CN114672721B - Non-stoichiometric rare earth-iron-based hydrogen storage alloy and preparation method and application thereof - Google Patents

Non-stoichiometric rare earth-iron-based hydrogen storage alloy and preparation method and application thereof Download PDF

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CN114672721B
CN114672721B CN202210335364.XA CN202210335364A CN114672721B CN 114672721 B CN114672721 B CN 114672721B CN 202210335364 A CN202210335364 A CN 202210335364A CN 114672721 B CN114672721 B CN 114672721B
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张旭
闫慧忠
赵玉园
李金�
王利
李宝犬
熊玮
周淑娟
徐津
郑天仓
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Baotou Rare Earth Research Institute
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/04—Making ferrous alloys by melting
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/383—Hydrogen absorbing alloys

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Abstract

The invention discloses a non-stoichiometric rare earth-iron-based hydrogen storage alloy, a preparation method and application thereof. The chemical composition of the hydrogen storage alloy is Y x R y Fe 2.8 Wherein Y is yttrium element, and x represents the molar coefficient of the Y element; fe represents an iron element; r is selected from one or more of La, ce, gd, pr, nd, sm and Dy, y represents the mole coefficient of R element, 0.01<y is less than or equal to 0.3; x+y=1.0. The hydrogen storage alloy has higher multiple effective hydrogen absorption capacity.

Description

Non-stoichiometric rare earth-iron-based hydrogen storage alloy and preparation method and application thereof
Technical Field
The invention relates to a hydrogen storage alloy, in particular to a non-stoichiometric rare earth-iron-based hydrogen storage alloy, a preparation method and application thereof.
Background
The hydrogen energy is used as clean and pollution-free secondary energy and becomes one of the potential energy sources in the future. The hydrogen storage material can solve the problems of storage, transportation, safety and the like in the use process of hydrogen, and is one of key materials for hydrogen application.
Rare earth-nickel-based hydrogen storage alloys are currently commonly used hydrogen storage alloy materials, however, nickel in the rare earth-nickel-based hydrogen storage alloys is a main element, the cost is high, and in order to reduce the production cost, the rare earth-iron-based hydrogen storage alloys are increasingly receiving widespread attention. The rare earth-iron-based alloy has higher theoretical capacity, but the alloy has disproportionation reaction, and the alloy capacity is suddenly attenuated after multiple times of hydrogen absorption and desorption, and the effective hydrogen absorption capacity is low.
CN111471912a discloses doped AB 3 A hydrogen storage alloy having RE x Gd y Ni z Mn a Al b M c Zr d Ti e The composition of the representation; RE is selected from one or more of rare earth metal elements except Gd; m is selected from one or more of Cu, fe, co, sn, V, W, cr, zn, mo and Si; x, y, z, a, b, c, d and e represent the mole fractions of the respective elements, respectively; the hydrogen storage alloy does not contain metal element Mg; x is x>0，y>0.1，x+y＝3；3≥a+b>0，2≥c≥0，3≥d+e>0, and 9.5>z+a+b+c is not less than 7.8. The nickel element is still used in the hydrogen storage alloy.
CN101417786A discloses a La 15 Fe 77 B 8 The lanthanum in the alloy can be partially or completely replaced by other rare earth elements; the iron can be partially or completely replaced by transition metal elements such as nickel, manganese, aluminum, cobalt, copper and the like, and non-transition metal elements such as gallium, tin, lead and the like; the boron may be partially or wholly substituted with metallic elements nickel, manganese, aluminum, iron, cobalt, etc., and nonmetallic elements silicon, sulfur, carbon, phosphorus, etc.
CN108517470A discloses an yttrium-zirconium-iron hydrogen storage alloy with a chemical formula of Y 1-x Zr x Fe 2 Wherein x is more than or equal to 0.1 and less than or equal to 0.5.
CN108220739A discloses an yttrium-containing rare earth iron-based hydrogen storage alloy, the composition of which is Y 1-x M x Fe 3-y N y Wherein x is more than or equal to 0 and less than or equal to 0.5, y is more than or equal to 0 and less than or equal to 1.5, and M is one of La, ce, pr, nd, sm, gd, zr, ti, mgOr more than two kinds of N is one or more than two kinds of Ni, co, mn, ca.
