CN117403121A - Cerium-containing lanthanum yttrium nickel hydrogen storage alloy, preparation method thereof and application of cerium - Google Patents
Cerium-containing lanthanum yttrium nickel hydrogen storage alloy, preparation method thereof and application of cerium Download PDFInfo
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- CN117403121A CN117403121A CN202311590656.9A CN202311590656A CN117403121A CN 117403121 A CN117403121 A CN 117403121A CN 202311590656 A CN202311590656 A CN 202311590656A CN 117403121 A CN117403121 A CN 117403121A
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 127
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 127
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 238000003860 storage Methods 0.000 title claims abstract description 108
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 101
- 239000000956 alloy Substances 0.000 title claims abstract description 101
- KIAWGYDYRNHVFC-UHFFFAOYSA-N [Ni].[Y].[La] Chemical compound [Ni].[Y].[La] KIAWGYDYRNHVFC-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 37
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title abstract description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 79
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 13
- 239000012298 atmosphere Substances 0.000 claims description 8
- 238000003723 Smelting Methods 0.000 claims description 7
- 238000000137 annealing Methods 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 4
- 238000010791 quenching Methods 0.000 claims description 3
- 230000000171 quenching effect Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 6
- 239000011572 manganese Substances 0.000 description 42
- 238000010438 heat treatment Methods 0.000 description 8
- 230000002441 reversible effect Effects 0.000 description 6
- 238000003795 desorption Methods 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 229910052727 yttrium Inorganic materials 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
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 150000002910 rare earth metals Chemical class 0.000 description 4
- 239000011575 calcium Substances 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229910020791 La—Mg—Ni Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000007789 gas Substances 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
- 230000006698 induction Effects 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- 229910000636 Ce alloy Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 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
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 238000003991 Rietveld refinement Methods 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000005280 amorphization Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- IKBUJAGPKSFLPB-UHFFFAOYSA-N nickel yttrium Chemical compound [Ni].[Y] IKBUJAGPKSFLPB-UHFFFAOYSA-N 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- C22F1/10—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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a lanthanum yttrium nickel hydrogen storage alloy containing cerium, a preparation method thereof and application of cerium. The lanthanum yttrium nickel hydrogen storage alloy has the composition shown in a formula (I): la (La) m Ce p Y 6‑m‑p Ni 21‑q Mn q (I) The method comprises the steps of carrying out a first treatment on the surface of the Wherein, the value range of m is 0.1-2, the value range of p is 0.1-2, and the value range of q is 0.1-1; wherein m represents the mole fraction of La, p represents the mole fraction of Ce, 6-m-p represents the mole fraction of Y, 21-q represents the mole fraction of Ni, and q represents the mole fraction of Mn. The lanthanum yttrium nickel series hydrogen storage alloy has higher dischargeHydrogen plateau pressure.
Description
Technical Field
The invention relates to a lanthanum yttrium nickel hydrogen storage alloy containing cerium, a preparation method thereof and application of cerium.
Background
The safe and efficient storage and transportation of hydrogen is a difficulty in the development and application of hydrogen energy. Superlattice AB 3-3.8 Although the La-Mg-Ni rare earth hydrogen storage alloy has a great improvement in the hydrogen storage amount, the volatile metal Mg contained in the La-Mg-Ni rare earth hydrogen storage alloy causes great potential safety hazard for alloy preparation, and increases the difficulty in controlling the content and phase composition of Mg. The La-Y-Ni rare earth hydrogen storage alloy is superior to the materials in the safety aspect of the preparation process, can inhibit hydrogen-induced amorphization, and has good application prospect in the field of solid hydrogen storage.
CN117012943a discloses a hydrogen storage alloy, which comprises the following components in parts by weight: 36-51 parts of nickel, 7-12 parts of manganese, 0.9-3 parts of aluminum, 5.5-13.0 parts of copper, 0-1.5 parts of yttrium, 0-0.5 part of zirconium, 12-24 parts of lanthanum, 6-20 parts of cerium, 0-0.4 part of praseodymium and 0-0.3 part of neodymium. The hydrogen storage alloy has lower hydrogen discharge platform pressure.
