CN116065055A - Yttrium-nickel hydrogen storage alloy and preparation method thereof - Google Patents
Yttrium-nickel hydrogen storage alloy and preparation method thereof Download PDFInfo
- Publication number
- CN116065055A CN116065055A CN202310167052.7A CN202310167052A CN116065055A CN 116065055 A CN116065055 A CN 116065055A CN 202310167052 A CN202310167052 A CN 202310167052A CN 116065055 A CN116065055 A CN 116065055A
- Authority
- CN
- China
- Prior art keywords
- equal
- yttrium
- nickel
- hydrogen storage
- storage alloy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 91
- 239000000956 alloy Substances 0.000 title claims abstract description 91
- 239000001257 hydrogen Substances 0.000 title claims abstract description 77
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 77
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 238000003860 storage Methods 0.000 title claims abstract description 73
- IKBUJAGPKSFLPB-UHFFFAOYSA-N nickel yttrium Chemical compound [Ni].[Y] IKBUJAGPKSFLPB-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title abstract description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 9
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 5
- 229910000878 H alloy Inorganic materials 0.000 claims abstract 2
- 238000010438 heat treatment Methods 0.000 claims description 44
- 239000011261 inert gas Substances 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 13
- 239000012798 spherical particle Substances 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 238000007670 refining Methods 0.000 claims description 7
- 230000009471 action Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 20
- 239000011572 manganese Substances 0.000 description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 6
- 238000003723 Smelting Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000010949 copper Substances 0.000 description 4
- 239000001307 helium Substances 0.000 description 4
- 229910052734 helium Inorganic materials 0.000 description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 229910052743 krypton Inorganic materials 0.000 description 4
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 4
- 229910052754 neon Inorganic materials 0.000 description 4
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 238000000889 atomisation Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- 229910004247 CaCu Inorganic materials 0.000 description 1
- KXLUWEYBZBGJRZ-POEOZHCLSA-N Canin Chemical compound O([C@H]12)[C@]1([C@](CC[C@H]1C(=C)C(=O)O[C@@H]11)(C)O)[C@@H]1[C@@]1(C)[C@@H]2O1 KXLUWEYBZBGJRZ-POEOZHCLSA-N 0.000 description 1
- GPFVKTQSZOQXLY-UHFFFAOYSA-N Chrysartemin A Natural products CC1(O)C2OC2C34OC3(C)CC5C(CC14)OC(=O)C5=C GPFVKTQSZOQXLY-UHFFFAOYSA-N 0.000 description 1
- 102100034013 Gamma-glutamyl phosphate reductase Human genes 0.000 description 1
- 229910020791 La—Mg—Ni Inorganic materials 0.000 description 1
- 229910001122 Mischmetal Inorganic materials 0.000 description 1
- 229910018007 MmNi Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910003286 Ni-Mn Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 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
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/065—Spherical particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/142—Thermal or thermo-mechanical treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
- B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
-
- 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
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Thermal Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Mechanical Engineering (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Metallurgy (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention discloses an yttrium-nickel hydrogen storage alloy and a preparation method thereof. The yttrium-nickel hydrogen storage alloy has the composition shown in a formula (I): RE (RE) x Y y Ni e Mn a Fe b Si c M d (I) The method comprises the steps of carrying out a first treatment on the surface of the Wherein RE is selected from one or more of La, ce, pr, nd, sm and Gd, and M is selected from one or more of Al, co, cu, zn, B; wherein x is more than or equal to 0.3 and less than or equal to 0.9, x+y= 2,0.05 and less than or equal to a and less than or equal to 0.5, b is more than or equal to 0.1 and less than or equal to 0.6,0.005 and less than or equal to c is more than or equal to 0.3,0.005 and less than or equal to d is more than or equal to 0.3,6.9 and less than or equal to a+b+c+d+e is more than or equal to 7.1; x, y, a, b, c, d and e represent the mole parts of each element respectively; the yttrium-nickel series storageA in hydrogen alloy 2 B 7 The abundance of the phase is more than or equal to 95 percent. A in the yttrium-nickel hydrogen storage alloy 2 B 7 The abundance of the phase is higher.
Description
Technical Field
The invention relates to an yttrium-nickel hydrogen storage alloy and a preparation method thereof.
Background
The La-Mg-Ni based hydrogen storage alloy has a superlattice structure, which can be applied to a self-discharge battery. However, the alloy has magnesium element with low melting point and easy volatilization, the composition is difficult to control by adopting a vacuum induction smelting preparation method, and fine magnesium powder volatilized in the preparation process is easy to burn and explode, so that potential safety hazards exist.
