CN114457260A - MgCu4Sn type hydrogen storage alloy and preparation method thereof - Google Patents

MgCu4Sn type hydrogen storage alloy and preparation method thereof Download PDF

Info

Publication number
CN114457260A
CN114457260A CN202210092926.2A CN202210092926A CN114457260A CN 114457260 A CN114457260 A CN 114457260A CN 202210092926 A CN202210092926 A CN 202210092926A CN 114457260 A CN114457260 A CN 114457260A
Authority
CN
China
Prior art keywords
temperature
alloy
equal
hydrogen storage
stage
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.)
Granted
Application number
CN202210092926.2A
Other languages
Chinese (zh)
Other versions
CN114457260B (en
Inventor
李媛
张永玺
周迪
谢一超
韩树民
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yanshan University
Original Assignee
Yanshan University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Yanshan University filed Critical Yanshan University
Priority to CN202210092926.2A priority Critical patent/CN114457260B/en
Publication of CN114457260A publication Critical patent/CN114457260A/en
Application granted granted Critical
Publication of CN114457260B publication Critical patent/CN114457260B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Powder Metallurgy (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses MgCu4Sn type hydrogen storage alloy and a preparation method thereof. The chemical composition of the hydrogen storage alloy is R1‑ xMgxNiyMa(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, and y is more than or equal to 1.70 and less than or equal to 2And 20, 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 MgCu4The 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 1.00 wt.%, 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

MgCu4Sn type hydrogen storage alloy and preparation method thereof
Technical Field
The invention relates to the technical field of hydrogen storage alloys, in particular to MgCu4Sn 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 CaCu5AB of type5Subunits and a Laves phase (MgZn)2Or MgCu2Type A) of2B4The subunits are stacked. Wherein A is2B4Subunit and AB5The sub-units have more hydrogen storage sites and higher hydrogen storage capacity than each other. From the analysis of the crystal structure, if A2B4The tetrahedral or octahedral gaps in the subunits are all occupied by hydrogen atoms, and hydride AB can be generated2H17Therefore AB2The subunit has great hydrogen storage potential (if La is used)0.5Mg0.5Ni2H17Calculated to yield a hydrogen storage of about 8.5 wt.%). Currently there are few single-phase AB2Synthesis of type alloys, reported on the existing AB composition2The alloy reported by the type alloy can only generate AB after absorbing hydrogen2H6Far from the possible hydrogen storage capacity. And there are studies showing AB2Type rare earth alloy containerThe hydrogen-induced non-crystallization phenomenon is easy to generate, and the decay of the hydrogen storage capacity is fast.
Z.L.Chen,T.Z.Si,Q.A.Zhang,Hydrogen absorption-desorption cycle durability of SmMgNi4Journal of Alloys and Compounds 621(2015) 42-46 reported the preparation of a single AB using powder sintering2SmMgNi of type phase structure4The 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 AB2In the structure of the type phase, the ternary Sm-Mg-Ni system can provide fewer active hydrogen absorption sites, and further improvement is still needed. 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 needed4An Sn-type alloy. However, MgCu4The 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 generated4The difficulty of the Sn-type phase structure is greatly increased. MgCu doped with multiple elements at present4The Sn type single-phase hydrogen storage alloy has not been reported.
Disclosure of Invention
Aiming at the technical problem, the invention provides MgCu4A hydrogen storage alloy of Sn type, the alloy being MgCu in solid state4The 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 achieve the purpose, the invention adopts the technical scheme that:
in one aspect, the present invention provides a MgCu alloy4Sn type hydrogen storage alloy, said MgCu4The chemical composition of the Sn-type hydrogen storage alloy is R1-xMgxNiyMa；
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 MgCu4The intensity (I) of the strongest peak of Sn-type hydrogen storage alloy appearing in the range of 36-37 DEG 2 theta when measured by X-ray diffraction using Cu-Ka ray as X-ray sourceA) And the strongest peak intensity (I) occurring within 42-43 DEG of 2 thetaB) Intensity ratio (I) ofA/IB) Below 0.4, the alloy provided by the invention has a single phase structure.
In another aspect, the invention also provides the MgCu4The 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 carrying out 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: heating from room temperature to 550-650 ℃, and preserving heat 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 a heat preservation temperature, and preserving heat for 3-5 days at the heat preservation temperature;
and a second cooling stage: cooling from the holding temperature toRoom temperature to obtain the MgCu4A 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 the mixture from room temperature to 600 ℃, and keeping the temperature for 1 h;
a second temperature rising stage: continuously heating from 600 ℃ to 750 ℃, and preserving heat for 1 h;
a third temperature rise stage: continuously heating from 750 ℃ to 900 ℃, and preserving heat for 4 h;
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 MgCu4A Sn-type hydrogen storage alloy;
wherein the heat preservation temperature is 820-870 ℃.