CN115992319A discloses a rare earth hydrogen storage alloy, the chemical composition of which is RE x Ca y Ni d-a-b Mn a M b The method comprises the steps of carrying out a first treatment on the surface of the Wherein x is more than or equal to 0.5 and less than or equal to 0.9, y is more than or equal to 0.1 and less than or equal to 0.5, and x+y=1; a is more than or equal to 0.05 and less than or equal to 0.35,0, b is more than or equal to 0.3,4.5, d is more than or equal to 5.5,4.68, and d-a-b is more than or equal to 4.95; wherein RE is selected from one or more of La, ce, pr, nd, pm, sm, eu, gd, tb, dy, ho, er, tm, yb, lu, sc, and must contain La and Ce; wherein M is selected from one or more of Cu, sn, V, ti, zr, cr, zn, mo and Si; wherein x, y, a, b and d-a-b represent the mole fraction of each element, respectively. The hydrogen storage alloy is not A 2 B 7 Hydrogen storage alloy.
CN114703400a discloses a 5 B 19 Rare earth-yttrium-nickel hydrogen storage alloyThe composition is as follows: RE (RE) x Y 3-x Ni y M z The method comprises the steps of carrying out a first treatment on the surface of the Wherein Y is yttrium element, ni is nickel element, RE is one or more of La, ce, pr, nd, sm and Gd element, M is one or more of Mn, al, cu, fe and Co; wherein x, 3-x, Y, z represent molar coefficients of RE, Y, ni and M, respectively; wherein 0.75<x≤1.2；0.55<z is less than or equal to 1.4 and 11.0 is less than or equal to y+z is less than or equal to 12.0. The hydrogen storage alloy is A 5 B 19 Hydrogen storage alloy.
Disclosure of Invention
Accordingly, it is an object of the present invention to provide a cerium-containing lanthanum yttrium nickel hydrogen storage alloy having a high hydrogen desorption plateau pressure. Further, the hydrogen storage alloy has a higher hydrogen storage amount ratio of more than 0.1 MPa. Further, the hydrogen storage alloy has a high reversible hydrogen storage capacity. Another object of the present invention is to provide a method for preparing the above cerium-containing lanthanum yttrium nickel hydrogen storage alloy. It is a further object of the present invention to provide a use of cerium.
The technical aim is achieved through the following technical scheme.
In one aspect, the invention provides a lanthanum yttrium nickel based hydrogen storage alloy of cerium, having a composition as shown in formula (I):
La m Ce p Y 6-m-p Ni 21-q Mn q (I)；
wherein, the value range of m is 0.1-2, the value range of p is 0.1-2, and the value range of q is 0.1-1;
wherein m represents the mole fraction of La, p represents the mole fraction of Ce, 6-m-p represents the mole fraction of Y, 21-q represents the mole fraction of Ni, and q represents the mole fraction of Mn.
Preferably, the value of m+p is in the range of 1.5-2.5.
The lanthanum yttrium nickel hydrogen storage alloy according to the present invention preferably has a value of 6-m-p ranging from 3.5 to 4.5 and a value of 21-q ranging from 20 to 20.9.
Preferably, the lanthanum yttrium nickel based hydrogen storage alloy according to the present invention does not contain alkali metal and alkaline earth metal.
According to the lanthanum-yttrium-nickel-series hydrogen storage alloy of the present invention, preferably, the lanthanum-yttrium-nickel-series hydrogen storage alloy is composed of only the element represented by the formula (I), except for unavoidable impurities.
