CN114892062B - Porous high-entropy alloy material for efficiently producing hydrogen and preparation method thereof - Google Patents
Porous high-entropy alloy material for efficiently producing hydrogen and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a porous high-entropy alloy material for 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 percentages of V and Mn are 20-50%. The porous high-entropy material has rich pores and excellent mechanical properties, irregular pore shapes and mutual communication, has higher surface area, simple and environment-friendly preparation process and better hydrogen evolution catalytic activity, and can be used for high-efficiency electrolytic hydrogen production and industrial filtration in alkaline environment. The material disclosed by the invention utilizes the synergistic effect of Ni, cr, fe, V, mn elements, combines solid solution and aging precipitation to carry out heat treatment strengthening, and has the catalytic performance of V, mn elements, so that the material has relatively high electrocatalytic hydrogen evolution activity and low reaction overpotential, can realize a good catalytic effect, is favorable for adsorbing and separating ions in the electrolytic hydrogen evolution process, and realizes the efficient and stable hydrogen preparation effect.
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 efficiently producing hydrogen and a preparation method thereof.
Background
Today, where petrochemical resources are becoming depleted and environmental problems are becoming serious, efforts are being made worldwide to develop clean renewable resources to accommodate future development needs. Hydrogen energy is an ideal renewable secondary energy source and has great development potential. Currently, hydrogen energy has been considered as the third largest source of fossil fuels following coal, petroleum. Therefore, the hydrogen energy industry has received extensive attention from the international society. Among various resource systems, hydrogen energy has the remarkable advantages of high combustion heat value, abundant reserve, cleanness, no pollution and the like, and has become a main development direction, and related hydrogen energy development strategies are formulated in various countries around the world.
In China, the 2019 proposes that hydrogen energy sources are greatly developed, and then various policies for encouraging development are sequentially introduced. The method has the advantages of being capable of supporting the research and development of hydrogen energy technology, demonstration and popularization, market construction and the like. Therefore, the application research of the development and conversion of the hydrogen energy source is helpful to improve the energy source structure of China, pull the economic growth of related industries, help to realize sustainable development, assist carbon neutralization and carbon peak, and finally realize clean sustainable development. At the global level, statistics show that hydrogen energy occupies 13% of the total global energy consumption by 2050 and the emission of CO can be reduced every year 2 75 million tons.
At present, common hydrogen production methods include fossil fuel hydrogen production, microbial hydrogen production, photocatalytic hydrogen evolution, water electrolysis hydrogen production and the like. The main approaches for preparing hydrogen from fossil fuel are coal gasification, heavy oil partial oxidation, hydrocarbon steam conversion and the like, and if the desulfurization technology is not closed, sulfur-containing waste gas is inevitably discharged, so that environmental pollution is caused. The microorganism grows slowly and the requirement on the irradiation time of the light source is high, so that the progress of the large-scale and industrialized application of the light source is greatly limited. The hydrogen production by water photolysis has the advantages of high efficiency, environmental protection, low cost and the like, and becomes one of the research hotspots in recent years. The photocatalytic active material comprises TiO 2 (anatase type), pt/C catalysts, noble metal nanomaterials, and the like. In 1972, the article of Tengshima Sho et al, university Tokyo, japan, found that a battery device composed of titanium dioxide and metallic platinum could catalyze the decomposition of water to produce hydrogen under light conditions, but the major disadvantage at present was inefficiency. The hydrogen production by electrolysis of water is to decompose water in water solution under the action of an external electric field to obtain hydrogen, and then produceThe hydrogen is generated and simultaneously the oxygen with commercial value is generated, the process is simple, no pollution is generated basically, the purity of the obtained hydrogen is high, and the cost of hydrogen production by water electrolysis is continuously reduced because nuclear energy, solar energy, wind energy, water energy and the like are applied to power generation in a large amount. In the long term development, the hydrogen production by water electrolysis is a feasible and easily industrialized technology.
