CN112080766B - Y-Al-Ni intermediate alloy and preparation method and application thereof - Google Patents
Y-Al-Ni intermediate alloy and preparation method and application thereof Download PDFInfo
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- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
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- C25C3/36—Alloys obtained by cathodic reduction of all their ions
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C19/03—Alloys based on nickel or cobalt based on nickel
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Abstract
The invention provides a Y-Al-Ni intermediate alloy and a preparation method and application thereof, belonging to the technical field of alloy materials. The Y-Al-Ni intermediate alloy provided by the invention comprises 20-60% of Y, 2-30% of Al, and the balance of nickel and inevitable impurities. The Y-Al-Ni intermediate alloy provided by the invention does not need higher smelting temperature when being used for preparing the rare earth hydrogen storage alloy, the components of the rare earth hydrogen storage alloy are easy to control, and meanwhile, the segregation problem after metal aluminum is directly added in the production process can be solved, so that the components of the rare earth hydrogen storage alloy are more uniform. The invention provides a preparation method of the Y-Al-Ni intermediate alloy. The Y-Al-Ni intermediate alloy is prepared based on a molten salt electrolysis method, the raw materials of molten salt electrolyte and electrolysis raw materials are low in price, and the problem of high cost when metal yttrium and metal aluminum are directly used as raw materials for preparing the rare earth hydrogen storage material is solved.
Description
Technical Field
The invention relates to the technical field of alloy materials, in particular to a Y-Al-Ni intermediate alloy and a preparation method and application thereof.
Background
Since the rare earth hydrogen storage alloy is applied to the current over twenty years, the rare earth hydrogen storage alloy still has wide development space and application prospect as a hydrogen storage carrier for hydrogen energy utilization at present in a new energy age. The rare earth hydrogen storage alloy mainly comprises La and Ni, is prepared by a mixing and melting method in production, and is specifically prepared by heating metal lanthanum and metal nickel to a certain temperature for melting under a vacuum condition, uniformly mixing and cooling. However, rare earth hydrogen storage alloys containing La and Ni as main components have problems of high cost, poor oxidation resistance, easy pulverization, and low cycle life. In order to improve the comprehensive performance of the rare earth hydrogen storage alloy, researchers do a great deal of research work on the performance optimization of the rare earth hydrogen storage alloy, wherein element substitution is the most effective modification mode.
Researches show that the substitution of the element Y and the substitution of the element A1 are beneficial to improving the comprehensive performance of the rare earth hydrogen storage alloy. In the prior art, during the process of preparing the rare earth hydrogen storage alloy by adopting a mixed melting method, an element Y and an element Al are respectively added according to a stoichiometric ratio in a mode of metal yttrium and metal aluminum. Although the rare earth hydrogen storage alloy has better hydrogen storage performance after adding metal yttrium and metal aluminum, the melting point (660 ℃) of the metal aluminum is lower, and alloy segregation is easily caused in the smelting process of preparing the rare earth hydrogen storage alloy; moreover, the melting point of lanthanum metal is 920 ℃, the melting point of nickel metal is 1455 ℃, the melting point of yttrium metal is 1522 ℃, the melting point is higher, and higher melting temperature is required for melting yttrium metal, so that the volatilization of metals such as lanthanum metal, nickel metal and aluminum metal is serious, thereby causing the rare earth hydrogen storage alloy components to be difficult to control, and the yield of the rare earth hydrogen storage alloy to be reduced, generally lower than 97.5%.
Disclosure of Invention
The invention aims to provide a Y-Al-Ni intermediate alloy and a preparation method and application thereof, when the Y-Al-Ni intermediate alloy provided by the invention is used for preparing the rare earth hydrogen storage alloy, the smelting temperature of the rare earth hydrogen storage alloy can be reduced, the yield is improved, the components of the rare earth hydrogen storage alloy are easy to control, the segregation problem after metal aluminum is directly added in the production process can be solved, and the components of the rare earth hydrogen storage alloy are more uniform.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a Y-Al-Ni intermediate alloy which comprises, by mass, Y20-60%, Al 2-30%, the balance of nickel and inevitable impurities.
Preferably, the alloy comprises Y30-55%, Al 4-10% and Ni 35-60%.
