CN114892062A - Porous high-entropy alloy material for efficient hydrogen production and preparation method thereof - Google Patents
Porous high-entropy alloy material for efficient hydrogen production and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a porous high-entropy alloy material capable of efficiently producing hydrogen and a preparation method thereof, wherein the porous high-entropy alloy material comprises 10-25% of Cr, 10-15% of Fe, 3-8% of V, 5-15% of Mn and the balance of Ni according to the atomic percentage of metal elements, and the percentage of V and Mn is 20-50%. The porous high-entropy material has rich pores and excellent mechanical properties, the pores are irregular in shape and are communicated with one another, the porous high-entropy material has a higher surface area, the preparation process is simple and environment-friendly, and the porous high-entropy material has better hydrogen evolution catalytic activity and can be used for efficient electrolytic hydrogen production and industrial filtration in an alkaline environment. The material utilizes the synergistic effect among Ni, Cr, Fe, V and Mn elements, combines solid solution and aging precipitation for heat treatment strengthening, has relatively high electrocatalytic hydrogen evolution activity and low reaction overpotential due to the catalytic performance of V, Mn elements, can realize better catalytic action, is favorable for the adsorption and separation effect on ions in the electrolytic hydrogen evolution process, and realizes the preparation effect of efficient and stable hydrogen.
Description
Technical Field
The invention belongs to the field of porous high-entropy alloy materials and preparation methods thereof, and particularly relates to a porous high-entropy alloy material capable of being used for efficient hydrogen production and a preparation method thereof.
Background
In the present day that petrochemical resources are being exhausted and environmental problems caused thereby are becoming more serious, efforts are being made to develop clean renewable resources to meet future development demands on the global scale. Hydrogen energy is an ideal renewable secondary energy source and has great development potential. At present, hydrogen energy has been considered as the third largest fossil fuel source following coal, petroleum. Therefore, the hydrogen energy industry has received a great deal of attention from international society. Among various resource systems, hydrogen energy has the remarkable advantages of high combustion heat value, abundant reserves, cleanness, no pollution and the like, becomes a main development direction, and relevant hydrogen energy development strategies are made in various countries in the world.
In China, the development of hydrogen energy is vigorously proposed in 2019, and then various policies for encouraging the development are also successively proposed. The hydrogen energy technology research and development, demonstration and popularization, market construction and other aspects are greatly supported. Therefore, the application research of the development and conversion of hydrogen energy is helpful for improving the energy structure of China, pulling the economic growth of related industries and helping to realize sustainable development, assisting carbon neutralization and carbon peak reaching, and finally realizing clean sustainable development. From the global level, statistics show that hydrogen energy occupies 13% of the global energy consumption by 2050, and the emission of CO can be reduced every year 2 75 hundred million tons.
At present, common hydrogen production methods include hydrogen production by fossil fuel, microbial hydrogen production, photocatalytic hydrogen evolution, hydrogen production by water electrolysis and the like. The main ways of producing hydrogen from fossil fuel are coal gasification, partial oxidation of heavy oil, hydrocarbon steam conversion, etc., and if the desulfurization technology is not critical, sulfur-containing waste gas is inevitably discharged, thereby causing environmental pollution. Because the microorganisms grow slowly and the requirement on the irradiation time of the light source is high, the process of scale and industrial application of the microorganisms is greatly limited. The hydrogen production by photolysis of water has the advantages of high efficiency, environmental protection, low price and the like, and becomes one of the research hotspots in recent years. The photocatalytically active substance comprises TiO 2 (anatase type), Pt/C catalyst, noble metal nano-materials, and the like. In 1972, tokyo university, tokyo showa, et al, japan discovered that a battery device composed of titanium dioxide and platinum metal can catalytically decompose water to produce hydrogen under light conditions, but the current major deficiency is inefficiency. The hydrogen production by water electrolysis is that water is decomposed to react in water solution under the action of an external electric field to obtain hydrogen, and oxygen with high commercial value is generated while the hydrogen is generated. From the long-term development point of view, the hydrogen production by water electrolysis is a feasible and easily industrialized technology.