Preferably, the lanthanum yttrium nickel based hydrogen storage alloy according to the present invention comprises Ce 2 Ni 7 Phase, ce 5 Co 19 Phase and LaNi 5 Phase, and Ce 2 Ni 7 The content of the phase is more than or equal to 75 weight percent.
The lanthanum yttrium nickel-based hydrogen storage alloy according to the present invention, preferably, the Ce 2 Ni 7 The space group of the phases is P63/mmc, and the average length of the a axis of the unit cell isThe average length of the c-axis is +.>
The lanthanum yttrium nickel based hydrogen storage alloy according to the present invention preferably has a composition as shown in one of the following:
(1)La 0.2 Ce 1.8 Y 4 Ni 20.2 Mn 0.8 ；
(2)La 0.5 Ce 1.5 Y 4 Ni 20.2 Mn 0.8 ；
(3)La 0.8 Ce 1.2 Y 4 Ni 20.2 Mn 0.8 ；
(4)La 1.1 Ce 0.9 Y 4 Ni 20.2 Mn 0.8 ；
(5)La 1.4 Ce 0.6 Y 4 Ni 20.2 Mn 0.8 ；
(6)La 1.7 Ce 0.3 Y 4 Ni 20.2 Mn 0.8 ；
(7)La 1.1 Ce 0.9 Y 4 Ni 20.4 Mn 0.6 ；
(8)La 1.1 Ce 0.9 Y 4 Ni 20.6 Mn 0.4 。
on the other hand, the invention provides a preparation method of the lanthanum yttrium nickel hydrogen storage alloy, which comprises the following steps:
smelting raw materials provided according to the composition of the lanthanum yttrium nickel hydrogen storage alloy in an inert atmosphere, and then rapidly quenching the raw materials into alloy sheets; annealing the alloy sheet, and then crushing to obtain the cerium-containing lanthanum yttrium nickel hydrogen storage alloy.
In still another aspect, the invention provides an application of cerium in improving the hydrogen desorption platform pressure of a lanthanum yttrium nickel hydrogen storage alloy, wherein the lanthanum yttrium nickel hydrogen storage alloy comprises 0.1-2 parts by mole of La, 3.5-4.5 parts by mole of Y, 20-20.9 parts by mole of Ni and 0.1-1 part by mole of Mn, and the Ce in the lanthanum yttrium nickel hydrogen storage alloy is used in an amount of 0.1-2 parts by mole.
The lanthanum yttrium nickel series hydrogen storage alloy containing cerium is A 2 B 7 La-Y-Ni superlattice hydrogen storage alloy. The A side of the hydrogen storage alloy of the invention uses a proper amount of Ce to replace La and/or Y, the B side uses a proper amount of Mn to replace Ni, and the A side element and the B side element are mutually matched, thus improving the hydrogen discharge platform pressure of the lanthanum yttrium nickel series hydrogen storage alloy. In the preferred embodiment of the invention, the lanthanum yttrium nickel series hydrogen storage alloy has higher hydrogen discharge platform pressure, hydrogen storage amount ratio of more than 0.1MPa and reversible hydrogen storage capacity.
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.
< lanthanum yttrium-nickel series hydrogen storage alloy containing cerium >
The lanthanum yttrium nickel series hydrogen storage alloy containing cerium has the composition shown in a formula (I):
La m Ce p Y 6-m-p Ni 21-q Mn q (I)
the yttrium-nickel hydrogen storage alloy of the invention does not contain alkali metal and alkaline earth metal. Examples of alkali metals include, but are not limited to, lithium, sodium, potassium. Examples of alkaline earth metals include, but are not limited to, beryllium, magnesium, calcium, strontium, barium. In certain embodiments, the cerium-containing lanthanum yttrium nickel-based hydrogen storage alloy of the present invention consists of only the elements represented by formula (I), except for unavoidable impurities.
m represents the mole fraction of La. La represents lanthanum. m is 0.1-2. In certain embodiments, m ranges from 0.2 to 0.5. In other embodiments, m ranges from 1 to 1.5; preferably 1.1 to 1.3.
p represents the mole fraction of Ce. Ce represents a cerium element. The value range of p is 0.1-2. In certain embodiments, p ranges from 1.5 to 1.8. In other embodiments, p has a value in the range of 0.7 to 1.3; preferably 0.9 to 1.1.
