CN117385258A - Aluminum-containing hydrogen storage alloy, preparation method thereof and application of calcium element - Google Patents
Aluminum-containing hydrogen storage alloy, preparation method thereof and application of calcium element Download PDFInfo
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- CN117385258A CN117385258A CN202311590661.XA CN202311590661A CN117385258A CN 117385258 A CN117385258 A CN 117385258A CN 202311590661 A CN202311590661 A CN 202311590661A CN 117385258 A CN117385258 A CN 117385258A
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 108
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 108
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 239000000956 alloy Substances 0.000 title claims abstract description 98
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 98
- 238000003860 storage Methods 0.000 title claims abstract description 93
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 69
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 65
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 239000011575 calcium Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000003723 Smelting Methods 0.000 claims description 9
- 238000000137 annealing Methods 0.000 claims description 9
- 230000002441 reversible effect Effects 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 47
- 239000011572 manganese Substances 0.000 description 37
- 229910052761 rare earth metal Inorganic materials 0.000 description 7
- 150000002910 rare earth metals Chemical class 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 229910052746 lanthanum Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000011232 storage material Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 229910052754 neon Inorganic materials 0.000 description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- IKBUJAGPKSFLPB-UHFFFAOYSA-N nickel yttrium Chemical compound [Ni].[Y] IKBUJAGPKSFLPB-UHFFFAOYSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-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
- C22C30/00—Alloys containing less than 50% by weight of each constituent
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
-
- 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
- C22C1/023—Alloys based on 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
-
- 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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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
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Abstract
The invention discloses an aluminum-containing hydrogen storage alloy, a preparation method thereof and application of calcium element. The aluminum-containing hydrogen storage alloy has a composition represented by formula (1): la (La) a Ce b Y c Ca d Ni x Mn y Al z (1) The method comprises the steps of carrying out a first treatment on the surface of the Wherein x, y, z, a, b, c, d represents the mole fraction of each element; 2. not less than a 0.1,2.3 not less than b 0.8,4.2 not less than c 1.8,1 not less than d not less than 0, not less than 20.5 not less than x 19.5,0.8 not less than y not less than 0.4, not less than 0.5 not less than z not less than 0.05, and a+b+c+d=6, x+y+z=21. The aluminum-containing hydrogen storage alloy has the advantages that the hydrogen storage amount of more than 0.1MPa is more than the ratio, and the hydrogen release platform is low.
Description
Technical Field
The invention relates to an aluminum-containing hydrogen storage alloy, a preparation method thereof and application of calcium element.
Background
The hydrogen energy has the advantages of abundant reserves, wide sources, zero pollution and the like, and is considered as an ideal novel energy source. The transportation of hydrogen is a key link in the popularization and application of hydrogen energy. The hydrogen is easy to leak and contact with air in the transportation process, so that the hidden danger of explosion exists. How to efficiently and conveniently store and transport hydrogen becomes an important subject for promoting the development of a hydrogen energy system. Rare earth metal hydrides are distinguished from various hydrogen storage materials by mild hydrogen storage conditions, safety and high efficiency.
CN116479287a discloses a 5 B 19 La-Y-Ni hydrogen storage alloy having a chemical composition of La 5-x Y x Ni 19- y R y Wherein x is more than or equal to 2.78 and less than or equal to 3.34,0, y is more than or equal to 1.5, and R is one or more of Mn, al, co, zr, cr, sc, ti, V, nb, mo. The hydrogen storage alloy is A 5 B 19 The hydrogen storage amount of the catalyst is more than 0.1MPa, and the catalyst occupies a relatively small amount.
CN116024459A discloses a superlattice rare earth hydrogen storage material, the chemical formula of which is A a Ce b Y c Ni x Mn y B z B is more than or equal to 0.3 and less than or equal to 0.9,1.6, c is more than or equal to 2.5, a+b+c= 3,0.3, y is more than or equal to 0.7,0, z is more than or equal to 0.3, x+y+z is more than or equal to 10.8 and less than or equal to 12.6, wherein one or more La is selected from A is La, pr, nd, gd or Sm, and B is one or more of Al, cu, fe, zn, co, si, zr, ti. The rare earth hydrogen storage material has less hydrogen storage amount more than 0.1 MPa.