Preferably, the unavoidable impurities include C, Si and Ca, and the content of C in the Y-Al-Ni master alloy is less than or equal to 500ppm, the content of Si is less than or equal to 500ppm, and the content of Ca is less than or equal to 500 ppm.
The invention provides a preparation method of the Y-Al-Ni intermediate alloy in the technical scheme, which comprises the following steps:
putting the molten salt electrolyte into an electrolytic cell, and heating until the molten salt electrolyte is completely molten to obtain an electrolyte melt;
adding an electrolysis raw material into the electrolyte melt, placing a receiving crucible in an electrolytic cell, carrying out electrolysis by taking a graphite plate as an anode and matching with a corresponding cathode, forming liquid alloy on the surface of the cathode, and collecting the liquid alloy in the receiving crucible;
casting the liquid alloy to obtain a Y-Al-Ni intermediate alloy;
the molten salt electrolyte is YF3、AlF3And LiF, or YF3And LiF;
when the molten salt electrolyte is YF3、AlF3And LiF, the electrolysis raw material is Y2O3And Al2O3In the mixing ofThe cathode is a metal nickel rod;
when the molten salt electrolyte is YF3And LiF, the electrolysis raw material is Y2O3And the cathode is an aluminum-nickel alloy rod.
Preferably, the current of the electrolysis is 1000-30000A, and the temperature of the electrolysis is 850-1200 ℃.
Preferably, when the molten salt electrolyte is YF3、AlF3And LiF, said molten salt electrolyte comprising YF in percent by mass380-90%, LiF 5-15%, and the balance of AlF3；
When the electrolytic raw material is Y2O3And Al2O3In the case of the mixture of (1), Y in the electrolytic raw material2O3The mass percentage of (B) is 31-96%.
Preferably, when the molten salt electrolyte is YF3And LiF, YF in the molten salt electrolyte3The mass percentage of the component (A) is 80-95%;
the mass percentage of aluminum in the aluminum-nickel alloy bar is 2-55%.
Preferably, the purity of each component in the molten salt electrolyte and the electrolysis raw material is more than or equal to 99%.
Preferably, the receiving crucible comprises a molybdenum crucible, a tungsten crucible or a nickel crucible.
The invention provides the application of the Y-Al-Ni intermediate alloy in the technical scheme or the Y-Al-Ni intermediate alloy prepared by the preparation method in the technical scheme in the preparation of rare earth hydrogen storage alloy.
The invention provides a Y-Al-Ni intermediate alloy which comprises, by mass, Y20-60%, Al 2-30%, the balance of nickel and inevitable impurities. The melting point of the Y-Al-Ni intermediate alloy provided by the invention is 900-1200 ℃, and the smelting temperature of the rare earth hydrogen storage alloy is lower than that of the rare earth hydrogen storage alloy prepared by directly adopting metal yttrium, so that the problems that the components are not easy to control and the yield of the rare earth hydrogen storage alloy is lower due to overhigh smelting temperature after adding metal yttrium in the production process of the rare earth hydrogen storage alloy can be solved, the segregation problem after directly adding metal aluminum in the production process can be solved, and the components of the rare earth hydrogen storage alloy are more uniform. When the Y-Al-Ni intermediate alloy provided by the invention is used for preparing the yttrium-aluminum-containing rare earth hydrogen storage alloy, the yield of the rare earth hydrogen storage alloy is higher and can reach 98.8%. Therefore, the Y-Al-Ni intermediate alloy provided by the invention has very important application value in research and development of high-performance rare earth hydrogen storage alloy, improvement of economic benefit of hydrogen storage alloy enterprises and promotion of progress of rare earth hydrogen storage alloy industry.
The invention provides a preparation method of the Y-Al-Ni intermediate alloy. The Y-Al-Ni intermediate alloy is prepared based on a molten salt electrolysis method, the raw materials of molten salt electrolyte and electrolysis raw materials are low in price, and the Y-Al-Ni intermediate alloy is used for preparing the rare earth hydrogen storage material on the basis, so that the problem of high cost when metal yttrium and metal aluminum are directly used as raw materials for preparing the rare earth hydrogen storage material is solved. In addition, the method provided by the invention has the advantages of simple process flow, low cost, stable and easily-controlled product components, small environmental pollution in the process flow, and suitability for large-scale production.