The high-entropy alloy is composed of 5 or more than 5 alloy elements, and the element composition range of the high-entropy alloy is gradually expanded from an equal atomic ratio to an unequal ratio by the latest concept. For example, CN113151727A vacuum arc melting is used for preparing a high-entropy alloy element of Fe, Mn, Cr, Ni and Al with non-equal atomic ratio, wherein the molar ratio is (45-x):15:15:25: x; by utilizing the latest concept of the high-entropy alloy, the high-cost-performance non-equal atomic ratio high-entropy alloy is developed, the alloy range is expanded, and the performance is widened. The alloy has controllable economic cost, excellent mechanical property and corrosion resistance, simple phase structure of the high-entropy alloy and good low-temperature performance.
Therefore, the preparation of the high-entropy porous alloy is more and more widely concerned in the industry at present, for example, the CoCrFeNiMoMn high-entropy porous alloy is prepared by a powder metallurgy microwave one-stage sintering method adopted by CN111074292A, and the preparation method is simple in operation, low in energy consumption and short in preparation time. However, in the production process, a pore-forming agent magnesium powder needs to be added, so that the problem of subsequent removal exists, and the pore diameter is large. For example, CN110735078A adopts sectional sintering to prepare the crmenmosisi high-entropy porous alloy, Kirkendall pores can be generated by using the difference of diffusion rates between elements, so as to avoid adding a large amount of pore-forming agents, but the pore size and the porosity of the crmenmosisi high-entropy alloy prepared by the method are still to be further improved.
The selection of the electrode material is concerned with the efficiency of hydrogen production by electrolysis, and in principle, the cathode material with low overpotential for hydrogen production by electrolysis has two characteristics, namely high specific surface area and good intrinsic catalytic activity. In practical applications, metal oxides (such as manganese dioxide) are often used as anode materials in order to obtain efficient electrochemical performance. However, there are many problems due to structural defects of the metal oxide itself and the influence of surface properties thereof. The porous electrode is an electrode formed by mixing a powdery active material having a high specific surface area or inert solid particles having conductivity, and pressing, sintering, or compounding the mixture. The nickel-based porous electrode material can effectively increase the surface area of the electrode and improve the hydrogen evolution activity of the electrode material. A great deal of research shows that the nickel-based porous material has good performance in the aspect of hydrogen evolution performance by electrolysis, wherein the nickel-based electrode material is prepared by solid-state reaction diffusion, which is a simple and economic method. And V, Mn elements have good catalytic action, and can further improve the intrinsic catalytic activity of the electrode material and the stability of the catalyst. At present, the research on the adoption of the high-entropy alloy as an electrode material for hydrogen production by water electrolysis is less, so that the development of the high-entropy alloy for hydrogen production by water electrolysis has great research significance.
Disclosure of Invention
The invention aims to provide a porous high-entropy alloy material which has rich pores, larger specific surface area, excellent electro-catalytic activity, excellent corrosion resistance, chemical stability and mechanical property and can be used for efficiently producing hydrogen and a preparation method thereof; the porous high-entropy alloy material is used as an electrolytic hydrogen evolution cathode material and can efficiently electrolyze hydrogen evolution in an alkaline environment.
The preparation method of the porous high-entropy alloy material capable of efficiently producing hydrogen comprises the following steps:
1) weighing five powders of Ni, Cr, Fe, V and Mn according to a set atomic percentage, then putting the five powders into a powder mixing tank, and mixing the five powders to obtain mixed powder; the set atomic percentage is as follows: 10-25% of Cr powder, 10-15% of Fe powder, 3-8% of V powder, 5-15% of Mn powder and the balance of Ni powder, wherein the sum of the atomic percentages of the components is 100%; and a V-shaped mixer is adopted for mixing the powder, and the powder mixing time is 10-14 h.
2) Adding stearic acid into the mixed powder obtained in the step 1) for granulation, drying and sieving after granulation, putting sieved materials into a mold, and performing compression molding to obtain a green body; before the stearic acid is used, the stearic acid needs to be dried, and the adding mass of the stearic acid is 3-5% of the mixed powder; the drying temperature is 70-80 ℃, and the drying time is 4-6 h; when sieving, the mesh number of the sieve is 50-70 meshes; and the pressing adopts a hydraulic press, the pressing pressure is 40-60 MPa, and the pressing time is 30-60 s.
