CN115094414A - Novel flexible grading nano-porous high-entropy alloy and preparation method thereof - Google Patents

Novel flexible grading nano-porous high-entropy alloy and preparation method thereof Download PDF

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CN115094414A
CN115094414A CN202210690438.1A CN202210690438A CN115094414A CN 115094414 A CN115094414 A CN 115094414A CN 202210690438 A CN202210690438 A CN 202210690438A CN 115094414 A CN115094414 A CN 115094414A
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entropy
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entropy alloy
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张少飞
孟永强
孙金峰
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Hebei University of Science and Technology
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Abstract

The invention discloses a preparation method of a novel flexible graded nano-porous high-entropy alloy, which is characterized by comprising the following steps of: 1) cu a Ni b Mo c Fe d Al e Preparing alloy powder, mixing Cu, Al, Ni, Mo and Fe powder in different proportions, and performing high-energy ball milling to obtain the alloy powder for plasma cladding with different components; 2) cu (copper) a Ni b Mo c Fe d Al e The preparation of the high-entropy intermetallic compound foil strip adopts a plasma cladding process to clad on the surface of a 45 steel substrate to obtain the high-entropy intermetallic compound coating. 3) And (3) putting the foil strip for preparing the flexible graded nano-porous high-entropy alloy into 0.1mol/LKOH solution, corroding at the temperature of 50 ℃ for 2 hours, taking out the foil strip, and repeatedly washing the foil strip by using alcohol and deionized water to obtain the graded nano-porous high-entropy alloy. Compared with the traditional high-entropy alloy preparation method (chemical method or smelting process), the high-energy ball milling method has simple process and low cost; an integrated high-entropy intermetallic compound foil strip is obtained through plasma cladding and cutting rolling, and the strong metallurgical bonding performance of the high-entropy alloy and the substrate is realized.