Detailed Description
The invention provides a Y-Al-Ni intermediate alloy which comprises, by mass, Y20-60%, Al 2-30%, the balance of nickel and inevitable impurities.
The Y-Al-Ni intermediate alloy provided by the invention comprises, by mass, Y20-60%, preferably 30-55%. In the invention, the element Y can improve the electrochemical performance of the rare earth hydrogen storage alloy at room temperature and high temperature, improve the high-rate discharge capacity of the rare earth hydrogen storage alloy, and form an oxide protective film of Y on the surface of the rare earth hydrogen storage alloy after the element Y is added, thus slowing down the corrosion and pulverization of the rare earth hydrogen storage alloy and improving the cycling stability of the rare earth hydrogen storage alloy.
The Y-Al-Ni intermediate alloy provided by the invention comprises, by mass, Al 2-30%, preferably 4-10%. In the invention, the element A1 can improve the cycle performance of the rare earth hydrogen storage alloy and greatly reduce the plateau pressure of the rare earth hydrogen storage alloy.
The Y-Al-Ni intermediate alloy provided by the invention contains the balance of nickel and inevitable impurities, wherein the mass percentage of the Ni is preferably 35-60%, and more preferably 45-49%; the unavoidable impurities preferably include C, Si and Ca, and the C content in the Y-Al-Ni master alloy is preferably less than or equal to 500ppm, and more preferably less than or equal to 300 ppm; the Si content is preferably 500ppm or less, more preferably 200ppm or less; the Ca content is preferably 500ppm or less, more preferably 200ppm or less. The invention preferably limits the unavoidable impurities to the content range, which is beneficial to ensuring that the performance of the rare earth hydrogen storage alloy is not influenced when the Y-Al-Ni intermediate alloy is used for preparing the rare earth hydrogen storage alloy.
According to the invention, the contents of Y, Al and Ni are controlled within the above ranges, and the melting point of the obtained Y-Al-Ni intermediate alloy is 900-1200 ℃, so that the smelting temperature is lower when the Y-Al-Ni intermediate alloy provided by the invention is adopted than when metal yttrium is directly adopted to prepare the rare earth hydrogen storage alloy, and the problem that the rare earth hydrogen storage alloy yield is reduced because the smelting temperature is too high after metal yttrium is added in the production process of the rare earth hydrogen storage alloy, the components are not easy to control can be solved. Meanwhile, the segregation problem after metal aluminum is directly added in the production process can be solved, and the rare earth hydrogen storage alloy has more uniform components; specifically, when the rare earth hydrogen storage alloy is prepared, the aluminum element is added in a metal aluminum mode, the aluminum is melted at 660 ℃, the density of the aluminum is low, the aluminum is gathered to the upper part of a system to cause alloy segregation, and the aluminum element is added in a Y-Al-Ni intermediate alloy mode to alloy the aluminum element and increase the density, so that the problem of alloy segregation caused by aluminum element gathering can be effectively solved.
The invention provides a preparation method of the Y-Al-Ni intermediate alloy, which comprises the following steps:
putting the molten salt electrolyte into an electrolytic cell, and heating until the molten salt electrolyte is completely molten to obtain an electrolyte melt;
adding an electrolysis raw material into the electrolyte melt, placing a receiving crucible in an electrolytic cell, carrying out electrolysis by taking a graphite plate as an anode and matching with a corresponding cathode, forming liquid alloy on the surface of the cathode, and collecting the liquid alloy in the receiving crucible;
casting the liquid alloy to obtain a Y-Al-Ni intermediate alloy;
the molten salt electrolyte is YF3、AlF3And LiF, or YF3And LiF;
when the molten salt electrolyte is YF3、AlF3And LiF, the electrolysis raw material is Y2O3And Al2O3The cathode is a metallic nickel rod;
when the molten salt electrolyte is YF3And LiF, the electrolysis raw material is Y2O3And the cathode is an aluminum-nickel alloy rod.
The Y-Al-Ni intermediate alloy is prepared by a molten salt electrolysis method, and can be prepared by adopting different molten salt electrolytes, electrolysis raw materials and cathodes, which is specifically described below. In the invention, the purity of each component in the molten salt electrolyte and the electrolytic raw material is preferably equal to or more than 99%.