In the invention, the value range of m+p is 1.5-2.5; preferably 1.8 to 2.3; more preferably 2 to 2.1.
6-m-p represents the molar fraction of Y. Y represents yttrium element. The content of Y can be determined from m and p. The value range of 6-m-p can be 3.5-4.5; preferably 3.8 to 4.3; more preferably 4 to 4.1.
21-q represents the mole fraction of Ni. Ni represents a nickel element. The Ni content can be determined from q. The value range of 21-q can be 20 to 20.9. In certain embodiments, 21-q has a value in the range of 20.2 to 20.4. In other embodiments, 21-q ranges from 20.6 to 20.7.
q represents the mole fraction of Mn. Mn represents a manganese element. q is in the range of 0.1 to 1. In certain embodiments, q ranges from 0.6 to 0.8. In other embodiments, q ranges from 0.3 to 0.4.
In certain embodiments, the cerium-containing lanthanum yttrium nickel-based hydrogen storage alloy has a composition as shown in one of the following:
(1)La 0.2 Ce 1.8 Y 4 Ni 20.2 Mn 0.8 ；
(2)La 0.5 Ce 1.5 Y 4 Ni 20.2 Mn 0.8 ；
(3)La 0.8 Ce 1.2 Y 4 Ni 20.2 Mn 0.8 ；
(4)La 1.1 Ce 0.9 Y 4 Ni 20.2 Mn 0.8 ；
(5)La 1.4 Ce 0.6 Y 4 Ni 20.2 Mn 0.8 ；
(6)La 1.7 Ce 0.3 Y 4 Ni 20.2 Mn 0.8 ；
(7)La 1.1 Ce 0.9 Y 4 Ni 20.4 Mn 0.6 ；
(8)La 1.1 Ce 0.9 Y 4 Ni 20.6 Mn 0.4 。
the lanthanum yttrium nickel series hydrogen storage alloy containing cerium of the invention contains Ce 2 Ni 7 Phase, ce 5 Co 19 Phase and LaNi 5 And (3) phase (C). In certain embodiments, the cerium-containing lanthanum yttrium nickel-based hydrogen storage alloy consists of Ce 2 Ni 7 Phase, ce 5 Co 19 Phase and LaNi 5 Phase composition.
Ce 2 Ni 7 The content of the phase may be greater than or equal to 75wt%. In certain embodiments, ce 2 Ni 7 The content of the phase is more than or equal to 80 weight percent. In other embodiments, ce 2 Ni 7 The content of the phase is more than or equal to 85 weight percent.
Ce 2 Ni 7 The content of the phase may be less than or equal to 90wt%. In certain embodiments, ce 2 Ni 7 The content of the phase is less than or equal to 85wt%. In other embodiments, ce 2 Ni 7 The content of the phase is less than or equal to 82 weight percent.
Ce 2 Ni 7 The space group of the phases is P63/mmc. The average a-axis length of the unit cell is The average length of the c-axis is +.>
The hydrogen releasing platform pressure of the cerium-containing lanthanum yttrium nickel hydrogen storage alloy is more than or equal to 0.25MPa; preferably, 0.5MPa or more; more preferably, 0.65MPa or more.
The reversible hydrogen storage capacity of the cerium-containing lanthanum yttrium nickel hydrogen storage alloy is more than or equal to 1.5wt%; preferably, 1.6wt% or more; more preferably 1.65wt% or more.
The hydrogen storage amount of the cerium-containing lanthanum yttrium nickel series hydrogen storage alloy is more than 0.1MPa and is more than or equal to 89wt%; preferably, 92wt% or more; more preferably, 95wt% or more.