CN107326243A discloses a Mn-Fe-Dy hydrogen storage alloy comprising (Mn 1-x Fe x ) 23 Dy 6 ，0≤x≤1.0。
The rare earth-iron-based hydrogen storage alloy has low effective hydrogen absorption capacity for many times, poor reversibility and poor cycle performance.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a non-stoichiometric rare earth-iron-based hydrogen storage alloy having a high effective hydrogen absorption capacity after a plurality of times of hydrogen absorption and desorption. Another object of the present invention is to provide a method for producing the above hydrogen storage alloy. It is a further object of the present invention to provide the use of the non-stoichiometric rare earth-iron-based hydrogen storage alloy described above. The invention adopts the following technical scheme to realize the aim.
In one aspect, the present invention provides a non-stoichiometric rare earth-iron-based hydrogen storage alloy having a chemical composition of Y x R y Fe 2.8 The method comprises the steps of carrying out a first treatment on the surface of the Wherein Y is yttrium element, and x represents the molar coefficient of the Y element; fe represents an iron element; r is selected from one or more of La, ce, gd, pr, nd, sm and Dy, y represents the mole coefficient of R element, 0.01<y≤0.3；x+y＝1.0。
According to the non-stoichiometric rare earth-iron-based hydrogen storage alloy of the present invention, preferably, the hydrogen storage alloy does not contain Ni element and Co element.
The non-stoichiometric rare earth-iron-based hydrogen storage alloy according to the present invention preferably has a y of 0.03< 0.3.
The non-stoichiometric rare earth-iron-based hydrogen storage alloy according to the invention preferably has a y of 0.05< 0.3.
According to the non-stoichiometric rare earth-iron-based hydrogen storage alloy of the present invention, preferably, R meets one of the following conditions:
(1) R is Ce, y is more than or equal to 0.1 and less than or equal to 0.2;
(2) R is Gd, y is more than or equal to 0.15 and less than or equal to 0.3;
(3) R is Sm, y is more than or equal to 0.1 and less than or equal to 0.25;
(4) R is a combination of Ce and Sm, y is more than or equal to 0.15 and less than or equal to 0.3, wherein Ce is 30-50 mol% of the total mole number of R;
(5) R is the combination of La and Nd, 0.05< y is less than or equal to 0.2, wherein La is 40-60 mol% of the total mole number of R.
The non-stoichiometric rare earth-iron-based hydrogen storage alloy according to the present invention preferably has a main phase of AB 3 AB of it 3 The abundance of the phase is greater than 70%.
The non-stoichiometric rare earth-iron-based hydrogen storage alloy according to the present invention preferably has a composition represented by one of the following formulas:
Y 0.85 Ce 0.15 Fe 2.8 ，
Y 0.75 Gd 0.25 Fe 2.8 ，
Y 0.8 Sm 0.2 Fe 2.8 ，
Y 0.75 Ce 0.1 Sm 0.15 Fe 2.8 ，
Y 0.9 La 0.05 Nd 0.05 Fe 2.8 。
in another aspect, the present invention also provides a method for preparing the non-stoichiometric rare earth-iron-based hydrogen storage alloy as described above, comprising the steps of:
1) According to chemical composition Y x R y Fe 2.8 Raw materials are prepared and placed in a smelting device for smelting, and a smelting product is obtained; cooling the smelting product to obtain a solid alloy;
2) Crushing the solid alloy, and then carrying out heat treatment for 15-95 h at 1020-1200 ℃ to obtain the non-stoichiometric rare earth-iron-based hydrogen storage alloy.
According to the preparation method of the present invention, preferably, the temperature of the heat treatment is 1025 to 1180 ℃, and the time of the heat treatment is 20 to 95 hours.
In yet another aspect, the invention also provides the use of a non-stoichiometric rare earth-iron-based hydrogen storage alloy as described above for a hydrogen fuel cell.
The non-stoichiometric rare earth-iron of the inventionThe base hydrogen storage alloy has higher effective hydrogen absorption capacity for multiple times (more than three times). By controlling the types and the proportions of the metal elements, AB can be ensured 3 The abundance of the phase is more than 70%, and the stability is good, so that the hydrogen storage alloy almost has no disproportionation reaction after absorbing and releasing hydrogen for many times, the capacity of absorbing hydrogen for many times is still higher, and the reversibility is better. The three-time effective hydrogen absorption capacity of the hydrogen storage alloy can reach 1.62 weight percent.
