CN114990367A - Aluminum-containing yttrium-containing hydrogen storage alloy and preparation method thereof - Google Patents
Aluminum-containing yttrium-containing hydrogen storage alloy and preparation method thereof Download PDFInfo
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- 229910052727 yttrium Inorganic materials 0.000 title claims abstract description 68
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 title claims abstract description 68
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 53
- 239000001257 hydrogen Substances 0.000 title claims abstract description 53
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 48
- 239000000956 alloy Substances 0.000 title claims abstract description 48
- 238000003860 storage Methods 0.000 title claims abstract description 46
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 41
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 239000011575 calcium Substances 0.000 claims abstract description 39
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 36
- 239000002893 slag Substances 0.000 claims abstract description 35
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910000946 Y alloy Inorganic materials 0.000 claims abstract description 17
- RFEISCHXNDRNLV-UHFFFAOYSA-N aluminum yttrium Chemical compound [Al].[Y] RFEISCHXNDRNLV-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000003723 Smelting Methods 0.000 claims abstract description 14
- 238000000137 annealing Methods 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000005266 casting Methods 0.000 claims abstract description 7
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 7
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 18
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 8
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 238000003795 desorption Methods 0.000 abstract description 5
- 230000001351 cycling effect Effects 0.000 abstract description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 21
- 150000002910 rare earth metals Chemical class 0.000 description 18
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 230000006698 induction Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002386 leaching Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 4
- 238000011160 research Methods 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- -1 rare earth compounds Chemical class 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- PHIQPXBZDGYJOG-UHFFFAOYSA-N sodium silicate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-][Si]([O-])=O PHIQPXBZDGYJOG-UHFFFAOYSA-N 0.000 description 2
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0031—Intermetallic compounds; Metal alloys; Treatment thereof
- C01B3/0047—Intermetallic compounds; Metal alloys; Treatment thereof containing a rare earth metal; Treatment thereof
- C01B3/0057—Intermetallic compounds; Metal alloys; Treatment thereof containing a rare earth metal; Treatment thereof also containing nickel
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Mechanical Engineering (AREA)
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- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Combustion & Propulsion (AREA)
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- Environmental & Geological Engineering (AREA)
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Abstract
The invention belongs to the technical field of hydrogen storage alloy preparation, and particularly discloses an aluminum-containing yttrium-containing hydrogen storage alloy and a preparation method thereof. The invention firstly mixes Ca, Al and the calcium thermal reduction yttrium slag for reaction, and casting is carried out after the reaction is finished, thus obtaining the aluminum-yttrium alloy. Then mixing the aluminum yttrium alloy, La, Ce, Ni, Co, Mn and Zr for high-temperature smelting, and after the smelting is finished, carrying out vacuum annealing to obtain the aluminum-containing yttrium-containing hydrogen storage alloy. The preparation method of the aluminum-containing yttrium-containing hydrogen storage alloy takes the calcium thermal reduction yttrium slag as the raw material, reduces the preparation cost of the aluminum-containing yttrium-containing hydrogen storage alloy, and simultaneously ensures the hydrogen absorption and desorption performance, the specific discharge capacity and the cycling stability of the aluminum-containing yttrium-containing hydrogen storage alloy.
Description
Technical Field
The invention relates to the technical field of hydrogen storage alloy preparation, in particular to an aluminum-containing yttrium-containing hydrogen storage alloy and a preparation method thereof.
Background
The calcium thermal reduction process is an applicable process for producing terbium, dysprosium, holmium, erbium, lutetium, yttrium and other heavy rare earth metals with high melting points and boiling points. The process takes rare earth compounds and metallic calcium as raw materials, and can produce a large amount of calcium hot reduction slag besides rare earth metals. The main component of the calcium hot reduction slag is calcium fluoride and contains a certain amount of rare earth, and the rare earth exists in the forms of metal, oxide and fluoride. The calcium thermal reduction slag is an important heavy rare earth secondary resource, and if the rare earth in the calcium thermal reduction slag can be recovered, the calcium thermal reduction slag has great significance for promoting the sustainable development of the rare earth resource, saving energy and protecting the environment.