3) Placing the green body obtained in the step 2) in a vacuum sintering furnace, carrying out 4-section heat preservation vacuum sintering, and cooling to room temperature along with the furnace after sintering is finished to obtain a porous composite material; vacuum sintering under heat preservation condition, wherein the vacuum degree needs to be controlled to be not less than 2 multiplied by 10 -3 Pa; the specific process of 4-stage heat-preservation vacuum sintering comprises the following steps: firstly, heating from room temperature to 120 ℃ at a heating rate of 8-10 ℃/min, and preserving heat for 20-40 min at the temperature; secondly, heating to 400 ℃ at a heating rate of 13-15 ℃/min, and preserving heat at the temperature for 50-70 min; thirdly, heating to 600 ℃ at a heating speed of 4-6 ℃/min; and preserving the heat for 50-70 min at the temperature; and fourthly, finally heating to 850 ℃ at the heating speed of 12-13 ℃/min, and preserving the heat for 50-70 min at the temperature.
4) Carrying out full solid solution treatment on the porous composite material in the step 3), and rapidly quenching to room temperature after the treatment is finished to obtain an alloy material after solid solution; the solid solution temperature is 950-1050 ℃, and the solid solution treatment time is 1.5-2.5 h
5) Carrying out precipitation strengthening treatment on the alloy material subjected to solid solution in the step 4) to obtain a strengthened alloy; the precipitation strengthening treatment process comprises the following steps: tempering for 2-3 times at 420-560 ℃ for 2-4 h each time.
6) And 5), soaking the reinforced alloy in a hydrochloric acid solution, then soaking the alloy in an alkaline solution, and cleaning the alloy with water after soaking to obtain the porous high-entropy alloy material. The concentration of the hydrochloric acid is 0.05-0.15M, and the soaking time is 20-40 min, mainly for removing an oxide film on the surface of the alloy; the alkali is one of sodium hydroxide or potassium hydroxide, the concentration of the alkali is 5-7M, the soaking time is 10-14 h, and the main purpose is to enable the solution to fully infiltrate pores.
The porous high-entropy alloy material disclosed by the invention is applied to serving as an electrolytic hydrogen evolution cathode material or an industrial filter material.
The principle of the invention is as follows: the invention utilizes four core effects of the high-entropy alloy, which are respectively as follows: high entropy effects, lattice distortion effects, delayed diffusion effects, and "cocktail" effects. The high entropy effect can inhibit the generation of intermetallic compounds and promote the formation of a single solid solution structure, and the lattice distortion effect of the high entropy alloy enables the solid solution strengthening effect to be obvious, so that the performance of the high entropy alloy can be correspondingly improved. The 'cocktail' effect is a composite effect of interaction of basic properties of main elements in the alloy, and different elements are selected to influence the properties of the alloy. The high-entropy alloy shows a plurality of excellent performances such as high hardness, excellent wear resistance, high-temperature oxidation resistance and the like after a series of strengthening effects, so that the generated nano-porous high-entropy alloy is further presumed to have good mechanical properties, and the service life of the porous electrode material can be greatly prolonged.
The invention has the beneficial effects that:
(1) the porous high-entropy material has rich pores and excellent mechanical properties, the pores are irregular in shape and are communicated with one another, the porous high-entropy material has a higher surface area, the preparation process is simple and environment-friendly, and the porous high-entropy material has better hydrogen evolution catalytic activity and can be used for efficient electrolytic hydrogen production and industrial filtration in an alkaline environment.
(2) The material of the invention utilizes the synergistic effect among Ni, Cr, Fe, V and Mn elements, and V, Mn element has excellent catalytic action, so that the material has relatively high electro-catalytic hydrogen evolution activity and low reaction overpotential, can realize better catalytic action, is beneficial to the adsorption and separation of ions in the process of electrolytic hydrogen evolution, and realizes the preparation effect of high-efficiency and stable hydrogen.