< preparation method of cerium-containing lanthanum yttrium nickel-based Hydrogen storage alloy >
The preparation method of the lanthanum yttrium nickel series hydrogen storage alloy containing cerium comprises the following steps: smelting raw materials provided according to the composition of the lanthanum yttrium nickel hydrogen storage alloy in an inert atmosphere, and then rapidly quenching the raw materials into alloy sheets; annealing the alloy sheet, and then crushing to obtain the cerium-containing lanthanum yttrium nickel hydrogen storage alloy.
Smelting may be performed in an intermediate frequency induction smelting furnace.
Annealing may be performed in an inert atmosphere. Preferably, the gas providing the inert atmosphere is selected from one or more of nitrogen, argon, helium.
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 heating to 1000-1200 deg.C, preferably 1050-1100 deg.C at a heating rate of 1-10 deg.C/min, preferably 3-7 deg.C/min, and maintaining for 10-20 h, preferably 13-17 h; the temperature is kept and then cooled to room temperature, preferably the temperature is kept and then cooled to room temperature along with the furnace.
The pulverization may be performed in an inert atmosphere. Preferably, the gas providing the inert atmosphere is selected from one or more of nitrogen, argon, helium.
The crushing can be performed by combining mechanical crushing and grinding. Mechanical crushing can be performed first, and then grinding can be performed.
< use of cerium >
The invention discovers that adding proper cerium element into lanthanum yttrium nickel hydrogen storage alloy can improve the hydrogen discharge platform pressure of the lanthanum yttrium nickel hydrogen storage alloy. Therefore, the invention provides the application of cerium in improving the hydrogen desorption platform pressure of the lanthanum-yttrium-nickel hydrogen storage alloy.
La, Y, ni and Mn are contained in La-Y-Ni hydrogen storage alloy. Preferably, the lanthanum yttrium nickel based hydrogen storage alloy does not contain alkali metals and alkaline earth metals. Examples of alkali metals include, but are not limited to, lithium, sodium, potassium. Examples of alkaline earth metals include, but are not limited to, beryllium, magnesium, calcium, strontium, barium. In certain embodiments, the lanthanum yttrium nickel based hydrogen storage alloy consists of only the above elements, except for unavoidable impurities.
In the lanthanum yttrium nickel hydrogen storage alloy, the La content is 0.1-2 mol parts. In certain embodiments, the La content is 0.2 to 0.5 molar parts. In other embodiments, the La content is 1 to 1.5 molar parts; preferably 1.1 to 1.3 molar parts.
In the lanthanum yttrium nickel hydrogen storage alloy, the content of Y is 3.5 to 4.5 mol parts; preferably 3.8 to 4.3 molar parts; more preferably 4 to 4.1 parts by mole.
In the lanthanum yttrium nickel hydrogen storage alloy, the content of Ni is 20 to 20.9 mol parts. In certain embodiments, the Ni is present in an amount of 20.2 to 20.4 parts by mole. In other embodiments, the Ni content is 20.6 to 20.7 parts by mole.
In the lanthanum yttrium nickel hydrogen storage alloy of the invention, the content of Mn is 0.1-1 mol part. In certain embodiments, the Mn content is 0.6 to 0.8 molar parts. In other embodiments, the Mn content is 0.3 to 0.4 molar parts.
In the lanthanum yttrium nickel hydrogen storage alloy, the using amount of Ce is 0.1-2 mol parts. In certain embodiments, ce is used in an amount of 1.5 to 1.8 molar parts. In other embodiments, ce is used in an amount of 0.7 to 1.3 molar parts; preferably 0.9 to 1.1 molar parts.