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.
In the present invention, the absolute vacuum represents the actual pressure in the container. The relative vacuum represents the difference between the pressure of the container and 1 normal atmospheric pressure. The inert gas includes nitrogen or argon, etc.
< Hydrogen absorbing alloy >
The chemical composition of the non-stoichiometric rare earth-iron-based hydrogen storage alloy of the invention is Y x R y Fe 2.8 。
The hydrogen storage alloy of the invention does not contain metal elements Ni and Co; preferably, ca is also absent. Of course, the presence of trace amounts of Ni, co and Ca impurities in the alloy is not precluded. The main phase structure of the hydrogen storage alloy is AB 3 And (3) phase (C). AB (AB) 3 The abundance ratio of the phase is 70% or more and 100% or less, preferably 72% or less and 100% or less, and more preferably 74% or less and 100% or less. According to one embodiment of the invention, the AB of the non-stoichiometric rare earth-iron-based hydrogen storage alloy of the invention 3 The abundance of the phase is 100%. According to another embodiment of the invention, AB of the non-stoichiometric rare earth-iron-based hydrogen storage alloy of the invention 3 The abundance of the phase was 74%.
According to one embodiment of the present invention, the hydrogen occluding alloy of the present invention does not add any additional components other than some unavoidable impurities.
In the present invention, Y is yttrium element. Fe represents an iron element, and subscript 2.8 represents a molar coefficient of the Fe element.
In the present invention, R is selected from one or more of La, ce, gd, pr, nd, sm and Dy elements. Preferably, R is selected from one or more of La, ce, gd, pr, nd and Sm elements. More preferably, R is selected from one or more of La, ce, gd, nd and Sm elements.
In the present invention, x represents the molar coefficient of Y. 0.65< x.ltoreq.0.98, preferably 0.7< x.ltoreq.0.95, more preferably 0.75.ltoreq.x.ltoreq.0.9, still more preferably 0.8.ltoreq.x.ltoreq.0.9.
In the present invention, y represents the molar coefficient of R. 0.01< y.ltoreq.0.3, preferably 0.03< y.ltoreq.0.3, more preferably 0.05< y.ltoreq.0.3, even more preferably 0.1.ltoreq.y.ltoreq.0.25.
In the present invention, x+y=1.0. Y and R are side A hydrogen absorption elements, and Fe is side B non-hydrogen absorption element. Thus, the stability of the phase structure of the hydrogen storage alloy is improved, so that the hydrogen storage alloy almost has no disproportionation reaction after the hydrogen is absorbed and released for many times, thereby improving the reversibility of the hydrogen storage alloy and improving the effective hydrogen absorption capacity after the hydrogen is absorbed and released for many times.
In certain embodiments, R is Ce, 0.1.ltoreq.y.ltoreq.0.2, preferably 0.15.ltoreq.y.ltoreq.0.2.
In other specific embodiments, R is Gd, 0.15.ltoreq.y.ltoreq.0.3, preferably 0.2.ltoreq.y.ltoreq.0.3.
In still other embodiments, R is Sm, 0.1.ltoreq.y.ltoreq.0.25, preferably 0.15.ltoreq.y.ltoreq.0.25.
In still other embodiments, R is a combination of Ce and Sm, 0.15.ltoreq.y.ltoreq.0.3, preferably 0.2.ltoreq.y.ltoreq.0.3, where Ce is 30 to 50 mole%, preferably 35 to 45 mole%, more preferably 38 to 42 mole% of the total moles of R.
In still other specific embodiments, R is a combination of La and Nd, 0.05< y.ltoreq.0.2, preferably 0.05< y.ltoreq.0.15, where La is 40 to 60mol%, preferably 45 to 55mol%, more preferably 47 to 50mol% of the total moles of R.
In certain further preferred embodiments, R is Gd, 0.23.ltoreq.y.ltoreq.0.27. In still further preferred embodiments, R is Sm, 0.18.ltoreq.y.ltoreq.0.22.
