CN114457260B - MgCu 4 Sn type hydrogen storage alloy and preparation method thereof - Google Patents

MgCu 4 Sn type hydrogen storage alloy and preparation method thereof Download PDF

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CN114457260B
CN114457260B CN202210092926.2A CN202210092926A CN114457260B CN 114457260 B CN114457260 B CN 114457260B CN 202210092926 A CN202210092926 A CN 202210092926A CN 114457260 B CN114457260 B CN 114457260B
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hydrogen storage
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temperature
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storage alloy
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CN114457260A (en
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李媛
张永玺
周迪
谢一超
韩树民
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Yanshan University
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    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/1017—Multiple heating or additional steps
    • 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
    • B22F9/04—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
    • C01B3/0057—Intermetallic compounds; Metal alloys; Treatment thereof containing a rare earth metal; Treatment thereof also containing nickel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • 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
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0433—Nickel- or cobalt-based alloys
    • C22C1/0441—Alloys based on intermetallic compounds of the type rare earth - Co, Ni
    • 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
    • C22C19/007—Alloys based on nickel or cobalt with a light metal (alkali metal Li, Na, K, Rb, Cs; earth alkali metal Be, Mg, Ca, Sr, Ba, Al Ga, Ge, Ti) or B, Si, Zr, Hf, Sc, Y, lanthanides, actinides, as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C2202/00—Physical properties
    • C22C2202/04—Hydrogen absorbing

Abstract

The invention discloses MgCu 4 Sn type hydrogen storage alloy and a preparation method thereof. The chemical composition of the hydrogen storage alloy is R 1‑ x Mg x Ni y M a (ii) a Wherein R is selected from any one or more of lanthanide, Y, ca, zr and Ti; m is selected from any one or more of fourth and fifth period transition metal elements, B, al, ga, in, gn, sn and Sb; and R is not equal to M; the value ranges of x, y and a are as follows: x is more than or equal to 0.15 and less than or equal to 0.49, y is more than or equal to 1.70 and less than or equal to 2.20, and a is more than or equal to 0 and less than or equal to 0.30. The hydrogen storage alloy provided by the invention has single MgCu 4 The Sn phase structure can be kept stable and is not easy to decompose in a cycle test; the gas-solid hydrogen storage capacity is more than 1.00wt.%, and the retention rate of the hydrogen absorption and desorption capacity is high; the preparation method provided by the invention is simple and convenient to operate, the raw materials are easy to obtain, and the price is low.

Description

MgCu 4 Sn type hydrogen storage alloy and preparation method thereof
Technical Field
The invention relates to the technical field of hydrogen storage alloys, in particular to MgCu 4 Sn type hydrogen storage alloy and a preparation method thereof.
Background
The hydrogen energy is regarded as the clean energy with the most development potential in the 21 st century, has a plurality of advantages which are not possessed by the traditional energy, wherein the most prominent advantages are zero carbon and high efficiency, and is the only way for realizing the cross-energy network cooperative optimization in the foreseeable future. However, the potential is insufficient, a plurality of technical bottlenecks exist in the preparation, storage, application and other links of hydrogen, so that hydrogen can really occupy equivalent market share in the energy field, the whole industry needs to objectively treat advantages and short plates, and meanwhile basic research and technical innovation are enhanced. The situation of hydrogen storage development in various application links is particularly severe, and the key point is to search a hydrogen storage material which can absorb and release a large amount of hydrogen under the environmental conditions of room temperature and medium pressure.
The rare earth-magnesium-nickel superlattice hydrogen storage alloy has higher hydrogen storage capacity and relatively mild hydrogen absorption and desorption conditions, and is widely researched. The rare earth-magnesium-nickel superlattice hydrogen storage alloy unit cell is composed of a plurality of CaCu 5 AB of type 5 Subunits and a Laves phase (MgZn) 2 Or MgCu 2 Type A) of 2 B 4 The subunits are stacked. Wherein A is 2 B 4 Subunit and AB 5 The sub-units have more hydrogen storage sites and higher hydrogen storage capacity than each other. From the analysis of the crystal structure, if A 2 B 4 The tetrahedral or octahedral gaps in the subunits are all occupied by hydrogen atoms, and hydride AB can be generated 2 H 17 Therefore AB 2 The subunits have a great hydrogen storage potential (if La is used) 0.5 Mg 0.5 Ni 2 H 17 Calculated to yield a hydrogen storage of about 8.5 wt.%). Currently there are few single-phase AB 2 Synthesis of type alloys, existing reports on the composition AB 2 The alloy reported by type alloy can only generate AB after absorbing hydrogen 2 H 6 Far from the possible hydrogen storage capacity. And there are studies showing AB 2 The rare earth alloy is easy to generate hydrogen-induced amorphization and has quick decay of hydrogen storage capacity.
Z.L.Chen,T.Z.Si,Q.A.Zhang,Hydrogen absorption-desorption cycle durability of SmMgNi 4 The preparation of a single AB having a single particle size using powder sintering is reported in Journal of Alloys and Compounds 621 (2015) 42-46 2 SmMgNi of type phase structure 4 The alloy has good cycling stability, can keep stable structure in a plurality of hydrogen absorption and desorption periods, but has low mass hydrogen storage capacity, is difficult to meet the requirement of practical application and needs to be further improved. This is due to the fact that at AB 2 In the form phase structure, the ternary Sm-Mg-Ni system can provide less active hydrogen absorption sites and still needs to provideFurther improve the quality. In order to further improve the hydrogen absorption amount and the circulation stability of the Sm-Mg-Ni alloy, the preparation of single-phase MgCu doped with multiple elements is urgently needed 4 An Sn type alloy. However, mgCu 4 The generation conditions of the Sn type phase structure are harsh, the phase transformation reaction of the alloy becomes more complex after a plurality of elements are introduced for doping, and single MgCu is generated 4 The difficulty of the Sn-type phase structure is greatly increased. At present, mgCu doped with various elements 4 The Sn type single-phase hydrogen storage alloy has not been reported.