Description

Novel flexible grading nano-porous high-entropy alloy and preparation method thereof
Technical Field
The invention relates to the technical field of preparation of electrolytic water evolution hydrogen materials, in particular to a novel flexible grading nano-porous high-entropy alloy and a preparation method thereof.
Background
At present, the carbon peak reaching and carbon neutralization development targets are provided in China, and the carbon reduction process is further accelerated. The hydrogen energy is used as a zero-carbon energy carrier, and has wide application prospects in the fields of energy storage, metallurgy, distributed power generation and the like. The hydrogen production by electrolyzing water by utilizing renewable energy can avoid CO 2 Is a typical green hydrogen production mode. The policy of successive delivery of hydrogen and green hydrogen production in the United states and China promotes the green and low-carbon transformation of energy. The hydrogen production by water electrolysis involves two half reactions, cathodic Hydrogen Evolution (HER) and anodic Oxygen Evolution (OER). In HER, hydrogen evolution electrocatalysts are the key to directly affect hydrogen productivity and stability. Therefore, it is crucial to develop and design an efficient hydrogen evolution electrocatalyst.
The high-entropy alloy has unique cocktail effect, high-entropy effect, lattice distortion effect, delayed diffusion effect and the like, and has wide application in improving the catalytic performance and stability of cathode hydrogen evolution in the water electrolysis processHas wide application prospect. However, two problems still exist in the use of the high-entropy alloy at present, firstly, the electrode structure is not ideal: in particular, the block and powder high-entropy alloy has few catalytic active sites and is not beneficial to electrons/ions and H in the hydrogen evolution process 2 Transport of the molecules. Second, H ad The binding energy regulation mechanism is not clear: the intermediate product adsorbs hydrogen (H) according to the mechanism of hydrogen evolution reaction ad ) The binding energy is the key to hydrogen-hydrogen bonding, and the regulation of the electronic structure of the catalyst surface and the catalytic activity influence H ad The main factor of binding energy, however, the high-entropy alloy has the influence on H due to the complexity of electronic structure and catalytic active sites of the high-entropy alloy due to the multi-component metal elements ad And (3) regulating and controlling binding energy.
In order to solve the problems, researchers find that the surface electronic structure of the coupling catalyst is regulated and controlled and the catalytic activity site pair H is improved through research ad The optimization of the adsorption energy is most efficient and easy to implement. Li and the like find that the synergistic effect among various elements in the high-entropy alloy can effectively modify the center of a d band and directly manage intrinsic activity and adsorption and activation of intermediates through calculation. On the basis, Jia et al find that the nano-structure high-entropy alloy can improve catalytic activity sites and further reduce H generated by alkaline electrolyte water decomposition ad Energy barrier to promote H ad Coupling to generate H 2 However, the use of binder/Nafion blocks electrons/ions and H 2 And (4) molecular transportation. These studies indicate that graded-pore high-entropy alloys with integral structure are more likely to meet the requirements of high-performance hydrogen evolution catalysts. However, the conventional graded-pore high-entropy alloy prepared at present has obvious macroscopic brittleness due to rich pore defects. The invention realizes the metallurgical bonding of the high-entropy alloy layer and the substrate by carrying out plasma cladding on the surface of the metal substrate through the high-entropy alloy; and then constructing a rich hierarchical nano porous structure on the high-entropy alloy layer by adopting a dealloying process. The method has the characteristics that the purpose of strong interface bonding of the graded nano-porous high-entropy alloy and the metal substrate is realized, and simultaneously, the high catalytic activity of the graded nano-porous high-entropy alloy is met.
Disclosure of Invention
The invention aims to provide a method for electrocatalytic waterDecomposed flexible grading nano-porous high-entropy alloy and a preparation method thereof. With Cu a Ni b Mo c Fe d Al e High entropy intermetallic compound (containing high entropy CuNiMoFe, alpha-Al and CuAl) 2 And a + b + c + d + e is 100) as a substrate material, and a high-entropy alloy phase is retained through dealloying to obtain the graded nano-porous high-entropy alloy.
In order to solve the technical problems, the technical scheme provided by the invention is as follows: a preparation method of a novel flexible grading nano-porous high-entropy alloy is characterized by comprising the following steps:
1)Cu a Ni b Mo c Fe d Al e preparation of alloy powder
Mixing pure metal powder of Cu, Al, Ni, Mo and Fe in different proportions, and obtaining alloy powder for plasma cladding with different components by high-energy ball milling;
in a preferred embodiment, in the alloy proportion, the content of Al is between 60% and 85%, and the proportion of the rest metal components is between 1% and 20%;
in a preferred embodiment, the high-energy ball milling speed is 1000-1500 rpm, and the ball milling time is 10-24 hours.
2)Cu a Ni b Mo c Fe d Al e Preparation of high-entropy intermetallic compound foil strip
And cladding the obtained alloy material on the surface of the 45 steel matrix by adopting a plasma cladding process to obtain the high-entropy intermetallic compound coating. And then cutting and rolling the high-entropy intermetallic compound coating to obtain the foil strip.
In a preferred embodiment, the plasma cladding conditions are arc voltage (35-45V), current (100-150A) and powder feeding speed (10-20 g min) -1 )；
In a preferred embodiment, the thickness of the foil strip after cutting and rolling is 50 to 300 μm.
3) Preparation of flexible grading nano porous high-entropy alloy
Immersing the foil strip in the step 2) into 0.1mol/LKOH solution, corroding at 50 ℃ for 2h, taking out, and repeatedly washing with alcohol and deionized water to obtain the graded nano-porous high-entropy alloy.
In a preferred embodiment, the corrosive liquid is KOH, NaOH or NaHCO 3 Or a mixed solvent thereof;
in a preferred embodiment, the concentration of the corrosive liquid is 0.1-5 mol/L;
in a preferred embodiment, the corrosion temperature is 20-100 ℃;
in a preferred embodiment, the etching time is 2 to 48 hours.