CN1148629A discloses a spherical hydrogen-storing alloy powder, which comprises MmNi u A x B y C z D w The method comprises the steps of carrying out a first treatment on the surface of the Wherein Mm is mischmetal, a=mn, sn, V; b= Cr, co, ti, nb, zr, zn, si; c=al, mg, ca; d=li, na, K; u is more than or equal to 1 and less than or equal to 5, x is more than or equal to 0 and less than or equal to 0.95, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 0.7,0, w is more than or equal to 0.9,4.4 and less than or equal to u+x+y+z+w is more than or equal to 5.6. The spherical hydrogen storage alloy powder is not A 2 B 7 Hydrogen storage alloy.
CN115141943a discloses a Ti-Fe-Ni-Mn based hydrogen storage alloy consisting of titanium, iron, nickel, manganese and rare earth elements. The chemical formula comprises the following components: ti (Ti) 1.1 Fe 0.8-x Ni x Mn 0.2 +y wt.% RE. x is an atomic ratio, x is more than or equal to 0 and less than or equal to 0.2, y is a mass percent, and y is more than 0 and less than or equal to 0.8%; RE is one of rare earth elements lanthanum, cerium, praseodymium, neodymium, samarium, yttrium and gadolinium. The hydrogen storage alloy is not A 2 B 7 Hydrogen storage alloy.
Disclosure of Invention
Accordingly, an object of the present invention is to provide an yttrium-nickel-based hydrogen storage alloy in which A 2 B 7 The abundance of the phase is higher. Further, the yttrium-nickel-based hydrogen storage alloy has a spherical or spheroidal microstructure. Furthermore, the yttrium-nickel hydrogen storage alloy has higher electrochemical capacity and capacity retention rate. Another object of the present invention is to provide a method for producing an yttrium-nickel-based hydrogen storage alloy, which is capable of improving A in the yttrium-nickel-based hydrogen storage alloy 2 B 7 Abundance of the phases.
The technical aim is achieved through the following technical scheme.
In one aspect, the present invention provides an yttrium-nickel-based hydrogen storage alloy having a composition represented by formula (I):
RE x Y y Ni e Mn a Fe b Si c M d (I)；
wherein RE is selected from one or more of La, ce, pr, nd, sm and Gd, and M is selected from one or more of Al, co, cu, zn, B;
wherein x is more than or equal to 0.3 and less than or equal to 0.9, x+y= 2,0.05 and less than or equal to a and less than or equal to 0.5, b is more than or equal to 0.1 and less than or equal to 0.6,0.005 and less than or equal to c is more than or equal to 0.3,0.005 and less than or equal to d is more than or equal to 0.3,6.9 and less than or equal to a+b+c+d+e is more than or equal to 7.1; x, y, a, b, c, d and e represent the mole parts of each element respectively;
a in the yttrium-nickel hydrogen storage alloy 2 B 7 The abundance of the phase is more than or equal to 95 percent.
Preferably, the yttrium-nickel-based hydrogen storage alloy according to the present invention is a in the yttrium-nickel-based hydrogen storage alloy 2 B 7 The abundance of the phase is more than or equal to 99 percent.
Preferably, the yttrium-nickel-based hydrogen storage alloy according to the present invention has a single a therein 2 B 7 And (3) phase (C).
According to the yttrium-nickel-based hydrogen storage alloy of the present invention, preferably, the yttrium-nickel-based hydrogen storage alloy is in a powder form, and has a spherical or spheroidal microstructure.
According to the yttrium-nickel-based hydrogen storage alloy of the present invention, preferably, the yttrium-nickel-based hydrogen storage alloy does not contain an alkali metal element and/or an alkaline earth metal element.
The yttrium-nickel-based hydrogen storage alloy according to the present invention preferably has y.ltoreq. 1.7,6.ltoreq.e.ltoreq.6.9.
The yttrium-nickel based hydrogen storage alloy according to the present invention preferably must contain La.
According to the yttrium-nickel-based hydrogen storage alloy of the present invention, preferably, the yttrium-nickel-based hydrogen storage alloy has a composition as shown in one of the following:
(1)La 0.5 Y 1.5 Ni 6.55 Mn 0.1 Fe 0.2 Si 0.05 Al 0.05 ；
(2)La 0.5 Ce 0.1 Y 1.4 Ni 6.53 Mn 0.2 Fe 0.2 Si 0.02 Al 0.05 ；
(3)La 0.6 Y 1.4 Ni 6.2 Mn 0.3 Fe 0.3 Si 0.1 Co 0.1 ；
(4)La 0.4 Pr 0.2 Y 1.4 Ni 6.25 Mn 0.3 Fe 0.4 Si 0.05 Cu 0.05 ；
(5)La 0.5 Nd 0.2 Y 1.3 Ni 6.25 Mn 0.25 Fe 0.45 Si 0.1 Zn 0.05 ；
(6)La 0.5 Sm 0.1 Y 1.4 Ni 6.33 Mn 0.2 Fe 0.45 Si 0.05 B 0.02 。
on the other hand, the invention provides a preparation method of the yttrium-nickel hydrogen storage alloy, which comprises the following steps:
(1) Melting raw materials obtained according to the composition of the yttrium-nickel-based hydrogen storage alloy, and refining to obtain molten liquid;
(2) Placing the molten liquid in a container with a nozzle, enabling the molten liquid to pass through the nozzle, simultaneously introducing inert gas into the nozzle, and forming spherical particles by the molten liquid flowing down from the nozzle under the action of the gas flow of the inert gas; cooling the spherical particles to obtain alloy powder;
(3) And (3) carrying out heat treatment on the alloy powder under the conditions that the pressure is less than or equal to 0.1Pa and the temperature is 750-950 ℃, and then forcibly cooling to 20-35 ℃ to obtain the yttrium-nickel hydrogen storage alloy.