In the present invention, when the molten salt electrolyte is YF3、AlF3And LiF (denoted as first molten salt electrolyte), the electrolysis feedstock is Y2O3And Al2O3The cathode is a metallic nickel rod (denoted as the first electrolysis feedstock). In the present invention, the first molten salt electrolyte preferably includes YF in mass percentage380-90%, LiF 5-15%, and the balance of AlF3(ii) a The YF3Further preferably 83 to 85%, and further preferably 7 to 8% of LiF. In the present invention, Y in the first electrolytic raw material2O3The content of (b) is preferably 31 to 96% by mass, and more preferably 65 to 86% by mass.
In the present invention, when the molten salt electrolyte is YF3And LiF (denoted as second molten salt electrolyte), the electrolysis raw material is Y2O3(denoted as second electrolysis feedstock), the cathode is an aluminum nickel alloy rod. In the present invention, the YF in the second molten salt electrolyte3Is preferably 80 to95%, and more preferably 85 to 90%. In the invention, the mass percentage of aluminum in the aluminum-nickel alloy bar is preferably 2-55%, and more preferably 5-10%.
The Y-Al-Ni intermediate alloy is prepared based on a molten salt electrolysis method, the raw materials of molten salt electrolyte and electrolysis raw materials are low in price, and the Y-Al-Ni intermediate alloy is used for preparing the rare earth hydrogen storage material on the basis, so that the problem of high cost when metal yttrium and metal aluminum are directly used as raw materials for preparing the rare earth hydrogen storage material is solved (the metal yttrium cannot be prepared by using the traditional electrolysis process and can only be prepared by using a calcium thermal reduction method, so that the metal yttrium is high in price). The invention preferably controls the content of each component in the molten salt electrolyte and the electrolytic raw material within the range, which is beneficial to ensuring that each component in the obtained Y-Al-Ni intermediate alloy meets the expected requirements, and reducing the impurity content, so that the Y-Al-Ni intermediate alloy meets the use requirements of the rare earth hydrogen storage alloy.
The method comprises the steps of placing a molten salt electrolyte in an electrolytic cell, and heating until the molten salt electrolyte is completely melted to obtain an electrolyte melt. In the present invention, the electrolytic cell is preferably a graphite electrolytic cell, and the shape of the electrolytic cell is preferably circular or square.
After an electrolyte melt is obtained, the invention adds an electrolysis raw material into the electrolyte melt, places a receiving crucible into an electrolytic tank, takes a graphite plate as an anode and is matched with a corresponding cathode for electrolysis, and forms a liquid alloy on the surface of the cathode and collects the liquid alloy in the receiving crucible. According to the invention, the graphite plate is preferably placed in an electrolytic cell, the molten salt electrolyte is added into the electrolytic cell, the graphite plate is heated until the molten salt electrolyte is completely melted to obtain an electrolyte melt, then the graphite plate is preferably continuously heated to the electrolysis temperature, the cathode is inserted into the electrolyte melt, the receiving crucible is placed in the electrolytic cell, and then the electrolysis raw material is added into the electrolyte melt for electrolysis. In the invention, in order to keep the whole electrolytic system in a stable state, the electrolytic raw material is preferably added into the electrolytic cell periodically or continuously during the electrolytic process, namely, part of the electrolytic raw material is added into the electrolytic cell before the electrolysis starts, then the electrolytic raw material is added into the electrolytic cell periodically or continuously during the electrolytic process, and the molten salt electrolyte is supplemented in time according to the electrolytic condition; the specific adding mode and adding amount of the electrolysis raw materials are not particularly limited, and the technical scheme familiar to the technical personnel in the field can be adopted.
In the invention, the current of the electrolysis is preferably 1000-30000A, more preferably 1500-10000A, further preferably 2000-3000A, and specifically 2400A, 2420A, 2500A or 2520A; the electrolysis temperature is preferably 850-1200 ℃, more preferably 950-1150 ℃, and specifically can be 980 ℃, 1020 ℃, 1050 ℃ or 1100 ℃. The invention is particularly directed to the electrolysis by direct current. In the invention, when a first molten salt electrolyte and a first electrolysis raw material are adopted and a metal nickel rod is used as a cathode, Y and Al are electrochemically separated out together on the cathode in the electrolysis process and are alloyed with Ni of the cathode to form a liquid alloy; when the second molten salt electrolyte and the second electrolysis raw material are adopted and the aluminum-nickel alloy bar is used as the cathode, in the electrolysis process, Y is electrochemically precipitated on the cathode and is alloyed with Al and Ni of the cathode to form liquid alloy.
