1 - 1 mol / L complexing agent and 0.1 - 1 mol / L reducing agent, and the electroless plating time is 5 - 15 min. By using these process conditions, a metal coating with appropriate thickness can be obtained and an ordered structure can be avoided.

[0050] In one embodiment, the metal source includes at least one of sulfates, nitrates, and chlorides containing a second metal element, and is not limited thereto.

[0051] In one embodiment, the complexing agent includes at least one of sodium tartrate, sodium citrate, ethylenediaminetetraacetic acid, and sodium pyrophosphate, and is not limited thereto.

[0052] In one embodiment, the reducing agent includes at least one of sodium hypophosphite, sodium borohydride, and borane, and is not limited thereto.

[0053] More preferably, in the electroplating process, the metal source is a sulfate containing a second metal element, and the complexing agent is sodium citrate to obtain a more uniform metal coating.

[0054] More preferably, in the electroless 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 to obtain a more uniform metal coating.

[0055] In one embodiment, the heat treatment includes: heating the composite metal material to 100 - 1100 °C at a heating rate of 2 - 10 °C / min in a protective atmosphere and holding for 20 - 480 min.

[0056] In one embodiment, the protective atmosphere includes a mixed atmosphere of hydrogen and argon or a nitrogen atmosphere. For example, the mixed atmosphere of hydrogen and argon contains 95 v / v% argon and 5 v / v% hydrogen.

[0057] In one embodiment, the metal substrate is a nickel substrate or a copper substrate with a purity higher than 99%.

[0058] Furthermore, the nickel substrate includes at least one of nickel sheets, nickel meshes, and nickel foams, and the copper substrate includes at least one of copper sheets, copper meshes, and copper foams.

[0059] In one embodiment, the pretreatment includes: removing contaminants on the surface of the metal substrate using at least an organic solvent and / or an alkali solution; and removing the oxide layer on the surface of the metal substrate using at least an acidic reagent. Among them, the contaminants are mainly oil stains.

[0060] In one embodiment, the lye includes at least one of sodium hydroxide and potassium hydroxide, and is not limited thereto.

[0061] In some cases, the concentration of the lye is 0.5 mol / L to 5 mol / L.

[0062] In some cases, the acidic reagent includes any one of sulfuric acid and hydrochloric acid, and the concentration is 0.5 mol / L to 5 mol / L.

[0063] In one embodiment, the organic solvent includes at least one of absolute ethanol and absolute acetone, and is not limited thereto.

[0064] Some embodiments of the present invention provide a high surface energy nickel-based binary metal material prepared by the method for increasing the surface energy of nickel metal.

[0065] Some embodiments of the present invention provide a high surface energy nickel-based binary metal material having uniformly mixed nickel atoms and modified metal atoms on the surface, 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 at 30 mJ / m 2 above, preferably greater than 30 mJ / m 2 and less than or equal to 80 mJ / m 2 , wherein the modified metal can form a solid solution with nickel metal.

[0066] In one embodiment, the modified metal includes but is not limited to at least one of copper, iron, cobalt, and manganese.

[0067] In one embodiment, the high surface energy nickel-based binary metal material includes 1 to 5 at% modified metal atoms and 95 to 99 at% nickel atoms.

[0068] Some embodiments of the present invention provide a nickel-copper binary metal material, in which nickel atoms and copper atoms are uniformly mixed on the surface of the metal material, and the content of copper atoms on the surface of the metal material is 1 to 10 at%, so that the surface energy of the metal material is at 30 mJ / m 2 above, preferably greater than 30 mJ / m 2 and less than or equal to 80 mJ / m 2 .

[0069] In one embodiment, the nickel-copper binary metal material includes 1 to 5 at% copper atoms and 95 to 99 at% nickel atoms.

[0070] Some embodiments of the present invention provide the use of the high surface energy nickel-based binary metal material or the nickel-copper binary metal material in the field of electrolytic water, such as hydrogen production by electrolytic water.

[0071] Some embodiments of the present invention provide an electrode for hydrogen production by electrolyzing water, which comprises the high surface energy nickel-based binary metal material or the nickel-copper binary metal material.

[0072] Some embodiments of the present invention provide a hydrogen production system by electrolyzing water, comprising a hydrogen evolution electrode and an oxygen evolution electrode, wherein at least one of the hydrogen evolution electrode and the oxygen evolution electrode comprises the high surface energy nickel-based binary metal material or the nickel-copper binary metal material.

[0073] The present invention will be more fully understood from the following detailed description to be read in conjunction with the accompanying drawings. Specific embodiments of the present invention are disclosed herein; however, it should be understood that the disclosed embodiments are merely exemplary of the present invention, which can be embodied in various forms. Therefore, the specific functional details disclosed herein should not be construed as limiting, but merely as a basis for the claims and as a representative basis for teaching those skilled in the art to employ the present invention in any appropriate detailed embodiment in different ways.

[0074] Example 1 This example provides a nickel-copper binary metal material, and its preparation method includes:

[0075] First, using a nickel sheet as the substrate, it is pretreated, including: successively immersing the nickel substrate in absolute ethanol and absolute acetone and ultrasonically treating for 5 minutes each to remove the oil stains on the surface, and immersing the nickel substrate in a 0.5 mol / L sulfuric acid solution and ultrasonically treating for 5 minutes to remove the surface oxides.

[0076] Then, using a copper nitrate solution as the electroplating solution and citric acid as the complexing agent, the concentration of copper nitrate in the electroplating solution is 0.01 mol / L, the concentration of citric acid is 0.01 mol / L, electroplating is 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, and the electroplating is carried out at 25°C.

[0077] After that, heat treatment is carried out in a reducing mixed gas atmosphere of 5% hydrogen and 95% argon, the heat treatment temperature is 100°C, the heating rate is 10°C / min, the heat treatment time is 20 minutes, and then it is cooled in the furnace to obtain the nickel-copper binary metal material Ni-Cu@1.

[0078] Example 2 The only difference between this example and Example 1 is that: in Example 2, 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, 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 are the same as those in Example 1.

[0079] This example obtains the nickel-copper binary metal material Ni-Cu@11.

[0080] Example 3 This example provides a nickel-copper binary metal material, and its preparation method includes:

[0081] First, using a nickel sheet as the substrate, perform pretreatment on it, including: successively immerse the nickel substrate in absolute ethanol and anhydrous acetone and ultrasonically treat for 5 minutes each to remove the oil stains on the surface, and immerse the nickel substrate in a 2 mol / L sulfuric acid solution and ultrasonically treat for 5 minutes to remove the surface oxides.