CN114955988A discloses a rare earth yttrium nickel hydrogen storage alloy, which has A 2 B 7 A chemical composition of RE x Y y Ni z-a-b Mn a Al b RE is one or more of La, ce, pr, nd, sm and Gd, x is more than 0, y is more than 0, x+y=3, and y/x is more than or equal to 1.6 and less than or equal to 2.4,0, a+b is more than or equal to 1,9.15 and less than or equal to z is more than or equal to 11.85. The hydrogen storage alloy has less hydrogen storage amount more than 0.1 MPa.
Disclosure of Invention
In view of the above, an object of the present invention is to provide an aluminum-containing hydrogen storage alloy having a large hydrogen storage amount ratio of 0.1MPa or more and a low hydrogen release platform. Further, the aluminum-containing hydrogen storage alloy has a relatively high reversible hydrogen storage capacity. Another object of the present invention is to provide a method for producing the above aluminum-containing hydrogen storage alloy. It is an object of the present invention to provide a use of calcium in increasing the reversible hydrogen storage capacity of an aluminum-containing hydrogen storage alloy.
The technical aim is achieved by the following technical scheme.
In one aspect, the present invention provides an aluminum-containing hydrogen storage alloy characterized by having a composition represented by formula (1):
La a Ce b Y c Ca d Ni x Mn y Al z (1)
wherein x, y, z, a, b, c, d represents the mole fraction of each element; 2. not less than a not less than 0.1,2.3 not less than b not less than 0.8,4.2 not less than c not less than 1.8,1 not less than d not less than 0, not less than 20.5 not less than x not less than 19.5,0.8 not less than y not less than 0.4, not less than 0.5 not less than z not less than 0.05, and a+b+c+d=6, x+y+z=21.
The aluminum-containing hydrogen storage alloy according to the present invention preferably has 0.8.gtoreq.d.gtoreq.0.1.
Preferably, the aluminum-containing hydrogen storage alloy according to the present invention includes Ce 2 Ni 7 The content of the phase is 55wt% or more.
The aluminum-containing hydrogen storage alloy according to the present invention preferably has a value of 1.3.gtoreq.a.gtoreq. 0.8,1.3.gtoreq.b.gtoreq.1, 4.gtoreq.c.gtoreq.3.5, and d=0.
The aluminum-containing hydrogen storage alloy according to the present invention preferably has 2.gtoreq.a.gtoreq. 1.8,1.8.gtoreq.b.gtoreq.1.5, 2.5.gtoreq.c.gtoreq. 2,0.6.gtoreq.d.gtoreq.0.3.
The aluminum-containing hydrogen storage alloy according to the present invention preferably has a value of 20.3.gtoreq.x.gtoreq. 20,0.7.gtoreq.y.gtoreq. 0.5,0.4.gtoreq.z.gtoreq.0.1.
The aluminum-containing hydrogen storage alloy according to the present invention preferably has a composition represented by one of the following formulas:
LaCeY 4 Ni 20.1 Mn 0.6 Al 0.3 ；
LaCeY 4 Ni 20.2 Mn 0.6 Al 0.2 ；
LaCeY 4 Ni 20.3 Mn 0.6 Al 0.1 ；
La 0.6 Ce 1.4 Y 4 Ni 20.2 Mn 0.6 Al 0.2 ；
La 0.6 Ce 1.4 Y 4 Ni 20.3 Mn 0.6 Al 0.1 ；
La 0.4 Ce 1.6 Y 4 Ni 20.3 Mn 0.6 Al 0.1 ；
La 0.2 Ce 1.8 Y 4 Ni 20.3 Mn 0.6 Al 0.1 ；
La 2 CeY 3 Ni 20.3 Mn 0.6 Al 0.1 ；
La 2 Ce 1.5 Y 2.5 Ni 20.3 Mn 0.6 Al 0.1 ；
La 2 Ce 1.5 Y 2 Ca 0.5 Ni 20.3 Mn 0.6 Al 0.1 ；
LaCeY 4 Ni 20 Mn 0.6 Al 0.4 ；
La 2 Ce 2 Y 2 Ni 20.3 Mn 0.6 Al 0.1 。
in another aspect, the present invention provides a method for preparing the aluminum-containing hydrogen storage alloy, comprising the steps of:
(1) Providing raw materials according to the chemical composition shown in the formula (1), smelting and forming the raw materials to obtain alloy sheets;
(2) Annealing the alloy sheet in an inert atmosphere to obtain an annealed alloy sheet;
(3) And crushing the annealed alloy sheet to obtain the aluminum-containing hydrogen storage alloy.