According to the invention, the pore structure is regulated and controlled by regulating and controlling the components of the high-entropy alloy and chemical dealloying parameters (type, concentration, dealloying time, temperature and the like of corrosive liquid), so that the flexible graded nano-porous high-entropy alloy is obtained. The whole body is used as a functional material, and has great development potential when being applied to the field of electrocatalysis.
Compared with the prior art, the invention has the advantages that:
1) compared with the traditional high-entropy alloy preparation method (chemical method or smelting process), the high-energy ball milling method has simple process and low cost;
2) an integrated high-entropy intermetallic compound foil strip is obtained through plasma cladding and cutting rolling, so that the strong metallurgical bonding performance of the high-entropy alloy and the substrate is realized;
3) the hierarchical nano-porous high-entropy alloy is obtained by adopting a one-step dealloying method, the existence of hierarchical pores improves the ion/electron transmission efficiency on one hand, increases the specific surface area of the material on the other hand, exposes more active sites, and further improves the catalytic activity (overpotential under the current density of 10mA cm & lt-2 & gt)
Figure BDA0003699312680000031
20 to 100 mV; stability about 20 h).
Drawings
FIG. 1 is a flow chart of the plasma cladding preparation of the present invention.
Fig. 2 is a metallographic picture of a substrate-supported super-entropy alloy formed by cladding according to the invention.
FIG. 3 is a microscopic topography of the graded pores after dealloying in accordance with the present invention.
Detailed Description
The following further describes embodiments of the present invention with reference to the accompanying drawings.
Example one
Preparing metal powder (the particle size of the powder is 60 microns) according to the atomic ratio of 10 percent of Cu, 10 percent of Ni, 10 percent of Mo, 10 percent of Fe and 60 percent of Al, and then performing ball milling for 10 hours at the high-energy ball milling rotating speed of 1000r/min to obtain Cu 10 Ni 10 Mo 10 Fe 10 Al 60 Alloy powder; controlling arc voltage 35V, current 120A) and powder feeding speed 10g min by adopting a plasma cladding process -1 Cladding on a pure metal Ni matrix and obtaining Ni @ Cu supported by Ni 10 Ni 10 Mo 10 Fe 10 Al 60 Compounding alloy; and then adopting 1mol/L NaOH alkaline solution to perform dealloying to obtain the Ni-supported flexible graded nano-porous Ni @ CuNiMoFe electrode. 10mA cm in the cathodic hydrogen evolution electrocatalytic test in 1mol/L KOH electrolyte -2 Current density of
Figure BDA0003699312680000032
71mV, 20 hours of circulation without increasing overpotential; 100mA cm -2 Current density of
Figure BDA0003699312680000033
311mV, and 20 hours of cycling did not increase overpotential.
Example two
Preparing metal powder (the particle size of the powder is 60 microns) according to the atomic ratio of 4 percent of Cu, 4 percent of Ni, 4 percent of Mo, 4 percent of Fe and 84 percent of Al, and then performing ball milling for 10 hours at the high-energy ball milling rotating speed of 1000r/min to obtain Cu 4 Ni 4 Mo 4 Fe 4 Al 84 Alloy powder; controlling arc voltage 35V, current 120A) and powder feeding speed 10g min by adopting a plasma cladding process -1 Melting on pure metal Ni matrixNi @ Cu coated and supported by Ni 4 Ni 4 Mo 4 Fe 4 Al 84 Compounding alloy; and finally, adopting 1mol/L NaOH alkaline solution to perform dealloying to obtain the Ni-supported flexible graded nano-porous Ni @ CuNiMoFe-2 electrode. 10mA cm in the cathodic hydrogen evolution electrocatalytic test in 1mol/L KOH electrolyte -2 Current density of
Figure BDA0003699312680000034
65mV, 20 hours of circulation without increasing overpotential; 100mA cm -2 Current density of
Figure BDA0003699312680000035
292mV, and 20 hours of cycling without an increase in overpotential.
Example three
Preparing metal powder (the particle size of the powder is 60 microns) according to the atomic ratio of Cu being 7%, Ni being 2.5%, Mo being 7.5%, Fe being 3% and Al being 80%, and then performing ball milling for 10 hours at the high-energy ball milling rotating speed of 1000r/min to obtain Cu 7 Ni 2.5 Mo 7.5 Fe 3 Al 80 Alloy powder; the arc voltage of 35V, the current of 120A and the powder feeding speed of 10g min are controlled by adopting a plasma cladding process -1 Cladding on a pure metal Ni matrix and obtaining Ni @ Cu supported by Ni 7 Ni 2.5 Mo 7.5 Fe 3 Al 80 Compounding alloy; and finally, adopting 1mol/L NaOH alkaline solution to perform dealloying to obtain the Ni-supported flexible graded nanoporous Ni @ CuNiMoFe-3 electrode. 10mA cm in the cathodic hydrogen evolution electrocatalytic test in 1mol/L KOH electrolyte -2 Current density of
Figure BDA0003699312680000041
47mV, 40 hours of circulation, the overpotential does not increase; 100mA cm -2 Current density of
Figure BDA0003699312680000042
284mV and 40 hours of cycling with no increase in overpotential.
Example four
Preparing metal powder (the powder has the diameter of 60 microns) according to the atomic ratio of 7 percent of Cu, 2.5 percent of Ni, 7.5 percent of Mo, 3 percent of Fe and 80 percent of Al, and then performing ball milling for 20 hours at a high-energy ball milling rotating speed of 1800r/min to obtain Cu 7 Ni 2.5 Mo 7.5 Fe 3 Al 80 Alloying powder; the arc voltage is controlled to be 45V, the current is controlled to be 133A, and the powder feeding speed is controlled to be 25g min by adopting a plasma cladding process -1 Cladding on a pure metal Ni matrix and obtaining Ni @ Cu supported by Ni 7 Ni 2.5 Mo 7.5 Fe 3 Al 80 Compounding alloy; and finally, adopting 1mol/L NaOH alkaline solution to perform dealloying to obtain the Ni-supported flexible graded nanoporous Ni @ CuNiMoFe-3 electrode. 10mA cm in the cathodic hydrogen evolution electrocatalytic test in 1mol/L KOH electrolyte -2 Current density of
Figure BDA0003699312680000043
42mV, 40 hours of circulation over-potential does not increase; 100mA cm -2 Current density of
Figure BDA0003699312680000044
281mV, and 40 hours of circulation the overpotential does not increase.
The present invention and the embodiments thereof have been described above, and the description is not restrictive, and the embodiments shown in the detailed description are only a part of the embodiments of the present invention, not all embodiments, and the actual configuration is not limited thereto. In summary, those skilled in the art should appreciate that they can readily use the disclosed conception and specific embodiments as a basis for designing or modifying other structures for carrying out the same purposes of the present invention without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (6)