The high-entropy alloy consists of 5 or more than 5 alloy elements, and the latest concept proposes that the element composition range of the high-entropy alloy is gradually expanded from an equal atomic ratio to an unequal ratio. Vacuum arc melting as in CN113151727A produces a non-equiatomic Fe, mn, cr, ni, al high entropy alloy element with a molar ratio of (45-x): 15:15:25:x; by utilizing the latest concept of the high-entropy alloy, the non-equal atomic ratio high-entropy alloy with high cost performance is developed, the alloy range is expanded, and the performance is widened. The alloy has the advantages of controllable economic cost, excellent mechanical property and corrosion resistance, simple phase structure of high-entropy alloy and good low-temperature performance.
Therefore, the preparation of the high-entropy porous alloy is more and more widely focused in the industry at present, for example, the CoCrFeNiMoMn high-entropy porous alloy is prepared by adopting a powder metallurgy microwave one-stage sintering method adopted by CN111074292A, and the preparation method is simple to operate, low in energy consumption and short in preparation time. However, the pore-forming agent magnesium powder needs to be added in the production process, the subsequent removal problem exists, and the pore diameter is larger. In addition, as in CN110735078A, sectional sintering is adopted to prepare the CrFeMnMoSiZr high-entropy porous alloy, kirkendall pores can be generated by utilizing the difference of diffusion rates among elements, a large amount of pore formers are prevented from being added, but the pore size and the porosity of the CrFeMnMoSiZr high-entropy alloy prepared by the method are still to be further improved.
The choice of electrode material is related to the efficiency of electrolytic hydrogen production, and in principle, the cathode material with low overpotential for electrolytic hydrogen production should have two characteristics, namely, high specific surface area and good intrinsic catalytic activity. In practical applications, in order to obtain efficient electrochemical performance, a metal oxide (e.g., manganese dioxide) is generally used as the anode material. However, there are many problems due to structural defects of the metal oxide itself and the influence of its surface properties. The porous electrode is an electrode formed by mixing a powdered active material having a high specific surface area or an inert solid fine particle having conductivity, and pressing, sintering, or chemical combination. 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. Numerous studies have shown that nickel-based porous materials perform well in terms of electrolytic hydrogen evolution, where the preparation of nickel-based electrode materials by solid state reactive diffusion is a simple and economical process. The V, mn element has good catalytic effect, 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 which can be used 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 electrocatalytic 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 can be used as an electrolytic hydrogen evolution cathode material, and can be used for high-efficiency electrolytic hydrogen evolution in alkaline environment.
The preparation method of the porous high-entropy alloy material for efficiently producing hydrogen comprises the following steps:
1) Weighing Ni, cr, fe, V, mn five kinds of powder according to the set atomic percentage, and then placing the five kinds of powder into a powder mixing tank for powder mixing to obtain mixed powder; the atomic percentages set are: 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%; the powder mixing adopts a V-shaped mixer, and the powder mixing time is 10-14 h.
2) Adding stearic acid into the mixed powder in the step 1) for granulating, drying and sieving after granulating, putting the sieved material into a mould, and pressing and forming to obtain a green body; before using, the stearic acid needs to be dried, and the adding mass of the stearic acid is 3-5% of that 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 mesh; 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 the sintering is finished to obtain a porous composite material; vacuum sintering under heat preservation, wherein the vacuum degree is controlled to be not lower than 2 multiplied by 10 -3 Pa; the specific process of 4-section heat-preservation vacuum sintering is as follows: (1) firstly, heating from room temperature to 120 ℃ at a heating rate of 8-10 ℃/min, and preserving heat at the temperature for 20-40 min; (2) then the temperature is increased to 400 ℃ at a heating rate of 13-15 ℃/min, and the temperature is kept for 50-70 min; (3) then the temperature is increased to 600 ℃ at a heating rate of 4-6 ℃/min; and preserving the temperature for 50-70 min; (4) finally, the temperature is increased to 850 ℃ at a heating rate of 12-13 ℃/min, and the temperature is kept for 50-70 min.
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 a solid solution alloy material; 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 at 420-560 deg.c for 2-3 times and 2-4 hr each time.