According to the production method of the present invention, preferably, the pressure of the inert gas introduced into the nozzle is 1 to 10MPa.
A in the yttrium-nickel hydrogen storage alloy of the invention 2 B 7 The abundance of the phase is high, with a spherical or spheroidal microstructure. The yttrium-nickel hydrogen storage alloy has higher electrochemical capacity and capacity retention rate.
Drawings
FIG. 1 is a scanning electron microscope image of the yttrium-nickel hydrogen storage alloy obtained in example 2.
FIG. 2 is a scanning electron microscope image of the yttrium-nickel-based hydrogen storage alloy obtained in comparative example 1.
FIG. 3 is an XRD pattern of the yttrium-nickel hydrogen storage alloy obtained in example 2.
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.
< yttrium-nickel-based Hydrogen storage alloy >
The yttrium-nickel hydrogen storage alloy has the composition shown in a formula (I):
RE x Y y Ni e Mn a Fe b Si c M d (I)
the yttrium-nickel hydrogen storage alloy has higher A 2 B 7 Phase abundance. A is that 2 B 7 The abundance of the phase may be 95% or more; preferably, A 2 B 7 The abundance of the phase is greater than or equal to 99%; more preferably, the yttrium-nickel based hydrogen storage alloy has a single A 2 B 7 And (3) phase (C). This is advantageous in improving the electrochemical capacity and the electrochemical capacity of the hydrogen storage alloyCapacity retention rate.
The yttrium-nickel based hydrogen storage alloy of the present invention may be in the form of powder, which is spherical or spheroidal powder. The yttrium-nickel hydrogen storage alloy has a spherical or spheroid-like microcosmic appearance. This is advantageous in improving A 2 B 7 Abundance of phases, and electrochemical capacity and capacity retention.
RE is selected from one or more of La, ce, pr, nd, sm and Gd. Preferably, RE must contain La. In certain embodiments, RE is La. In other embodiments, RE consists of La and Mm; wherein Mm is selected from one or more of Ce, pr, nd, sm and Gd. The mole ratio of La to Mm can be 5 (0.5-3); preferably 5 (1-2.5); more preferably 5 (1.5-2).
x represents the mole fraction of RE. X is more than or equal to 0.3 and less than or equal to 0.9; preferably, 0.5.ltoreq.x.ltoreq.0.7; more preferably, 0.6.ltoreq.x.ltoreq.0.65.
Y represents yttrium element. Y represents the molar fraction of Y. x+y=2. Y is more than or equal to 1.1 and less than or equal to 1.7; preferably, y is 1.2.ltoreq.y.ltoreq.1.5; more preferably, 1.3.ltoreq.y.ltoreq.1.4.
Mn represents a manganese element. a represents the mole fraction of Mn. A is more than or equal to 0.05 and less than or equal to 0.5; preferably, a is more than or equal to 0.1 and less than or equal to 0.4; more preferably, 0.2.ltoreq.a.ltoreq.0.3.
Fe represents iron element. b represents the mole fraction of Fe. B is more than or equal to 0.1 and less than or equal to 0.6; preferably, b is more than or equal to 0.2 and less than or equal to 0.5; more preferably, 0.3.ltoreq.b.ltoreq.0.4.
Si represents a silicon element. c represents the mole fraction of Si. C is more than or equal to 0.005 and less than or equal to 0.3; preferably, c is more than or equal to 0.01 and less than or equal to 0.15; more preferably, 0.05.ltoreq.c.ltoreq.0.1.
M is selected from one or more of Al, co, cu, zn, B. In certain embodiments, M is Zn. In other embodiments, M is Co. d represents the molar fraction of M. D is more than or equal to 0.005 and less than or equal to 0.3; preferably, d is more than or equal to 0.01 and less than or equal to 0.2; more preferably, 0.05.ltoreq.d.ltoreq.0.1.