Examples 1 to 8 and comparative examples 1 to 2
The raw materials provided according to the composition of the lanthanum yttrium nickel based hydrogen storage alloy shown in table 1 were melted in an inert atmosphere and then rapidly quenched into alloy pieces. Smelting is performed in an intermediate frequency induction smelting furnace. Annealing the alloy sheet in an argon atmosphere; then mechanically crushing in argon atmosphere, and grinding to obtain the lanthanum yttrium nickel hydrogen storage alloy containing cerium. The annealing process conditions are specifically as follows: heating from room temperature to 800 ℃ at a heating rate of 10 ℃/min; then heating to 1050 ℃ at a heating rate of 5 ℃/min, and preserving heat for 16h at 1050 ℃; and (5) cooling to room temperature along with the furnace after heat preservation.
TABLE 1
| Sequence number | Lanthanum yttrium nickel series hydrogen storage alloy composition |
| Example 1 | La 0.2 Ce 1.8 Y 4 Ni 20.2 Mn 0.8 |
| Example 2 | La 0.5 Ce 1.5 Y 4 Ni 20.2 Mn 0.8 |
| Example 3 | La 0.8 Ce 1.2 Y 4 Ni 20.2 Mn 0.8 |
| Example 4 | La 1.1 Ce 0.9 Y 4 Ni 20.2 Mn 0.8 |
| Example 5 | La 1.4 Ce 0.6 Y 4 Ni 20.2 Mn 0.8 |
| Example 6 | La 1.7 Ce 0.3 Y 4 Ni 20.2 Mn 0.8 |
| Example 7 | La 1.1 Ce 0.9 Y 4 Ni 20.4 Mn 0.6 |
| Example 8 | La 1.1 Ce 0.9 Y 4 Ni 20.6 Mn 0.4 |
| Comparative example 1 | La 2 Y 4 Ni 20.2 Mn 0.8 |
| Comparative example 2 | Ce 2 Y 4 Ni 20.2 Mn 0.8 |
Experimental example
1. Phase composition and major phase content:
test sample: alloy powder smaller than 200 meshes in lanthanum yttrium nickel hydrogen storage alloy.
Test instrument: an X' Pert PRO powder X-ray diffractometer (Cu target, K.alpha.).
Test conditions: the power is 40kV multiplied by 40mA, the step length is 0.01 DEG, the residence time of each step is 30s, and the scanning range is 10-80 deg.
As can be seen from the X-ray diffraction pattern, the cerium-containing lanthanum yttrium nickel hydrogen storage alloy of the invention is composed of Ce 2 Ni 7 Phase, ce 5 Co 19 Phase and LaNi 5 Phase composition.
Rietveld refinement of the X-ray diffraction pattern using Maud software to obtain the major phase (Ce) 2 Ni 7 The mass content of phase) is shown in table 2.
2. Reversible hydrogen storage capacity, hydrogen release platform pressure and hydrogen storage volume ratio of more than 0.1 MPa:
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, cooling to room temperature, and performing P-C-T curve test at 40 ℃ by adopting a Sievels device. Reversible hydrogen storage capacity, hydrogen release platform pressure and hydrogen storage amount ratio above 0.1MPa are obtained according to the P-C-T curve test, and are shown in Table 2.
TABLE 2
Comparing examples 1-8, it is known that the contents of La, ce and Mn have an important effect on the hydrogen desorption plateau pressure of the lanthanum-yttrium-nickel-based hydrogen storage alloy, and that the proper contents of La, ce and Mn can significantly improve the hydrogen desorption plateau pressure. The La, ce and Mn contents are set in a specific range, so that the lanthanum-yttrium-nickel hydrogen storage alloy has higher hydrogen discharge platform pressure, hydrogen storage volume ratio of more than 0.1MPa and reversible hydrogen storage capacity.
As is clear from the comparison between examples 1 to 6 and comparative examples 1 to 2, the addition of La or Ce-free hydrogen storage alloy does not allow for a high hydrogen storage capacity, hydrogen discharge plateau pressure and hydrogen storage capacity ratio of 0.1MPa or more.