At present, the extraction of rare earth from calcium thermal reduction slag by adopting a hydrometallurgical method is a mature process, and the product is mainly rare earth oxide (possibly intermediate rare earth chloride). The comprehensive utilization research of the vacuum calcium thermal reduction furnace slag (Chendong, European red, Lunedi, J, Jiangxi nonferrous metals, 2004,03:27-30) of Chendong and the like adopts mixed acid leaching treatment on the calcium thermal reduction furnace slag containing 5-7% of rare earth, the recovery rate of the rare earth is only 65.41%, and the acid leaching slag still contains about 2.28% of rare earth. The method for extracting the rare earth in the calcium thermal reduction rare earth smelting slag by roasting sodium silicate and leaching the hydrochloric acid by roasting the sodium silicate nonahydrate is developed by Beam warong and the like (Beam warong, Riyongkang, Linrudan and the like, research on extracting the rare earth in the calcium thermal reduction rare earth smelting slag by roasting sodium silicate [ J ], China Redtest journal, 2018,36(6):739-744), and the rare earth extraction rate reaches 99.05 percent under the conditions that the mass ratio of the raw material to the sodium silicate nonahydrate is 1:1, the roasting temperature is 850 ℃, the roasting time is 2h, the hydrochloric acid concentration is 4mol/L, the acid leaching temperature is 60 ℃, the acid leaching time is 1.5h and the liquid-solid ratio is 11: 1.
The REO (total rare earth) content in the calcium thermal reduction yttrium slag is 15-20% which is far higher than that in other calcium thermal reduction rare earth slag (generally 5-7%), but the process for recovering yttrium oxide by adopting a wet method has no economic advantage because yttrium oxide is low in price (5 ten thousand yuan/ton of 5N-grade yttrium oxide).
In the research of hydrogen storage alloy, the yttrium element is used for improving the performance of the hydrogen storage alloy, which has important significance and can improve the discharge capacity and the cycle life, but the preparation process of metal yttrium is complex, so that the yttrium is expensive (31 ten thousand yuan/ton), and the price of the hydrogen storage alloy is higher.
Therefore, how to provide the aluminum-containing yttrium-containing hydrogen storage alloy and the preparation method thereof, which improve the economic value of the calcium thermal reduction yttrium slag and reduce the preparation cost of the hydrogen storage alloy is a difficult problem to be solved in the field.
Disclosure of Invention
In view of the above, the invention provides an aluminum-containing yttrium-containing hydrogen storage alloy and a preparation method thereof, solves the problems of low economic value and high manufacturing cost of the yttrium-containing hydrogen storage alloy in wet recovery of yttrium oxide, and also improves the discharge specific capacity and the cycling stability of the hydrogen storage alloy.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing aluminum-containing yttrium-containing hydrogen storage alloy comprises the following steps:
1) mixing Ca, Al and the calcium thermal reduction yttrium slag, reacting, and casting after the reaction is finished to obtain an aluminum-yttrium alloy;
2) mixing and smelting aluminum yttrium alloy, La, Ce, Ni, Co, Mn and Zr, and then carrying out vacuum annealing to obtain the aluminum-containing yttrium-containing hydrogen storage alloy.
Preferably, the mass fraction of REO in the calcareous thermally reduced yttrium slag is 10-20%.
Preferably, the mass ratio of the Ca to the Al to the calcium thermal reduction yttrium slag is 0.5-1: 3-4: 10 to 15.
Preferably, the reaction temperature in the step 1) is 1200-1500 ℃, and the reaction time is 10-15 min.
Preferably, the mass ratio of the aluminum yttrium alloy, La, Ce, Ni, Co, Mn and Zr in the step 2) is 1-10: 15-30: 1-10: 50-70: 0.1-15: 0.5-15: 0.01 to 0.5.
Preferably, the smelting temperature in the step 2) is 1300-1500 ℃, and the smelting time is 10-15 min.