According to the production method of the present invention, preferably, annealing the alloy sheet in an inert atmosphere includes the steps of:
heating the alloy sheet from room temperature to 700-900 ℃ at a heating rate of 5-15 ℃/min in an inert atmosphere, then heating to 1000-1200 ℃ at a heating rate of 1-10 ℃/min, and preserving heat for 10-20 h.
In still another aspect, the present invention provides an application of a calcium element in improving a reversible hydrogen storage capacity of an aluminum-containing hydrogen storage alloy, wherein the aluminum-containing hydrogen storage alloy contains, in terms of mole parts, 1.8 to 2 parts of La,1.5 to 1.8 parts of Ce,2 to 2.5 parts of Y,20 to 20.3 parts of Ni,0.5 to 0.7 part of Mn, and 0.1 to 0.4 part of Al; the dosage of the calcium in the aluminum-containing hydrogen storage alloy is 0.3 to 0.6 part by mol.
The aluminum-containing hydrogen storage alloy of the invention has the advantages that La, ce and Y are controlled at proper contents on the A side, and Ni is replaced by specific amounts of Mn and Al on the B side, so that the hydrogen storage amount ratio of the hydrogen storage alloy above 0.1MPa is improved, and the hydrogen release platform pressure is reduced. The calcium element can improve the reversible hydrogen storage capacity of the aluminum-containing hydrogen storage alloy.
Detailed Description
The present invention will be further described with reference to specific examples, but the scope of the present invention is not limited thereto.
< aluminum-containing Hydrogen storage alloy >
The aluminum-containing hydrogen storage alloy of the present invention has a composition represented by formula (1):
La a Ce b Y c Ca d Ni x Mn y Al z (1)。
the hydrogen storage alloy does not contain Mg, but may contain some unavoidable impurities.
La is a rare earth element lanthanum. a represents the mole fraction of La. In the invention, la is an essential element, and 2 is more than or equal to a is more than or equal to 0.1. In certain embodiments, 1.3.gtoreq.a.gtoreq.0.8; preferably, 1.1.gtoreq.a.gtoreq.1. In other embodiments, 2.gtoreq.a.gtoreq.1.8; preferably, 2.gtoreq.a.gtoreq.1.9.
Ce is a rare earth element cerium. b represents the mole fraction of Ce. In the invention, ce is an essential element, and b is more than or equal to 2.3 and more than or equal to 0.8. In certain embodiments, 1.3.gtoreq.b.gtoreq.1; preferably, 1.1.gtoreq.b.gtoreq.1. In other embodiments, 1.8.gtoreq.b.gtoreq.1.5; preferably, 1.6.gtoreq.b.gtoreq.1.5.
In the invention, 3.5 is more than or equal to a+b is more than or equal to 1.5. In certain embodiments, 2.2. Gtoreq.a+b.gtoreq.2. In other embodiments, 3.7. Gtoreq.a+b. Gtoreq.3.5.
Y is a rare earth yttrium. c represents the molar fraction of Y. In the invention, Y is an essential element, and c is more than or equal to 4.2 and more than or equal to 1.8. In certain embodiments, 4.gtoreq.c.gtoreq.3.5; preferably, 4.gtoreq.c.gtoreq.3.8. In other embodiments, 2.5.gtoreq.c.gtoreq.2; preferably, 2.2.gtoreq.c.gtoreq.2.
Ca is an alkaline earth metal element. d represents the mole fraction of Ca. In the invention, 1 is more than or equal to d is more than or equal to 0. In certain embodiments, d=0. In other embodiments, 0.6.gtoreq.d.gtoreq.0.3; preferably, 0.5.gtoreq.d.gtoreq.0.4.
In the present invention, a+b+c+d=6.
Ni is a metallic element nickel. x represents the mole fraction of Ni. In the invention, ni is an essential element, and x is more than or equal to 20.5 and more than or equal to 19.5. Preferably, 20.3.gtoreq.x.gtoreq.20. In certain embodiments, 20.1.gtoreq.x.gtoreq.20. In other embodiments, 20.3.gtoreq.x.gtoreq.20.2.
Mn is a metallic element manganese. y represents the mole fraction of Mn. In the invention, mn is an essential element, and y is more than or equal to 0.8 and more than or equal to 0.4. Preferably, 0.7.gtoreq.y.gtoreq.0.5; more preferably, 0.6.gtoreq.y.gtoreq.0.5.