[0082] After that, using a copper sulfate solution as the electroplating solution and sodium pyrophosphate as the complexing agent, the concentration of copper sulfate in the electroplating solution is 0.01 mol / L, the concentration of sodium pyrophosphate is 0.01 mol / L, electroplate at a voltage of -0.3 V for 5 minutes to obtain a nickel substrate with a copper layer plated on the surface, and the electroplating is carried out at 25 °C.

[0083] Then, perform heat treatment in an inert atmosphere of nitrogen, the heat treatment temperature is 100 °C, the heating rate is 10 °C / min, the heat treatment time is 20 minutes, and then cool with the furnace.

[0084] The nickel-copper binary metal material Ni-Cu@2 is obtained in this example.

[0085] Example 4 This example provides a nickel-copper binary metal material, and its preparation method includes:

[0086] The only difference between this example and Example 3 is that: in Example 4, 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, 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 are the same as those in Example 3.

[0087] The nickel-copper binary metal material Ni-Cu@22 is obtained in this example.

[0088] Example 5 This example provides a nickel-copper binary metal material, and its preparation method includes:

[0089] First, using a nickel sheet as the substrate, perform pretreatment on it, including: immerse the nickel substrate in a 2 mol / L sodium hydroxide solution and ultrasonically treat for 5 minutes to remove the oil stains on the surface, and then immerse the nickel substrate in a 2 mol / L hydrochloric acid solution and ultrasonically treat for 5 minutes to remove the surface oxides.

[0090] After that, using a copper chloride solution as the electroplating solution and ethylenediaminetetraacetic acid (EDTA) as the complexing agent, the concentration of copper chloride in the electroplating solution is 0.01 mol / L, the concentration of EDTA is 0.01 mol / L, electroplate at a voltage of -0.3 V for 5 minutes to obtain a nickel substrate with a copper layer plated on the surface, and the electroplating is carried out at 25 °C.

[0091] Then, heat treatment is carried out in a reducing atmosphere of 5% hydrogen and 95% argon. The heat treatment temperature is 100 °C and the heat treatment time is 20 minutes.

[0092] The nickel-copper binary metal material Ni-Cu@3 is obtained in this example.

[0093] Example 6 This example provides a nickel-copper binary metal material, and its preparation method includes:

[0094] The only difference between Example 6 and Example 5 is that: in Example 6, 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 copper chloride in the electroplating solution is 0.1 mol / L, 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 are the same as those in Example 5.

[0095] The nickel-copper binary metal material Ni-Cu@33 is prepared in this example.

[0096] Example 7 This example provides a nickel-copper binary metal material, and its preparation method includes:

[0097] First, using a nickel mesh as the substrate, it is pretreated, including: successively immersing the nickel substrate in absolute ethanol and anhydrous acetone and ultrasonically treating for 5 minutes each to remove the surface oil stains, and then immersing the nickel substrate in a 2 mol / L sulfuric acid solution and ultrasonically treating for 5 minutes to remove the surface oxides.

[0098] Subsequently, using a copper nitrate solution as the electroplating solution and citric acid as the complexing agent, the concentration of copper nitrate in the electroplating solution is 0.01 mol / L, the concentration of citric acid is 0.01 mol / L, electroplating is carried out at a voltage of -0.3 V for 5 minutes to obtain a nickel substrate with a copper layer plated on its surface, and the electroplating is carried out at 25 °C.

[0099] After that, heat treatment is carried out in a reducing mixed gas atmosphere of 5% hydrogen and 95% argon. The heat treatment temperature is 100 °C, the heating rate is 10 °C / min, the heat treatment time is 20 minutes, and it is cooled in the furnace to obtain the nickel-copper binary metal material Ni-Cu@4.

[0100] Example 8 This example provides a nickel-copper binary metal material, and its preparation method includes:

[0101] The only difference between Example 8 and Example 7 is that: in Example 8, 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, 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 are the same as those in Example 7.

[0102] The nickel-copper binary metal material Ni-Cu@44 was prepared in this example.

[0103] Example 9 This example provides a nickel-copper binary metal material, and its preparation method includes:

[0104] First, using a nickel mesh as the substrate, it is pretreated, including: successively immersing the nickel substrate in absolute ethanol and anhydrous acetone and ultrasonically treating for 5 minutes each to remove the oil stains on the surface, and then immersing the nickel substrate in a 2 mol / L sulfuric acid solution and ultrasonically treating for 5 minutes to remove the surface oxides.

[0105] After that, using a copper sulfate solution as the electroplating solution and sodium pyrophosphate as the complexing agent, the concentration of copper sulfate in the electroplating solution is 0.01 mol / L, the concentration of sodium pyrophosphate is 0.01 mol / L, electroplating is 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, and the electroplating is carried out at 25 °C.

[0106] After that, heat treatment is carried out under a nitrogen atmosphere, the heat treatment temperature is 100 °C, the heating rate is 10 °C / min, the heat treatment time is 20 minutes, and it is cooled in the furnace to obtain the nickel-copper binary metal material Ni-Cu@5.

[0107] Example 10 This example provides a nickel-copper binary metal material, and its preparation method includes:

[0108] The only difference between this example and Example 9 is that: in Example 10, 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, 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 are the same as those in Example 9.

[0109] The nickel-copper binary metal material Ni-Cu@55 was prepared in this example.

[0110] Example 11 This example provides a nickel-copper binary metal material, and its preparation method includes:

[0111] First, using a nickel mesh as the substrate, it is pretreated, including: immersing the nickel substrate in a 2 mol / L sodium hydroxide solution and ultrasonically treating for 5 minutes to remove the oil stains on the surface, and then immersing the nickel substrate in a 2 mol / L hydrochloric acid solution and ultrasonically treating for 5 minutes to remove the surface oxides.

[0112] After that, using a copper chloride solution as the electroplating solution and EDTA as the complexing agent, the concentration of copper chloride in the electroplating solution is 0.01 mol / L, the concentration of EDTA is 0.01 mol / L, electroplating is 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, and the electroplating is carried out at 25 °C.

[0113] After that, heat treatment is carried out in a reducing atmosphere of 5% hydrogen and 95% argon. The heat treatment temperature is 100 °C and the heat treatment time is 20 minutes to obtain the nickel-copper binary metal material Ni-Cu@6.