6) And (3) soaking the reinforced alloy in the step (5) in hydrochloric acid solution, soaking in alkaline solution, and washing with water after the soaking is finished to obtain the porous high-entropy alloy material. The concentration of the hydrochloric acid is 0.05-0.15M, the soaking time is 20-40 min, and the method is mainly used for removing the 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, and the soaking time is 10-14 h, mainly for the solution to fully infiltrate the pores.
The porous high-entropy alloy material 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 high-entropy alloy, which are respectively: high entropy effects, lattice distortion effects, delayed diffusion effects, and "cocktail" effects. The high entropy effect can inhibit the generation of intermetallic compounds, promote the formation of a single solid solution structure, and the lattice distortion effect of the high entropy alloy makes the solid solution strengthening effect 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 principal elements in an alloy, and the selection of different elements can have an effect on 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 produced nano-porous high-entropy alloy is further estimated 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, irregular pore shapes and mutual communication, has higher surface area, simple and environment-friendly preparation process and better hydrogen evolution catalytic activity, and can be used for high-efficiency electrolytic hydrogen production and industrial filtration in alkaline environment.
(2) The material of the invention utilizes the synergistic effect between Ni, cr, fe, V, mn elements, and V, mn element has excellent catalytic effect, so that the material has relatively high electrocatalytic hydrogen evolution activity and low reaction overpotential, can realize better catalytic effect, is favorable for the adsorption and separation of ions in the electrolytic hydrogen evolution process, and realizes the efficient and stable hydrogen preparation effect.
(3) The preparation method adopts a heat treatment process of multi-stage sintering and solid solution strengthening and aging precipitation strengthening: in the middle-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 number of pores with uniform distribution and controllable pore structures are generated in a green body by adjusting a sintering process by utilizing the principle of partial diffusion among Ni, cr, fe, V, mn elements and the difference of diffusion rates among the elements; at 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 utilizing solid solution precipitation strengthening treatment. The whole process flow consists of the steps of powder preparation, ball milling, drying, pressing, sectional sintering, solid solution treatment, precipitation strengthening treatment and the like, and the refinement of material structure can be realized without thermal processing deformation, and the method has the characteristics of short flow, small pollution, low energy consumption, high production efficiency and the like. The high-entropy alloy prepared by the method has uniform and fine structure, uniform pore diameter and larger specific surface area, can provide more active sites for the hydrogen evolution process of the electrode, simultaneously precipitates a large amount of precipitation strengthening phases, greatly improves the toughness of the material, and has excellent high-temperature oxidation resistance and wear resistance.
(4) The cathode material of the invention is of a porous structure, has uniform and communicated holes, has higher porosity and larger specific surface area, and can realize the filtration effect.
(5) Compared with noble metal Pt, the material has stronger dissociative hydrogen absorption capacity, easily available 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 high hardness, good stability and corrosion resistance, so that the prepared material has excellent mechanical properties and is beneficial to prolonging the service life of the material.
Drawings
FIG. 1 is a 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 pole 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 is a surface morphology of a Ni-Cr-Fe-V-Mn porous high entropy alloy material sintered 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 embodiment is as follows:
the invention will be further illustrated with reference to specific examples, but the invention is not limited to these examples.
Example 1
Weighing Ni, cr, fe, V, mn five element powders with purity up to 99.99% according to a certain atomic ratio, wherein the content of Ni powder is 54%, the content of Cr powder is 18.11%, the content of Fe powder is 10.3%, the content of V powder is 5.02%, the content of Mn powder is 12.57%, and the average particle size of the five powders is 4 μm; placing the weighed powder on a V-shaped powder mixer to uniformly mix for 12 hours to obtain mixed powder; then adding the dried stearic acid accounting for 4 percent of the mass of the mixed powder for granulation, and then placing the mixture into a vacuum drying oven for drying at 75 ℃ for 5 hours; sieving the dried powder with a 60-mesh screen, taking the sieved powder, and carrying out compression molding under a hydraulic press with the parameters of 50MPa pressure and 40 seconds dwell time to obtain a green body.