(3) The preparation method of the invention adopts a heat treatment process of multi-stage sintering and solid solution strengthening and aging precipitation strengthening: at the medium-low temperature stage, mainly removing air, water vapor and other gases adsorbed on the surfaces of the green body powder particles, and removing stearic acid through thermal decomposition; in the medium-temperature stage, a large amount of pores which are uniformly distributed and have controllable pore structures are generated in the blank by utilizing the partial diffusion principle among Ni, Cr, Fe, V and Mn elements and the difference of diffusion rates among the elements and adjusting a sintering process; in the high-temperature stage, the homogenization of the components of the material is mainly realized; and in the heat treatment stage, the performance of the high-entropy alloy is further optimized by using solid solution precipitation strengthening treatment. The whole process flow comprises the steps of powder preparation, ball milling, drying, pressing, segmented sintering, solid solution treatment, precipitation strengthening treatment and the like, the refining of the material structure can be realized without hot working deformation, and the method has the characteristics of short flow, low pollution, low energy consumption, high production efficiency and the like. The high-entropy alloy prepared by the method has uniform and fine tissue, uniform aperture and larger specific surface area, can provide more active sites for the hydrogen evolution process of the electrode, and simultaneously precipitates a large amount of precipitation strengthening phases, thereby greatly improving the toughness of the material and having excellent high-temperature oxidation resistance and wear resistance.
(4) The cathode material has a porous structure, uniform and communicated holes, high porosity and large specific surface area, and can realize the filtering effect.
(5) Compared with the noble metal Pt, the material has stronger hydrogen dissociating and absorbing capacity, easily obtained raw materials, simple preparation process, green and pollution-free preparation process and lower cost, and can realize batch production.
(5) The material belongs to high-entropy alloy, has very high hardness, good stability and corrosion resistance, and therefore, the prepared material has excellent mechanical property and is beneficial to prolonging the service life of the material.
Drawings
FIG. 1 shows the surface morphology of the Ni-Cr-Fe-V-Mn porous high-entropy alloy material prepared in example 1.
FIG. 2 is a cathode polarization curve of the Ni-Cr-Fe-V-Mn porous high-entropy alloy material electrode prepared in example 1 as a working electrode.
Fig. 3 is a cathode polarization curve using a Pt electrode as a working electrode in example 1.
FIG. 4 shows the surface morphology of the Ni-Cr-Fe-V-Mn porous high-entropy alloy material sintered in one stage in the sintering process of comparative example 1.
FIG. 5 is a cathode polarization curve of the Ni-Fe-Cr porous cathode material prepared in comparative example 3 as a working electrode.
The specific implementation mode is as follows:
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 five element powders of Ni, Cr, Fe, V and Mn with the purity of 99.99 percent according to a certain atomic proportion, wherein the content of Ni powder is 54 percent, the content of Cr powder is 18.11 percent, the content of Fe powder is 10.3 percent, the content of V powder is 5.02 percent, the content of Mn powder is 12.57 percent, and the average particle size of the five element powders is 4 mu m; placing the weighed powder on a V-shaped powder mixer to mix for 12 hours at a constant speed to obtain mixed powder; adding dried stearic acid accounting for 4% of the mass of the mixed powder for granulation, and then placing the mixture in a vacuum drying oven for drying for 5 hours at 75 ℃; and sieving the dried powder by using a 60-mesh sieve, and pressing and forming the sieved powder under a hydraulic press at the pressure of 50MPa for 40 seconds under the pressure maintaining time parameter to obtain a green body.
The green compact was placed in a vacuum of 2X 10 -3 Sintering under Mpa, wherein the sintering process comprises the following steps: heating from room temperature to 120 ℃ at a heating rate of 9 ℃/min, and keeping the temperature for 60 min; heating to 400 deg.C at a rate of 14 deg.C/min, and maintaining for 60 min; heating to 600 ℃ at the heating rate of 5 ℃/min,preserving the heat for 60 min; heating to 850 deg.C at a rate of 12.5 deg.C/min, and maintaining for 60 min; and finally, cooling to room temperature along with the furnace to obtain the primary high-entropy alloy material.
Placing the obtained primary high-entropy alloy in a muffle furnace for full solution treatment, wherein the full solution treatment temperature is 1000 ℃, the time is 2 hours, quickly placing the alloy into distilled water after the treatment, and performing water quenching to room temperature; then placing the sample after the solution treatment in a tempering furnace for precipitation strengthening treatment, wherein the tempering temperature is 450 ℃, the tempering time is 4 hours, and the continuous tempering is carried out for 3 times; air cooling to room temperature; then placing the sample subjected to precipitation strengthening treatment in 0.1M HCl solution for soaking for 0.5h, and removing an oxide film on the surface of the sample; then soaking in 6M KOH solution for 12h to allow the solution to fully infiltrate pores, thus obtaining the porous high-entropy alloy material; the surface of the porous high-entropy alloy material has no obvious cracks.