Preferably, the temperature of the vacuum annealing in the step 2) is 700-1000 ℃, the time of the vacuum annealing is 2-5 h, and the vacuum degree is 10 -3 ～10 -2 Pa。
The invention also aims to provide the aluminum-containing yttrium-containing hydrogen storage alloy prepared by the preparation method of the aluminum-containing yttrium-containing hydrogen storage alloy.
According to the technical scheme, compared with the prior art, the invention has the following beneficial effects:
1. the preparation method disclosed by the invention can take the calcium thermal reduction yttrium slag as a raw material and directly prepare the aluminum-containing yttrium-containing hydrogen storage alloy, and the preparation method disclosed by the invention has the advantages of simple process, high added value of products, good social and environmental benefits and obvious economic benefits;
2. the aluminum-containing yttrium-containing hydrogen storage alloy prepared by the invention has excellent hydrogen absorption and desorption performance, discharge specific capacity and cycling stability.
Detailed Description
The invention provides a method for preparing aluminum-containing yttrium-containing hydrogen storage alloy, which comprises the following steps:
1) mixing Ca, Al and the calcium thermal reduction yttrium slag, reacting, and casting after the reaction is finished to obtain an aluminum-yttrium alloy;
2) mixing and smelting aluminum yttrium alloy, Ni, Co, Mn and Zr, and then carrying out vacuum annealing to obtain the aluminum-containing yttrium-containing hydrogen storage alloy.
In the invention, the REO mass fraction in the calcareous thermally reduced yttrium slag is 10-20%, preferably 15-20%, more preferably 17-19%, and still more preferably 18%.
In the invention, the rare earth element in the calcium thermal reduction yttrium slag is only yttrium element.
In the invention, the mass ratio of Ca, Al and the calcium thermal reduction yttrium slag is 0.5-1: 3-4: 10 to 15, preferably 0.7 to 0.9: 3.2-3.8: 11 to 13, and more preferably 0.8: 3.5: 12.
in the invention, the reaction temperature in the step 1) is 1200-1500 ℃, preferably 1300-1400 ℃, and more preferably 1350 ℃; the reaction time is 10-15 min, preferably 12-14 min, and more preferably 13 min.
In the invention, the mass ratio of the aluminum yttrium alloy, Ni, Co, Mn and Zr in the step 2) is 1-10: 15-30: 1-10: 50-70: 0.1-15: 0.5-15: 0.01 to 0.5. Preferably 2 to 10: 20-30: 2-10: 50-65: 0.1-12: 0.5-12: 0.01 to 0.3, more preferably 2 to 6: 20-28: 3-9: 52-62: 0.1 to 9: 1-10: 0.01-0.2, and the preferable proportion of the other step is 4: 25: 6: 58: 4: 5: 0.1.
in the invention, the smelting temperature in the step 2) is 1300-1500 ℃, preferably 1350-1450 ℃, and further preferably 1400 ℃; the smelting time is 10-15 min, preferably 12-14 min, and more preferably 13 min.
In the invention, the temperature of vacuum annealing in the step 2) is 700-1000 ℃, preferably 800-900 ℃, and more preferably 850 ℃; the time of vacuum annealing is 2-5 h, preferably 2-4 h, and further preferably 3 h; vacuum degree of 10 -3 ～10 -2 Pa, preferably 10 -2 Pa。
The invention also provides the aluminum-containing yttrium-containing hydrogen storage alloy prepared by the preparation method of the aluminum-containing yttrium-containing hydrogen storage alloy.