In the present invention, the receiving crucible preferably comprises a molybdenum crucible, a tungsten crucible or a nickel crucible.
After the liquid alloy is obtained, the Y-Al-Ni intermediate alloy is obtained by casting the liquid alloy. In the invention, when the liquid alloy in the receiving crucible is full, the receiving crucible is preferably clamped by a clamp and then casting is carried out; the casting method is not particularly limited in the present invention, and a casting method known to those skilled in the art may be used.
The invention provides the application of the Y-Al-Ni master alloy in the technical scheme or the Y-Al-Ni master alloy prepared by the preparation method in the technical scheme in the preparation of rare earth hydrogen storage alloy, and particularly, the Y-Al-Ni master alloy provided by the invention is suitable for preparing rare earth hydrogen storage alloy containing Y, Al and Ni, such as La0.7Ce0.2Y0.1Ni3.9Mn0.4Al0.1Co0.6A hydrogen storage alloy.
In the present invention, the method for preparing the rare earth hydrogen storage alloy preferably comprises the following steps:
and calculating and accurately weighing each raw material according to the proportion of each element in the rare earth hydrogen storage alloy, putting each raw material into a crucible, smelting in a protective atmosphere, and cooling to obtain the rare earth hydrogen storage alloy.
The crucible material is not limited in the invention, and the crucible known to those skilled in the art can be used, such as Al2O3A crucible is provided. The protective gas for providing the protective atmosphere in the present invention is not particularly limited, and a protective gas known to those skilled in the art, such as argon, may be used. The smelting temperature is not specially limited and can be selected according to actual needs; the smelting time is preferably 5-10 min, and more preferably 8 min. In the invention, the equipment used for cooling is preferably a copper roller wire, the linear speed of the copper roller wire during cooling is preferably 3.5m/s, and the copper roller wire is preferably cooled by cooling water at 25 ℃ usually.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
YF is added3、AlF3Mixing the electrolyte with LiF according to the mass ratio of 83:7:10 to obtain molten salt electrolyte; will Y2O3And Al2O3Mixing the raw materials according to the mass ratio of 3:1 to obtain an electrolysis raw material;
placing a graphite plate in a circular graphite electrolytic cell, placing the molten salt electrolyte in the electrolytic cell, and heating to completely melt the molten salt electrolyte to obtain an electrolyte melt; continuously heating to 1020 ℃, inserting a metal nickel rod into the electrolyte melt, placing a molybdenum crucible at the bottom of an electrolytic cell, then adding an electrolysis raw material into the electrolytic cell, and electrolyzing by electrifying direct current by taking the graphite plate as an anode and the metal nickel rod as a cathode; in the electrolysis process, continuously adding an electrolysis raw material into an electrolytic cell, and timely supplementing molten salt electrolyte according to the electrolysis condition; wherein the current of the electrolysis is 2420A, and the temperature is 1020 ℃; forming liquid alloy on the surface of the cathode in the electrolysis process, and collecting the liquid alloy in a molybdenum crucible; after electrolysis for 60min, the molybdenum crucible was clamped out by a jig, and then casting was performed to obtain 4.4kg of a Y-Al-Ni master alloy, the compositional analysis results of which are shown in Table 1:
TABLE 1 analysis results of the composition of Y-Al-Ni master alloy prepared in example 1
| Element(s) | Y | Al | Ni | C | Ca | Si |
| Content (%) | 43.0 | 9.6 | 47.2 | 0.026 | 0.018 | 0.015 |
Example 2
YF is added3、AlF3Mixing with LiF according to the mass ratio of 80:8:12 to obtain molten salt electrolyte; will Y2O3And Al2O3Mixing the raw materials according to the mass ratio of 11:5 to obtain an electrolysis raw material;