The microscopic surface topography of the porous high-entropy alloy material prepared by the embodiment is shown in fig. 1, and it can be seen that: the porous high-entropy alloy material has rich pores, the pore shapes are irregular and are mutually communicated, the specific surface area of the porous high-entropy alloy electrode material consisting of the Ni-Cr-Fe-V-Mn elements is increased, active sites in the electrochemical hydrogen production process can be effectively increased, and the method is one of reasons for increasing the hydrogen evolution activity of the porous high-entropy alloy electrode material.
The electrochemical test of the porous high-entropy alloy material is carried out by adopting a CS350 electrochemical test workstation, the scanning speed is 4mV/s, and the scanning range is 0V-2V. All electrochemical test processes are three-electrode systems, wherein a platinum sheet is used as an auxiliary electrode, an Hg/HgO electrode is used as a reference electrode, the prepared Ni-Cr-Fe-V-Mn porous high-entropy alloy material electrode sample is used as a working electrode, the reference electrode is communicated with the working electrode through a Lu capillary (salt bridge), and the working area of the electrode is 1.1cm 2 The electrolyte was 6M KOH. All tests controlled the temperature of the test electrolyte, which was monitored at 25 ℃ using water bath heating.
The polarization curve of the Ni-Cr-Fe-V-Mn porous high-entropy alloy electrode prepared by the embodiment is shown in FIG. 2, when the current density is 100mA/cm 2 The overpotential was 1234mV (vs. Hg/HgO) and the exchange current density was 9.8 x 10 -4 A cm -2 . The porous high-entropy alloy electrode in the embodiment has good hydrogen evolution performance, and the electrocatalytic hydrogen evolution activity of the porous cathode material benefits from the synergistic effect among elements.
The electrode polarization curve of the Pt electrode used as the working electrode is shown in FIG. 3: when the current density is 100mA/cm 2 At 1374mV overpotential (vs. Hg/HgO), the exchange current density is 6.4 x 10 -4 A cm -2 Compared with the Pt electrode, the electrocatalytic hydrogen evolution activity of the porous high-entropy alloy electrode in the embodiment is better.
Comparative example 1
Compared with the embodiment 1, the difference is that the sintering process adopts one-stage sintering: raising the temperature to 850 ℃ at the heating rate of 12.5 ℃/min, and preserving the heat for 60 min. The surface of the prepared porous high-entropy alloy material has a small amount of cracks, as shown in FIG. 4.
Comparative example 2
Compared with the embodiment 1, the difference is that the porous high-entropy alloy material prepared without subsequent solid solution and precipitation strengthening treatment steps has the current density of 100mA/cm 2 At an overpotential of 1580mV (vs. Hg/HgO), the exchange current density was 4.2 x 10 -4 A cm -2 Much lower than the exchange current density of example 1.
Comparative example 3
The procedure of example 1 was followed except that V and Mn were removed from the elements in an unchanged atomic ratio to the 3 kinds of powders; the prepared Ni-Fe-Cr porous cathode material has the porosity of 32.5%, and the electrochemical steady polarization of the material is measured in 6mol/L KOH alkaline solution, and the exchange current density is 7 x 10 at room temperature -4 A/cm -2 The electrode polarization curve is shown in fig. 5.
Compared with the Ni-Cr-Fe-V-Mn porous high-entropy alloy material in the embodiment 1, the porous high-entropy alloy material in the embodiment 1 has richer pores, more excellent mechanical property and better hydrogen evolution property. The reason is that: because the added V and Mn elements have excellent catalytic action, the material has relatively high electrocatalytic hydrogen evolution activity and low reaction overpotential, which is the key of the hydrogen evolution reaction by electrolysis, and the five elements form a high-entropy alloy, the material has good thermal stability and mechanical stability and excellent corrosion resistance, and therefore, the material also has excellent mechanical property.