[0114] Example 12 This example provides a nickel-copper binary metal material, and its preparation method includes:

[0115] The only difference between this example and Example 11 is that: in Example 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 copper chloride in the electroplating solution is 0.1 mol / L, 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 are the same as those in Example 11.

[0116] The nickel-copper binary metal material Ni-Cu@66 is obtained in this example.

[0117] Example 13 This example provides a nickel-copper binary metal material, and its preparation method includes:

[0118] First, using nickel foam as the substrate, it is pretreated, including: successively immersing the substrate in absolute ethanol and anhydrous acetone and ultrasonically treating for 5 minutes each to remove the surface oil stains, and then immersing the substrate in a 2 mol / L sulfuric acid solution and ultrasonically treating for 5 minutes to remove the surface oxides.

[0119] After that, using copper nitrate as the electroplating solution and citric acid as the complexing agent, the concentration of copper nitrate in the electroplating solution is 0.01 mol / L, the concentration of citric acid is 0.01 mol / L, electroplating is 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, and the electroplating is carried out at 25 °C.

[0120] Then, heat treatment is carried out in a reducing mixed gas atmosphere of 5% hydrogen and 95% argon. The heat treatment temperature is 100 °C, the heating rate is 10 °C / min, and it is cooled in the furnace. The heat treatment time is 20 minutes to obtain the nickel-copper binary metal material Ni-Cu@7.

[0121] Example 14 This example provides a nickel-copper binary metal material, and its preparation method includes:

[0122] 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, 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 are the same as those in Example 13.

[0123] The nickel-copper binary metal material Ni-Cu@77 is obtained in this example.

[0124] Example 15 This example provides a nickel - copper binary metal material, and its preparation method includes:

[0125] First, using nickel foam as the substrate, it is pretreated, including: successively immersing the substrate in absolute ethanol and anhydrous acetone and ultrasonically treating for 5 minutes each to remove surface oil stains, and then immersing the substrate in a 2 mol / L sulfuric acid solution and ultrasonically treating for 5 minutes to remove surface oxides.

[0126] Then, using copper sulfate as the electroplating solution and sodium pyrophosphate as the complexing agent, with the concentration of copper sulfate in the electroplating solution being 0.01 mol / L and the concentration of sodium pyrophosphate being 0.01 mol / L, electroplating is carried out at a voltage of - 0.3 V for 5 minutes to obtain a nickel substrate with a copper layer plated on its surface. The electroplating is carried out at 25 °C.

[0127] After that, heat treatment is carried out under an inert atmosphere of nitrogen, with the heat treatment temperature being 100 °C, the heating rate being 10 °C / min, cooling in the furnace, and the heat treatment time being 20 minutes to obtain the nickel - copper binary metal material Ni - Cu@8.

[0128] Example 16 This example provides a nickel - copper binary metal material, and its preparation method includes:

[0129] 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, 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 are the same as those in Example 15.

[0130] This example obtains the nickel - copper binary metal material Ni - Cu@88.

[0131] Example 17 This example provides a nickel - copper binary metal material, and its preparation method includes:

[0132] First, using nickel foam as the substrate, it is pretreated, including: immersing the substrate in a 2 mol / L sodium hydroxide solution and ultrasonically treating for 5 minutes to remove surface oil stains, and then immersing the substrate in a 2 mol / L hydrochloric acid solution and ultrasonically treating for 5 minutes to remove surface oxides.

[0133] After that, using copper chloride as the electroplating solution and EDTA as the complexing agent, with the concentration of copper chloride in the electroplating solution being 0.01 mol / L and the concentration of EDTA being 0.01 mol / L, electroplating is carried out at a voltage of - 0.3 V for 5 minutes to obtain a nickel substrate with a copper layer plated on its surface. The electroplating is carried out at 25 °C.

[0134] Then, heat treatment was carried out in a reducing atmosphere of 5% hydrogen and 95% argon at a heat treatment temperature of 100 °C for 20 minutes. The nickel-copper binary metal material Ni-Cu@9 was obtained.

[0135] Example 18 This example provides a nickel-copper binary metal material, and its preparation method includes:

[0136] 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 copper chloride in the electroplating solution is 0.1 mol / L, 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 are the same as those in Example 17.

[0137] The nickel-copper binary metal material Ni-Cu@99 was prepared in this example.

[0138] Example 19 This example provides a nickel-copper binary metal material, and its preparation method includes:

[0139] First, using a copper sheet as the substrate, it was pretreated, including: successively immersing the substrate in absolute ethanol and anhydrous acetone and ultrasonically treating for 5 minutes each to remove the surface oil stains, and then immersing the substrate in a 2 mol / L sulfuric acid solution and ultrasonically treating for 5 minutes to remove the surface oxides.

[0140] Thereafter, using nickel nitrate as the electroplating solution and citric acid as the complexing agent, the concentration of nickel nitrate in the electroplating solution is 0.01 mol / L, the concentration of citric acid is 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, and the electroplating was carried out at 25 °C.

[0141] Then, heat treatment was carried out in a reducing mixed gas atmosphere of 5% hydrogen and 95% argon at a heat treatment temperature of 100 °C, a heating rate of 10 °C / min, a heat treatment time of 20 minutes, and furnace cooling to obtain the nickel-copper binary metal material Ni@1-Cu.

[0142] Example 20 This example provides a nickel-copper binary metal material, and its preparation method includes:

[0143] 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, 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 are the same as those in Example 19.

[0144] The nickel-copper binary metal material Ni@11-Cu was prepared in this example.

[0145] Example 21 This example provides a nickel-copper binary metal material, and its preparation method includes:

[0146] First, using a copper sheet as the substrate, perform pretreatment on it, including: successively immersing the substrate in absolute ethanol and anhydrous acetone and ultrasonically treating for 5 minutes each to remove surface oil stains, and then immersing the substrate in a 2 mol / L sulfuric acid solution and ultrasonically treating for 5 minutes to remove surface oxides.

[0147] After that, using nickel sulfate as the electroplating solution and sodium pyrophosphate as the complexing agent, with the nickel sulfate concentration in the electroplating solution being 0.01 mol / L and the sodium pyrophosphate concentration being 0.01 mol / L, electroplate at a voltage of -0.3 V for 5 minutes to obtain a copper substrate with a nickel layer plated on its surface. The electroplating is carried out at 25°C.

[0148] Then, perform heat treatment in an inert atmosphere of nitrogen, with a heat treatment temperature of 100°C, a heating rate of 10°C / min, a heat treatment time of 20 minutes, and cool with the furnace. The nickel-copper binary metal material Ni@2-Cu is prepared.

[0149] Example 22 This example provides a nickel-copper binary metal material, and its preparation method includes:

[0150] 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 nickel sulfate concentration in the electroplating solution is 0.1 mol / L, the sodium pyrophosphate concentration 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 are the same as those in Example 21.

[0151] The nickel-copper binary metal material Ni@22-Cu is prepared in this example.

[0152] Example 23 This example provides a nickel-copper binary metal material, and its preparation method includes:

[0153] First, using a copper sheet as the substrate, perform pretreatment on it, 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.

[0154] After that, using nickel chloride as the electroplating solution and EDTA as the complexing agent, with the nickel chloride concentration in the electroplating solution being 0.01 mol / L and the EDTA concentration being 0.01 mol / L, electroplate at a voltage of -0.3 V for 5 minutes to obtain a copper substrate with a nickel layer plated on its surface. The electroplating is carried out at 25°C.

[0155] The heat treatment was carried out in a reducing atmosphere of 5% hydrogen and 95% argon at a heat treatment temperature of 100 °C for 20 minutes. The nickel-copper binary metal material Ni@3-Cu was obtained.

[0156] Example 24 This example provides a nickel-copper binary metal material, and its preparation method includes:

[0157] 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, 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 are the same as those in Example 23.

[0158] The nickel-copper binary metal material Ni@33-Cu was obtained in this example.

[0159] Example 25 This example provides a nickel-copper binary metal material, and its preparation method includes:

[0160] First, using a copper mesh as the substrate, it was pretreated, including: successively immersing the substrate in absolute ethanol and anhydrous acetone and ultrasonically treating for 5 minutes each to remove the surface oil stains, and then immersing the substrate in a 2 mol / L sulfuric acid solution and ultrasonically treating for 5 minutes to remove the surface oxides.

[0161] After that, using nickel nitrate as the electroplating solution and citric acid as the complexing agent, the concentration of nickel nitrate in the electroplating solution is 0.01 mol / L, the concentration of citric acid is 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, and the electroplating was carried out at 25 °C.

[0162] Then, heat treatment was carried out in a reducing gas mixture atmosphere of 5% hydrogen and 95% argon, the heat treatment temperature was 100 °C, the heating rate was 10 °C / min, and it was cooled with the furnace, and the heat treatment time was 20 minutes to obtain the nickel-copper binary metal material Ni@4-Cu.

[0163] Example 26 This example provides a nickel-copper binary metal material, and its preparation method includes:

[0164] 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, 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 are the same as those in Example 25.

[0165] The nickel-copper binary metal material Ni@44-Cu was obtained in this example.

[0166] Example 27 This example provides a nickel - copper binary metal material, and its preparation method includes:

[0167] First, using a copper mesh as the substrate, it is pretreated, including: successively immersing the substrate in absolute ethanol and anhydrous acetone and ultrasonically treating for 5 minutes each to remove surface oil stains, and then immersing the substrate in 2 mol / L sulfuric acid and ultrasonically treating for 5 minutes to remove surface oxides.

[0168] Thereafter, using copper sulfate as the electroplating solution and sodium pyrophosphate as the complexing agent, the concentration of copper sulfate in the electroplating solution is 0.01 mol / L, the concentration of sodium pyrophosphate is 0.01 mol / L, electroplating is carried out at a voltage of - 0.3 V for 5 minutes to obtain a nickel substrate with a copper layer plated on its surface, and the electroplating is carried out at 25°C.

[0169] Then, heat treatment is carried out in an inert atmosphere of nitrogen, the heat treatment temperature is 100°C, the heating rate is 10°C / min, cooling is carried out in the furnace, and the heat treatment time is 20 minutes. The nickel - copper binary metal material Ni - Cu@5 is prepared.

[0170] Example 28 This example provides a nickel - copper binary metal material, and its preparation method includes:

[0171] 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, 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 rest of the conditions are the same as those in Example 27.

[0172] The nickel - copper binary metal material Ni - Cu@55 is prepared in this example.

[0173] Example 29 This example provides a nickel - copper binary metal material, and its preparation method includes:

[0174] First, using a copper mesh as the substrate, it is pretreated, including: immersing the substrate in 2 mol / L sodium hydroxide solution and ultrasonically treating for 5 minutes to remove surface oil stains, and then immersing the substrate in 2 mol / L hydrochloric acid solution and ultrasonically treating for 5 minutes to remove surface oxides.

[0175] Thereafter, using nickel chloride as the electroplating solution and ethylenediaminetetraacetic acid (EDTA) as the complexing agent, electroplating is carried out at a voltage of - 0.3 V for 5 minutes to obtain a copper substrate with a nickel layer plated on its surface, the concentration of nickel chloride in the electroplating solution is 0.01 mol / L, the concentration of ethylenediaminetetraacetic acid (EDTA) is 0.01 mol / L, and the electroplating is carried out at 25°C.

[0176] Then, heat treatment is carried out in a reducing atmosphere of 5% hydrogen and 95% argon. The heat treatment temperature is 100 °C and the heat treatment time is 20 minutes. The nickel-copper binary metal material Ni@6-Cu is obtained.

[0177] Example 30 This example provides a nickel-copper binary metal material, and its preparation method includes:

[0178] 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, 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 are the same as those in Example 29.

[0179] The nickel-copper binary metal material Ni@66-Cu is obtained in this example.

[0180] Example 31 This example provides a nickel-copper binary metal material, and its preparation method includes:

[0181] First, using copper foam as the substrate, it is pretreated, including: immersing the substrate in anhydrous ethanol and anhydrous acetone in sequence and ultrasonically treating for 5 minutes each to remove the surface oil stains, and then immersing the substrate in 2 mol / L sulfuric acid and ultrasonically treating for 5 minutes to remove the surface oxides.

[0182] After that, using nickel nitrate as the electroplating solution and citric acid as the complexing agent, the concentration of nickel nitrate in the electroplating solution is 0.01 mol / L, and the concentration of citric acid is 0.01 mol / L. Electroplating is carried out at a voltage of -0.3 V for 5 minutes to obtain a copper substrate with a nickel layer plated on its surface. The electroplating is carried out at 25 °C.

[0183] Then, heat treatment is carried out in a reducing gas mixture atmosphere of 5% hydrogen and 95% argon. The heat treatment temperature is 100 °C, the heating rate is 10 °C / min, the heat treatment time is 20 minutes, and it is cooled in the furnace to obtain the nickel-copper binary metal material Ni@7-Cu.

[0184] Example 32 This example provides a nickel-copper binary metal material, and its preparation method includes:

[0185] 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, 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 are the same as those in Example 31.

[0186] The nickel-copper binary metal material Ni@77-Cu is obtained in this example.

[0187] Example 33 This example provides a nickel-copper binary metal material, and its preparation method includes:

[0188] First, using copper foam as the substrate, it is pretreated, including: successively immersing the substrate in absolute ethanol and anhydrous acetone and ultrasonically treating for 5 minutes each to remove surface oil stains, and then immersing the substrate in 2 mol / L sulfuric acid and ultrasonically treating for 5 minutes to remove surface oxides.

[0189] Subsequently, using nickel sulfate as the electroplating solution and sodium pyrophosphate as the complexing agent, with the concentration of nickel sulfate in the electroplating solution being 0.01 mol / L and the concentration of sodium pyrophosphate being 0.01 mol / L, electroplating is carried out at a voltage of -0.3 V for 5 minutes to obtain a copper substrate with a nickel layer plated on its surface. The electroplating is carried out at 25 °C.

[0190] Then, heat treatment is carried out in an inert atmosphere of nitrogen, with the heat treatment temperature being 100 °C, the heating rate being 10 °C / min, the heat treatment time being 20 minutes, and cooling in the furnace to obtain the nickel-copper binary metal material Ni@8-Cu.

[0191] Example 34 This example provides a nickel-copper binary metal material, and its preparation method includes:

[0192] 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, 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 are the same as those in Example 33.

[0193] This example obtains the nickel-copper binary metal material Ni@88-Cu.

[0194] Example 35 This example provides a nickel-copper binary metal material, and its preparation method includes:

[0195] First, using copper foam as the substrate, it is pretreated, including: immersing the substrate in 2 mol / L sodium hydroxide solution 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.

[0196] Subsequently, using nickel chloride as the electroplating solution and EDTA as the complexing agent, with the concentration of nickel chloride in the electroplating solution being 0.01 mol / L and the concentration of EDTA being 0.01 mol / L, electroplating is carried out at a voltage of -0.3 V for 5 minutes to obtain a copper substrate with a nickel layer plated on its surface. The electroplating is carried out at 25 °C.

[0197] Then, heat treatment is carried out in a reducing atmosphere of 5% hydrogen and 95% argon at a heat treatment temperature of 100 °C for 20 minutes. The nickel-copper binary metal material Ni@9-Cu is obtained.

[0198] Example 36 This example provides a nickel-copper binary metal material, and its preparation method includes:

[0199] 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, 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 are the same as those in Example 35.

[0200] The nickel-copper binary metal material Ni@99-Cu is prepared in this example.

[0201] Example 37 This example provides a nickel-copper binary metal material, and its preparation method includes:

[0202] First, using a nickel sheet as the substrate, it is pretreated, including: successively immersing the substrate in absolute ethanol and anhydrous acetone and ultrasonically treating for 5 minutes respectively to remove the oil stains on the surface, and then immersing the substrate in 2 mol / L sulfuric acid and ultrasonically treating for 5 minutes to remove the surface oxides.

[0203] Thereafter, using copper nitrate as the copper source, citric acid as the complexing agent, and sodium hypophosphite as the reducing agent, the concentration of copper nitrate in the electroless plating solution is 0.01 mol / L, the concentration of citric acid is 0.01 mol / L, and the concentration of sodium hypophosphite is 0.01 mol / L, and electroless plating is carried out for 5 minutes.

[0204] Then, heat treatment is carried out in a reducing atmosphere of 5% hydrogen and 95% argon at a heat treatment temperature of 100 °C for 20 minutes to obtain the nickel-copper binary metal material Ni-Cu@@1.

[0205] Example 38 This example provides a nickel-iron binary metal material, and its preparation method includes:

[0206] First, using a nickel sheet as the substrate, it is pretreated, including: successively immersing the nickel substrate in absolute ethanol and anhydrous acetone and ultrasonically treating for 5 minutes respectively to remove the oil stains on the surface, and immersing the nickel substrate in 0.5 mol / L sulfuric acid solution and ultrasonically treating for 5 minutes to remove the surface oxides.

[0207] Subsequently, ferric nitrate was used as the electroplating solution and sodium citrate was used as the complexing agent. The concentration of ferric nitrate in the electroplating 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 its surface. The electroplating was carried out at 25°C.

[0208] Then, heat treatment was carried out in a reducing mixed gas atmosphere of 5% hydrogen and 95% argon. The heat treatment temperature was 100°C, the heating rate was 10°C / min, the heat treatment time was 20 minutes, and it was cooled in the furnace to obtain the nickel-iron metal material Ni-Fe@1.

[0209] Example 39 This example provides a nickel-cobalt binary metal material. The preparation method includes:

[0210] First, using a nickel sheet as the substrate, it was pretreated, including: immersing the nickel substrate in anhydrous ethanol and anhydrous acetone successively and ultrasonically for 5 minutes each to remove the oil stains on the surface, and immersing the nickel substrate in a 0.5 mol / L sulfuric acid solution and ultrasonically for 5 minutes to remove the surface oxides.

[0211] Subsequently, cobalt nitrate was used as the electroplating solution and sodium citrate was used as the complexing agent. The concentration of cobalt nitrate in the electroplating 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 -0.8 V for 5 minutes to obtain a nickel substrate with a cobalt layer plated on its surface. The electroplating was carried out at 25°C.

[0212] Then, heat treatment was carried out in a reducing mixed gas atmosphere of 5% hydrogen and 95% argon. The heat treatment temperature was 100°C, the heating rate was 10°C / min, the heat treatment time was 20 minutes, and it was cooled in the furnace to obtain the nickel-cobalt metal material Ni-Co@1.

[0213] Example 40 This example provides a nickel-manganese binary metal material. The preparation method includes:

[0214] First, using a nickel sheet as the substrate, it was pretreated, including: immersing the nickel substrate in anhydrous ethanol and anhydrous acetone successively and ultrasonically for 5 minutes each to remove the oil stains on the surface, and immersing the nickel substrate in a 0.5 mol / L sulfuric acid solution and ultrasonically for 5 minutes to remove the surface oxides.

[0215] Subsequently, manganese nitrate was used as the electroplating solution and sodium citrate was used as the complexing agent. The concentration of manganese nitrate in the electroplating 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 its surface. The electroplating was carried out at 25°C.

[0216] Then, heat treatment was carried out in a reducing mixed gas atmosphere of 5% hydrogen and 95% argon. The heat treatment temperature was 100 °C, the heating rate was 10 °C / min, and it was cooled in the furnace. The heat treatment time was 20 minutes to obtain the nickel-manganese metal material Ni-Mn@1.

[0217] Comparative Example 1 The only difference between this comparative example and Example 9 is that no heat treatment was carried out in Comparative Example 1, and the other conditions were the same as those in Example 9.

[0218] 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 was 0.2 mol / L, and the other conditions were the same as those in Example 9.

[0219] Comparative Example 3 The only difference between this comparative example and Example 9 is that the heat treatment in Comparative Example 3 was carried out in air, and the other conditions were the same as those in Example 9.

[0220] Comparative Example 4 The only difference between this comparative example and Example 9 is that the heat treatment time in Comparative Example 4 was 5 minutes, and the other conditions were the same as those in Example 9.

[0221] Comparative Example 5 The only difference between this comparative example and Example 9 is that the heat treatment time in Comparative Example 5 was 600 minutes, and the other conditions were the same as those in Example 9.

[0222] 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 Owens formula. The test results are shown in Table 1 below.

[0223] Owens formula: γ SL =γ S +γ L -2(γ SD ·γ LD ) 1 / 2 -2(γ SP ·γ LP ) 1 / 2

[0224] Where, γ SL is the solid-liquid interfacial tension; γ S is the solid surface energy; γ L is the liquid surface tension; 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 polar force.

[0225] Table 1 Comparison table of contact angles and surface energies of alloys prepared in Examples 1-40 and Comparative Examples 1-5

[0226]

[0227]

[0228] As shown in Table 1 above, after plating copper on the pretreated nickel metal substrate or plating nickel on the pretreated copper metal substrate, and then performing short-time heat treatment in a reducing atmosphere or an inert atmosphere, a nickel-copper binary metal material with uniformly mixed surface atoms, no element segregation and phase separation, and high surface energy can be obtained. It shows relatively large surface energy and good hydrophilicity, and the surface energy is significantly improved compared with the nickel metal substrate. In the samples of the comparative examples, since nickel and copper atoms are not uniformly mixed, and the surface energy of copper metal is less than that of nickel metal, the surface energy has decreased to varying degrees compared with the nickel metal substrate.

[0229] Similarly, after plating iron, cobalt or manganese on the pretreated nickel metal substrate and then performing short-time heat treatment in a reducing atmosphere or an inert atmosphere, a binary metal material with high surface energy can also be obtained.

[0230] Further, please refer to Figure 1 , which is the XRD diffraction pattern of the nickel-copper binary metal material prepared in Example 9. The characteristic peaks of nickel appear, and the characteristic peaks of copper do not appear, indicating that the doping amount of copper is relatively 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 the ordered structure of the alloy either. Therefore, in the present invention, the expression related to "nickel-copper alloy" in the domestic priority text (i.e., CN202311153662.8) has been corrected.

[0231] Figures 2 - 3 It is the SEM morphology diagram of the nickel-copper binary metal material prepared in Example 9, which has no obvious difference from the pure nickel mesh.

[0232] Figures 4 - 7 It is the element distribution and content diagram of the nickel-copper binary metal material prepared in Example 9. It can be seen that copper elements are uniformly distributed on the surface of the nickel metal substrate, and the content is less than 5 at%.

[0233] Figure 8 It is the AC-HADDF-STEM Fourier transform diagram, atomic image and element distribution diagram 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 substrate, and nickel atoms and copper atoms are uniformly mixed without element segregation and phase separation.

[0234] Figures 9 - 10 They are respectively the three-dimensional atomic reconstruction diagram and high-resolution atomic distribution diagram obtained by detecting the nickel-copper binary metal material prepared in Example 9 using the three-dimensional atom probe technique. It can be seen that copper atoms are uniformly dispersed in the nickel metal substrate, and nickel atoms and copper atoms are uniformly mixed without element segregation and phase separation.

[0235] The surface energy of the metal material prepared in Comparative Example 1 is small and its hydrophilicity is poor, indicating that copper atoms need to be evenly dispersed on the surface of the nickel matrix and cannot be phase-separated from the nickel metal. The atomic disorder has a great influence on the surface properties of the metal material.

[0236] The surface energy of the metal material prepared in Comparative Example 2 is small and its hydrophilicity is poor, indicating that the amount of copper element should not be too much. Excessive copper elements 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.

[0237] Figure 11 Figure of SEM morphology of the nickel-copper binary metal material prepared in Comparative Example 3 Figures 12 - 14 Respectively are the distribution diagrams of nickel, copper, and oxygen elements of the nickel-copper binary metal material prepared in Comparative Example 3. It can be seen that after heat treatment in air, an oxide film appears on the surface of the metal material, and the distributions of nickel and copper elements are uneven, which results in small surface energy and poor hydrophilicity of the metal material prepared in Comparative Example 3, as shown in Table 1.

[0238] The surface energy of the metal materials prepared in Comparative Example 4 and Comparative Example 5 is small and their hydrophilicity is poor, indicating that the heat treatment time should not be too long or too short. Heat treatment has a great influence on the surface properties of the metal materials.

[0239] Figure 15 Figure of the contact angle between the nickel-copper binary metal material prepared in Example 9 and water. It can be seen that the contact angle between the Ni-Cu@5 metal material and water is 0°, and the surface energy of the metal material can reach 77.58 mJ / m 2 . Figure 16 Figure of the contact angle between the nickel mesh and water. It can be seen that the contact angle between the nickel mesh and water is 108 - 109°, and its surface energy is less than 31.86 mJ / m 2 .

[0240] Figure 17 Figure of the hydrogen evolution performance of electrolyzed water of the nickel-copper binary metal material prepared in Example 9. Compared with pure nickel metal, due to the increase in its hydrophilicity, its current density can reach 200 mA / cm at -0.46 V 2 , far lower than -0.75 V of pure nickel.

[0241] Figure 18 Figure of the hydrogen evolution performance of electrolyzed water of the nickel-copper binary metal material prepared in Example 20. Compared with pure nickel metal, due to the increase in its hydrophilicity, its current density can reach 200 mA / cm at -0.55 V 2 , far lower than -0.75 V of pure nickel.

[0242] Figure 19Hydrogen evolution performance graph of the nickel-copper binary metal material prepared in Example 28. Compared with pure nickel metal, due to the increase in its hydrophilicity, the current density can reach 200 mA / cm² at -0.50 V, 2 which is much lower than -0.75 V of pure nickel.

[0243] Figure 20 Hydrogen evolution performance graph of the nickel-copper binary metal material prepared in Comparative Example 1. Compared with pure nickel metal, due to the decrease in its hydrophilicity, the current density reaches 200 mA / cm² at -0.95 V, 2 which is much higher than -0.75 V of pure nickel.

[0244] In summary, the present invention provides a method for increasing the surface energy of a nickel metal matrix. By depositing another metal that can form a solid solution with nickel metal on the surface of the nickel metal matrix and then performing short-time heat treatment in a reducing atmosphere or an inert atmosphere, the surface energy of the nickel metal matrix is effectively increased, and the surface energy of the prepared binary metal material is between 30 mJ / m² 2 and 80 mJ / m², 2 thus obtaining high hydrophilicity, and further enabling it to play a greater application advantage as a hydrogen evolution / oxygen evolution electrode in the field of electrolyzed water.

[0245] All aspects, embodiments, features, and examples of the present invention should be considered illustrative in all respects and are not intended to limit the present invention. The scope of the present invention is only defined by the claims. Without departing from the spirit and scope of the claimed invention, those skilled in the art will appreciate other embodiments, modifications, and uses.

Claims

1. A use of a nickel-copper binary metal material in hydrogen production by electrolysis of water, characterized in that: The surface of the nickel-copper binary metal material has uniformly mixed nickel atoms and copper atoms, and the surface energy of the nickel-copper binary metal material is 76.41 mJ / m 2 , and the preparation method of the nickel-copper binary metal material comprises: Firstly, 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 then immersing the nickel substrate in a 0.5 mol / L sulfuric acid solution and ultrasonicating for 5 minutes to remove surface oxides; Then, copper nitrate solution was used as the electroplating solution, citric acid was used as the complexing agent, the concentration of copper nitrate in the electroplating solution was 0.01 mol / L, and the concentration of citric acid was 0.01 mol / L. The nickel substrate was electroplated 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. Afterwards, the nickel substrate with a copper layer plated on the surface was heat treated in a reducing mixed gas atmosphere containing 5% hydrogen and 95% argon. The heat treatment temperature was 100 °C, the heating rate was 10 °C / min, and the heat treatment time was 20 min. It was then cooled in the furnace to obtain a nickel-copper binary metal material named Ni-Cu@1.

2. A use of a nickel-copper binary metal material in hydrogen production by electrolysis of water, characterized in that: The surface of the nickel-copper binary metal material has uniformly mixed nickel atoms and copper atoms, and the surface energy of the nickel-copper binary metal material is 77.66 mJ / m 2 , and the preparation method of the nickel-copper binary metal material comprises: Firstly, 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 min respectively to remove surface oil stains, and then immersing the nickel substrate in a 2 mol / L sulfuric acid solution and ultrasonicating for 5 min to remove surface oxides; Afterwards, copper sulfate solution was used as the electroplating solution, sodium pyrophosphate was used as the complexing agent, the copper sulfate concentration in the electroplating solution was 0.01 mol / L, and the sodium pyrophosphate concentration was 0.01 mol / L. The nickel substrate was electroplated at a voltage of -0.3 V for 5 min to obtain a nickel substrate with a copper layer on the surface. The electroplating was carried out at 25 °C. Afterwards, the nickel substrate with a copper layer plated on the surface was heat treated in a nitrogen atmosphere at a temperature of 100 °C, a heating rate of 10 °C / min, and a heat treatment time of 20 min. It was then cooled in the furnace to obtain a nickel-copper binary metal material named Ni-Cu@2.

3. A use of a nickel-copper binary metal material in hydrogen production by water electrolysis, characterized in that: The surface of the nickel-copper binary metal material has uniformly mixed nickel atoms and copper atoms, and the surface energy of the nickel-copper binary metal material is 67.65 mJ / m 2 , and the preparation method of the nickel-copper binary metal material comprises: Firstly, 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; Afterwards, copper chloride solution was used as the plating solution, EDTA was used as the complexing agent, the concentration of copper chloride in the plating solution was 0.01 mol / L, and the concentration of EDTA was 0.01 mol / L. The nickel substrate was electroplated at a voltage of -0.3 V for 5 min to obtain a nickel substrate with a copper layer on the surface. The electroplating was carried out at 25 °C. Then, the nickel substrate with a copper layer plated on the surface was heat treated in a reducing atmosphere containing 5% hydrogen and 95% argon at a temperature of 100 °C for 20 min to obtain a nickel-copper binary metal material named Ni-Cu@3.

4. A use of a nickel-copper binary metal material in the production of hydrogen by electrolysis of water, characterized in that: The surface of the nickel-copper binary metal material has uniformly mixed nickel atoms and copper atoms, and the surface energy of the nickel-copper binary metal material is 77.13 mJ / m 2 , and the preparation method of the nickel-copper binary metal material comprises: Firstly, the nickel mesh was used as a substrate and pretreated, including: immersing the nickel substrate in anhydrous ethanol and anhydrous acetone in turn and ultrasonicating for 5 min respectively to remove the oil on the surface, and then immersing the nickel substrate in a 2 mol / L sulfuric acid solution and ultrasonicating for 5 min to remove the surface oxide; Afterwards, copper nitrate solution was used as the plating solution, citric acid was used as the complexing agent, the concentration of copper nitrate in the plating solution was 0.01 mol / L, and the concentration of citric acid was 0.01 mol / L. The nickel substrate was electroplated at a voltage of -0.3 V for 5 min to obtain a nickel substrate with a copper layer plated on the surface. The electroplating was carried out at 25°C. Afterwards, the nickel substrate with a copper layer plated on the surface was heat treated in a reducing mixed gas atmosphere containing 5% hydrogen and 95% argon. The heat treatment temperature was 100 °C, the heating rate was 10 °C / min, the heat treatment time was 20 min, and the furnace was cooled to obtain a nickel-copper binary metal material named Ni-Cu@4.

5. A use of a nickel-copper binary metal material in hydrogen production by electrolysis of water, characterized in that: The surface of the nickel-copper binary metal material has uniformly mixed nickel atoms and copper atoms, and the surface energy of the nickel-copper binary metal material is 77.58 mJ / m 2 , and the preparation method of the nickel-copper binary metal material comprises: Firstly, the nickel mesh was used as a substrate and pretreated, including: immersing the nickel substrate in anhydrous ethanol and anhydrous acetone in turn and ultrasonicating for 5 min respectively to remove the oil on the surface, and then immersing the nickel substrate in a 2 mol / L sulfuric acid solution and ultrasonicating for 5 min to remove the surface oxide; Afterwards, copper sulfate solution was used as the electroplating solution, sodium pyrophosphate was used as the complexing agent, the copper sulfate concentration in the electroplating solution was 0.01 mol / L, and the sodium pyrophosphate concentration was 0.01 mol / L. The nickel substrate was electroplated at a voltage of -0.3 V for 5 min to obtain a nickel substrate with a copper layer on the surface. The electroplating was carried out at 25 °C. Afterwards, the nickel substrate with a copper layer plated on the surface was heat treated in a nitrogen atmosphere at a temperature of 100 °C, a heating rate of 10 °C / min, and a heat treatment time of 20 min. The nickel-copper binary metal material was obtained by cooling in the furnace and named Ni-Cu@5.

6. Use of a nickel-copper binary metal material in hydrogen production by water electrolysis, characterized in that: The surface of the nickel-copper binary metal material has uniformly mixed nickel atoms and copper atoms, and the surface energy of the nickel-copper binary metal material is 53.69 mJ / m 2 , and the preparation method of the nickel-copper binary metal material comprises: Firstly, the nickel mesh was used as a substrate and pretreated, including: immersing the nickel substrate in a 2 mol / L sodium hydroxide solution and ultrasonicating for 5 min to remove surface oil stains, and then immersing the nickel substrate in a 2 mol / L hydrochloric acid solution and ultrasonicating for 5 min to remove surface oxides; Afterwards, copper chloride solution was used as the plating solution, EDTA was used as the complexing agent, the concentration of copper chloride in the plating solution was 0.01 mol / L, and the concentration of EDTA was 0.01 mol / L. The nickel substrate was electroplated at a voltage of -0.3 V for 5 min to obtain a nickel substrate with a copper layer on the surface. The electroplating was carried out at 25 °C. Afterwards, the nickel substrate with a copper layer plated on the surface was heat treated in a reducing atmosphere containing 5% hydrogen and 95% argon at a heat treatment temperature of 100 °C and a heat treatment time of 20 min to obtain a nickel-copper binary metal material named Ni-Cu@6.

7. Use of a nickel-copper binary metal material in hydrogen production by water electrolysis, characterized in that: The surface of the nickel-copper binary metal material has uniformly mixed nickel atoms and copper atoms, and the surface energy of the nickel-copper binary metal material is 65.21 mJ / m 2 , and the preparation method of the nickel-copper binary metal material comprises: Firstly, nickel foam was used as a substrate and pretreated, including: immersing the substrate in anhydrous ethanol and anhydrous acetone in turn and ultrasonicating for 5 min respectively to remove surface oil stains, and then immersing the substrate in 2 mol / L sulfuric acid solution and ultrasonicating for 5 min to remove surface oxides; Afterwards, copper nitrate was used as the plating solution, citric acid was used as the complexing agent, the concentration of copper nitrate in the plating solution was 0.01 mol / L, and the concentration of citric acid was 0.01 mol / L. The nickel substrate was electroplated 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. Then, the nickel substrate with a copper layer plated on the surface was heat treated in a reducing mixed gas atmosphere containing 5% hydrogen and 95% argon. The heat treatment temperature was 100 °C, the heating rate was 10 °C / min, and the furnace was cooled. The heat treatment time was 20 min to obtain a nickel-copper binary metal material named Ni-Cu@7.

8. Use of a nickel-copper binary metal material in producing hydrogen by electrolysis of water, characterized in that: The surface of the nickel-copper binary metal material has uniformly mixed nickel atoms and copper atoms, and the surface energy of the nickel-copper binary metal material is 75.75 mJ / m 2 , and the preparation method of the nickel-copper binary metal material comprises: Firstly, nickel foam was used as a substrate and pretreated, including: immersing the substrate in anhydrous ethanol and anhydrous acetone in turn and ultrasonicating for 5 min respectively to remove surface oil stains, and then immersing the substrate in 2 mol / L sulfuric acid solution and ultrasonicating for 5 min to remove surface oxides; Then, copper sulfate was used as the electroplating solution, sodium pyrophosphate was used as the complexing agent, the concentration of copper sulfate in the electroplating solution was 0.01 mol / L, and the concentration of sodium pyrophosphate was 0.01 mol / L. The nickel substrate was electroplated at a voltage of -0.3 V for 5 minutes to obtain a nickel substrate with a copper layer on the surface. The electroplating was carried out at 25 °C. Subsequently, the nickel substrate with a copper layer plated on the surface was heat treated in a nitrogen atmosphere at a temperature of 100 °C, a heating rate of 10 °C / min, and furnace cooling for 20 minutes to obtain a nickel-copper binary metal material named Ni-Cu@8.

9. Use of a nickel-copper binary metal material in hydrogen production by water electrolysis, characterized in that: The surface of the nickel-copper binary metal material has uniformly mixed nickel atoms and copper atoms, and the surface energy of the nickel-copper binary metal material is 74.66 mJ / m 2 , and the preparation method of the nickel-copper binary metal material comprises: Firstly, 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 min to remove surface oil stains, and then immersing the substrate in a 2 mol / L hydrochloric acid solution and ultrasonicating for 5 min to remove surface oxides; Afterwards, copper chloride was used as the plating solution, EDTA was used as the complexing agent, the concentration of copper chloride in the plating solution was 0.01 mol / L, and the concentration of EDTA was 0.01 mol / L. The nickel substrate was electroplated at a voltage of -0.3 V for 5 min to obtain a nickel substrate with a copper layer on the surface. The electroplating was carried out at 25 °C. Then, the nickel substrate with a copper layer plated on the surface was heat treated in a reducing atmosphere containing 5% hydrogen and 95% argon at a heat treatment temperature of 100 °C and a heat treatment time of 20 min to obtain a nickel-copper binary metal material named Ni-Cu@9.

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