Placing the green body under a vacuum degree of 2×10 -3 Sintering is carried out in the environment of Mpa, and the sintering process is as follows: raising the temperature from room temperature to 120 ℃ at a heating rate of 9 ℃/min, and preserving the temperature for 60min; raising the temperature to 400 ℃ at a heating rate of 14 ℃/min, and preserving the temperature for 60min; raising the temperature to 600 ℃ at a heating rate of 5 ℃/min, and preserving the temperature for 60min; raising the temperature to 850 ℃ at a heating rate of 12.5 ℃/min, and preserving the temperature for 60min; 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 complete solution treatment, wherein the temperature of the complete solution treatment is 1000 ℃ and the duration is 2 hours, rapidly placing the treated primary high-entropy alloy in distilled water, and quenching the primary high-entropy alloy to room temperature; then placing the sample after 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 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 12 hours to fully infiltrate the pores with the solution, thus obtaining the much Kong Gaoshang alloy material; the surface of the porous high-entropy alloy material has no obvious cracks.
The microscopic surface morphology of the porous high-entropy alloy material prepared in the embodiment is shown in fig. 1, and it can be seen that: the porous high-entropy alloy material has rich pores, irregular pore shapes and mutual communication, has higher surface area, and the specific surface area of the porous high-entropy alloy electrode material formed by Ni-Cr-Fe-V-Mn element can be effectively increased, so that the active site in the electrochemical hydrogen production process can be effectively increased, and the porous high-entropy alloy material is one of the 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 adopts a CS350 electrochemical test workstation for testing, 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 an auxiliary electrode, an Hg/HgO electrode is used as a reference electrode, a 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 robust 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 and the monitoring of the temperature at 25 ℃ was performed using water bath heating.
The polarization curve of the Ni-Cr-Fe-V-Mn porous high-entropy alloy electrode prepared in the embodiment is shown in FIG. 2, when the current density is 100mA/cm 2 At the time of overpotential 1234mV (vs. Hg/HgO), 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 Pt electrode was used as the working electrode, and the electrode polarization curve thereof was as shown in fig. 3: when the current density is 100mA/cm 2 At the time of overpotential 1374mV (vs. Hg/HgO), the exchange current density was 6.4 x 10 -4 A cm -2 The electrocatalytic hydrogen evolution activity of the porous high-entropy alloy electrode in the embodiment is better than that of the Pt electrode.
Comparative example 1
Compared with example 1, the difference is that the sintering process adopts a one-stage sintering: raising the temperature to 850 ℃ at a heating rate of 12.5 ℃/min, and preserving the temperature for 60min. The surface of the prepared porous high-entropy alloy material has a small amount of cracks, as shown in figure 4.
Comparative example 2
In comparison with example 1, the difference is that there is noThe subsequent solid solution and precipitation strengthening treatment steps are carried out, and the prepared porous high-entropy alloy material has the current density of 100mA/cm 2 At the time of overpotential 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, and the atomic ratio to 3 powders was unchanged; the Ni-Fe-Cr porous cathode material prepared by the method has the porosity of 32.5 percent, the electrochemical steady-state polarization is measured in an alkaline solution of 6mol/L KOH, 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 and better mechanical properties, and has better hydrogen evolution performance. The reason for this is: 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 are key to the electrolytic hydrogen evolution reaction, and the five elements form high-entropy alloy, so that the material has good thermal stability, mechanical stability and excellent corrosion resistance, and therefore, the material also has excellent mechanical properties.
Example 2
In order to verify the influence of the addition amount of the catalytic element V, mn element powder on the pore space and the different porosities of the porous high-entropy alloy electrode material on the hydrogen evolution performance of the porous high-entropy alloy electrode material in the preparation method provided by the invention, the method uses the example 1 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 by adjusting the mass percentages of the total mass of catalytic elements V and Mn with Ni, cr, fe, V, mn, as shown in table 1.
TABLE 1 influence of different mass percentages of V and Mn powders on the porosity and different porosities of porous high entropy alloy electrode materials on the Hydrogen evolution Performance of porous high entropy alloy electrode materials
As can be seen from table 1, as the mass percentage of V, mn powder increases, the porosity increases and then decreases, and the hydrogen evolution overpotential increases and then decreases, when the mass percentage of V, mn powder is 20-50%, the porous high-entropy alloy electrode material has better porosity and hydrogen evolution overpotential, so that the atomic mass percentage of V, mn powder is preferably 20-50%.