Specific examples of the non-stoichiometric rare earth-iron-based hydrogen storage alloys of the present invention include, but are not limited to, alloys represented by one of the following formulas:
Y 0.85 Ce 0.15 Fe 2.8 ，
Y 0.75 Gd 0.25 Fe 2.8 ，
Y 0.8 Sm 0.2 Fe 2.8 ，
Y 0.75 Ce 0.1 Sm 0.15 Fe 2.8 ，
Y 0.9 La 0.05 Nd 0.05 Fe 2.8 。
the non-stoichiometric rare earth-iron-based hydrogen storage alloy of the present invention has a triple effective hydrogen absorption capacity (hydrogen storage amount) of greater than 1.2wt%, preferably greater than 1.3wt%, more preferably greater than 1.4wt%, still more preferably greater than 1.5wt%, and still more preferably greater than 1.6wt% at 313K.
In certain specific embodiments, the non-stoichiometric rare earth-iron-based hydrogen storage alloys of the present invention have a triple effective hydrogen absorption capacity of 1.41wt% at 313K.
In other specific embodiments, the non-stoichiometric rare earth-iron-based hydrogen storage alloys of the present invention have a triple effective hydrogen absorption capacity of 1.58wt% at 313K.
In still other specific embodiments, the non-stoichiometric rare earth-iron-based hydrogen storage alloys of the present invention have a triple effective hydrogen absorption capacity of 1.62wt% at 313K.
< preparation method >
The preparation method of the hydrogen storage alloy comprises the following steps: (1) a solid alloy forming step; and (2) a heat treatment step. The following is a detailed description.
Solid alloy forming step
According to chemical composition Y x R y Fe 2.8 Raw materials are prepared, and the raw materials are placed in a smelting device for smelting, so that a smelting product is obtained. In the present invention, the purity of the metal raw material is 99wt% or more.
Before placing the raw materials, the smelting device needs to be vacuumized and filled with inert gas. Vacuumizing a smelting device until the absolute vacuum degree is below 3 Pa; preferably 2Pa or less; more preferably 1Pa or less. After vacuumizing, filling inert gas into the smelting device until the relative vacuum degree is-500 to-600 Pa; preferably-520 to-600 Pa; more preferably-550 to-600 Pa. In the present invention, the smelting apparatus may include a vacuum induction furnace.
The power of the smelting apparatus may be adjusted to 7 to 17kW, preferably 7 to 16kW, more preferably 8 to 15kW, and then smelting is performed to obtain a smelting product (i.e., alloy liquid).
And cooling the smelting product to obtain the solid alloy. For example, solid alloys can be formed by rapid quenching of the melt-spun strip. As another example, a solid alloy may be obtained by casting. In the present invention, the solid alloy is preferably obtained by casting.
Heat treatment step
First, the solid alloy is crushed. The size after crushing is preferably less than 1cm by 1cm. The crushing means may be those known in the art, and will not be described in detail herein.
Placing the crushed alloy into a heat treatment device, and then vacuumizing and filling inert gas into the heat treatment device. The vacuum is applied until the absolute vacuum degree is less than 0.03Pa, preferably 0.02Pa or less, and more preferably 0.01Pa or less. The heat treatment apparatus is charged with an inert shielding gas to a relative vacuum of-300 to-500 Pa, preferably-350 to-500 Pa, and more preferably-350 to-450 Pa.
The non-stoichiometric rare earth-iron-based hydrogen storage alloy is obtained through heat treatment. The heat treatment is preferably performed by temperature programming. Heating the heat treatment device filled with the inert gas to a first temperature at a first heating rate, then heating to a second temperature at a second heating rate, and performing heat treatment at the second temperature. The first heating rate may be 8 to 12 ℃/min, preferably 9 to 11 ℃/min, more preferably 9.5 to 10.5 ℃/min. The first temperature may be 750 to 850 ℃, preferably 770 to 830 ℃, more preferably 780 to 820 ℃. The second heating rate may be 1 to 3.5 ℃/min, preferably 1 to 3.2 ℃/min, more preferably 1 to 3 ℃/min. The second temperature may be 1020 to 1200 ℃, preferably 1025 to 1180 ℃, more preferably 1050 to 1175 ℃. The heat treatment time may be 15 to 95 hours, preferably 20 to 95 hours, more preferably 25 to 90 hours. Such heat treatment conditions are advantageous for improving the effective hydrogen absorption capacity after multiple absorption and desorption of hydrogen. In addition, the hydrogen storage alloy obtained by the invention has high hydrogen absorption rate at room temperature.