Ni represents a nickel element. e represents the mole fraction of Ni. 6.9.ltoreq.a+b+c+d+e.ltoreq.7.1; preferably, 6.95.ltoreq.a+b+c+d+e.ltoreq.7.05. E is more than or equal to 6 and less than or equal to 6.9; preferably, e is 6.2.ltoreq.e.ltoreq.6.6; more preferably, 6.3.ltoreq.e.ltoreq.6.5.
In certain embodiments, the yttrium nickel based hydrogen storage alloy has a composition as shown in one of the following:
(1)La 0.5 Y 1.5 Ni 6.55 Mn 0.1 Fe 0.2 Si 0.05 Al 0.05 ；
(2)La 0.5 Ce 0.1 Y 1.4 Ni 6.53 Mn 0.2 Fe 0.2 Si 0.02 Al 0.05 ；
(3)La 0.6 Y 1.4 Ni 6.2 Mn 0.3 Fe 0.3 Si 0.1 Co 0.1 ；
(4)La 0.4 Pr 0.2 Y 1.4 Ni 6.25 Mn 0.3 Fe 0.4 Si 0.05 Cu 0.05 ；
(5)La 0.5 Nd 0.2 Y 1.3 Ni 6.25 Mn 0.25 Fe 0.45 Si 0.1 Zn 0.05 ；
(6)La 0.5 Sm 0.1 Y 1.4 Ni 6.33 Mn 0.2 Fe 0.45 Si 0.05 B 0.02 。
the A can be improved by controlling the element composition and the element content of the yttrium-nickel hydrogen storage alloy within the above ranges 2 B 7 The phase abundance can also improve electrochemical capacity and capacity retention.
< method for producing yttrium-nickel-based Hydrogen storage alloy >
The preparation method of the yttrium-nickel hydrogen storage alloy comprises the following steps: (1) a melting and refining step; (2) an atomization molding step; (3) a post-treatment step.
Melting and refining step
The raw material formed according to the composition of the yttrium-nickel-based hydrogen storage alloy is melted and then refined to obtain a molten liquid.
The raw materials may be melted by heating. The heat source may be provided by a heating coil. The power of the heating coil can be 5-20 kW; preferably 10-18 kW; more preferably 12 to 15kW.
The raw materials may be melted in an inert gas atmosphere. Examples of inert gases include, but are not limited to, nitrogen, helium, neon, argon, krypton, xenon.
The raw materials can be heated and melted under the pressure of 0.02-0.08 MPa; preferably, the raw materials are heated and melted under the pressure of 0.03-0.06 MPa; more preferably, the raw materials are melted by heating under a pressure of 0.04 to 0.05 MPa.
The following steps may also be performed prior to melting the feedstock: the raw material obtained according to the composition of the hydrogen storage alloy is pressed at the pressure P 1 And the heating coil has a power W 1 Heating t under the condition of (2) 4 For that time, the power of the heating coil was then adjusted to 0kW. Vacuumizing the reaction system to the pressure P 2 The method comprises the steps of carrying out a first treatment on the surface of the Then, inert gas is filled into the reaction system, thereby forming the melting atmosphere and the pressure.
P 1 Less than or equal to 15Pa; preferably, P 1 Less than or equal to 10Pa; more preferably, P 1 ≤5Pa。
W 1 Can be 2-12 kW; preferably 3-10 kW; more preferably 4 to 7kW. t is t 4 Can be 1 to 10 minutes; preferably 2 to 7 minutes; more preferably 3 to 4 minutes.
P 2 Less than or equal to 15Pa; preferably, P 2 Less than or equal to 10Pa; more preferably, P 2 ≤4Pa。
The power of the heating coil during refining can be 5-15 kW; preferably 7-12 kW; more preferably 8 to 10kW.
The refining time can be 2-15 min; preferably 4 to 10 minutes; more preferably 5 to 7 minutes.
Atomization molding step
Placing the molten liquid in a container with a nozzle, enabling the molten liquid to pass through the nozzle, simultaneously introducing inert gas into the nozzle, and forming spherical particles by the molten liquid flowing down from the nozzle under the action of inert gas flow; and cooling the spherical particles to obtain the alloy powder.
Examples of inert gases include, but are not limited to, nitrogen, helium, neon, argon, krypton, xenon. The pressure of the inert gas can be 1-10 MPa; preferably 3-8 MPa; more preferably 4 to 7MPa. This helps to increase A 2 B 7 Phase enlargementDegree.
The molten liquid may be heated before passing through the nozzle. The power of the heating coil during heating can be 3-20 kW; preferably 5-15 kW; more preferably 10 to 12kW. The heating time can be 1-10 min; preferably 3 to 8 minutes; more preferably 3 to 5 minutes.