In a preferred embodiment, the temperature rise rate of the first temperature rise stage is 3 to 5 ℃/min;
preferably, the temperature rise rate of the second temperature rise 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 meshes, and preferably 200 to 400 meshes.
In a preferred embodiment, the pressure in the sintering heat treatment is 0.07 to 0.12MPa, preferably 0.08 to 0.11 MPa.
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 MgCu4The Sn phase structure is obtained through X-ray diffraction and full-spectrum fitting analysis, the space group is F-43m, the phase abundance is 100%, and in a cycle test, the phase structure of the alloy with the pure phase structure can be kept stable, 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 1.00 wt.%, and is higher than 0.8 wt.% 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 invention4X-ray diffraction pattern of Sn type hydrogen storage alloy.
FIG. 2 shows MgCu prepared in example 2 of the present invention4PCT curve for Sn-type hydrogen storage alloy at 323K.
FIG. 3 shows MgCu prepared in example 3 of the present invention4PCT curve for Sn-type hydrogen storage alloy at 323K.
FIG. 4 shows MgCu prepared in example 4 of the present invention4PCT curve for Sn-type hydrogen storage alloy at 323K.
Detailed Description
The following examples are only a part of the present invention, and 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 invention, the room temperature is 20-30 ℃.
MgCu4Sn type hydrogen storage alloy
The invention provides MgCu4The Sn type hydrogen storage alloy comprises the following chemical components: r1-xMgxNiyMa；
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 intensity (I) of the strongest peak appearing in the range of 36-37 degrees 2 theta when the hydrogen storage alloy is measured by X-ray diffraction by taking Cu-Kalpha ray as an X-ray sourceA) And the strongest peak intensity (I) occurring within 42-43 DEG of 2 thetaB) Intensity ratio (I) ofA/IB) At 0.4, the XRD result is a reaction of the phase structure, and the above characterization results prove thatIt is clear 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. The Ni element cannot absorb hydrogen but contributes to dissociation of hydrogen molecules and adjustment of hydride stability during absorption and desorption of hydrogen in the hydrogen storage alloy. 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 hydrogen pressure balance and the like. 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 constructed4The 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.
MgCu4Preparation 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; uniformly mixing the first raw material powder and the second raw material powder in proportion, and carrying out sintering heat treatment.
Preferably, in the invention, the sintering heat treatment is preferably a step-by-step operation, and comprises a plurality of temperature rise stages and temperature reduction stages;
preferably, the sintering heat treatment sequentially comprises three temperature-rising stages and two temperature-lowering stages:
a first temperature rise stage: heating the mixture from room temperature to 550-650 ℃, and preserving heat 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 a heat preservation temperature, and preserving 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 MgCu4A 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 the temperature to 820 ℃, 830 ℃, 840 ℃, 850 ℃, 860 ℃, 870 ℃ or any value in between.
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 36-37 degrees 2 theta when the hydrogen storage alloy is subjected to X-ray diffraction measurement by taking Cu-Ka line as an X-ray sourceA) And the strongest peak intensity (I) occurring within 42-43 DEG of 2 thetaB) Intensity ratio (I) ofA/IB) Below 0.4.
Explanation on the setting of the temperature raising, holding, and cooling programs: firstly, raising the temperature from room temperature to 550-650 ℃ (the temperature is 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 to ensure that the magnesium-containing alloyStart decomposition and thermal diffusion without producing significant volatilization of magnesium; continuously heating to 700-800 ℃ (preferably 750 ℃) and preserving heat to fully decompose the magnesium-containing alloy and perform heat penetration; continuously heating to 900-950 ℃ (preferably 900 ℃) and preserving heat to enable the high-melting-point metal to fully perform 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 structure4Sn type multielement hydrogen storage alloy.
In a preferred embodiment, the temperature rise rate of the first temperature rise stage is 3 to 5 ℃/min;
preferably, the temperature rise rate of the second temperature rise 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.
In a preferred embodiment, the R-Ni-M master alloy is prepared by induction melting, and can obtain high-purity alloys, preferably 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 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 MgCu4And preparing the Sn type multi-element single-phase hydrogen storage alloy. The invention provides MgCu4The 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 invention adopts particles with the particle size of 50-400 meshes to facilitate the diffusion of components, and more preferably 200-400 meshes. 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, the 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 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 0.11 MPa.