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. 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
Placing 15.0kg of calcium thermal reduction yttrium slag (REO content is 17 wt.%), 1.0kg of metallic calcium and 3.65kg of metallic aluminum into a crucible of a vacuum induction furnace, heating to 1300 ℃, keeping for 12min to melt the metal and slag, pouring the crucible after the reaction is finished, discharging and casting to obtain 6.3kg of aluminum yttrium alloy;
1.0kg of the aluminum-yttrium alloy, 5.20kg of La, 2.16kg of Ce, 13.42kg of Ni, 2.08kg of Co, 1.10kg of Mn and 0.04kg of Zr are taken to be smelted for 12min in a vacuum induction smelting furnace at 1400 ℃, and then annealed for 3h (the vacuum degree is 10) in a vacuum annealing furnace at 900 DEG C -2 Pa) to obtain the aluminum-containing yttrium-containing hydrogen storage alloy.
Example 2
20.0kg of calcium thermal reduction yttrium slag (REO content is 18 wt.%), 1.34kg of metallic calcium and 6.8kg of metallic aluminum are put into a crucible of a vacuum induction furnace, the temperature is increased to 1200 ℃, then the temperature is kept for 15min, so that the metal and the slag are melted, and after the reaction is finished, the crucible is poured out for tapping and casting, so that 10.4kg of aluminum yttrium alloy is obtained;
1.0kg of the aluminum-yttrium alloy, 9.19kg of La, 2.10kg of Ce, 27.53kg of Ni, 0.12kg of Co, 3.00kg of Mn and 0.06kg of Zr are taken to be smelted for 15min at 1300 ℃ in a vacuum induction smelting furnace, and then annealed for 2h at 1000 ℃ in a vacuum annealing furnace (the vacuum degree is 10) -2 Pa) to obtain the aluminum-containing yttrium-containing hydrogen storage alloy.
Example 3
Putting 24.0kg of calcium thermal reduction yttrium slag (yttrium content REOwt.%), 1.6kg of metallic calcium and 24.4kg of metallic aluminum into a crucible of a vacuum induction furnace, heating to 1500 ℃, keeping for 10min to melt the metal and slag, pouring the crucible after the reaction is finished, discharging and casting to obtain 28.8kg of aluminum-yttrium alloy;
1.0kg of the aluminum-yttrium alloy, 14.00kg of La, 1.50kg of Ce, 30.15kg of Ni, 1.50kg of Co and 1.85kg of Mn are taken to be smelted in a vacuum induction smelting furnace at the temperature of 1500 ℃ for 10min, and then annealed in a vacuum annealing furnace at the temperature of 800 ℃ for 5h (the vacuum degree is 10) -3 Pa) to obtain the aluminum-containing yttrium-containing hydrogen storage alloy.
Comparative example 1
The raw materials for preparing the hydrogen storage alloy are metal yttrium and metal aluminum (the mass ratio is 1.70: 2.30), and other raw materials and parameters are the same as those of example 1, so that the hydrogen storage alloy is obtained.
Comparative example 2
The hydrogen storage alloy was prepared from yttrium metal and aluminum metal (mass ratio 0.90: 1.70), and the other raw materials and parameters were the same as in example 2.
Comparative example 3
The hydrogen storage alloy was prepared from yttrium metal and aluminum metal (mass ratio 0.30: 1.70), and the other raw materials and parameters were the same as in example 2.
The electrochemical performances of the products obtained in the examples 1 to 3 and the comparative examples 1 to 3, such as PCT hydrogen absorption and desorption performance (detected by a hydrogen absorption and desorption PCT detector), 0.2C specific discharge capacity, 1C charge-discharge cycle life and the like, are tested. The results of the experiment are shown in table 1.
TABLE 1 Hydrogen storage alloy Performance test results
It can be seen from table 1 that the specific discharge capacity and cycle life of the aluminum-containing yttrium-containing hydrogen storage alloy prepared by using the calcareous thermic reduced yttrium slag to replace yttrium metal are close to those of the aluminum-containing yttrium-containing hydrogen storage alloy prepared by using yttrium metal, and the hydrogen absorption and desorption performance is slightly superior to that of a comparative example, and the scheme of the aluminum-containing yttrium-containing hydrogen storage alloy prepared by using the calcareous thermic reduced yttrium slag to replace yttrium metal is feasible.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. A method for preparing a hydrogen storage alloy containing aluminum and yttrium is characterized by comprising the following steps:
1) mixing Ca, Al and the calcium thermal reduction yttrium slag, reacting, and casting after the reaction is finished to obtain an aluminum-yttrium alloy;
2) mixing and smelting aluminum yttrium alloy, La, Ce, Ni, Co, Mn and Zr, and then carrying out vacuum annealing to obtain the aluminum-containing yttrium-containing hydrogen storage alloy.