The spherical particles may be cooled in a cooling tower.
Post-treatment step
And (3) carrying out heat treatment on the alloy powder under the conditions that the pressure is less than or equal to 0.1Pa and the temperature is 750-950 ℃, and then forcibly cooling to 20-35 ℃ to obtain the yttrium-nickel hydrogen storage alloy. The heat treatment may be performed in a heat treatment furnace.
The heat treatment pressure is less than or equal to 0.1Pa; preferably, 0.05Pa or less; more preferably, 0.03Pa or less. This helps to increase A 2 B 7 Abundance of the phases.
The heat treatment temperature is 750-950 ℃; preferably 850-950 ℃; more preferably 870 to 930 ℃. This helps to increase A 2 B 7 Abundance of the phases.
The heating rate from the initial temperature to the heat treatment temperature may be 5-20 ℃/min; preferably 8-15 ℃/min; more preferably 10 to 12 ℃/min.
The heat treatment time can be 5-19 h; preferably 10 to 18 hours; more preferably 14 to 17 hours. This helps to increase A 2 B 7 Abundance of the phases.
The pressure conditions for the heat treatment may be formed as follows: vacuumizing the reaction system to P 5 The method comprises the steps of carrying out a first treatment on the surface of the Then inert gas is introduced to make the pressure of the reaction system be P 7 The method comprises the steps of carrying out a first treatment on the surface of the And vacuumizing the reaction system to the heat treatment pressure.
P 5 Less than or equal to 0.1Pa; preferably, 0.05Pa or less; more preferably, 0.03Pa or less.
Examples of inert gases include, but are not limited to, nitrogen, helium, neon, argon, krypton, xenon. P (P) 7 Can be 0.03-0.1 MPa; preferably 0.05 to 0.09MPa; more preferably 0.07 to 0.08MPa.
The forced cooling mode canIn order to carry out forced air cooling under the protection of inert gas. This helps to increase A 2 B 7 Abundance of the phases. Examples of inert gases include, but are not limited to, nitrogen, helium, neon, argon, krypton, xenon.
The forced cooling time can be 2-10 h; preferably 4 to 8 hours; more preferably 4 to 6 hours. The test method is described as follows:
electrochemical capacity:
on an automatic charge-discharge tester, setting the specific capacity test parameters of activation and discharge as follows: standing for 24 hours; charging current density is 75mA/g, and charging time is 6h; the shelf time is 10min after charging; the discharge current density is 75mA/g, and the discharge current is discharged to the cutoff potential relative to the Hg/HgO reference electrode of-600 mV; the shelf time is 10min after discharging; the cycle test period was 10. Taking the maximum value of the discharge specific capacity as the electrochemical capacity.
Capacity retention rate for 300 charge and discharge cycles:
after the hydrogen storage alloy electrode is activated, an automatic charge-discharge tester is used for testing, the charge-discharge current density (IA) is set to 300mA/g, the charge time is 1.2h, the rest time after the charge is 10min, the rest time after the discharge is 10min, and the cut-off potential relative to the Hg/HgO reference electrode is 600mV. And carrying out cycle test for 300 times under the parameter condition, wherein the ratio of the 300 th discharge capacity to the maximum discharge capacity in the cycle process is the 300-time capacity retention rate of the charge-discharge cycle.
A 2 B 7 Phase and CaCu 5 Phase abundance:
samples were tested using an X-ray diffractometer and phase structure and phase abundance were analyzed and fit calculated by jade, fullprof and GSAS software.
Scanning electron microscope:
and uniformly scattering alloy powder on a test bench adhered with conductive adhesive, then blowing off unsticky powder by using an ear washing ball, and observing the microscopic morphology of the sample after vacuumizing.
The inert gas in the following examples and comparative examples was argon.
The forced cooling adopts a mode of forced air cooling under the protection of argon.
Examples 1 to 6
The raw material obtained according to the composition of the hydrogen storage alloy is pressed at the pressure P 1 And the heating coil has a power W 1 Heating t under the condition of (2) 4 For that time, the power of the heating coil was then adjusted to 0kW. Vacuumizing the reaction system to the pressure P 2 The method comprises the steps of carrying out a first treatment on the surface of the Then inert gas is filled into the reaction system to lead the pressure of the reaction system to be P 3 . The power of the heating coil is adjusted to W 2 Completely melting the raw materials; then the power of the heating coil is adjusted to W 3 Refining t 1 For a while, a molten liquid was obtained.
The molten liquid is placed in a tundish with a nozzle. Adjusting the power of the heating coil of the tundish to W 4 Heating t 2 After a while, the molten liquid is passed through the nozzle while the nozzle is fed with a pressure P 4 The molten liquid flowing down at the nozzle under the action of the inert gas flow forms spherical particles. And cooling the spherical particles in a cooling tower to obtain the alloy powder.