Example 2
In order to verify the influence of the addition of the catalytic element V, Mn element powder on the pores of the porous high-entropy alloy electrode material and the influence of different porosities on the hydrogen evolution performance of the porous high-entropy alloy electrode material in the preparation method provided by the invention, the following example 1 is taken as a reference, other process parameters are controlled to be unchanged, and the current density is 100mA/cm 2 A first set of comparative experiments was set up by adjusting the mass percentages of the catalytic elements V and Mn to the total mass of Ni, Cr, Fe, V, Mn, as shown in Table 1.
TABLE 1 influence of V and Mn powders of different mass percentages on the porosity of porous high-entropy alloy electrode materials and different porosities on the hydrogen evolution performance of porous high-entropy alloy electrode materials
As can be seen from Table 1, with the increase of V, Mn powder mass percentage, the porosity is increased and then decreased, and the hydrogen evolution overpotential is increased and then decreased, when V, Mn powder mass percentage is in the range of 20-50%, the porous high-entropy alloy electrode material has better porosity and hydrogen evolution overpotential, therefore, the atomic mass percentage of V, Mn powder added is preferably 20-50%.
Example 3
In order to verify the influence of the final sintering temperature on the hydrogen evolution overpotential values of the electrode of the porous high-entropy alloy material under different hydrogen evolution current densities in the preparation method of the invention, the following example 1 is taken as a reference, other process parameters are controlled to be unchanged, a second group of comparative experiments are set by adjusting the final sintering temperature, and the results are shown in table 2.
TABLE 2
As can be seen from Table 2, when the sintering temperature is 800-900 ℃, the porous high-entropy alloy material has better hydrogen evolution performance, so the sintering temperature is preferably 800-900 ℃.
Example 4
Weighing five element powders of Ni, Cr, Fe, V and Mn with the purity of 99.99 percent according to certain atomic percentage, wherein the content of Ni powder is 53.8 percent, the content of Cr powder is 18.2 percent, the content of Fe powder is 11.5 percent, the content of V powder is 3.28 percent, the content of Mn powder is 13.22 percent, and the average particle size of the five element powders is 4 mu m; placing the weighed powder on a V-shaped powder mixer to mix for 12 hours at a constant speed to obtain mixed powder; adding dried stearic acid accounting for 4% of the mass of the mixed powder for granulation, and then placing the mixture in a vacuum drying oven for drying for 5 hours at 75 ℃; and sieving the dried powder by using a 60-mesh sieve, and pressing and forming the sieved powder under a hydraulic press at the pressure of 40MPa for 50 seconds under the pressure maintaining time parameter to obtain a green body.
The green compact was placed in a vacuum of 2X 10 -3 Sintering under the environment of Pa, wherein the sintering process comprises the following steps: heating from room temperature to 120 ℃ at a heating rate of 9 ℃/min, and keeping the temperature for 50 min; heating to 400 deg.C at a rate of 14 deg.C/min, and maintaining for 50 min; heating to 600 deg.C at a rate of 5 deg.C/min, and maintaining for 50 min; heating to 850 deg.C at a rate of 12.5 deg.C/min, and maintaining for 50 min; and finally, cooling to room temperature along with the furnace to obtain the primary high-entropy alloy material.
Placing the obtained primary high-entropy alloy in a muffle furnace for full solution treatment, wherein the full solution treatment temperature is 1000 ℃, the time is 2 hours, quickly placing the alloy into distilled water after the treatment, and performing water quenching to room temperature; then placing the sample after the solution treatment in a tempering furnace for precipitation strengthening treatment, wherein the tempering temperature is 500 ℃, the tempering time is 3 hours, and the continuous tempering is carried out for 3 times; air cooling to room temperature; then placing the sample subjected to precipitation strengthening treatment in 0.1M HCl solution for soaking for 0.5h, and removing an oxide film on the surface of the sample; then soaking in 6M KOH solution for 12h to allow the solution to fully infiltrate pores, thus obtaining the porous high-entropy alloy material; the surface of the porous high-entropy alloy material has no obvious cracks.