Example 3
In order to verify the influence of the final sintering temperature on the hydrogen evolution overpotential value of the electrode of the porous high-entropy alloy material under different hydrogen evolution current densities in the preparation method of the invention, other process parameters are controlled to be unchanged by taking example 1 as a reference, and a second set of comparison 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, the porous high-entropy alloy material has better hydrogen evolution property when the sintering temperature is 800-900 ℃, so that the sintering temperature is preferably 800-900 ℃.
Example 4
Weighing Ni, cr, fe, V, mn five element powders with purity up to 99.99% according to a certain atomic percentage, wherein the content of Ni powder is 53.8%, the content of Cr powder is 18.2%, the content of Fe powder is 11.5%, the content of V powder is 3.28%, the content of Mn powder is 13.22%, and the average particle size of the five powders is 4 mu m; placing the weighed powder on a V-shaped powder mixer to uniformly mix for 12 hours to obtain mixed powder; then adding the dried stearic acid accounting for 4 percent of the mass of the mixed powder for granulation, and then placing the mixture into a vacuum drying oven for drying at 75 ℃ for 5 hours; sieving the dried powder with a 60-mesh screen, taking the sieved powder, and carrying out compression molding under a hydraulic press with parameters of 40MPa pressure and 50 seconds dwell time to obtain a green body.
Placing the green body under a vacuum degree of 2×10 -3 Sintering is carried out in the Pa environment, and the sintering process is as follows: raising the temperature from room temperature to 120 ℃ at a heating rate of 9 ℃/min, and preserving the temperature for 50min; raising the temperature to 400 ℃ at a heating rate of 14 ℃/min, and preserving the temperature for 50min; raising the temperature to 600 ℃ at a heating rate of 5 ℃/min, and preserving the temperature for 50min; raising the temperature to 850 ℃ at a heating rate of 12.5 ℃/min, and preserving the temperature for 50min; 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 complete solution treatment, wherein the temperature of the complete solution treatment is 1000 ℃ and the duration is 2 hours, rapidly placing the treated primary high-entropy alloy in distilled water, and quenching the primary high-entropy alloy to room temperature; then placing the sample after solution treatment in a tempering furnace for precipitation strengthening treatment, wherein the tempering temperature is 500 ℃, the tempering time is 3 hours, and the tempering is continuously 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 12 hours to fully infiltrate the pores with the solution, thus obtaining the much Kong Gaoshang alloy material; the surface of the porous high-entropy alloy material has no obvious cracks.
The porous high-entropy alloy material of this example was tested according to the electrochemical test procedure of example 1, when the current density was 100mA/cm 2 At the time of overpotential 1316mV (vs. Hg/HgO), the exchange current density was 7.9 x 10 -4 Acm -2 。
Example 5
Weighing Ni, cr, fe, V, mn five element powders with purity up to 99.99% according to a certain atomic percentage, wherein the content of Ni powder is 55.2%, the content of Cr powder is 18.4%, the content of Fe powder is 10.4%, the content of V powder is 4.8%, the content of Mn powder is 11.2%, and the average particle size of the five powders is 5 mu m; placing the weighed powder on a V-shaped powder mixer to uniformly mix for 12 hours to obtain mixed powder; then adding the dried stearic acid accounting for 4 percent of the mass of the mixed powder for granulation, and then placing the mixture into a vacuum drying oven for drying at 75 ℃ for 5 hours; sieving the dried powder with a 60-mesh screen, taking the sieved powder, and carrying out compression molding under a hydraulic press with parameters of 60MPa pressure and 40 seconds dwell time to obtain a green body.