Al is a metallic element, aluminum. z represents the mole fraction of Al. In the invention, al is an essential element, and z is more than or equal to 0.5 and more than or equal to 0.05. Preferably, 0.4.gtoreq.z.gtoreq.0.1. In certain embodiments, 0.4. Gtoreq.z.gtoreq.0.3. In other embodiments, 0.2. Gtoreq.z.gtoreq.0.1.
In the present invention, x+y+z=21.
Specific embodiments of the aluminum-containing hydrogen storage alloys of the present invention include, but are not limited to, one of the following compositions:
LaCeY 4 Ni 20.1 Mn 0.6 Al 0.3 ；
LaCeY 4 Ni 20.2 Mn 0.6 Al 0.2 ；
LaCeY 4 Ni 20.3 Mn 0.6 Al 0.1 ；
La 0.6 Ce 1.4 Y 4 Ni 20.2 Mn 0.6 Al 0.2 ；
La 0.6 Ce 1.4 Y 4 Ni 20.3 Mn 0.6 Al 0.1 ；
La 0.4 Ce 1.6 Y 4 Ni 20.3 Mn 0.6 Al 0.1 ；
La 0.2 Ce 1.8 Y 4 Ni 20.3 Mn 0.6 Al 0.1 ；
La 2 CeY 3 Ni 20.3 Mn 0.6 Al 0.1 ；
La 2 Ce 15 Y 25 Ni 203 Mn 06 Al 01 ；
La 2 Ce 1.5 Y 2 Ca 0.5 Ni 20.3 Mn 0.6 Al 0.1 ；
LaCeY 4 Ni 20 Mn 0.6 Al 0.4 ；
La 2 Ce 2 Y 2 N i20.3 Mn 0.6 Al 0.1 。
ce in the aluminum-containing hydrogen storage alloy of the present invention 2 Ni 7 The content of the phase is 55wt% or more. Ce (Ce) 2 Ni 7 The content of the phase is 90wt% or less. In certain embodiments, ce 2 Ni 7 The content of the phase is 60wt% or more and 65wt% or less. In other embodiments, ce 2 Ni 7 The content of the phase is 73wt% or more and 77wt% or less.
Ce is removed from the aluminum-containing hydrogen storage alloy of the invention 2 Ni 7 In addition to the phase, also contains LaNi 5 Phase and/or Ce 5 Co 19 And (3) phase (C).
< preparation method >
The preparation method of the aluminum-containing hydrogen storage alloy comprises the following steps: (1) Providing raw materials according to the chemical composition of the hydrogen storage alloy, smelting and forming the raw materials to obtain alloy sheets; (2) Annealing the alloy sheet in an inert atmosphere to obtain an annealed alloy sheet; (3) And crushing the annealed alloy sheet to obtain the aluminum-containing hydrogen storage alloy.
In the step (1), the smelting may be performed under the protection of inert gas. Smelting may be performed in an intermediate frequency induction smelting furnace.
In the step (1), the alloy is formed by a rapid quenching process, so that the alloy liquid obtained by smelting is formed into an alloy sheet.
In step (2), annealing may be performed in an inert atmosphere. Inert atmospheres such as nitrogen, argon, helium, neon.
The annealing process conditions are as follows: heating from room temperature to 700-900 deg.c, preferably 750-850 deg.c at a heating rate of 5-15 deg.c/min, preferably 8-12 deg.c/min; then the temperature is raised to 1000-1200 ℃, preferably 1050-1100 ℃ at a heating rate of 1-10 ℃/min, preferably 3-7 ℃/min, and the temperature is kept for 10-20 h, preferably 13-17 h.
In the step (3), the powder is crushed under the protection of inert gas. Inert gases include, but are not limited to, nitrogen, argon, helium, neon.
The crushing can be performed by mechanical crushing, grinding and the like. In some embodiments, mechanical disruption is performed before grinding.
< use of calcium element >
The invention discovers that adding a proper amount of calcium element into the aluminum-containing hydrogen storage alloy can improve the reversible hydrogen storage capacity of the aluminum-containing hydrogen storage alloy. Thus, the invention provides the use of a calcium element for increasing the reversible hydrogen storage capacity of an aluminum-containing hydrogen storage alloy.
The aluminum-containing hydrogen storage alloy contains 1.8-2 parts of La, 1.5-1.8 parts of Ce, 2-2.5 parts of Y, 20-20.3 parts of Ni, 0.5-0.7 part of Mn and 0.1-0.4 part of Al in terms of mole parts.