According to one embodiment of the invention, according to Y x R y Fe 2.8 The preparation of the raw materials is completed, the raw materials are sequentially placed into a crucible from high to low according to the melting point of the raw materials, rare earth metal is positioned at the uppermost layer of the raw materials, and the raw materials are sealed in a vacuum induction furnace; vacuumizing the vacuum induction furnace until the absolute vacuum degree is less than 3Pa, and filling inert shielding gas until the relative vacuum degree is-500 to-600 Pa; adjusting the power of the vacuum induction furnace to 7kW, and keeping the power for 5min; and then adjusting the power of the vacuum induction furnace to 15kW, keeping for 4-6 min until alloy liquid is formed by the alloy, reducing the power to 0kW, adjusting the power of the vacuum induction furnace to 12kW after a protective film is formed on the alloy liquid surface, and casting the alloy liquid in a water-cooled copper mold after the alloy protective film is opened and the alloy liquid surface is exposed to obtain the solid alloy. Crushing the solid alloy, placing the crushed solid alloy into a heat treatment device, vacuumizing until the absolute vacuum degree is less than 0.03Pa, charging inert protective gas until the relative vacuum degree is-300 to-500 Pa, heating to 750-850 ℃ at a first heating rate of 8-12 ℃/min, heating to 1020-1180 ℃ at a second heating rate of 1-3.5 ℃/min, and performing heat treatment for 15-95 h at 1020-1180 ℃ to obtain the non-stoichiometric rare earth-iron-based hydrogen storage alloy.
< application >
The invention also provides application of the non-stoichiometric rare earth-iron-based hydrogen storage alloy. The non-stoichiometric rare earth-iron based hydrogen storage alloy described above may be used in hydrogen fuel cells. The hydrogen storage alloy provides hydrogen gas for a hydrogen fuel cell.
< analytical methods >
Phase structure and phase abundance: XRD diffractograms were obtained from X-ray powder diffractometer measurements. XRD test conditions: the granularity of the alloy powder is less than 200 meshes, the Cu target and the K alpha ray are adopted, the tube voltage is 40kV, the tube current is 40mA, the scanning range is 10-80 degrees, and the scanning speed is 0.01 degrees/s. The phase structure is determined by software jade 6.0; the phase abundance of the alloy was refined according to Rietveld full spectrum fit and structure, obtained using GSAS software.
Examples 1 to 5 and comparative example 1
According to the chemical compositions of table 1, the non-stoichiometric rare earth-iron-based hydrogen storage alloy of the present invention and the rare earth-iron-based hydrogen storage alloy of the comparative example were prepared:
preparing raw materials, sequentially placing the raw materials into a crucible from high to low according to the melting point of the raw materials, and positioning rare earth metals at the uppermost layer of the raw materials. Placing the crucible in a vacuum induction furnace; and then vacuumizing the vacuum induction furnace until the absolute vacuum degree is less than 1Pa, and filling argon until the relative vacuum degree is-550 Pa. Setting the power of the vacuum induction furnace to 7kW, maintaining for 5min, then adjusting the power of the vacuum induction furnace to 15kW, and maintaining for 5min until all the metals form alloy liquid. And reducing the power of the vacuum induction furnace to 0kW, adjusting the power of the vacuum induction furnace to 12kW after the protective film is formed on the alloy liquid surface, and casting the alloy liquid in a water-cooled copper mold after the alloy protective film is opened and the alloy liquid surface is exposed to obtain the solid alloy.
Crushing the solid alloy, putting the crushed solid alloy into a quartz tube, vacuumizing until the absolute vacuum degree is less than 0.01Pa, filling argon until the relative vacuum degree is-350 Pa, repeating for 3 times, cleaning oxygen in the quartz tube, and sealing the quartz tube; and placing the sealed quartz tube with the solid alloy in a heat treatment tube furnace, then heating to a first temperature T1 at a first heating rate of V1, then heating to a second temperature T2 at a second heating rate of V2, and preserving heat for 90 hours under T2 to obtain the corresponding hydrogen storage alloy.