1. A preparation method of a novel flexible grading nano-porous high-entropy alloy is characterized by comprising the following steps:
1)Cu a Ni b Mo c Fe d Al e preparation of alloy powder
Mixing pure metal powder of Cu, Al, Ni, Mo and Fe in different proportions, and obtaining alloy powder for plasma cladding with different components by high-energy ball milling;
2)Cu a Ni b Mo c Fe d Al e preparation of high-entropy intermetallic compound foil strip
Cladding the obtained alloy material on the surface of a 45 steel substrate by adopting a plasma cladding process to obtain a high-entropy intermetallic compound coating; then cutting and rolling the high-entropy intermetallic compound coating to obtain a foil strip;
3) preparation of flexible grading nano porous high-entropy alloy
Immersing the foil strip in the step 2) into 0.1mol/LKOH solution, corroding at 50 ℃ for 2h, taking out, and repeatedly washing with alcohol and deionized water to obtain the graded nano-porous high-entropy alloy.
2. The preparation method of the novel flexible graded nano-porous high entropy alloy according to claim 1, wherein in the proportion of the metal powder in step 1), the content of Al is 60% -85%, and the proportion of the rest metal components is 1% -20%.
3. The preparation method of the novel flexible graded nanoporous high-entropy alloy as claimed in claim 1, wherein the high-energy ball milling speed in step 1) is 1000-1500 rpm, and the ball milling time is 10-24 hours.
4. The preparation method of the novel flexible graded nanoporous high-entropy alloy according to claim 1, wherein the plasma cladding conditions in the step 2) are arc voltage (35-45V), current (100-150A) and powder feeding speed (10-20 gmin) -1 ) (ii) a The thickness of the foil strip after cutting and rolling is 50-300 mu m.
5. The method for preparing the novel flexible graded nano-porous high-entropy alloy as claimed in claim 1, wherein the corrosive liquid in step 3) is KOH, NaOH or NaHCO 3 Or a mixed solvent thereof.
6. The preparation method of the novel flexible graded nano-porous high-entropy alloy according to claim 1, wherein the concentration of the corrosive liquid in the step 3) is 0.1-5 mol/L, the corrosion temperature is 20-100 ℃, and the corrosion time is 2-48 h.
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Citations (4)

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