Placing the green body under a vacuum degree of 2×10 -3 Sintering is carried out in the Pa environment, and the sintering process is as follows: raising the temperature from room temperature to 120 ℃ at a heating rate of 9 ℃/min, and preserving the temperature for 60min; raising the temperature to 400 ℃ at a heating rate of 15 ℃/min, and preserving the temperature for 60min; raising the temperature to 600 ℃ at a heating rate of 6 ℃/min, and preserving the temperature for 60min; raising the temperature to 850 ℃ at a heating rate of 12.5 ℃/min, and preserving the temperature for 70min; 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 complete solution treatment, wherein the temperature of the complete solution treatment is 1000 ℃ and the duration is 2 hours, rapidly placing the treated primary high-entropy alloy in distilled water, and quenching the primary high-entropy alloy to room temperature; then placing the sample after 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 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 12 hours to fully infiltrate the pores with the solution, thus obtaining the much Kong Gaoshang alloy material; the surface of the porous high-entropy alloy material has no obvious cracks.
The porous high-entropy alloy material of this example was tested according to the electrochemical test procedure of example 1, when the current density was 100mA/cm 2 At the time of overpotential 1243mV (vs. Hg/HgO), the exchange current density was 9.7 x 10 -4 A cm -2 。
Example 6
Weighing Ni, cr, fe, V, mn five element powders with purity up to 99.99% according to a certain atomic percentage, wherein the content of Ni powder is 48.8%, the content of Cr powder is 18.55%, the content of Fe powder is 13.58%, the content of V powder is 5.4%, the content of Mn powder is 13.67%, and the average particle size of the five powders is 4 mu m; placing the weighed powder on a V-shaped powder mixer to uniformly mix for 12 hours to obtain mixed powder; then adding the dried stearic acid accounting for 4 percent of the mass of the mixed powder for granulation, and then placing the mixture into a vacuum drying oven for drying at 75 ℃ for 5 hours; sieving the dried powder with a 60-mesh screen, taking the sieved powder, and carrying out compression molding under a hydraulic press with the parameters of 50MPa pressure and 50 seconds dwell time to obtain a green body.
Placing the green body under a vacuum degree of 2×10 -3 Sintering is carried out in the Pa environment, and the sintering process is as follows: raising the temperature from room temperature to 120 ℃ at a heating rate of 8 ℃/min, and preserving the temperature for 60min; raising the temperature to 400 ℃ at a heating rate of 13 ℃/min, and preserving the temperature for 60min; raising the temperature to 600 ℃ at a heating rate of 4 ℃/min, and preserving the temperature for 60min; raising the temperature to 850 ℃ at a heating rate of 13 ℃/min, and preserving the temperature for 70min; 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 complete solution treatment, wherein the temperature of the complete solution treatment is 1000 ℃ and the duration is 2 hours, rapidly placing the treated primary high-entropy alloy in distilled water, and quenching the primary high-entropy alloy to room temperature; then placing the sample after 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 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 12 hours to fully infiltrate the pores with the solution, thus obtaining the much Kong Gaoshang alloy material; the surface of the porous high-entropy alloy material has no obvious cracks.
The porous high-entropy alloy material of this example was tested according to the electrochemical test procedure of example 1, when the current density was 100mA/cm 2 At the time of overpotential 1238mV (vs. Hg/HgO), the exchange current density was 9.71 x 10 -4 A cm -2 。
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent changes and modification made to the above embodiment according to the technical substance of the present invention fall within the scope of the technical solution of the present invention.