In the aluminum-containing hydrogen storage alloy, the La content is preferably 1.9 to 2 parts by mole. In certain embodiments, the La content is 2 parts.
The content of Ce in the aluminum-containing hydrogen storage alloy is preferably 1.5 to 1.6 parts by mole. In certain embodiments, the Ce content is 1.5 parts.
In the aluminum-containing hydrogen storage alloy, the content of Y is preferably 2 to 2.2 parts by mole. In certain embodiments, the content of Y is 2 parts.
The content of Ni in the aluminum-containing hydrogen storage alloy is preferably 20.2 to 20.3 parts by mole. In certain embodiments, the Ni content is 20.3 parts.
In the aluminum-containing hydrogen storage alloy, the Mn content is preferably 0.5 to 0.6 parts by mole. In certain embodiments, the Mn content is 0.6 parts.
The Al content in the aluminum-containing hydrogen storage alloy is preferably 0.1 to 0.2 parts by mole. In certain embodiments, the Al content is 0.1 parts.
The dosage of calcium in the aluminum-containing hydrogen storage alloy is 0.3 to 0.6 part by mol; preferably 0.4 to 0.5 parts.
The following test methods for the aluminum-containing hydrogen storage alloys obtained in the following examples and comparative examples are described:
phase composition and major phase content: alloy powder smaller than 200 meshes in the aluminum-containing hydrogen storage alloy is selected as a sample. An X' Pert PRO powder X-ray diffractometer (Cu target, K alpha ray) is adopted, under the power of 40kV multiplied by 40mA, an X-ray diffraction (XRD) spectrum is obtained in a step-by-step scanning mode that the step length is 0.01 DEG and the stay time is 30s in each step, and the scanning range is 10-80 deg. And determining the phase composition and the main phase content according to the X-ray diffraction pattern.
Gaseous hydrogen storage performance: the P-C-T curve of an aluminum-containing hydrogen storage alloy was determined using a Sievels device. The specific method comprises the following steps: taking 1.5-1.7 g of hydrogen storage alloy with granularity smaller than 100 meshes, vacuumizing for 30min at 300 ℃ to fully activate the hydrogen storage alloy, and performing P-C-T curve test at 40 ℃ after cooling to room temperature. And testing according to the P-C-T curve to obtain the reversible hydrogen storage capacity, the hydrogen release platform pressure and the hydrogen storage volume ratio of more than 0.1 MPa.
Examples 1 to 12 and comparative example 1
The starting materials were provided according to the chemical compositions shown in table 1. Smelting the raw materials in a furnace chamber of an intermediate frequency induction smelting furnace protected by inert gas to obtain alloy liquid. And (3) adopting a rapid quenching process to the alloy liquid to obtain an alloy sheet.
And (3) annealing the alloy sheet in an argon atmosphere. The annealing process conditions are specifically as follows: the temperature was raised from room temperature to 800℃at a heating rate of 10℃per minute, then to 1050℃at a heating rate of 5℃per minute, and the temperature was maintained at 1050℃for 16 hours.
And mechanically crushing and grinding the annealed alloy sheet cooled to room temperature under the protection of argon atmosphere to obtain the aluminum-containing hydrogen storage alloy.
The composition and properties of the aluminum-containing hydrogen storage alloy are shown in Table 1.
TABLE 1
As can be seen from XRD patterns, the aluminum-containing hydrogen storage alloy of the invention is prepared from Ce 2 Ni 7 Phase, ce 5 Co 19 Phase and LaNi 5 Phase composition.
From examples 10 and 12, it is understood that the addition of appropriate calcium can increase the reversible hydrogen storage capacity of the aluminum-containing hydrogen storage alloy.
From examples 1,2 and 3 and 11, it is known that the contents of Ni, mn, and Al have important effects on the hydrogen storage amount ratio of 0.1MPa or more and the hydrogen discharge plateau pressure of the aluminum-containing hydrogen storage alloy, and that the appropriate contents of Ni, mn, and Al in combination with the a-side element can not only increase the hydrogen storage amount ratio of 0.1MPa or more but also significantly reduce the hydrogen discharge plateau pressure.
The present invention is not limited to the above-described embodiments, and any modifications, improvements, substitutions, and the like, which may occur to those skilled in the art, fall within the scope of the present invention without departing from the spirit of the invention.