2. The method of claim 1, wherein the REO content in the Ca-reduced Yttrium slag is 10-20% by weight.
3. The method for preparing the aluminum-containing yttrium-containing hydrogen storage alloy according to claim 2, wherein the mass ratio of the Ca, the Al and the calcium thermal reduction yttrium slag is 0.5-1: 3-4: 10 to 15.
4. The method for preparing a hydrogen occluding alloy containing aluminum and yttrium according to any one of claims 1 to 3, wherein the temperature of the reaction in step 1) is 1200 to 1500 ℃ and the reaction time is 10 to 15 min.
5. The method for preparing the aluminum-containing yttrium-containing hydrogen storage alloy according to claim 4, wherein the mass ratio of the aluminum yttrium alloy, La, Ce, Ni, Co, Mn and Zr in the step 2) is 1-10: 15-30: 1-10: 50-70: 0.1-15: 0.5-15: 0.01 to 0.5.
6. The method for preparing the aluminum-containing yttrium-containing hydrogen storage alloy according to claim 5, wherein the melting temperature in the step 2) is 1300-1500 ℃, and the melting time is 10-15 min.
7. The method for preparing hydrogen occluding alloy containing aluminum and yttrium according to claim 5 or 6, wherein the temperature of vacuum annealing in step 2) is 700-1000 ℃, the time of vacuum annealing is 2-5 h, and the degree of vacuum is 10 -3 ～10 -2 Pa。
8. The aluminum-containing yttrium-containing hydrogen storage alloy prepared by the method for preparing the aluminum-containing yttrium-containing hydrogen storage alloy according to any one of claims 1 to 7.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07268519A (en) * | 1994-04-01 | 1995-10-17 | Toshiba Corp | Hydrogen storage alloy for battery, its production and nickel hydrogen battery |
| US20090148770A1 (en) * | 2005-08-26 | 2009-06-11 | Gs Yuasa Corporation | Hydrogen Absorbing Alloy, Production Method Thereof, and Secondary Battery |
| CN109585790A (en) * | 2018-11-30 | 2019-04-05 | 华南理工大学 | A kind of preparation method of AB5 base hydrogen-storing alloy, nickel-hydrogen cell electrode, secondary cell and its hydrogen-storage alloy |
| CN111349803A (en) * | 2020-03-25 | 2020-06-30 | 赣州有色冶金研究所 | Method for preparing yttrium intermediate alloy |
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2022
- 2022-06-08 CN CN202210638221.6A patent/CN114990367A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07268519A (en) * | 1994-04-01 | 1995-10-17 | Toshiba Corp | Hydrogen storage alloy for battery, its production and nickel hydrogen battery |
| US20090148770A1 (en) * | 2005-08-26 | 2009-06-11 | Gs Yuasa Corporation | Hydrogen Absorbing Alloy, Production Method Thereof, and Secondary Battery |
| CN109585790A (en) * | 2018-11-30 | 2019-04-05 | 华南理工大学 | A kind of preparation method of AB5 base hydrogen-storing alloy, nickel-hydrogen cell electrode, secondary cell and its hydrogen-storage alloy |
| US20220006070A1 (en) * | 2018-11-30 | 2022-01-06 | South China University Of Technology | AB5-BASED HYDROGEN STORAGE ALLOY, ELECTRODE FOR Ni-MH BATTERY, SECONDARY BATTERY, AND PREPARATION METHOD OF HYDROGEN STORAGE ALLOY |
| CN111349803A (en) * | 2020-03-25 | 2020-06-30 | 赣州有色冶金研究所 | Method for preparing yttrium intermediate alloy |
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