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 smelting0.72Y0.28Ni3.56Co0.09Al0.16(first raw Material) with SmMg14.38The alloy (commercially available, second raw material) is mechanically ground to 200-400 meshes respectively, and the two kinds of powder are mechanically mixed to be uniform according to the following molar ratio: sm0.72Y0.28Ni3.56Co0.09Al0.16：SmMg14.381.000: 0.05; 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 1 h; then heating to 750 ℃ at the heating rate of 1 ℃/min, and preserving heat for 1 h; continuously heating to 900 ℃ at the heating rate of 1 ℃/min, and keeping the temperature for 4 h; then cooling to 850 ℃ at a 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(ii) a The obtained alloy is Sm0.44Y0.16Mg0.40Ni2.01Co0.05Al0.09。
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 alloy4A 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 1.55 wt.%. It can be seen that MgCu prepared using the present method4The 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 2
Precursor alloy Nd obtained by induction melting0.73Y0.27Ni3.42Co0.06Al0.15(first raw Material) with SmMg14.38The alloy (commercially available, second raw material) is mechanically ground to 100-300 meshes respectively, and the two kinds of powder are mechanically mixed to be uniform according to the following molar ratio: nd (neodymium)0.73Y0.27Ni3.98Co0.06Al0.15：SmMg14.381.000: 0.05; and (3) putting the uniformly mixed alloy powder into an annealing tank, keeping the argon pressure in an 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 1 h; then heating to 750 ℃ at the heating rate of 1 ℃/min, and preserving heat for 1 h; continuously heating to 900 ℃ at the heating rate of 1 ℃/min, and keeping the temperature for 4 h; 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 alloy0.41Sm0.0 3Y0.15Mg0.41Ni1.93Co0.03Al0.08。
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 alloy4A Sn phase. Will make intoThe obtained 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 1.10 wt.%. It can be seen that MgCu prepared using the present method4The 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 melting0.62Y0.39Ni3.60Co0.10Al0.13(first raw Material) with SmMg14.38The alloy (commercially available, second raw material) is mechanically ground to 300-400 meshes respectively, and the two kinds of powder are mechanically mixed to be uniform according to the following molar ratio: pr (Pr) of0.62Y0.39Ni3.60Co0.10Al0.13：SmMg14.381.000: 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 1 h; then heating to 750 ℃ at the heating rate of 1 ℃/min, and preserving heat for 1 h; continuously heating to 900 ℃ at the heating rate of 1 ℃/min, and keeping the temperature for 4 h; 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 Pr0.31Sm0.0 3Y0.19Mg0.47Ni1.79Co0.05Al0.06。
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 alloy4A Sn phase. The prepared alloy is mechanically crushed to 200 meshes and can be directly used as a hydrogen storage material, and FIG. 3 shows the PCT curve of the alloy in the embodiment when the alloy is crushed to 200 meshes at 323KThe hydrogen can be completely activated by first hydrogen absorption, and the solid line and the dotted line respectively represent 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 1.21 wt.%. It can be seen that MgCu prepared using the present method4The 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 4
Precursor alloy La obtained by induction melting0.62Y0.38Ni2.54Co0.12Al0.13(first feedstock) with LaMg13.20Mechanically grinding (second raw material sold in market) alloy to 50-200 meshes, and mechanically mixing two kinds of powder according to the following molar ratio until the two kinds of powder are uniform: la0.62Y0.38Ni2.54Co0.12Al0.13：LaMg13.201.000: 0.015. and (3) putting the uniformly mixed alloy powder into an annealing tank, keeping the argon pressure in an annealing furnace at 0.07-0.09 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 1 h; then heating to 750 ℃ at the heating rate of 1 ℃/min, and preserving heat for 1 h; continuously heating to 900 ℃ at the heating rate of 1 ℃/min, and keeping the temperature for 4 h; 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 La alloy0.52Y0.31Mg0.16Ni2.10Co0.10Al0.10。
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 alloy4A Sn phase. The prepared alloy is mechanically crushed to 200 meshes, namely can be directly used as a hydrogen storage material, fig. 4 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 1.36 wt.%. Therefore, the use of the present invention is clearMgCu prepared by the method4The 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 5
Precursor alloy Pr obtained by induction melting0.62La0.38Ni2.80Mn0.10Al0.15(first raw Material) with Mg2The Ni alloy (commercially available, second raw material) is mechanically ground to 300-400 meshes respectively, and the two kinds of powder are mechanically mixed according to the following molar ratio until the two kinds of powder are uniform: pr (Pr) of0.62La0.38Ni2.80Mn0.10Al0.15：Mg2Ni ═ 1.000: 0.201. and (3) putting the uniformly mixed alloy powder into an annealing tank, keeping the argon pressure in an 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 1 h; then heating to 750 ℃ at the heating rate of 1 ℃/min, and preserving heat for 1 h; continuously heating to 900 ℃ at the heating rate of 1 ℃/min, and keeping the temperature for 4 h; 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 Pr0.44La0.26Mg0.30Ni2.00Mn0.07Al0.11。