Claims (8)
1. The porous high-entropy alloy material for efficiently producing hydrogen is characterized in that the raw material powder comprises Ni, cr, fe, V, mn, wherein the atomic mass percentage of the powder is 40% -60%, 10% -25%, 10% -15%, 3% -8%, 5% -15%, and the atomic percentage of V and Mn is 20% -50%, and the porous high-entropy alloy material can be prepared by the following steps:
s1, firstly weighing Ni, cr, fe, V, mn powder, performing ball milling mechanical mixing, adding stearic acid with the mass of 3-5% relative to the powder for granulating, drying in a common drying oven at 70-80 ℃ for 4-6 hours after granulating, sieving, taking the sieved powder by a press machine, and pressing to prepare a green body;
s2, placing the green body manufactured in the step S1 in a sintering furnace for sintering, wherein the sintering process comprises the following steps: firstly, heating from room temperature to 120 ℃ at a heating rate of 8-10 ℃/min, and preserving heat for 50-70 min; then the temperature is increased to 400 ℃ at the heating rate of 13-15 ℃/min, and the temperature is kept for 50-70 min; then the temperature is raised to 600 ℃ at the heating rate of 4-6 ℃/min, and the temperature is kept for 50-70 min; then the temperature is raised to 850 ℃ at a heating rate of 12-13 ℃/min, and the temperature is kept for 50-70 min; finally, closing the sintering furnace to cool the alloy material to room temperature along with the furnace;
s3, carrying out solution treatment on the porous high-entropy alloy rough blank in the step S2, wherein the solution treatment temperature is 950-1050 ℃, preserving heat for 1.5-2.5 h, and then rapidly quenching to room temperature;
s4, performing aging precipitation strengthening treatment on the porous high-entropy alloy subjected to the solution treatment in the step S3, wherein the process comprises the following steps: tempering for 2-3 times at 420-560 ℃ for 2-4 h each time;
and S5, performing electrochemical activation treatment on the porous high-entropy alloy in the step S4 by adopting a cyclic voltammetry to obtain the porous high-entropy alloy material for efficiently producing hydrogen.
2. A method for preparing the porous high-entropy alloy material for efficient hydrogen production according to claim 1, characterized in that reasonable sintering conditions, solution treatment and aging precipitation strengthening treatment are adopted, comprising the following steps:
s1, firstly weighing Ni, cr, fe, V, mn powder, performing ball milling mechanical mixing, adding stearic acid with the mass of 3-5% relative to the powder for granulating, drying in a common drying oven at 70-80 ℃ for 4-6 hours after granulating, sieving, taking the sieved powder by a press machine, and pressing to prepare a green body;
s2, placing the green body manufactured 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 in the step S2;
s4, performing 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 to obtain the porous high-entropy alloy material for efficiently producing hydrogen.
3. The method for preparing a porous high-entropy alloy material for efficient hydrogen production according to claim 2, wherein the powder purity in step S1 is greater than or equal to 99.99%, and the particle size is 3-5 μm.
4. The method for preparing the porous high-entropy alloy material for efficient hydrogen production according to claim 2, wherein the parameters of the step S1 when the hydraulic press is adopted for pressing are as follows: 40-60 MPa, dwell time: 30-60 s.
5. The method for preparing a porous high-entropy alloy material for efficient hydrogen production according to claim 2, wherein the step S2 sintering furnace has a vacuum degree higher than 2 x 10 during sintering -3 Pa。
6. The method for preparing the porous high-entropy alloy material for efficient hydrogen production according to claim 2, wherein the step S2 sintering process is as follows: firstly, heating from room temperature to 120 ℃ at a heating rate of 8-10 ℃/min, and preserving heat for 50-70 min; then the temperature is increased to 400 ℃ at the heating rate of 13-15 ℃/min, and the temperature is kept for 50-70 min; then the temperature is raised to 600 ℃ at the heating rate of 4-6 ℃/min, and the temperature is kept for 50-70 min; then the temperature is raised to 850 ℃ at a heating rate of 12-13 ℃/min, and the temperature is kept for 50-70 min; and finally, closing the sintering furnace to cool 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 950-1050 ℃, the temperature is kept for 1.5-2.5 h, and then the quenching is performed rapidly to room temperature.
8. The method according to claim 2, wherein the aging precipitation strengthening treatment process in step S4 is: tempering at 420-560 deg.c for 2-3 times and 2-4 hr each time.
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| CN104694808A (en) * | 2015-03-26 | 2015-06-10 | 北京科技大学 | High-entropy alloy with dispersion nano-sized precipitate strengthening effect and preparing method thereof |
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| KR101888300B1 (en) * | 2016-03-21 | 2018-08-16 | 포항공과대학교 산학협력단 | High Entropy Alloy Based Chromium, Iron, Manganese, Nickel and Vanadium |
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| CN107587158B (en) * | 2017-08-11 | 2019-08-16 | 天津工业大学 | A kind of nanoporous high-entropy alloy electrode and its preparation method and application |
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| US11359266B2 (en) * | 2018-11-20 | 2022-06-14 | City University Of Hong Kong | High entropy alloy structure and a method of preparing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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