Claims (10)
1. An aluminum-containing hydrogen storage alloy characterized by having a composition represented by formula (1):
La a Ce b Y c Ca d Ni x Mn y Al z (1)
wherein x, y, z, a, b, c, d represents the mole fraction of each element; 2. not less than a not less than 0.1,2.3 not less than b not less than 0.8,4.2 not less than c not less than 1.8,1 not less than d not less than 0, not less than 20.5 not less than x not less than 19.5,0.8 not less than y not less than 0.4, not less than 0.5 not less than z not less than 0.05, and a+b+c+d=6, x+y+z=21.
2. The aluminum-containing hydrogen storage alloy according to claim 1, wherein 0.8.gtoreq.d.gtoreq.0.1.
3. The aluminum-containing hydrogen storage alloy according to claim 1, wherein Ce in the aluminum-containing hydrogen storage alloy 2 Ni 7 The content of the phase is 55wt% or more.
4. The aluminum-containing hydrogen storage alloy according to claim 1, wherein 1.3.gtoreq.a.gtoreq. 0.8,1.3.gtoreq.b.gtoreq.1, 4.gtoreq.c.gtoreq.3.5, and d=0.
5. The aluminum-containing hydrogen storage alloy according to claim 1, wherein 2.gtoreq.a.gtoreq. 1.8,1.8.gtoreq.b.gtoreq.1.5, 2.5.gtoreq.c.gtoreq. 2,0.6.gtoreq.d.gtoreq.0.3.
6. The aluminum-containing hydrogen storage alloy according to claim 1, wherein 20.3.gtoreq.x.gtoreq. 20,0.7.gtoreq.y.gtoreq. 0.5,0.4.gtoreq.z.gtoreq.0.1.
7. The aluminum-containing hydrogen storage alloy according to claim 1, wherein the aluminum-containing hydrogen storage alloy has a composition represented by one of the following formulas:
LaCeY 4 Ni 20.1 Mn 0.6 Al 0.3 ；
LaCeY 4 Ni 20.2 Mn 0.6 Al 0.2 ；
LaCeY 4 Ni 20.3 Mn 0.6 Al 0.1 ；
La 0.6 Ce 1.4 Y 4 Ni 20.2 Mn 0.6 Al 0.2 ；
La 0.6 Ce 1.4 Y 4 Ni 20.3 Mn 0.6 Al 0.1 ；
La 04 Ce 16 Y 4 Ni 203 Mn 06 Al 01 ；
La 0.2 Ce 1.8 Y 4 Ni 20.3 Mn 0.6 Al 0.1 ；
La 2 CeY 3 Ni 20.3 Mn 0.6 Al 0.1 ；
La 2 Ce 1.5 Y 2.5 Ni 20.3 Mn 0.6 Al 0.1 ；
La 2 Ce 1.5 Y 2 Ca 0.5 Ni 20.3 Mn 0.6 Al 0.1 ；
LaCeY 4 Ni 20 Mn 0.6 Al 0.4 ；
La 2 Ce 2 Y 2 Ni 20.3 Mn 0.6 Al 0.1 。
8. the method for producing an aluminum-containing hydrogen storage alloy according to any one of claims 1 to 7, comprising the steps of:
(1) Providing raw materials according to the chemical composition shown in the formula (1), smelting and forming the raw materials to obtain alloy sheets;
(2) Annealing the alloy sheet in an inert atmosphere to obtain an annealed alloy sheet;
(3) And crushing the annealed alloy sheet to obtain the aluminum-containing hydrogen storage alloy.
9. The method of claim 8, wherein annealing the alloy sheet in an inert atmosphere comprises the steps of:
heating the alloy sheet from room temperature to 700-900 ℃ at a heating rate of 5-15 ℃/min in an inert atmosphere, then heating to 1000-1200 ℃ at a heating rate of 1-10 ℃/min, and preserving heat for 10-20 h.
10. The use of calcium element in improving reversible hydrogen storage capacity of aluminum-containing hydrogen storage alloy is characterized in that the aluminum-containing hydrogen storage alloy contains 1.8-2 parts of La, 1.5-1.8 parts of Ce, 2-2.5 parts of Y, 20-20.3 parts of Ni, 0.5-0.7 part of Mn and 0.1-0.4 part of Al in terms of mole parts; the dosage of calcium in the aluminum-containing hydrogen storage alloy is 0.3 to 0.6 part by mol.
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