placing a graphite plate in a circular graphite electrolytic cell, placing the molten salt electrolyte in the electrolytic cell, and heating to completely melt the molten salt electrolyte to obtain an electrolyte melt; continuously heating to 1050 ℃, inserting a metal nickel rod into the electrolyte melt, placing a molybdenum crucible at the bottom of an electrolytic cell, then adding an electrolysis raw material into the electrolytic cell, and electrifying direct current to electrolyze by taking the graphite plate as an anode and the metal nickel rod as a cathode; in the electrolysis process, continuously adding an electrolysis raw material into an electrolytic cell, and timely supplementing molten salt electrolyte according to the electrolysis condition; wherein the current of the electrolysis is 2500A, and the temperature is 1050 ℃; forming liquid alloy on the surface of the cathode in the electrolysis process, and collecting the liquid alloy in a molybdenum crucible; after electrolysis for 60min, the molybdenum crucible was clamped out by a jig, and then casting was performed to obtain 4.6kg of a Y-Al-Ni master alloy, the compositional analysis results of which are shown in Table 2:
TABLE 2 analysis results of the composition of the Y-Al-Ni master alloy prepared in example 2
| Element(s) | Y | Al | Ni | C | Ca | Si |
| Content (%) | 44.4 | 13.5 | 41.9 | 0.022 | 0.017 | 0.017 |
Example 3
YF is added3Mixing the electrolyte with LiF according to the mass ratio of 88:12 to obtain molten salt electrolyte;
placing a graphite plate in a circular graphite electrolytic cell, placing the molten salt electrolyte in the electrolytic cell, and heating to completely melt the molten salt electrolyte to obtain an electrolyte melt; continuously heating to 980 ℃, inserting an aluminum-nickel alloy bar (the aluminum content is 10%) into the electrolyte melt, placing a tungsten crucible at the bottom of an electrolytic cell, and then adding an electrolysis raw material Y into the electrolytic cell2O3Electrolyzing by using direct current with the graphite plate as an anode and the aluminum-nickel alloy bar as a cathode; in the electrolysis process, continuously adding an electrolysis raw material into an electrolytic cell, and timely supplementing molten salt electrolyte according to the electrolysis condition; wherein the current of the electrolysis is 2400A, and the temperature is 980 ℃; forming liquid alloy on the surface of the cathode in the electrolysis process, and collecting the liquid alloy in a tungsten crucible; after 50min of electrolysis, the tungsten crucible was clamped by a jig, and then casting was performed to obtain 3.6kg of a Y-Al-Ni master alloy, the compositional analysis results of which are shown in Table 3:
TABLE 3 analysis results of the composition of the Y-Al-Ni master alloy prepared in example 3
| Element(s) | Y | Al | Ni | C | Ca | Si |
| Content (%) | 52.3 | 4.74 | 42.66 | 0.020 | 0.016 | 0.015 |
Example 4
YF is added3Mixing with LiF according to the mass ratio of 90:10 to obtain molten salt electrolyte;
placing a graphite plate in a circular graphite electrolytic cell, placing the molten salt electrolyte in the electrolytic cell, and heating to completely melt the molten salt electrolyte to obtain an electrolyte melt; heating to 1100 deg.C, inserting Al-Ni alloy rod (5% of Al) into the electrolyte melt, placing molybdenum crucible at the bottom of electrolytic bath, and adding electrolysis raw material Y into the electrolytic bath2O3Electrolyzing by using direct current with the graphite plate as an anode and the aluminum-nickel alloy bar as a cathode; in the electrolysis process, continuously adding an electrolysis raw material into an electrolytic cell, and timely supplementing molten salt electrolyte according to the electrolysis condition; wherein the current of the electrolysis is 2520A, and the temperature is 1100 ℃;forming liquid alloy on the surface of the cathode in the electrolysis process, and collecting the liquid alloy in a molybdenum crucible; after electrolysis for 60min, the molybdenum crucible was clamped with a jig, and then casting was performed to obtain 5.0kg of a Y-Al-Ni master alloy, the compositional analysis results of which are shown in Table 4:
TABLE 4 analysis results of the composition of the Y-Al-Ni master alloy prepared in example 4
| Element(s) | Y | Al | Ni | C | Ca | Si |
| Content (%) | 48.3 | 2.6 | 48.9 | 0.018 | 0.014 | 0.017 |
Application example 1
Preparation of La from the Y-Al-Ni intermediate alloy prepared in example 20.7Ce0.2Y0.1Ni3.9Mn0.4Al0.1Co0.6A hydrogen storage alloy, a hydrogen absorbing alloy,the method comprises the following steps:
according to La0.7Ce0.2Y0.1Ni3.9Mn0.4Al0.1Co0.6Calculating the ratio of each element in the hydrogen storage alloy, accurately weighing each raw material, and filling the raw material into Al2O3Vacuumizing the crucible, and filling inert gas Ar; heating and smelting, keeping the temperature for 8min, then quickly solidifying at a copper roller linear speed of 3.5m/s (the copper roller line is always filled with 25 ℃ cooling water), and cooling to obtain the La0.7Ce0.2Y0.1Ni3.9Mn0.4Al0.1Co0.6A hydrogen storage alloy.