TABLE 1
Figure BDA0003574199290000101
Experimental example
The hydrogen occluding alloy obtained in the examples and the comparative examples was crushed and then passed through a 200-mesh standard sieve to obtain hydrogen occluding alloy powder having a particle diameter of less than 75 μm. 1g of hydrogen storage alloy powder is weighed and put into a PCT test device, vacuumized for 1h at 423K (high-temperature vacuuming step), and then maintained at 313K in a water bath. Filling hydrogen gas of 5MPa to activate the hydrogen storage alloy powder, recording the hydrogen absorption amount of the alloy powder, repeating 423K high-temperature vacuumizing if the maximum hydrogen absorption amount is not reached within 10min, preserving heat in 313K water bath, and activating under the hydrogen pressure of 5MPa until the maximum hydrogen absorption amount can be reached by the hydrogen storage alloy powder for 10min, and drawing a time-hydrogen absorption amount relation chart, wherein the time-hydrogen absorption amount relation chart is an alloy one-time hydrogen absorption test. The results are shown in Table 2. The phase structure and phase abundance results are shown in Table 3.
TABLE 2
Figure BDA0003574199290000102
TABLE 3 Table 3
Numbering device Phase structure and phase abundance
Example 1 AB 3 100 percent of
Example 2 AB 3 100 percent of
Example 3 AB 3 100 percent of
Example 4 AB 3 100 percent of
Example 5 AB 3 74% + AB 2 26%
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 (7)

1. A non-stoichiometric rare earth-iron-based hydrogen storage alloy is characterized in that the chemical composition is Y x R y Fe 2.8 The method comprises the steps of carrying out a first treatment on the surface of the Wherein Y is yttrium element, and x represents the molar coefficient of the Y element; fe represents an iron element; r is selected from one or more of La, ce, gd, pr, nd, sm and Dy, y represents the mole coefficient of R element, 0.03<y≤0.3；x+y=1.0；
The main phase of the hydrogen storage alloy is AB 3 AB of it 3 The abundance of the phase is greater than 70%;
the hydrogen storage alloy does not contain Ni element and Co element.
2. The hydrogen occluding alloy of claim 1, wherein 0.05< y is less than or equal to 0.3.
3. The hydrogen occluding alloy of claim 2, wherein R meets one of the following conditions:
(1) R is Ce, y is more than or equal to 0.1 and less than or equal to 0.2;
(2) R is Gd, y is more than or equal to 0.15 and less than or equal to 0.3;
(3) R is Sm, y is more than or equal to 0.1 and less than or equal to 0.25;
(4) R is a combination of Ce and Sm, y is more than or equal to 0.15 and less than or equal to 0.3, wherein Ce is 30-50 mol% of the total mole number of R;
(5) R is the combination of La and Nd, 0.05< y is less than or equal to 0.2, wherein La is 40-60 mol% of the total mole number of R.
4. The hydrogen occluding alloy of claim 1 having a composition represented by one of the following formulas:
Y 0.85 Ce 0.15 Fe 2.8 ，
Y 0.75 Gd 0.25 Fe 2.8 ，
Y 0.8 Sm 0.2 Fe 2.8 ，
Y 0.75 Ce 0.1 Sm 0.15 Fe 2.8 ，
Y 0.9 La 0.05 Nd 0.05 Fe 2.8 。
5. the method for producing a non-stoichiometric rare earth-iron-based hydrogen storage alloy according to any one of claims 1 to 4, comprising the steps of:
1) According to chemical composition Y x R y Fe 2.8 Raw materials are prepared and placed in a smelting device for smelting, and a smelting product is obtained; cooling the smelting product to obtain a solid alloy;
2) Crushing the solid alloy, and then carrying out heat treatment for 15-95 h at 1020-1200 ℃ to obtain the non-stoichiometric rare earth-iron-based hydrogen storage alloy.
6. The process according to claim 5, wherein the heat treatment is carried out at a temperature of 1025 to 1180℃for a period of 20 to 95 hours.
7. Use of a non-stoichiometric rare earth-iron-based hydrogen storage alloy according to any one of claims 1 to 4, characterized in that the non-stoichiometric rare earth-iron-based hydrogen storage alloy is used in a hydrogen fuel cell.
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