The alloy powder is placed in a heat treatment furnace. Vacuumizing the heat treatment furnace to P 5 The method comprises the steps of carrying out a first treatment on the surface of the Then inert gas is introduced to enable the pressure in the heat treatment furnace to be 0.08MPa; vacuumizing the heat treatment furnace to P 6 . Heating the temperature of the heat treatment furnace from room temperature to T, and preserving heat at the T temperature 3 Time; then cooling to 25 ℃ forcedly to obtain the yttrium-nickel hydrogen storage alloy.
The composition and properties of the hydrogen occluding alloy are shown in Table 2. The specific parameters in the preparation process are shown in table 1.
TABLE 1
Comparative example 1
The raw materials obtained according to the composition of the hydrogen storage alloy are placed in a smelting furnace. Vacuumizing the smelting furnace to below 5Pa; then inert gas is filled into the smelting furnace to enable the pressure in the smelting furnace to be 0.045MPa. The power of the heating coil is adjusted to 15kW, so that the raw materials are completely melted; then, the power of the heating coil was adjusted to 10kW and refined for 4 minutes to obtain a molten liquid.
The molten liquid was cooled by a rotating copper roll through which cooling water was passed to obtain an alloy sheet. The linear speed of the rotating copper roller is 3-5 m/s.
The alloy sheet was placed in a heat treatment furnace. Vacuumizing the heat treatment furnace to below 0.2 Pa; then inert gas is introduced to make the pressure in the heat treatment furnace be 0.055MPa. Heating the heat treatment furnace from room temperature to 960 ℃ at a heating rate of 10 ℃/min, and preserving heat for 20h at 960 ℃; and then cooling to 25 ℃ along with the furnace to obtain the heat-treated alloy sheet. And pulverizing the heat-treated alloy sheet by adopting a mechanical crushing mode to obtain the hydrogen storage alloy.
The composition of the hydrogen occluding alloy is specifically shown in table 2. The properties of the hydrogen occluding alloy are shown in table 2.
TABLE 2
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 yttrium-nickel-based hydrogen storage alloy characterized in that the yttrium-nickel-based hydrogen storage alloy has a composition represented by formula (I):
RE x Y y Ni e Mn a Fe b Si c M d (I)；
wherein RE is selected from one or more of La, ce, pr, nd, sm and Gd, and M is selected from one or more of Al, co, cu, zn, B;
wherein x is more than or equal to 0.3 and less than or equal to 0.9, x+y= 2,0.05 and less than or equal to a and less than or equal to 0.5, b is more than or equal to 0.1 and less than or equal to 0.6,0.005 and less than or equal to c is more than or equal to 0.3,0.005 and less than or equal to d is more than or equal to 0.3,6.9 and less than or equal to a+b+c+d+e is more than or equal to 7.1; x, y, a, b, c, d and e represent the mole parts of each element respectively;
the yttrium-nickel series storageA in hydrogen alloy 2 B 7 The abundance of the phase is more than or equal to 95 percent.
2. The yttrium-nickel-based hydrogen storage alloy according to claim 1, wherein a in the yttrium-nickel-based hydrogen storage alloy 2 B 7 The abundance of the phase is more than or equal to 99 percent.
3. The yttrium-nickel-based hydrogen storage alloy according to claim 1, wherein said yttrium-nickel-based hydrogen storage alloy has a single a therein 2 B 7 And (3) phase (C).
4. The yttrium-nickel-based hydrogen storage alloy according to claim 1, wherein the yttrium-nickel-based hydrogen storage alloy is in the form of powder having a spherical or spheroidal microstructure.
5. The yttrium-nickel-based hydrogen storage alloy according to claim 1, wherein the yttrium-nickel-based hydrogen storage alloy does not contain an alkali metal element and/or an alkaline earth metal element.
6. The yttrium-nickel-based hydrogen occluding alloy according to claim 1, wherein y is 1.1.ltoreq. 1.7,6.ltoreq.e.ltoreq.6.9.