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. A cerium-containing lanthanum yttrium nickel-based hydrogen storage alloy, which is characterized by having a composition as shown in formula (I):
La m Ce p Y 6-m-p Ni 21-q Mn q (I)；
wherein, the value range of m is 0.1-2, the value range of p is 0.1-2, and the value range of q is 0.1-1;
wherein m represents the mole fraction of La, p represents the mole fraction of Ce, 6-m-p represents the mole fraction of Y, 21-q represents the mole fraction of Ni, and q represents the mole fraction of Mn.
2. The lanthanum yttrium nickel series hydrogen storage alloy according to claim 1, wherein m+p has a value ranging from 1.5 to 2.5.
3. The lanthanum yttrium nickel series hydrogen storage alloy according to claim 1, wherein the value of 6-m-p is in the range of 3.5 to 4.5 and the value of 21-q is in the range of 20 to 20.9.
4. The lanthanum yttrium-nickel based hydrogen storage alloy according to claim 1, wherein the lanthanum yttrium-nickel based hydrogen storage alloy is free of alkali metals and alkaline earth metals.
5. The lanthanum yttrium-nickel based hydrogen occluding alloy according to claim 1, wherein the lanthanum yttrium-nickel based hydrogen occluding alloy is composed of only the element represented by formula (I), except for unavoidable impurities.
6. The lanthanum yttrium-nickel based hydrogen storage alloy according to claim 1, wherein the lanthanum yttrium-nickel based hydrogen storage alloy comprises Ce 2 Ni 7 Phase, ce 5 Co 19 Phase and LaNi 5 Phase, and Ce 2 Ni 7 The content of the phase is more than or equal to 75 weight percent.
7. The lanthanum yttrium nickel based hydrogen storage alloy according to claim 6, wherein Ce 2 Ni 7 The space group of the phases is P63/mmc, and the average length of the a axis of the unit cell is Average length of c-axis of
8. A lanthanum yttrium nickel based hydrogen storage alloy according to any one of claims 1 to 7, wherein the lanthanum yttrium nickel based hydrogen storage alloy has a composition as shown in one of:
(1)La 0.2 Ce 1.8 Y 4 Ni 20.2 Mn 0.8 ；
(2)La 0.5 Ce 1.5 Y 4 Ni 20.2 Mn 0.8 ；
(3)La 0.8 Ce 1.2 Y 4 Ni 20.2 Mn 0.8 ；
(4)La 1.1 Ce 0.9 Y 4 Ni 20.2 Mn 0.8 ；
(5)La 1.4 Ce 0.6 Y 4 Ni 20.2 Mn 0.8 ；
(6)La 1.7 Ce 0.3 Y 4 Ni 20.2 Mn 0.8 ；
(7)La 1.1 Ce 0.9 Y 4 Ni 20.4 Mn 0.6 ；
(8)La 1.1 Ce 0.9 Y 4 Ni 20.6 Mn 0.4 。
9. the method for producing a lanthanum yttrium nickel based hydrogen storage alloy according to any one of claims 1 to 8, comprising the steps of:
smelting raw materials provided according to the composition of the lanthanum yttrium nickel hydrogen storage alloy in an inert atmosphere, and then rapidly quenching the raw materials into alloy sheets; annealing the alloy sheet, and then crushing to obtain the cerium-containing lanthanum yttrium nickel hydrogen storage alloy.
10. The application of cerium in improving the hydrogen discharge platform pressure of the lanthanum yttrium nickel hydrogen storage alloy is characterized in that the lanthanum yttrium nickel hydrogen storage alloy comprises 0.1-2 mol parts of La, 3.5-4.5 mol parts of Y, 20-20.9 mol parts of Ni and 0.1-1 mol part of Mn, and the Ce in the lanthanum yttrium nickel hydrogen storage alloy is used in an amount of 0.1-2 mol parts.
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