Disclosure of Invention
Aiming at the technical problem, the invention provides MgCu 4 A hydrogen storage alloy of Sn type, the alloy being MgCu in solid state 4 The Sn type single-phase structure has the characteristics of higher hydrogen storage capacity, better platform characteristic, stable structure and good circulation stability in the process of repeatedly absorbing and releasing hydrogen.
In order to realize the purpose, the invention adopts the technical scheme that:
in one aspect, the present invention provides a MgCu alloy 4 Sn type hydrogen storage alloy, said MgCu 4 The chemical composition of the Sn-type hydrogen storage alloy is R 1-x Mg x Ni y M a ；
Wherein R is selected from any one or more of lanthanide, Y, ca, zr and Ti; m is selected from any one or more of a fourth transition metal element, a fifth period transition metal element, B, al, ga, in, gn, sn and Sb; and R is not equal to M;
the value ranges of x, y and a are as follows: x is more than or equal to 0.15 and less than or equal to 0.49; y is more than or equal to 1.70 and less than or equal to 2.20; a is more than or equal to 0 and less than or equal to 0.30.
As a preferred embodiment, the value ranges of x, y, and a are: x is more than or equal to 0.30 and less than or equal to 0.45; y is more than or equal to 1.80 and less than or equal to 2.10; a is more than or equal to 0.05 and less than or equal to 0.20.
In the technical scheme of the invention, the MgCu 4 The Sn-type hydrogen storage alloy has an intensity (I) of the strongest peak appearing in the range of 2 theta =36 to 37 DEG when measured by X-ray diffraction using Cu-Ka ray as an X-ray source A ) With the strongest peak intensity (I) occurring within 2 θ = 42-43 ° B ) Intensity ratio (I) of A /I B ) Below 0.4, the alloy provided by the invention is reacted withA phase structure of one.
In another aspect, the invention also provides the MgCu 4 The preparation method of the Sn type hydrogen storage alloy comprises the following steps:
(1) Mechanically grinding R-Ni-M intermediate alloy serving as a precursor alloy into powder to obtain first raw material powder; mechanically grinding Mg-R, mg-Ni and/or Mg-M magnesium-containing alloy into powder to obtain second raw material powder;
(2) And (2) uniformly mixing the first raw material powder and the second raw material powder obtained in the step (1) in proportion, and performing sintering heat treatment.
As a preferred embodiment, the sintering heat treatment is a step-by-step treatment comprising a plurality of temperature-raising stages and temperature-lowering stages.
As a preferred embodiment, the sintering heat treatment comprises three temperature-raising stages and two temperature-lowering stages in sequence:
a first temperature rise stage: raising the temperature from room temperature to 550-650 ℃, and preserving the heat for 0.5-1.5 h;
a second temperature rise stage: continuously heating from 550-650 ℃ to 700-800 ℃, and preserving heat for 0.5-1.5 h;
a third temperature rise stage: continuously heating from 700-800 ℃ to 900-950 ℃, and preserving heat for 3-5 h;
a first cooling stage: cooling to the heat preservation temperature from 900-950 ℃, and preserving the heat for 3-5 days at the heat preservation temperature;
and a second cooling stage: cooling to room temperature from the heat preservation temperature to obtain the MgCu 4 A Sn-type hydrogen storage alloy;
wherein the heat preservation temperature is 820-870 ℃;
preferably, the sintering heat treatment comprises:
a first temperature rise stage: heating from room temperature to 600 ℃, and preserving heat for 1h;
a second temperature rise stage: continuously heating from 600 ℃ to 750 ℃, and preserving heat for 1h;
a third temperature rise stage: continuously heating from 750 ℃ to 900 ℃, and preserving heat for 4h;
a first cooling stage: cooling to the heat preservation temperature from 900 ℃, and preserving heat for 3 days at the heat preservation temperature;
and a second cooling stage: cooling to room temperature from the heat preservation temperature to obtain the MgCu 4 A Sn-type hydrogen storage alloy;
wherein the heat preservation temperature is 820-870 ℃.
In a preferred embodiment, the temperature increase rate of the first temperature increase stage is 3 to 5 ℃/min;
preferably, the heating rate of the second heating stage is 0.5-1.5 ℃/min;
preferably, the heating rate of the third heating stage is 0.5-1.5 ℃/min;
preferably, the cooling rate of the first cooling stage is 0.5-1.5 ℃/min;
preferably, the temperature reduction in the second temperature reduction stage is natural cooling.
As a preferred embodiment, the R-Ni-M master alloy is prepared by induction melting, and preferably comprises rare earth-Ni-M alloy, rare earth-Ca-Ni-M alloy, rare earth-Zr-Ni-M alloy and the like.
As a preferred embodiment, the magnesium-containing alloy is selected from any one or more of R-Mg, ni-Mg and M-Mg; preferred magnesium-containing alloys include commercially available Sm-Mg, la-Mg, ni-Mg alloys, and the like.
In a preferred embodiment, the first raw material powder has a particle size of 50 to 400 mesh, preferably 200 to 400 mesh;
preferably, the particle size of the second raw material powder is 50 to 400 mesh, preferably 200 to 400 mesh.
In a preferred embodiment, the pressure in the sintering heat treatment is 0.07 to 0.12MPa, preferably 0.08 to 0.11MPa.
In certain specific embodiments, the sintering heat treatment is performed in a protective atmosphere, such as Ar gas or the like.