The porous high-entropy alloy material of the embodiment is tested according to the electrochemical experimental procedure in the embodiment 1, and when the current density is 100mA/cm 2 Overpotential 1316mV (vs. Hg/HgO), exchange current density 7.9 x 10 -4 Acm -2 。
Example 5
Weighing five element powders of Ni, Cr, Fe, V and Mn with the purity of 99.99 percent according to certain atomic percentage, wherein the content of Ni powder is 55.2 percent, the content of Cr powder is 18.4 percent, the content of Fe powder is 10.4 percent, the content of V powder is 4.8 percent, the content of Mn powder is 11.2 percent, and the average particle size of the five element powders is 5 mu m; placing the weighed powder on a V-shaped powder mixer to mix for 12 hours at a constant speed to obtain mixed powder; adding dried stearic acid accounting for 4% of the mass of the mixed powder for granulation, and then placing the mixture in a vacuum drying oven for drying for 5 hours at 75 ℃; and sieving the dried powder by using a 60-mesh sieve, and pressing and forming the sieved powder under a hydraulic press at the pressure of 60MPa for 40 seconds under the pressure maintaining time parameter to obtain a green body.
The green compact was placed in a vacuum of 2X 10 -3 Sintering under the environment of Pa, wherein the sintering process comprises the following steps: heating from room temperature to 120 ℃ at the heating rate of 9 ℃/min, and keeping the temperature for 60 min; heating to 400 deg.C at a temperature rise rate of 15 deg.C/min, and maintaining for 60 min; heating to 600 deg.C at a temperature rise rate of 6 deg.C/min, and maintaining for 60 min; heating to 850 deg.C at a rate of 12.5 deg.C/min, and maintaining for 70 min; and finally, cooling to room temperature along with the furnace to obtain the primary high-entropy alloy material.
Placing the obtained primary high-entropy alloy in a muffle furnace for full solution treatment, wherein the full solution treatment temperature is 1000 ℃, the time is 2 hours, quickly placing the alloy into distilled water after the treatment, and performing water quenching to room temperature; then placing the sample after the solution treatment in a tempering furnace for precipitation strengthening treatment, wherein the tempering temperature is 450 ℃, the tempering time is 4 hours, and the continuous tempering is carried out for 3 times; air cooling to room temperature; then placing the sample subjected to precipitation strengthening treatment in 0.1M HCl solution for soaking for 0.5h, and removing an oxide film on the surface of the sample; then soaking in 6M KOH solution for 12h to allow the solution to fully infiltrate pores, thus obtaining the porous high-entropy alloy material; the surface of the porous high-entropy alloy material has no obvious cracks.
The porous high-entropy alloy material of the embodiment is tested according to the electrochemical experimental procedure in the embodiment 1, and when the current density is 100mA/cm 2 An overpotential of 1243mV (vs. Hg/HgO) and a crossover current density of 9.7 x 10 -4 A cm -2 。
Example 6
Weighing five element powders of Ni, Cr, Fe, V and Mn with the purity of 99.99 percent according to certain atomic percentage, wherein the content of Ni powder is 48.8 percent, the content of Cr powder is 18.55 percent, the content of Fe powder is 13.58 percent, the content of V powder is 5.4 percent, the content of Mn powder is 13.67 percent, and the average particle size of the five element powders is 4 mu m; placing the weighed powder on a V-shaped powder mixer to mix for 12 hours at a constant speed to obtain mixed powder; adding dried stearic acid accounting for 4% of the mass of the mixed powder for granulation, and then placing the mixture in a vacuum drying oven for drying for 5 hours at 75 ℃; and sieving the dried powder by using a 60-mesh sieve, and pressing and forming the sieved powder under a hydraulic press at 50MPa for 50 seconds under the pressure maintaining time parameter to obtain a green body.
The green compact was placed in a vacuum of 2X 10 -3 Sintering under the environment of Pa, wherein the sintering process comprises the following steps: heating from room temperature to 120 ℃ at the heating rate of 8 ℃/min, and keeping the temperature for 60 min; heating to 400 deg.C at a heating rate of 13 deg.C/min, and maintaining for 60 min; heating to 600 deg.C at a rate of 4 deg.C/min, and maintaining for 60 min; heating to 850 deg.C at a heating rate of 13 deg.C/min, and maintaining for 70 min; and finally, cooling to room temperature along with the furnace to obtain the primary high-entropy alloy material.