7. The yttrium-nickel based hydrogen storage alloy according to claim 1, wherein said RE must contain La.
8. The yttrium-nickel-based hydrogen storage alloy according to any one of claims 1 to 6, wherein the yttrium-nickel-based hydrogen storage alloy has a composition as shown in one of the following:
(1)La 0.5 Y 1.5 Ni 6.55 Mn 0.1 Fe 0.2 Si 0.05 Al 0.05 ；
(2)La 0.5 Ce 0.1 Y 1.4 Ni 6.53 Mn 0.2 Fe 0.2 Si 0.02 Al 0.05 ；
(3)La 0.6 Y 1.4 Ni 6.2 Mn 0.3 Fe 0.3 Si 0.1 Co 0.1 ；
(4)La 0.4 Pr 0.2 Y 1.4 Ni 6.25 Mn 0.3 Fe 0.4 Si 0.05 Cu 0.05 ；
(5)La 0.5 Nd 0.2 Y 1.3 Ni 6.25 Mn 0.25 Fe 0.45 Si 0.1 Zn 0.05 ；
(6)La 0.5 Sm 0.1 Y 1.4 Ni 6.33 Mn 0.2 Fe 0.45 Si 0.05 B 0.02 。
9. the method for producing an yttrium-nickel-based hydrogen storage alloy according to any one of claims 1 to 8, comprising the steps of:
(1) Melting raw materials obtained according to the composition of the yttrium-nickel-based hydrogen storage alloy, and refining to obtain molten liquid;
(2) Placing the molten liquid in a container with a nozzle, enabling the molten liquid to pass through the nozzle, simultaneously introducing inert gas into the nozzle, and forming spherical particles by the molten liquid flowing down from the nozzle under the action of the gas flow of the inert gas; cooling the spherical particles to obtain alloy powder;
(3) And (3) carrying out heat treatment on the alloy powder under the conditions that the pressure is less than or equal to 0.1Pa and the temperature is 750-950 ℃, and then forcibly cooling to 20-35 ℃ to obtain the yttrium-nickel hydrogen storage alloy.
10. The method according to claim 9, wherein the inert gas is introduced into the nozzle at a pressure of 1 to 10MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310167052.7A CN116065055A (en) | 2023-02-27 | 2023-02-27 | Yttrium-nickel hydrogen storage alloy and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310167052.7A CN116065055A (en) | 2023-02-27 | 2023-02-27 | Yttrium-nickel hydrogen storage alloy and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116065055A true CN116065055A (en) | 2023-05-05 |
Family
ID=86178536
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310167052.7A Pending CN116065055A (en) | 2023-02-27 | 2023-02-27 | Yttrium-nickel hydrogen storage alloy and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116065055A (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08180861A (en) * | 1994-12-26 | 1996-07-12 | Toshiba Corp | Hydrogen storage alloy for battery, its manufacture and nickel-hydrogen secondary battery |
| JPH0925529A (en) * | 1995-07-10 | 1997-01-28 | Santoku Kinzoku Kogyo Kk | Rare earth metal-nickel based hydrogen storage alloy and its production, and cathode for nickel-hydrogen secondary battery |
| JPH1060565A (en) * | 1996-08-20 | 1998-03-03 | Toshiba Corp | Hydrogen storage alloy and nickel-hydrogen secondary battery |
| JPH11350056A (en) * | 1998-06-10 | 1999-12-21 | Shin Etsu Chem Co Ltd | Hydrogen storage sintered body and cathode for alkaline battery |
| CN1591937A (en) * | 2004-05-28 | 2005-03-09 | 中国科学院上海微系统与信息技术研究所 | Metal negative electrode material for nickel-hydrogen battery and preparing process |
| JP2008300108A (en) * | 2007-05-30 | 2008-12-11 | Sanyo Electric Co Ltd | Hydrogen absorbing alloy for alkaline storage battery, manufacturing method thereof, and alkaline storage battery |
| US20170288217A1 (en) * | 2014-08-28 | 2017-10-05 | Baotou Research Institute of Rare Earths | Rare Earth Based Hydrogen Storage Alloy and Application Thereof |
| CN111118341A (en) * | 2019-09-16 | 2020-05-08 | 包头稀土研究院 | Rare earth-samarium-nickel type hydrogen storage alloy, negative electrode, battery and preparation method |
| CN111118342A (en) * | 2019-09-16 | 2020-05-08 | 包头稀土研究院 | A2B7 type RE-Sm-Ni series hydrogen storage alloy, negative electrode, battery and preparation method |
| CN111471895A (en) * | 2020-04-14 | 2020-07-31 | 包头稀土研究院 | Hydrogen storage alloy containing gadolinium and nickel, cathode, battery and preparation method |
| CN114955988A (en) * | 2022-05-30 | 2022-08-30 | 赣州有色冶金研究所有限公司 | Rare earth yttrium-nickel hydrogen storage alloy and preparation method and application thereof |
-
2023
- 2023-02-27 CN CN202310167052.7A patent/CN116065055A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08180861A (en) * | 1994-12-26 | 1996-07-12 | Toshiba Corp | Hydrogen storage alloy for battery, its manufacture and nickel-hydrogen secondary battery |