The mass of the obtained hydrogen storage alloy is accurately weighed, and the yield is 98.5 percent by calculation.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (6)
1. A preparation method of a Y-Al-Ni intermediate alloy comprises the following steps:
putting the molten salt electrolyte into an electrolytic cell, and heating until the molten salt electrolyte is completely molten to obtain an electrolyte melt;
adding an electrolysis raw material into the electrolyte melt, placing a receiving crucible in an electrolytic cell, carrying out electrolysis by taking a graphite plate as an anode and matching with a corresponding cathode, forming liquid alloy on the surface of the cathode, and collecting the liquid alloy in the receiving crucible; the current of the electrolysis is 2400-2520A, and the temperature of the electrolysis is 980-1100 ℃;
casting the liquid alloy to obtain a Y-Al-Ni intermediate alloy;
the molten salt electrolyte is YF3And LiF, the electrolysis raw material is Y2O3The cathode is an aluminum-nickel alloy bar; YF in the molten salt electrolyte3The mass percentage of the component (A) is 80-95%; the mass percentage of aluminum in the aluminum-nickel alloy bar is 2-55%.
2. The preparation method according to claim 1, wherein the Y-Al-Ni master alloy comprises, by mass percent, 20-60% of Y, 2-30% of Al, and the balance of nickel and unavoidable impurities; the unavoidable impurities comprise C, Si and Ca, the content of C in the Y-Al-Ni master alloy is less than or equal to 500ppm, the content of Si is less than or equal to 500ppm, and the content of Ca is less than or equal to 500 ppm.
3. The method of claim 1, wherein the Y-Al-Ni master alloy comprises 30-55% of Y, 4-10% of Al and 35-60% of Ni.
4. The method of claim 1, wherein the purity of each component of the molten salt electrolyte and the electrolysis raw material is not less than 99%.
5. The method of claim 1, wherein the receiving crucible comprises a molybdenum crucible, a tungsten crucible, or a nickel crucible.
6. The Y-Al-Ni intermediate alloy prepared by the preparation method of any one of claims 1 to 5 is applied to the preparation of rare earth hydrogen storage alloys.
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| US3855087A (en) * | 1972-10-11 | 1974-12-17 | Shinetsu Chemical Co | Method for producing rare earth metal-containing alloys |
| CN103540960A (en) * | 2013-09-30 | 2014-01-29 | 赣南师范学院 | Preparation method of rare-earth magnesium nickel based hydrogen storage alloy |
| CN104131315A (en) * | 2014-08-20 | 2014-11-05 | 赣南师范学院 | Electrolytic eutectoid alloying method for rare-earth-magnesium-nickel-based hydrogen storage alloy |
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2020
- 2020-09-22 CN CN202011001345.0A patent/CN112080766B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3855087A (en) * | 1972-10-11 | 1974-12-17 | Shinetsu Chemical Co | Method for producing rare earth metal-containing alloys |
| CN103540960A (en) * | 2013-09-30 | 2014-01-29 | 赣南师范学院 | Preparation method of rare-earth magnesium nickel based hydrogen storage alloy |
| CN104131315A (en) * | 2014-08-20 | 2014-11-05 | 赣南师范学院 | Electrolytic eutectoid alloying method for rare-earth-magnesium-nickel-based hydrogen storage alloy |
Non-Patent Citations (1)
| Title |
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| "Thermaldynamic Optimisation of the Ni-Al-Y ternary system";Jiapeng huang 等，;《Journal of phase equilibria and diffusion》;20150514;第36卷;第357-365页 * |
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