Placing the obtained primary high-entropy alloy in a muffle furnace for full solution treatment, wherein the full solution treatment temperature is 1000 ℃, the time is 2 hours, quickly placing the alloy into distilled water after the treatment, and performing water quenching to room temperature; then placing the sample after the solution treatment in a tempering furnace for precipitation strengthening treatment, wherein the tempering temperature is 560 ℃, the tempering time is 2 hours, and the continuous tempering is carried out for 3 times; air cooling to room temperature; then placing the sample subjected to precipitation strengthening treatment in 0.1M HCl solution for soaking for 0.5h, and removing an oxide film on the surface of the sample; then soaking in 6M KOH solution for 12h to allow the solution to fully infiltrate pores, thus obtaining the porous high-entropy alloy material; the surface of the porous high-entropy alloy material has no obvious cracks.
The porous high-entropy alloy material of the embodiment is tested according to the electrochemical experimental procedure in the embodiment 1, and when the current density is 100mA/cm 2 Overpotential 1238mV (vs. Hg/HgO), exchange current density 9.71 x 10 -4 A cm -2 。
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 (9)
1. The porous high-entropy alloy material for efficiently producing hydrogen is characterized in that raw material powder comprises the components of Ni, Cr, Fe, V and Mn, wherein the atomic mass percentages of the powder are respectively 40% -60%, 10% -25%, 10% -15%, 3% -8% and 5% -15%, and the atomic percentages of V and Mn are 20% -50%.
2. A preparation method of a porous high-entropy alloy material for efficiently producing hydrogen is characterized by adopting reasonable sintering conditions, solid solution treatment and aging precipitation strengthening treatment, and comprises the following steps:
s1, weighing Ni, Cr, Fe, V and Mn powder, then carrying out ball milling mechanical mixing, then adding stearic acid accounting for 3-5% of the powder mass for granulation, drying in a common drying oven at 70-80 ℃ for 4-6 h after granulation, then sieving, taking sieved powder by using a press machine, and pressing to prepare a green body;
s2, placing the green body prepared in the step S1 in a sintering furnace for sintering, and cooling along with the furnace after sintering to obtain the porous high-entropy alloy;
s3, carrying out solution treatment on the porous high-entropy alloy rough blank obtained in the step S2
And S4, carrying out aging precipitation strengthening treatment on the porous high-entropy alloy subjected to the solution treatment in the step S3.
And S5, performing electrochemical activation treatment on the porous high-entropy alloy in the step S4 by adopting a cyclic voltammetry method to obtain the porous high-entropy alloy material for efficiently producing hydrogen.
3. The preparation method of the porous high-entropy alloy material for high-efficiency hydrogen production according to claim 2, wherein in the step S1, the purity of the powder is greater than or equal to 99.99%, and the particle size is 3-5 μm.
4. The preparation method of the porous high-entropy alloy material for high-efficiency hydrogen production according to claim 2, wherein the parameters of the step S1 when the porous high-entropy alloy material is pressed by a hydraulic press are pressure: 40-60 MPa, pressure maintaining time: 30-60 s.
5. The preparation method of the porous high-entropy alloy material for high-efficiency hydrogen production according to claim 2, wherein the degree of vacuum of the sintering furnace in the step S2 is higher than 2 x 10 -3 Pa。
6. The preparation method of the porous high-entropy alloy material for high-efficiency hydrogen production according to claim 2, wherein the sintering process of step S2 is as follows: heating from room temperature to 120 ℃ at a heating rate of 8-10 ℃/min, and keeping the temperature for 50-70 min; then, heating to 400 ℃ at a heating rate of 13-15 ℃/min, and preserving heat for 50-70 min; then raising the temperature to 600 ℃ at a heating rate of 4-6 ℃/min, and preserving the heat for 50-70 min; then, raising the temperature to 850 ℃ at the heating rate of 12-13 ℃/min, and preserving the heat for 50-70 min; and finally, closing the sintering furnace, and cooling the alloy material to room temperature along with the furnace.
7. The method according to claim 2, wherein the solution treatment temperature in the step S3 is 950 to 1050 ℃, the temperature is kept for 1.5 to 2.5 hours, and then the steel is rapidly quenched to room temperature.
8. The method of claim 2, wherein the precipitation strengthening process in step S3 is: tempering for 2-3 times at 420-560 ℃ for 2-4 h each time.
9. A porous high-entropy alloy material for efficiently producing hydrogen is characterized in that:
the porous high-entropy alloy material is prepared by the method provided by any one of claims 1-8.
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