| JPH0925529A (en) * | 1995-07-10 | 1997-01-28 | Santoku Kinzoku Kogyo Kk | Rare earth metal-nickel based hydrogen storage alloy and its production, and cathode for nickel-hydrogen secondary battery |
| JPH1060565A (en) * | 1996-08-20 | 1998-03-03 | Toshiba Corp | Hydrogen storage alloy and nickel-hydrogen secondary battery |
| JPH11350056A (en) * | 1998-06-10 | 1999-12-21 | Shin Etsu Chem Co Ltd | Hydrogen storage sintered body and cathode for alkaline battery |
| CN1591937A (en) * | 2004-05-28 | 2005-03-09 | 中国科学院上海微系统与信息技术研究所 | Metal negative electrode material for nickel-hydrogen battery and preparing process |
| JP2008300108A (en) * | 2007-05-30 | 2008-12-11 | Sanyo Electric Co Ltd | Hydrogen absorbing alloy for alkaline storage battery, manufacturing method thereof, and alkaline storage battery |
| US20170288217A1 (en) * | 2014-08-28 | 2017-10-05 | Baotou Research Institute of Rare Earths | Rare Earth Based Hydrogen Storage Alloy and Application Thereof |
| CN111118341A (en) * | 2019-09-16 | 2020-05-08 | 包头稀土研究院 | Rare earth-samarium-nickel type hydrogen storage alloy, negative electrode, battery and preparation method |
| CN111118342A (en) * | 2019-09-16 | 2020-05-08 | 包头稀土研究院 | A2B7 type RE-Sm-Ni series hydrogen storage alloy, negative electrode, battery and preparation method |
| CN111471895A (en) * | 2020-04-14 | 2020-07-31 | 包头稀土研究院 | Hydrogen storage alloy containing gadolinium and nickel, cathode, battery and preparation method |
| CN114955988A (en) * | 2022-05-30 | 2022-08-30 | 赣州有色冶金研究所有限公司 | Rare earth yttrium-nickel hydrogen storage alloy and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110317974B (en) | Yttrium-nickel rare earth hydrogen storage alloy | |
| CN104532095A (en) | Yttrium-nickel rare earth-based hydrogen storage alloy | |
| CN107799735A (en) | One kind uses for nickel-hydrogen battery AB5Type hydrogen storage alloy and preparation method thereof | |
| CN106702191B (en) | A kind of ferrotianium yttrium base hydrogen storage material and intermediate alloy and preparation method | |
| CN104513925A (en) | Yttrium-nickel rare earth family hydrogen storage alloy, and secondary battery containing hydrogen storage alloy | |
| Li et al. | Structural characterization and electrochemical hydrogen storage properties of Ti2− xZrxNi (x= 0, 0.1, 0.2) alloys prepared by mechanical alloying | |
| CN111471894B (en) | Doped A5B19 type samarium-containing hydrogen storage alloy, battery and preparation method | |
| CN108149073B (en) | La-Mg-Ni series hydrogen storage alloy for low-temperature nickel-metal hydride battery and preparation method thereof | |
| CN112387976A (en) | Easily-activated RE-Ti-Fe alloy for fuel cell and preparation method thereof | |
| CN110629091B (en) | High-capacity multi-phase hydrogen storage alloy for fuel cell and preparation method thereof | |
| CN104513916A (en) | Zirconium and titanium-doped A2B7 type rare earth-yttrium-nickel family hydrogen storage alloy | |
| WO2007023901A1 (en) | Hydrogen storing alloy, process for producing the same and secondary battery | |
| CN109868390B (en) | Rare earth-nickel base AB2Hydrogen storage alloy material and preparation method thereof | |
| CN107099724B (en) | The preparation method of nanometer titanium trifluoride catalysis Mg-RE-Ni-Al-Ti-Co base hydrogen-storing alloy | |
| EP0806803B1 (en) | Hydrogen occluding alloy, process for its preparation and electrode | |
| CN116065055A (en) | Yttrium-nickel hydrogen storage alloy and preparation method thereof | |
| CN105463256B (en) | A kind of Hydrogen storage alloy for nickel-metal hydride battery and preparation method thereof | |
| JP5773878B2 (en) | RE-Fe-B hydrogen storage alloy and use thereof | |
| CN111411262B (en) | A5B19 type gadolinium-containing hydrogen storage alloy, negative electrode and preparation method | |
| CN111471893B (en) | Doped A5B19Gadolinium-containing hydrogen storage alloy, electrode, battery and preparation method thereof | |
| CN111342346B (en) | Element with functions of absorbing and releasing hydrogen and adsorbing impurity gas and preparation method thereof | |
| JP2012153929A (en) | Method for producing hydrogen storage alloy composite | |
| CN107154481B (en) | Hydrogen storage electrode alloy for Ni-MH battery and preparation method thereof | |
| CN103938052A (en) | High-capacity hydrogen storage electrode alloy and preparation method thereof | |
| CN111471912A (en) | Doped AB3 type hydrogen storage alloy, negative electrode, battery and preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |