CN113174513B - Ni-Cu-Ti/CNTs porous composite material and preparation method thereof - Google Patents

Ni-Cu-Ti/CNTs porous composite material and preparation method thereof Download PDF

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CN113174513B
CN113174513B CN202110469073.5A CN202110469073A CN113174513B CN 113174513 B CN113174513 B CN 113174513B CN 202110469073 A CN202110469073 A CN 202110469073A CN 113174513 B CN113174513 B CN 113174513B
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CN113174513A (en
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吴靓
黄佳佳
周子坤
肖逸锋
张乾坤
陈宇
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Xiangtan University
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/11—Making porous workpieces or articles
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/002—Alloys based on nickel or cobalt with copper as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
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    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
    • C22C2026/002—Carbon nanotubes
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
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    • Y02P20/133—Renewable energy sources, e.g. sunlight

Abstract

The invention discloses a Ni-Cu-Ti/CNTs porous composite material and a preparation method thereof. The invention mixes Ni, Cu, Ti element powder and dispersed CNTs evenly, ball-mills them, cold-presses them into green compact, then sinters them to prepare the porous composite material. The porous composite material has rich and uniformly distributed pores, simple and environment-friendly preparation process, excellent hydrogen evolution catalytic activity and mechanical property, and can be used for electrolytic hydrogen evolution and industrial filtration in alkaline environment.

Description

Ni-Cu-Ti/CNTs porous composite material and preparation method thereof
Technical Field
The invention relates to a preparation technology of a porous material, in particular to a preparation method of a Ni-Cu-Ti/CNTs (carbon nanotubes, CNTs for short) porous composite material which can be used for electrolytic hydrogen evolution and industrial filtration in an alkaline environment.
Background
At present, two thirds of world energy demand is realized by fossil fuels such as petroleum, natural gas and the like, and the main reasons are that the fuels are convenient to transport and store and easy to extract; furthermore, coal also accounts for a considerable proportion of the world's energy supply. However, these non-renewable energy sources are increasingly depleted. In order to solve the problems of increasing energy demand of human beings, environmental pollution caused by energy sources and the like, scientists are dedicated to searching new clean renewable energy sources. The heating value of hydrogen is two to three times of that of other fuels, only water is produced during hydrogen combustion, pollutants such as carbon dioxide and carbon monoxide are not produced, and the environment is not polluted. Therefore, hydrogen is one of the most economic and effective alternative energy sources as a clean, efficient, safe and renewable energy source. The large-scale use of hydrogen energy will make human beings enter a sustainable green era, and the large-scale and cheap production of hydrogen is an important prerequisite for the development and utilization of hydrogen energy. Among the numerous hydrogen production methods, the hydrogen production technology by water electrolysis has the most significant advantages: the hydrogen production raw material has low cost and wide resources, the water electrolysis hydrogen production equipment has low cost and high hydrogen purity, and the problem of carbon emission does not exist. One of the most common techniques for hydrogen production by electrolysis is the electrolysis of alkaline water. However, this technique is expensive. The cost of hydrogen production by water electrolysis mainly comes from the consumption of electric energy, energy consumption needs to be reduced for realizing large-scale and cheap hydrogen production, and the most important is to reduce the hydrogen evolution overpotential of an electrode.
The transition metal nickel and the alloy thereof have good chemical stability in alkaline medium, excellent corrosion resistance and high hydrogen evolution reaction activity, and are the most widely applied catalytic electrode materials for electrolyzing water and evolving hydrogen. In order to improve the catalytic activity of the electrode, the development of the nickel-based electrode mainly has the following directions: (1) a porous electrode. By increasing the real surface area of the electrode, the catalytic activity centers are increased, and the apparent catalytic activity of the electrode is improved. Raney Ni is a typical representative among such electrodes. It has lower hydrogen evolution overpotential and can keep hydrogen evolution activity unchanged within 10000 hours. At a current density of 2000A/m2The cell voltage was about 2V. However, the greatest disadvantage of this electrode is that the hydrogen evolution activity is easily lost with the oxidative dissolution of the active ingredient during the interruption of the current during the hydrogen evolution process, especially after a longer period of interruption of the current. Research shows that micron-sized pores can effectively avoid hydrogen from blocking pore channels and are easier to overflow hydrogen. (2) Alloy electrodes, including Ni-metals and Ni-nonmetal alloys. According to the 'volcano' theory of Engel-Brewer, when metals (such as Fe, Co, Ni) on the left of a transition system with unfilled or half-filled d orbitals are alloyed with metals (such as W, Mo, Cr, La, Ha, Zr) on the right of a transition system with paired d electrons which are not suitable for bonding in pure metals, a very significant electrocatalytic synergistic effect can be generated on hydrogen evolution reaction, and the intrinsic catalytic activity of the electrode can be effectively improved by the alloying method. The alloy electrode has good catalytic effect, but if a second phase such as graphene or carbon nano tube is introduced into the alloy electrode to prepare a composite electrode, the electrode can be further subjected toThe catalytic action is optimized, and the mechanical property of the electrode can be improved.
Carbon nanostructures can be used as catalyst supports due to their high conductivity and dispersibility. Carbon nanotubes, also known as buckytubes, are one-dimensional quantum materials with a special structure (radial dimension is nanometer magnitude, axial dimension is micrometer magnitude, both ends of the tube are basically sealed). The CNTs have the same structure as the graphite sheet structure, and have good electrical properties. In addition, carbon atoms in the CNTs are hybridized by SP2, and compared with SP3 hybridization, the S orbital component in SP2 hybridization is larger, so that the CNTs have high modulus and strength and excellent mechanical properties.
Therefore, the research considers that the CNTs with a proper amount are added into the Ni-Cu-Ti alloy porous electrode to prepare the composite electrode so as to further improve the hydrogen evolution performance and the service life of the electrode. The CNTs are dispersed and distributed in the Ni-Cu-Ti porous material and are used as a catalytic carrier in the electrolytic process, and the composite electrode has high conductivity, so that the intrinsic catalytic activity of the composite electrode is greatly improved.
Disclosure of Invention
The invention provides an effective composite porous hydrogen electrolysis cathode material for electrolysis hydrogen evolution and industrial filtration in an alkaline environment, and the composite porous hydrogen electrolysis cathode material has the advantages of rich pores, extremely large specific surface area, excellent electrocatalytic activity, excellent corrosion resistance, excellent chemical stability and excellent mechanical properties. The invention discloses a Ni-Cu-Ti/CNTs porous composite material and a preparation method thereof.
The preparation method of the Ni-Cu-Ti/CNTs porous composite material comprises the following steps:
1) weighing four kinds of powder of Ni, Cu, Ti and CNTs according to a certain mass proportion.
2) Adding the weighed CNTs powder into deionized water according to the content of 0.3g/L, and adding 2 multiplied by 10-3Sodium Dodecyl Sulfate (SDS) with mol/L concentration, and placing the mixed solution into an ultrasonic cleaning machine for ultrasonic dispersion treatment for 30 min;
3) mixing weighed Ni, Cu and Ti powders into the solution after ultrasonic dispersion, and placing the mixture on a magnetic stirrer for stirring until the solution is layered;
4) carrying out vacuum filtration on the stirred solution to obtain separated powder, and then drying the powder for 5 hours;
5) ball-milling the dried powder, drying and sieving the powder after ball-milling, and adding stearic acid accounting for 3-5% of the powder by mass for drying for 5 hours;
6) sieving the dried powder by a 60-mesh sieve, and taking the sieved powder for later use;
7) placing the sieved undersize powder into a mold, and pressing the undersize powder into a powder green body under a hydraulic press;
8) sintering the pressed powder green body in a vacuum furnace with a vacuum degree of not less than 2 × 10-3Mpa; the sintering process comprises the following steps: heating from room temperature to 300 ℃ at a heating rate of 4-6 ℃/min; secondly, preserving the heat for 50-70 min; thirdly, heating to 600 ℃ at a heating speed of 4-6 ℃/min; fourthly, preserving the heat for 50-70 min; raising the temperature to 900 ℃ at a temperature rise speed of 4-6 ℃/min; sixthly, preserving the heat for 50-70 min; seventhly, heating to 1000 ℃ at a heating speed of 2-3 ℃/min; eighthly, keeping the temperature for 50-70 min; and ninthly, cooling to room temperature along with the furnace to obtain the porous composite material.
The invention adopts the technical scheme that the method has the advantages that:
(1) the porous composite material has large specific surface area and high porosity. According to the technical scheme, the element powder forms an even and communicated hole structure in the sintering process through an element sintering method, the porosity is rich, the holes are large, the specific surface area of the surface of the material is increased, and the realization of the filtering function of the composite material is favorably ensured.
(2) The porous composite material has high catalytic activity. According to the scheme, CNTs are added, and the carbon nano structure can be used as a catalyst carrier due to high conductivity and dispersibility of the carbon nano structure, and the synergistic catalytic action, large specific surface area and high porosity of Ni, Cu and Ti elements are utilized, so that the porous composite material has the functions of adsorbing and desorbing ions in the electrolytic hydrogen evolution process, and has high hydrogen evolution catalytic activity.
(3) The porous composite material has the advantages of easily obtained raw materials and simple preparation process. The preparation process is green and environment friendly and has no pollutant produced. The raw materials are easy to obtain, the cost is low, the preparation process is simple, and the mass production can be realized.
(4) The porous composite material has excellent mechanical property and corrosion resistance. The scheme is prepared by mixing and sintering Ni, Cu, Ti and CNTs powder, and the CNTs are added, so that the composite material has high modulus, high strength and excellent mechanical properties. In addition, a corrosion-resistant product can be obtained after the element powder reacts, so that the material is ensured to have excellent mechanical property and corrosion resistance, and the service life of the material is greatly prolonged.
Drawings
FIG. I is a surface morphology diagram of the Ni-Cu-Ti/CNTs porous composite material prepared in example 1.
FIG. two is a cathode polarization curve of the Ni-Cu-Ti/CNTs porous composite prepared in example 1.
Detailed Description
The present invention will be further illustrated with reference to specific examples, but the present invention is not limited to these examples.
Example 1
Weighing three high-purity powders of Ni, Cu, Ti and CNTs according to a certain mass proportion, wherein the content of the Ni powder is 55 wt%, and the particle size of the powder is 5 mu m; the Cu powder content is 35 wt%, and the powder particle size is 5 μm; the Ti powder content is 10 wt%, the powder particle size is 5 μm, the CNTs content is 0.3 wt%, the powder is a multi-wall carbon nano-tube, and the length is 1 μm. Adding weighed CNTs into deionized water according to the proportion of 0.1g/L, adding 68% of sodium dodecyl benzene sulfonate, 150% of Tween-20 and 150% of polyvinylpyrrolidone relative to the mass of the CNTs respectively, and placing the mixed solution into an ultrasonic cleaning machine for ultrasonic dispersion for 30 min. And adding weighed Ni, Cu and Ti powder after the ultrasonic treatment, and stirring the mixture on a magnetic stirrer until the solution is layered. And (3) carrying out vacuum filtration after stirring, placing the separated powder in a vacuum drying oven for drying for 5 hours at 75 ℃, placing the dried powder into a ball mill, adding alcohol for ball milling, wherein the ball-material ratio is 12: 1, the rotating speed is 180r/min, the ball milling time is 16h, and drying and powder sieving are carried out after the ball milling is finished. Stearic acid was added in an amount of 5% by mass relative to the mass of the powder, and then dried in a vacuum oven at 75 degrees for 5 hours. The dried powder was sieved through a 60 mesh sieve.And (3) placing the undersize powder into a mold, pressing the undersize powder into a cuboid powder green body under a hydraulic press at the pressure of 200Mpa, and keeping the pressure for 90 s. Sintering the obtained powder green compact in vacuum with a vacuum degree of 2 × 10-4Mpa; the sintering process comprises the following steps: heating from room temperature to 300 ℃ at a heating rate of 5 ℃/min; ② preserving heat for 60 min; thirdly, raising the temperature to 600 ℃ at the temperature rise speed of 5 ℃/min; fourthly, preserving the heat for 60 min; raising the temperature to 900 ℃ at a temperature rise speed of 5 ℃/min; sixthly, keeping the temperature for 60 min; seventhly, heating to 1000 ℃ at the temperature rising speed of 2.5 ℃/min; eighthly, keeping the temperature for 60 min; and ninthly, cooling along with the furnace to room temperature to obtain the porous composite metal material.
The porosity of the obtained material is 42.57%, and the porosity is higher. The microscopic surface morphology is shown in the figure I, and the prepared material has more holes and more abundant pores.
In order to research the catalytic hydrogen evolution performance of the prepared porous composite material, the prepared sample is sealed by polytetrafluoroethylene and silicon rubber, and the exposed area of the electrode surface is 1.1cm2Electrochemical tests were performed in 6Mol/L KOH solution. Adopts a standard three-electrode system, the auxiliary electrode is a Pt sheet, and the reference electrode is Hg, HgO/OH-The working electrode is a prepared Ni-Cu-Ti/CNTs porous composite electrode sample. The instrument used for the test is a CS350 electrochemical workstation, the scanning speed is 4mV/s, the scanning range is 0V to-2V, and the electrolyte is placed in a constant-temperature water bath and kept at 25 ℃. The cathode polarization curve of the Ni-Cu-Ti/CNTs porous composite material is shown in the second figure, when the current density is 399 mA/cm2The overpotential was 750mV (vs. Hg/HgO).
Example 2
Weighing three high-purity powders of Ni, Cu, Ti and carbon nano tubes according to a certain mass ratio, wherein the content of the Ni powder is 56 wt%, and the particle size of the powder is 4 mu m; the content of Cu powder is 33 wt%, and the particle size of the powder is 4 mu m; the Ti powder content is 11 wt%, the powder particle size is 4 μm, the CNTs content is 0.4 wt%, the powder is a multi-wall carbon nano-tube, and the length is 2 μm. Adding weighed CNTs into deionized water according to the proportion of 0.1g/L, adding 68% of sodium dodecyl benzene sulfonate, 150% of Tween-20 and 150% of polyvinylpyrrolidone which are respectively relative to the mass of the CNTs, and placing the mixed solution into an ultrasonic cleaner for ultrasonic dispersion treatment for 30 min. Ultrasonic wave is used upAfter that, adding weighed Ni, Cu and Ti powder, and placing the mixture on a magnetic stirrer to stir until the solution is layered. And (3) carrying out vacuum filtration after stirring, placing the separated powder in a vacuum drying oven for drying for 5 hours at 75 ℃, placing the dried powder into a ball mill, adding alcohol for ball milling, wherein the ball-material ratio is 12: 1, the rotating speed is 200r/min, the ball milling time is 17h, and drying and powder sieving are carried out after the ball milling is finished. Stearic acid was added in an amount of 4% by mass relative to the mass of the powder, and then dried in a vacuum oven at 75 degrees for 5 hours. The dried powder was sieved through a 60 mesh sieve. And (3) placing the undersize powder into a mold, pressing the undersize powder into a cuboid powder green body under a hydraulic press at the pressure of 200Mpa, and keeping the pressure for 100 s. Sintering the prepared powder green compact in a vacuum molybdenum sheet furnace with the vacuum degree of 2 multiplied by 10-4Mpa; the sintering process comprises the following steps: heating from room temperature to 300 ℃ at a heating rate of 5 ℃/min; keeping the temperature for 60 min; thirdly, raising the temperature to 600 ℃ at the temperature rise speed of 5 ℃/min; fourthly, preserving the heat for 60 min; raising the temperature to 900 ℃ at a temperature rise speed of 5 ℃/min; sixthly, keeping the temperature for 60 min; seventhly, heating to 1000 ℃ at the temperature rising speed of 2.5 ℃/min; eighthly, keeping the temperature for 60 min; and ninthly, cooling to room temperature along with the furnace to obtain the porous composite metal material.
The sample preparation procedure and electrochemical experimental procedure in example 1 were repeated to obtain a pore structure and electrochemical properties similar to those in example 1.
Example 3
Weighing three high-purity powders of Ni, Cu, Ti and CNTs according to a certain mass proportion, wherein the content of the Ni powder is 59 wt%, and the particle size of the powder is 3 mu m; the Cu powder content is 33 wt%, and the powder particle size is 3 μm; the Ti powder content is 8 wt%, the powder particle size is 3 μm, the CNTs content is 0.5%, the multi-wall carbon nano tube is formed, and the length is 0.5 μm. Adding weighed CNTs into deionized water according to the proportion of 0.1g/L, adding 68% of sodium dodecyl benzene sulfonate, 150% of Tween-20 and 150% of polyvinylpyrrolidone which are respectively relative to the CNTs, and placing the mixed solution into an ultrasonic cleaner for ultrasonic dispersion treatment for 30 min. And adding weighed Ni, Cu and Ti powder after the ultrasonic treatment, and stirring the mixture on a magnetic stirrer until the solution is layered. Vacuum filtering after stirring, drying the separated powder in a vacuum drying oven at 75 deg.C for 5 hr, ball milling the dried powder, adding alcohol, and ball millingThe ball-material ratio is 12: 1, the rotating speed is 210r/min, the ball milling time is 18h, and drying and powder sieving are carried out after the ball milling is finished. Stearic acid was added in an amount of 3% by mass relative to the powder, and then dried in a vacuum oven at 75 degrees for 5 hours. The dried powder was sieved through a 60 mesh sieve. And (3) placing the undersize powder into a mold, pressing the undersize powder into a cuboid powder green body under a hydraulic press at the pressure of 200Mpa, and keeping the pressure for 110 s. Sintering the obtained powder green compact in a vacuum furnace with a vacuum degree of 2 × 10-4Mpa; the sintering process comprises the following steps: heating from room temperature to 300 ℃ at a heating rate of 5 ℃/min; ② preserving heat for 60 min; thirdly, raising the temperature to 600 ℃ at the temperature rise speed of 5 ℃/min; fourthly, preserving the heat for 60 min; raising the temperature to 900 ℃ at a temperature rise speed of 5 ℃/min; sixthly, keeping the temperature for 60 min; seventhly, heating to 1000 ℃ at the temperature rising speed of 2.5 ℃/min; eighthly, keeping the temperature for 60 min; and ninthly, cooling to room temperature along with the furnace to obtain the porous composite metal material.
Example 4
Weighing three high-purity powders of Ni, Cu, Ti and CNTs according to a certain mass proportion, wherein the content of the Ni powder is 55 wt%, and the particle size of the powder is 5 mu m; the Cu powder content is 33 wt%, and the powder particle size is 5 μm; the Ti powder content is 12wt%, the powder particle size is 5 μm, the CNTs content is 0.35%, the multi-wall carbon nano-tube is a multi-wall carbon nano-tube, and the length is 1.5 μm. Adding weighed CNTs into deionized water according to the proportion of 0.1g/L, adding 68% of sodium dodecyl benzene sulfonate, 150% of Tween-20 and 150% of polyvinylpyrrolidone which are respectively relative to the mass of the CNTs, and placing the mixed solution into an ultrasonic cleaner for ultrasonic dispersion treatment for 30 min. And adding weighed Ni, Cu and Ti powder after the ultrasonic treatment, and stirring the mixture on a magnetic stirrer until the solution is layered. And (3) carrying out vacuum filtration after stirring, placing the separated powder in a vacuum drying oven for drying for 5 hours at 75 ℃, placing the dried powder into a ball mill, adding alcohol for ball milling, wherein the ball-material ratio is 12: 1, the rotating speed is 190r/min, the ball milling time is 15h, and drying and powder sieving are carried out after the ball milling is finished. Stearic acid with 5 percent of the mass of the powder is added, and then the powder is dried for 5 hours in a vacuum drying oven at 75 ℃. The dried powder was sieved through a 60 mesh sieve. And (3) placing the undersize powder into a mold, pressing the undersize powder into a cuboid powder green body under a hydraulic press at the pressure of 200Mpa, and keeping the pressure for 100 s. The prepared powder green compact is placed in a vacuum furnace for sintering, and the vacuum degree is 2 in a large scale10-4Mpa; the sintering process comprises the following steps: heating from room temperature to 300 ℃ at a heating rate of 5 ℃/min; ② preserving heat for 60 min; thirdly, raising the temperature to 600 ℃ at the temperature rise speed of 5 ℃/min; fourthly, preserving the heat for 60 min; raising the temperature to 900 ℃ at a temperature rise speed of 5 ℃/min; sixthly, keeping the temperature for 60 min; seventhly, heating to 1000 ℃ at the temperature rising speed of 2.5 ℃/min; eighthly, keeping the temperature for 60 min; and ninthly, cooling to room temperature along with the furnace to obtain the porous composite metal material.
The sample preparation procedure and electrochemical experimental procedure in example 1 were repeated to obtain a pore structure and electrochemical properties similar to those in example 1.
Example 5
Weighing three high-purity powders of Ni, Cu, Ti and carbon nano tubes according to a certain mass ratio, wherein the content of the Ni powder is 55 wt%, and the particle size of the powder is 5 mu m; the content of Cu powder is 35 wt%, and the particle size of the powder is 5 mu m; the Ti powder content is 10 wt%, the powder particle size is 5 μm, the CNTs content is 0.5%, the multi-wall carbon nano-tube is a multi-wall carbon nano-tube, and the length is 2 μm. Adding weighed CNTs into deionized water according to the proportion of 0.1g/L, adding 68% of sodium dodecyl benzene sulfonate, 150% of Tween-20 and 150% of polyvinylpyrrolidone relative to the mass of the CNTs respectively, and placing the mixed solution into an ultrasonic cleaning machine for ultrasonic dispersion for 30 min. And adding weighed Ni, Cu and Ti powder after the ultrasonic treatment, and stirring the mixture on a magnetic stirrer until the solution is layered. And (3) carrying out vacuum filtration after stirring, placing the separated powder in a vacuum drying oven for drying for 5 hours at 75 ℃, placing the dried powder into a ball mill, adding alcohol for ball milling, wherein the ball-material ratio is 12: 1, the rotating speed is 190r/min, the ball milling time is 15h, and drying and powder sieving are carried out after the ball milling is finished. Stearic acid was added in an amount of 3% by mass relative to the powder, and then dried in a vacuum oven at 75 degrees for 5 hours. The dried powder was sieved through a 60 mesh sieve. And (3) placing the undersize powder into a mold, pressing the undersize powder into a cuboid powder green body under a hydraulic press at the pressure of 200Mpa, and keeping the pressure for 120 s. Sintering the obtained powder green compact in a vacuum furnace with a vacuum degree of 2 × 10-4Mpa; the sintering process comprises the following steps: heating from room temperature to 300 ℃ at a heating rate of 5 ℃/min; ② preserving heat for 60 min; thirdly, raising the temperature to 600 ℃ at the temperature rise speed of 5 ℃/min; fourthly, preserving the heat for 60 min; raising the temperature to 900 ℃ at a temperature rise speed of 5 ℃/min; sixthly, keeping the temperature for 60 min; at a rate of 2.5 deg.C/minThe temperature rise speed is increased to 1000 ℃; eighthly, keeping the temperature for 60 min; and ninthly, cooling to room temperature along with the furnace to obtain the porous composite metal material.
The sample preparation procedure and electrochemical experimental procedure in example 1 were repeated to obtain a pore structure and electrochemical properties similar to those in example 1.
The above description is only for the preferred embodiment of the present invention and is not intended to limit the present invention in any way, and all simple modifications, equivalent changes and modifications made to the above embodiment according to the technical spirit of the present invention are within the scope of the technical solution of the present invention.