The technical scheme has the following advantages or beneficial effects:
(1) The hydrogen storage alloy prepared by the invention has single MgCu 4 Sn phase structure obtained by X-ray diffraction and full spectrum fitting analysis, the space group is F-43m, the phase abundance is 100%, and pure phase junctions are found in a cyclic testThe alloy has stable phase structure, is not easy to decompose, and has high hydrogen absorption and desorption capacity retention rate; the hydrogen storage capacity is high, the gas-solid hydrogen storage capacity is more than 1.00wt.%, and is higher than 0.8wt.% in the prior report;
(2) According to the invention, the Mg content in the alloy is adjusted by combining an induction melting method and a sintering method, the Mg loss in the alloy preparation process is reduced, and the cost is reduced;
(3) The preparation method provided by the invention has the advantages of simple equipment, convenient process and operation conditions, stable reaction conditions, easy control of the composition of the hydrogen storage alloy, easy realization of control of the metallographic structure, easily obtained raw materials and low price.
Drawings
FIG. 1 shows MgCu prepared in examples 1-4 of the present invention 4 X-ray diffraction pattern of Sn-type hydrogen storage alloy.
FIG. 2 shows MgCu prepared in example 2 of the present invention 4 PCT curve for Sn-type hydrogen storage alloy at 323K.
FIG. 3 shows MgCu prepared in example 3 of the present invention 4 PCT curve for Sn-type hydrogen storage alloy at 323K.
FIG. 4 shows MgCu prepared in example 4 of the present invention 4 PCT curve for Sn-type hydrogen storage alloy at 323K.
Detailed Description
The following examples are only a part of the present invention, not all of them. Thus, the detailed description of the embodiments of the present invention provided below is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the invention without making creative efforts, belong to the protection scope of the invention.
In the present invention, all the equipment, materials and the like are commercially available or commonly used in the industry, if not specified. The methods in the following examples are conventional in the art unless otherwise specified.
In the present invention, room temperature means 20 to 30 ℃.
MgCu 4 Sn type reservoirHydrogen alloy
The invention provides MgCu 4 The Sn type hydrogen storage alloy comprises the following chemical components: r 1-x Mg x Ni y M a ；
Wherein R is selected from any one or more of lanthanide, Y, ca, zr and Ti; m is selected from any one or more of fourth and fifth period transition metal elements, B, al, ga, in, gn, sn and Sb; r is not equal to M;
the value ranges of x, y and a are as follows: x is more than or equal to 0.15 and less than or equal to 0.49, y is more than or equal to 1.70 and less than or equal to 2.20, and a is more than or equal to 0 and less than or equal to 0.30;
the preferable value ranges of x, y and a are as follows: x is more than or equal to 0.30 and less than or equal to 0.45, y is more than or equal to 1.80 and less than or equal to 2.10, and a is more than or equal to 0.05 and less than or equal to 0.20; the values of x, y and a represent the molar ratio of each element.
Specifically, the value of x is 0.15, 0.20, 0.25, 0.30, 0.35, 0.40, 0.45, 0.49 or any value therebetween; y is 1.70, 1.80, 1.90, 2.00, 2.10, 2.20 or any value therebetween; z is 0,0.05, 0.10, 0.15, 0.20, 0.25, 0.30 or any value in between.
The hydrogen storage alloy provided by the invention has the strongest peak intensity (I) appearing in the range of 2 theta = 36-37 degrees when the X-ray diffraction measurement is carried out by taking Cu-Ka line as an X-ray source A ) And the strongest peak intensity (I) occurring within 2 theta =42 to 43 DEG B ) Intensity ratio (I) of A /I B ) At 0.4, XRD results are phase structure reactions, and the above characterization results prove that the hydrogen storage alloy provided by the invention is an alloy with a single-phase structure.
In the invention, the gas-solid hydrogen storage performance of the R-Mg-Ni series hydrogen storage alloy is closely related to the structure and the composition of the alloy. In principle, R and Mg are essential as hydrogen-absorbing elements in the alloy; meanwhile, mg can be used as a hydrogen absorption element and a phase structure adjusting element, and the proportion relation (namely R/Mg molar ratio) of Mg and R is more important than the phase structure and the hydrogen storage performance of the alloy. The value of the parameter x which can represent the proportional relation is generally more than or equal to 0.15 and less than or equal to 0.49, and the preferable value range of x is more than or equal to 0.30 and less than or equal to 0.45.Ni element cannot absorb hydrogen but contributes to hydrogen molecules in the process of absorbing and desorbing hydrogen from the hydrogen absorbing alloyDissociation and modulation of hydride stability. The content of Ni element is generally 1.70. Ltoreq. Y.ltoreq.2.20, and the preferable content is 1.80. Ltoreq. Y.ltoreq.2.10. The function of M in the hydrogen storage alloy is to adjust hydrogen storage characteristics such as equilibrium hydrogen pressure. The content of the M element is generally 0. Ltoreq. A.ltoreq.0.30, and the content of the M element is preferably 0.05. Ltoreq. A.ltoreq.0.20. By adjusting and controlling the proportion of the elements of hydrogen storage alloy R, mg, ni, M and the like, stable MgCu can be constructed 4 The Sn-type single-phase hydrogen storage alloy provides necessary chemical composition guarantee, and can improve the solid-state hydrogen storage performance of the hydrogen storage alloy.
MgCu 4 Preparation method of Sn type hydrogen storage alloy
The preparation method of the hydrogen storage alloy comprises the following steps:
the preparation method comprises the steps of preparing by an induction melting method, taking R-Ni-M intermediate alloy as a precursor, and mechanically grinding the precursor into powder to obtain first raw material powder; selecting Mg-R, mg-Ni and/or Mg-M magnesium-containing alloy, and mechanically grinding the Mg-R, mg-Ni and/or Mg-M magnesium-containing alloy into powder to obtain second raw material powder; and uniformly mixing the first raw material powder and the second raw material powder in proportion, and performing sintering heat treatment.
Preferably, in the invention, the sintering heat treatment is preferably a step-by-step operation, and comprises a plurality of temperature rising stages and temperature lowering stages;
preferably, the sintering heat treatment sequentially comprises three temperature-rising stages and two temperature-lowering stages:
a first temperature rise stage: raising the temperature from room temperature to 550-650 ℃, and preserving the temperature for 0.5-1.5 h;
a second temperature rising stage: continuously heating from 550-650 ℃ to 700-800 ℃, and preserving heat for 0.5-1.5 h;
a third temperature rise stage: continuously heating from 700-800 ℃ to 900-950 ℃, and preserving heat for 3-5 h;
a first cooling stage: cooling from 900-950 ℃ to the heat preservation temperature, and preserving the heat for 3-5 days at the heat preservation temperature;
a second cooling stage: cooling to room temperature from the heat preservation temperature to obtain the MgCu 4 A Sn-type hydrogen storage alloy;
wherein the heat preservation temperature is 820-870 ℃.
Specifically, the first temperature raising stage is raising the temperature from room temperature to 550 ℃, 560 ℃, 570 ℃, 580 ℃, 590 ℃, 600 ℃, 610 ℃, 620 ℃, 630 ℃, 640 ℃, 650 ℃ or any value therebetween;
the second temperature raising stage is to raise the temperature to 700 deg.c, 710 deg.c, 720 deg.c, 730 deg.c, 740 deg.c, 750 deg.c, 760 deg.c, 770 deg.c, 780 deg.c, 790 deg.c, 800 deg.c or any value in between;
the third temperature rise stage is to continue to rise to 900 ℃, 910 ℃, 920 ℃, 930 ℃, 940 ℃, 950 ℃ or any value between the two;
the first cooling stage is to cool to 820 ℃, 830 ℃, 840 ℃, 850 ℃, 860 ℃, 870 ℃ or any value therebetween.
In the invention, the step-sintering heat treatment can improve the internal microstructure of the hydrogen storage alloy, reduce the segregation of Mg element in the hydrogen storage alloy, and ensure the strength (I) of the strongest peak appearing in the range of 2 theta = 36-37 degrees when the hydrogen storage alloy is subjected to X-ray diffraction measurement by taking Cu-Ka line as an X-ray source A ) And the strongest peak intensity (I) occurring within 2 theta =42 to 43 DEG B ) Intensity ratio (I) of A /I B ) Below 0.4.
Explanation on setting of temperature rise, heat retention, and temperature decrease procedures: firstly, raising the temperature from room temperature to 550-650 ℃ (less than or equal to the melting point of metal magnesium, preferably slightly lower than the melting point of metal magnesium, namely 600 ℃) and preserving the temperature, so that the magnesium-containing alloy starts to decompose and thermally diffuse, and a large amount of volatilization of magnesium is avoided; continuously heating to 700-800 ℃ (preferably 750 ℃) and preserving heat to ensure that the magnesium-containing alloy is fully decomposed and heat permeated; continuously heating to 900-950 ℃ (preferably 900 ℃) and preserving heat to ensure that the high-melting point metal is fully subjected to thermal diffusion; the temperature is reduced to the heat preservation temperature and the heat preservation is carried out for more than 3 days, so that the system fully carries out phase transformation under the heat balance condition to obtain MgCu with a single-phase structure 4 Sn type multielement hydrogen storage alloy.
In a preferred embodiment, the temperature increase rate of the first temperature increase stage is 3 to 5 ℃/min;
preferably, the heating rate of the second heating stage is 0.5-1.5 ℃/min;
preferably, the heating rate of the third heating stage is 0.5-1.5 ℃/min;
preferably, the temperature reduction rate of the first temperature reduction stage is 0.5-1.5 ℃/min;
preferably, the temperature reduction in the second temperature reduction stage is natural cooling.
As a preferable embodiment, the R-Ni-M intermediate alloy is prepared by induction melting, and can obtain a high-purity alloy, and a rare earth-Ni-M alloy, a rare earth-Ca-Ni-M alloy, a rare earth-Zr-Ni-M alloy and the like are preferable.
As a preferred embodiment, the magnesium-containing alloy is selected from any one or more of R-Mg, ni-Mg and M-Mg; preferred magnesium-containing alloys include commercially available Sm-Mg, la-Mg, ni-Mg alloys, and the like.
In the prior art, the problems of serious volatilization of Mg element and difficult control of Mg content exist in the preparation process of the rare earth-magnesium-nickel-based hydrogen storage alloy. Under the premise of accurately controlling the content of Mg element, the temperature and practice of decomposition, permeation and phase transition are accurately controlled to carry out solid-phase reaction, thereby realizing MgCu 4 And preparing the Sn type multi-element single-phase hydrogen storage alloy. MgCu provided by the invention 4 The Sn type multi-element single-phase hydrogen storage alloy has high hydrogen storage capacity and good cycle stability, and can keep the stability of the structure after a plurality of hydrogen absorption and desorption cycles.
Grinding the first raw material powder A and the second raw material powder into fine powder and fully mixing to facilitate thermal diffusion among the components: the particle distribution among the raw material particles has a significant influence on the thermal diffusion process; preferably, the present invention employs particles having a particle size of 50 to 400 mesh to facilitate diffusion of the ingredients, more preferably 200 to 400 mesh. In the technical scheme of the invention, the raw material powder is screened by adopting a standard screen, and the powder with the target particle size is obtained by screening between two standard screens.
In the sintering heat treatment process, volatilization of low-melting-point elements such as magnesium and the like is one of key factors influencing the phase structure of the hydrogen storage alloy, and the volatilization amount of the low-melting-point elements can be effectively controlled by controlling the atmosphere pressure at a certain stable value. In a preferred embodiment, the pressure of the sintering heat treatment is 0.07 to 0.12MPa, preferably 0.08 to 0.11MPa.
In certain specific embodiments, the sintering heat treatment is performed in a protective atmosphere, such as Ar gas or the like.
Examples
Example 1
Precursor alloy Sm obtained by induction smelting 0.72 Y 0.28 Ni 3.56 Co 0.09 Al 0.16 (first raw Material) with SmMg 14.38 The alloy (commercially available, second raw material) was mechanically ground to 200-400 mesh, and the two powders were mechanically mixed to homogeneity according to the following molar ratio: sm 0.72 Y 0.28 Ni 3.56 Co 0.09 Al 0.16 ：SmMg 14.38 =1.000:0.05; the uniformly mixed alloy powder is put into an annealing tank, the argon pressure in an annealing furnace is kept at 0.09-0.10 MPa, and the step-by-step sintering is carried out according to the following procedures: heating from room temperature to 600 ℃ at the heating rate of 4 ℃/min, and keeping the temperature for 1h; then heating to 750 ℃ at the heating rate of 1 ℃/min, and preserving heat for 1h; continuously heating to 900 ℃ at the heating rate of 1 ℃/min, and keeping the temperature for 4h; then cooling to 850 ℃ at the cooling rate of 1 ℃/min; preserving the heat for 3 days at 850 ℃, then cooling the sample to room temperature along with the furnace, and taking out; the obtained alloy is Sm 0.44 Y 0.16 Mg 0.40 Ni 2.01 Co 0.05 Al 0.09 。
And (3) testing the structure and hydrogen storage performance of the prepared alloy: as shown in FIG. 1, powder X-ray diffraction tests were performed on the sintered alloy and full spectrum fit analysis was performed, indicating that the alloy consists of a single MgCu alloy 4 A Sn phase. The prepared alloy is mechanically crushed to 200 meshes and can be directly used as a hydrogen storage material, and the maximum hydrogen absorption amount can reach 1.55wt.%. It can be seen that MgCu prepared using the present method 4 The Sn type multi-element single-phase hydrogen storage alloy has high capacity and is easy to activate; and after 100 times of hydrogen absorption and desorption cycles, the structure is basicNo change occurred.
Example 2
Precursor alloy Nd obtained by induction melting 0.73 Y 0.27 Ni 3.42 Co 0.06 Al 0.15 (first raw Material) with SmMg 14.38 The alloy (commercially available, second raw material) was mechanically ground to 100 to 300 mesh, and the two powders were mechanically mixed to homogeneity according to the following molar ratio: nd (neodymium) 0.73 Y 0.27 Ni 3.98 Co 0.06 Al 0.15 ：SmMg 14.38 =1.000:0.05; putting the uniformly mixed alloy powder into an annealing tank, keeping the argon pressure in the annealing furnace at 0.09-0.11 MPa, and sintering step by step according to the following procedures: heating from room temperature to 600 ℃ at the heating rate of 4 ℃/min, and keeping the temperature for 1h; then heating to 750 ℃ at the heating rate of 1 ℃/min, and preserving heat for 1h; continuously heating to 900 ℃ at the heating rate of 1 ℃/min, and keeping the temperature for 4h; then, cooling to 865 ℃ at a cooling rate of 1 ℃/min; keeping the temperature at 865 ℃ for 3 days, then cooling the sample to room temperature along with the furnace, and taking out the sample to obtain Nd alloy 0.41 Sm 0.0 3 Y 0.15 Mg 0.41 Ni 1.93 Co 0.03 Al 0.08 。
And (3) testing the structure and hydrogen storage performance of the prepared alloy: as shown in FIG. 1, powder X-ray diffraction tests and full spectrum fitting analysis were performed on the sintered alloy, and the results showed that the alloy consisted of a single MgCu alloy 4 A Sn phase. The prepared alloy is mechanically crushed to 200 meshes, namely can be directly used as a hydrogen storage material, fig. 2 shows a PCT curve of the alloy crushed to 200 meshes at 323K in the embodiment, the hydrogen storage alloy can be completely activated after absorbing hydrogen for the first time, solid lines and dotted lines respectively show hydrogen absorption and hydrogen desorption curves, and it can be seen that a hydrogen absorption and desorption platform of the hydrogen storage alloy is wide and flat, and the maximum hydrogen absorption amount can reach 1.10wt.%. It can be seen that MgCu prepared using the present method 4 The Sn type multi-element single-phase hydrogen storage alloy has high capacity and is easy to activate; and the structure is basically not changed after 100 times of hydrogen absorption and desorption cycles.
Example 3
Precursor alloy Pr obtained by induction melting 0.62 Y 0.39 Ni 3.60 Co 0.10 Al 0.13 (first raw Material) with SmMg 14.38 The alloy (commercially available, second raw material) was mechanically ground to 300-400 mesh, and the two powders were mechanically mixed to homogeneity according to the following molar ratios: pr (Pr) of 0.62 Y 0.39 Ni 3.60 Co 0.10 Al 0.13 ：SmMg 14.38 =1.000: 0.065, putting the uniformly mixed alloy powder into an annealing tank, keeping the argon pressure in an annealing furnace at 0.09-0.10 MPa, and sintering step by step according to the following procedures: heating from room temperature to 600 ℃ at the heating rate of 4 ℃/min, and keeping the temperature for 1h; then heating to 750 ℃ at the heating rate of 1 ℃/min, and preserving heat for 1h; continuously heating to 900 ℃ at the heating rate of 1 ℃/min, and keeping the temperature for 4h; then cooling to 845 ℃ at a cooling rate of 1 ℃/min; keeping the temperature at 845 ℃ for 3 days, then cooling the sample to room temperature along with the furnace, and taking out the sample to obtain the alloy Pr 0.31 Sm 0.0 3 Y 0.19 Mg 0.47 Ni 1.79 Co 0.05 Al 0.06 。
And (3) testing the structure and hydrogen storage performance of the prepared alloy: as shown in FIG. 1, powder X-ray diffraction tests were performed on the sintered alloy and full spectrum fit analysis was performed, indicating that the alloy consists of a single MgCu alloy 4 A Sn phase. The prepared alloy is mechanically crushed to 200 meshes, namely can be directly used as a hydrogen storage material, fig. 3 shows a PCT curve of the alloy crushed to 200 meshes at 323K in the embodiment, the hydrogen storage alloy can be completely activated after absorbing hydrogen for the first time, solid lines and dotted lines respectively show hydrogen absorption and hydrogen desorption curves, and it can be seen that a hydrogen absorption and desorption platform of the hydrogen storage alloy is wide and flat, and the maximum hydrogen absorption amount can reach 1.21wt.%. It can be seen that MgCu prepared using the present method 4 The Sn type multi-element single-phase hydrogen storage alloy has high capacity and is easy to activate; and the structure is basically not changed after 100 hydrogen absorption and desorption cycles.
Example 4
Precursor alloy La obtained by induction melting 0.62 Y 0.38 Ni 2.54 Co 0.12 Al 0.13 (first feedstock) with LaMg 13.20 (commercially available, second raw material) alloy was mechanically ground to 50 to 200 mesh, and the two kinds were groundThe powder is mechanically mixed to be uniform according to the following molar ratio: la 0.62 Y 0.38 Ni 2.54 Co 0.12 Al 0.13 ：LaMg 13.20 =1.000:0.015. the uniformly mixed alloy powder is put into an annealing tank, the argon pressure in the annealing furnace is kept at 0.07-0.09 MPa, and the step-by-step sintering is carried out according to the following procedures: heating from room temperature to 600 ℃ at the heating rate of 4 ℃/min, and keeping the temperature for 1h; then heating to 750 ℃ at the heating rate of 1 ℃/min, and preserving heat for 1h; continuously heating to 900 ℃ at the heating rate of 1 ℃/min, and keeping the temperature for 4h; then cooling to 825 deg.C at a cooling rate of 1 deg.C/min; keeping the temperature at 825 deg.C for 3 days, cooling the sample to room temperature with the furnace, and taking out to obtain alloy La 0.52 Y 0.31 Mg 0.16 Ni 2.10 Co 0.10 Al 0.10 。
And (3) testing the structure and hydrogen storage performance of the prepared alloy: as shown in FIG. 1, powder X-ray diffraction tests and full spectrum fitting analysis were performed on the sintered alloy, and the results showed that the alloy consisted of a single MgCu alloy 4 A Sn phase. The alloy obtained by preparation is mechanically crushed to 200 meshes, and can be directly used as a hydrogen storage material, fig. 4 shows a PCT curve of the alloy in the embodiment when the alloy is crushed to 200 meshes at 323K, the hydrogen storage alloy can be completely activated after first hydrogen absorption, and a solid line and a dotted line respectively show hydrogen absorption and hydrogen desorption curves, so that the hydrogen absorption and desorption platform of the hydrogen storage alloy is wide and flat, and the maximum hydrogen absorption amount can reach 1.36wt.%. It can be seen that MgCu prepared using the present method 4 The Sn type multi-element single-phase hydrogen storage alloy has high capacity and is easy to activate; and the structure is basically not changed after 100 hydrogen absorption and desorption cycles.
Example 5
Precursor alloy Pr obtained by induction melting 0.62 La 0.38 Ni 2.80 Mn 0.10 Al 0.15 (first raw Material) with Mg 2 The Ni alloy (commercially available, second raw material) was mechanically ground to 300 to 400 mesh, and the two powders were mechanically mixed to homogeneity in the following molar ratio: pr (Pr) of 0.62 La 0.38 Ni 2.80 Mn 0.10 Al 0.15 ：Mg 2 Ni =1.000:0.201. mixing all above materialsFilling the uniform alloy powder into an annealing tank, keeping the argon pressure in the annealing furnace at 0.09-0.11 MPa, and sintering step by step according to the following procedures: heating from room temperature to 600 ℃ at the heating rate of 4 ℃/min, and keeping the temperature for 1h; then heating to 750 ℃ at the heating rate of 1 ℃/min, and preserving heat for 1h; continuously heating to 900 ℃ at the heating rate of 1 ℃/min, and keeping the temperature for 4h; then cooling to 850 ℃ at the cooling rate of 1 ℃/min; keeping the temperature at 850 ℃ for 3 days, then cooling the sample to room temperature along with the furnace, and taking out the sample to obtain the alloy Pr 0.44 La 0.26 Mg 0.30 Ni 2.00 Mn 0.07 Al 0.11 。
And (3) testing the structure and hydrogen storage performance of the prepared alloy: powder X-ray diffraction test is carried out on the sintered alloy, full spectrum fitting analysis is carried out, and the result shows that the alloy consists of single MgCu 4 A Sn phase. The prepared alloy is mechanically crushed into 200 meshes, and can be directly used as a hydrogen storage material, and the alloy can be completely activated after first hydrogen absorption, and the maximum hydrogen absorption amount can reach 1.40wt.%. It can be seen that MgCu prepared using the present method 4 The Sn type multi-element single-phase hydrogen storage alloy has high capacity and is easy to activate; and the structure is basically not changed after 50 times of hydrogen absorption and desorption cycles.
Example 6
Precursor alloy La obtained by induction melting 0.50 Ca 0.50 Ni 3.32 Cu 0.30 (first raw Material) with Mg 2 The Ni alloy (commercially available, second raw material) was mechanically ground to 200 to 300 mesh, and the two powders were mechanically mixed to homogeneity in the following molar ratio: la 0.50 Ca 0.50 Ni 2.97 Cu 0.30 ：Mg 2 Ni =1.000:0.350 of; the uniformly mixed alloy powder is put into an annealing tank, the argon pressure in an annealing furnace is kept at 0.10-0.11 MPa, and the step-by-step sintering is carried out according to the following procedures: heating from room temperature to 600 ℃ at the heating rate of 4 ℃/min, and keeping the temperature for 1h; then heating to 750 ℃ at the heating rate of 1 ℃/min, and preserving heat for 1h; continuously heating to 900 ℃ at the heating rate of 1 ℃/min, and keeping the temperature for 4h; then cooling to 820 ℃ at a cooling rate of 1 ℃/min; maintaining the temperature at 820 deg.C for 3 days, cooling the sample to room temperature, and taking outAlloy of (A) La 0.29 Ca 0.29 Mg 0.42 Ni 1.95 Cu 0.18 。
And (3) testing the structure and hydrogen storage performance of the prepared alloy: powder X-ray diffraction test is carried out on the sintered alloy, full spectrum fitting analysis is carried out, and the result shows that the alloy consists of single MgCu 4 A Sn phase. The prepared alloy is mechanically crushed into 200 meshes and can be directly used as a hydrogen storage material, and the alloy can be completely activated after first hydrogen absorption, and the maximum hydrogen absorption amount can reach 1.48wt.%. It can be seen that MgCu prepared using the present method 4 The Sn type multi-element single-phase hydrogen storage alloy has high capacity and is easy to activate; and the structure is basically not changed after 40 times of hydrogen absorption and desorption cycles.
Example 7
Gd precursor alloy obtained by induction melting 0.85 Zr 0.15 Ni 3.64 Co 0.30 (first feedstock) with LaMg 13.20 The alloy (commercially available, second raw material) was mechanically ground to 300-400 mesh, and the two powders were mechanically mixed to homogeneity according to the following molar ratios: gd (Gd) 0.85 Zr 0.15 Ni 3.64 Co 0.30 ：LaMg 13.20 =1.000:0.05; putting the uniformly mixed alloy powder into an annealing tank, and keeping the argon pressure in an annealing furnace at 0.08-0.10 MPa; sintering step by step according to the following procedures: heating from room temperature to 600 ℃ at the heating rate of 4 ℃/min, and keeping the temperature for 1h; then heating to 750 ℃ at the heating rate of 1 ℃/min, and preserving heat for 1h; continuously heating to 900 ℃ at the heating rate of 1 ℃/min, and keeping the temperature for 4h; then cooling to 870 ℃ at a cooling rate of 1 ℃/min; keeping the temperature at 870 ℃ for 3 days, then cooling the sample to room temperature along with the furnace, and taking out the sample to obtain the alloy La 0.03 Gd 0.50 Zr 0.09 Mg 0.39 Ni 2.15 Co 0.18 。
And (3) testing the structure and hydrogen storage performance of the prepared alloy: powder X-ray diffraction test is carried out on the sintered alloy, full spectrum fitting analysis is carried out, and the result shows that the alloy consists of single MgCu 4 A Sn phase. The prepared alloy is mechanically crushed to 200 meshes and can be directly used as a hydrogen storage material for the first timeThe hydrogen absorption can be completely activated, and the maximum hydrogen absorption amount can reach 1.37wt.%. It can be seen that MgCu prepared using the present method 4 The Sn type multi-element single-phase hydrogen storage alloy has high capacity and is easy to activate; and the structure is basically not changed after 100 times of hydrogen absorption and desorption cycles.
Example 8
Precursor alloy SmNi obtained by induction melting 3 Al 0.5 (first raw Material) with Mg 2 The Ni alloy (commercially available, second raw material) was mechanically ground to 100 to 200 mesh, and the two powders were mechanically mixed to homogeneity in the following molar ratio: smNi 3 Al 0.5 ：Mg 2 Ni =3:1; the uniformly mixed alloy powder is put into an annealing tank, the argon pressure in the annealing furnace is kept at 0.10-0.12 MPa, and the step-by-step sintering is carried out according to the following procedures: heating from room temperature to 600 ℃ at the heating rate of 4 ℃/min, and keeping the temperature for 1h; then heating to 750 ℃ at the heating rate of 1 ℃/min, and preserving heat for 1h; continuously heating to 900 ℃ at the heating rate of 1 ℃/min, and keeping the temperature for 4h; then cooling to 835 ℃ at a cooling rate of 1 ℃/min; keeping the temperature at 835 ℃ for 3 days, then cooling the sample to room temperature along with the furnace, and taking out the sample to obtain Sm alloy 0.6 Mg 0.4 Ni 2.0 Al 0.30 。
And (3) testing the structure and hydrogen storage performance of the prepared alloy: powder X-ray diffraction test is carried out on the sintered alloy, and the test result shows that the alloy consists of single MgCu 4 A Sn phase. The prepared alloy is mechanically crushed to 200 meshes, and can be directly used as a hydrogen storage material, and the hydrogen can be completely activated after first hydrogen absorption, and the maximum hydrogen absorption amount can reach 1.34wt.%. It can be seen that MgCu is prepared using this method 4 The Sn type multi-element single-phase hydrogen storage alloy has high capacity and is easy to activate; and the structure is basically not changed after 80 times of hydrogen absorption and desorption cycles.
The above description is only of the preferred embodiments of the present invention, and it should be noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the invention and these are intended to be within the scope of the invention.

Claims (15)

1. MgCu 4 Sn type hydrogen storage alloy, characterized in that the MgCu is 4 The chemical composition of the Sn type hydrogen storage alloy is R 1- x Mg x Ni y M a Said hydrogen storage alloy having a single MgCu 4 Sn phase structure, the phase abundance is 100%;
wherein R is selected from any one or more of lanthanide, Y, ca, zr and Ti; m is selected from any one or more of a fourth transition metal element, a fifth period transition metal element, B, al, ga, in, gn, sn and Sb; and R is not equal to M;
the value ranges of x, y and a are as follows: x is more than or equal to 0.39 and less than or equal to 0.45; y is more than or equal to 1.80 and less than or equal to 2.10; a is more than or equal to 0.05 and less than or equal to 0.20;
the MgCu 4 The preparation method of the Sn type hydrogen storage alloy comprises the following steps:
(1) Mechanically grinding R-Ni-M intermediate alloy serving as a precursor alloy into powder to obtain first raw material powder; mechanically grinding Mg-R, mg-Ni and/or Mg-M magnesium-containing alloy into powder to obtain second raw material powder;
(2) Uniformly mixing the first raw material powder and the second raw material powder obtained in the step (1) in proportion, and carrying out sintering heat treatment;
the sintering heat treatment is step-by-step treatment and comprises a plurality of temperature rise stages and temperature reduction stages;
the sintering heat treatment sequentially comprises three temperature rising stages and two temperature lowering stages:
a first temperature rise stage: raising the temperature from room temperature to 550-650 ℃, and preserving the temperature for 0.5-1.5 h;
a second temperature rising stage: continuously heating from 550-650 ℃ to 700-800 ℃, and preserving heat for 0.5-1.5 h;
a third temperature rise stage: continuously heating from 700-800 ℃ to 900-950 ℃, and preserving heat for 3-5 h;
a first cooling stage: cooling to the heat preservation temperature from 900-950 ℃, and preserving the heat for 3-5 days at the heat preservation temperature;
and a second cooling stage: cooling to room temperature from the heat preservation temperature to obtain the MgCu 4 A Sn-type hydrogen storage alloy;
wherein the heat preservation temperature is 820-870 ℃.
2. The MgCu of claim 1 4 Sn-type hydrogen storage alloy, characterized in that the sintering heat treatment comprises:
a first temperature rise stage: heating from room temperature to 600 ℃, and preserving heat for 1h;
a second temperature rising stage: continuously heating from 600 ℃ to 750 ℃, and preserving heat for 1h;
a third temperature rise stage: continuously heating from 750 ℃ to 900 ℃, and preserving heat for 4h;
a first cooling stage: cooling to the heat preservation temperature from 900 ℃, and preserving heat for 3 days at the heat preservation temperature;
a second cooling stage: cooling to room temperature from the heat preservation temperature to obtain the MgCu 4 A Sn-type hydrogen storage alloy;
wherein the heat preservation temperature is 820-870 ℃.
3. The MgCu of claim 1 4 The Sn type hydrogen storage alloy is characterized in that the temperature rise rate of the first temperature rise stage is 3-5 ℃/min.
4. The MgCu of claim 1 4 The Sn type hydrogen storage alloy is characterized in that the temperature rise rate of the second temperature rise stage is 0.5-1.5 ℃/min.
5. The MgCu of claim 1 4 The Sn type hydrogen storage alloy is characterized in that the temperature rise rate of the third temperature rise stage is 0.5-1.5 ℃/min.
6. The MgCu of claim 1 4 The Sn type hydrogen storage alloy is characterized in that the temperature reduction rate of the first temperature reduction stage is 0.5-1.5 ℃/min.
7. The MgCu of claim 1 4 The Sn type hydrogen storage alloy is characterized in that the temperature reduction in the second temperature reduction stage is natural cooling.
8. The MgCu of claim 1 4 The Sn type hydrogen storage alloy is characterized in that the R-Ni-M intermediate alloy is prepared by induction melting.
9. The MgCu of claim 1 4 The Sn type hydrogen storage alloy is characterized in that the alloy containing magnesium is selected from any one or more of R-Mg, ni-Mg and M-Mg.
10. The MgCu of claim 1 4 The Sn-type hydrogen storage alloy is characterized in that the particle size of the first raw material powder is 50-400 meshes.
11. The MgCu of claim 1 4 The Sn type hydrogen storage alloy is characterized in that the grain diameter of the first raw material powder is 200-400 meshes.
12. The MgCu of claim 1 4 The Sn-type hydrogen storage alloy is characterized in that the particle size of the second raw material powder is 50-400 meshes.
13. The MgCu of claim 1 4 The Sn-type hydrogen storage alloy is characterized in that the particle size of the second raw material powder is 200-400 meshes.
14. The MgCu of claim 1 4 The Sn type hydrogen storage alloy is characterized in that the pressure in the sintering heat treatment is 0.07-0.12 MPa.
15. The MgCu of claim 1 4 The Sn type hydrogen storage alloy is characterized in that the pressure in the sintering heat treatment is 0.08-0.11 MPa.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108493436A (en) * 2018-03-09 2018-09-04 燕山大学 Ni-based quaternary hydrogen-storing alloy electrode material of a kind of super stacking provisions lanthanum-M-magnesium-of 2H types A5B19 and preparation method thereof
CN112877567A (en) * 2021-01-11 2021-06-01 包头中科轩达新能源科技有限公司 Hydrogen storage alloy suitable for low-pressure solid hydrogen storage and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108493436A (en) * 2018-03-09 2018-09-04 燕山大学 Ni-based quaternary hydrogen-storing alloy electrode material of a kind of super stacking provisions lanthanum-M-magnesium-of 2H types A5B19 and preparation method thereof
CN112877567A (en) * 2021-01-11 2021-06-01 包头中科轩达新能源科技有限公司 Hydrogen storage alloy suitable for low-pressure solid hydrogen storage and preparation method thereof

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