Claims (5)

1. A Ni-Cu-Ti/CNTs porous composite material is characterized in that: the carbon nano tube CNTs are added, the outstanding conductivity and adsorption characteristics of the CNTs are utilized, the electrolytic hydrogen evolution capacity of the material is improved, and the preparation steps are as follows:
1) weighing four kinds of powder of Ni, Cu, Ti and CNTs according to a certain mass proportion, wherein the percentage of Ti powder is 8-12 wt%, the percentage of Cu powder is 33-37 wt%, the percentage of CNTs is 0.3-0.5 wt%, and the balance is Ni;
2) adding the weighed CNTs powder into deionized water according to the content of 0.3g/L, and adding 2 multiplied by 10-3Carrying out ultrasonic dispersion treatment on the mixed solution in an ultrasonic cleaning machine for 30min by using Sodium Dodecyl Sulfate (SDS) with mol/L concentration;
3) mixing the weighed Ni, Cu and Ti powder into the solution after ultrasonic dispersion, and placing the mixture on a magnetic stirrer for stirring until the solution is layered;
4) carrying out vacuum filtration on the stirred solution to obtain separated powder, and then drying the powder for 5 hours;
5) ball-milling the dried powder, drying and sieving the powder after ball-milling, and adding stearic acid accounting for 3-5% of the powder by mass for drying for 5 hours;
6) sieving the dried powder by a 60-mesh sieve, and taking the sieved powder for later use;
7) placing the sieved undersize powder into a mold, and pressing the undersize powder into a powder green body under a hydraulic press;
8) will be pressedSintering the powder green compact in a vacuum furnace with a vacuum degree of not less than 2 × 10-3Pa; the sintering process comprises the following steps: heating the mixture from room temperature to 300 ℃ at a heating rate of 4-6 ℃/min; preserving the heat for 50-70 min; raising the temperature to 600 ℃ at a temperature rise speed of 4-6 ℃/min; preserving the heat for 50-70 min; raising the temperature to 900 ℃ at a temperature rise speed of 4-6 ℃/min; preserving the heat for 50-70 min; raising the temperature to 1000 ℃ at a temperature rise speed of 2-3 ℃/min; preserving the heat for 50-70 min; and cooling to room temperature along with the furnace to obtain the porous composite material.
2. The Ni-Cu-Ti/CNTs porous composite material of claim 1, characterized in that in step 1), the particle size of Ni is 3-5 μm, the particle size of Cu is 3-5 μm, the particle size of Ti is 3-5 μm, CNTs are multi-walled carbon nanotubes, and the length is 0.5-2 μm.
3. A preparation method of Ni-Cu-Ti/CNTs composite porous material is characterized by comprising the following steps: the CNTs are added, the outstanding conductivity and adsorption characteristics of the CNTs are utilized, the electrolytic hydrogen evolution capacity of the material is improved, and the preparation steps are as follows:
1) weighing four kinds of powder of Ni, Cu, Ti and CNTs according to a certain mass proportion, wherein the percentage of Ti powder is 8-12 wt%, the percentage of Cu powder is 33-37 wt%, the percentage of CNTs is 0.3-0.5 wt%, and the balance is Ni;
2) adding the weighed CNTs powder into deionized water according to the content of 0.3g/L, and adding 2 x 10-3Carrying out ultrasonic dispersion treatment on the mixed solution in an ultrasonic cleaning machine for 30min by using Sodium Dodecyl Sulfate (SDS) with mol/L concentration;
3) mixing weighed Ni, Cu and Ti powders into the solution after ultrasonic dispersion, and placing the mixture on a magnetic stirrer for stirring until the solution is layered;
4) carrying out vacuum filtration on the stirred solution to obtain separated powder, and then drying the powder for 5 hours;
5) ball-milling the dried powder, drying and sieving the powder after ball-milling, and adding stearic acid accounting for 3-5% of the powder by mass for drying for 5 hours;
6) sieving the dried powder by a 60-mesh sieve, and taking the sieved powder for later use;
7) placing the sieved undersize powder into a mold, and pressing the undersize powder into a powder green body under a hydraulic press;
8) sintering the pressed powder green body in a vacuum furnace with a vacuum degree of not less than 2 × 10-3Pa; the sintering process comprises the following steps: heating the mixture from room temperature to 300 ℃ at a heating rate of 4-6 ℃/min; preserving the heat for 50-70 min; raising the temperature to 600 ℃ at a temperature rise speed of 4-6 ℃/min; preserving the heat for 50-70 min; raising the temperature to 900 ℃ at a temperature rise speed of 4-6 ℃/min; preserving the heat for 50-70 min; raising the temperature to 1000 ℃ at a temperature rise speed of 2-3 ℃/min; preserving the heat for 50-70 min; and cooling to room temperature along with the furnace to obtain the porous composite material.
4. The preparation method of the Ni-Cu-Ti/CNTs porous composite material according to claim 3, characterized in that the ball-to-material ratio of ball milling in step 5) is 12: 1, the ball milling speed is 180-210 r/min, and the ball milling time is 15-18 h.
5. The preparation method of the Ni-Cu-Ti/CNTs porous composite material according to claim 3, characterized in that in step 7), the pressure of a hydraulic press is 180-220 MPa, and the dwell time is 90-120 s.
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