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 MgCu4A 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 1.40 wt.%. It can be seen that MgCu prepared using the present method4The 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 melting0.50Ca0.50Ni3.32Cu0.30(first raw Material) with Mg2Ni alloy (commercially available, second raw material)Respectively mechanically grinding the powder to 200-300 meshes, and mechanically mixing the two kinds of powder according to the following molar ratio until the two kinds of powder are uniform: la0.50Ca0.50Ni2.97Cu0.30：Mg2Ni ═ 1.000: 0.350 parts of; and (3) putting the uniformly mixed alloy powder into an annealing tank, keeping the argon pressure in an annealing furnace at 0.10-0.11 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 1 h; then heating to 750 ℃ at the heating rate of 1 ℃/min, and preserving heat for 1 h; continuously heating to 900 ℃ at the heating rate of 1 ℃/min, and keeping the temperature for 4 h; then cooling to 820 ℃ at a cooling rate of 1 ℃/min; keeping the temperature at 820 ℃ for 3 days, then cooling the sample to room temperature along with the furnace, and taking out the sample to obtain the alloy La0.29Ca0.29Mg0.42Ni1.95Cu0.18。
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 MgCu4A 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 1.48 wt.%. It can be seen that MgCu prepared using the present method4The 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 melting0.85Zr0.15Ni3.64Co0.30(first feedstock) with LaMg13.20The alloy (commercially available, second raw material) is mechanically ground to 300-400 meshes respectively, and the two kinds of powder are mechanically mixed to be uniform according to the following molar ratio: gd (Gd)0.85Zr0.15Ni3.64Co0.30：LaMg13.201.000: 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 1 h; then the temperature is raised at a heating rate of 1 ℃/minKeeping the temperature for 1h at 750 ℃; continuously heating to 900 ℃ at the heating rate of 1 ℃/min, and keeping the temperature for 4 h; 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 La0.03Gd0.50Zr0.09Mg0.39Ni2.15Co0.18。
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 MgCu4A 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 1.37 wt.%. It can be seen that MgCu prepared using the present method4The 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 melting3Al0.5(first raw Material) with Mg2The Ni alloy (commercially available, second raw material) is mechanically ground to 100-200 meshes respectively, and the two kinds of powder are mechanically mixed to be uniform according to the following molar ratio: SmNi3Al0.5：Mg2Ni ═ 3: 1; and (3) putting the uniformly mixed alloy powder into an annealing tank, keeping the argon pressure in an annealing furnace at 0.10-0.12 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 1 h; then heating to 750 ℃ at the heating rate of 1 ℃/min, and preserving heat for 1 h; continuously heating to 900 ℃ at the heating rate of 1 ℃/min, and keeping the temperature for 4 h; 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 alloy0.6Mg0.4Ni2.0Al0.30。
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 MgCu4A Sn phase. Will make intoThe obtained 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 1.34 wt.%. It can be seen that MgCu is prepared using this method4The 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 (10)

1. MgCu4Sn type hydrogen storage alloy, characterized in that the MgCu is4The chemical composition of the Sn-type hydrogen storage alloy is R1- xMgxNiyMa；
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.
2. The hydrogen occluding alloy of claim 1, wherein x, y, a have a value in the range of: 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.
3. A method for producing a hydrogen occluding alloy as recited in claim 1 or 2, comprising the steps of:
(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 carrying out sintering heat treatment.
4. The method according to claim 3, wherein the sintering heat treatment is a step-by-step treatment including a plurality of temperature-raising stages and temperature-lowering stages.
5. The method according to claim 4, wherein the sintering heat treatment comprises three temperature-raising stages and two temperature-lowering stages in sequence:
a first temperature rise stage: heating the mixture from room temperature to 550-650 ℃, and preserving heat 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 a heat preservation temperature, and preserving 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 MgCu4A 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 the mixture from room temperature to 600 ℃, and keeping the temperature for 1 h;
a second temperature rising stage: continuously heating from 600 ℃ to 750 ℃, and preserving heat for 1 h;
a third temperature rise stage: continuously heating from 750 ℃ to 900 ℃, and preserving heat for 4 h;
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 MgCu4A Sn-type hydrogen storage alloy;
wherein the heat preservation temperature is 820-870 ℃.
6. The preparation method according to claim 5, wherein the temperature rise rate of the first temperature rise stage is 3 to 5 ℃/min;
preferably, the temperature rise rate of the second temperature rise 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.
7. The method of claim 3, wherein the R-Ni-M master alloy is produced by induction melting.
8. The method according to claim 3, wherein the magnesium-containing alloy is selected from any one or more of R-Mg, Ni-Mg and M-Mg.
9. The preparation method according to claim 3, wherein the particle size of the first raw material powder is 50 to 400 mesh, preferably 200 to 400 mesh;
preferably, the particle size of the second raw material powder is 50 to 400 meshes, and preferably 200 to 400 meshes.
10. The method according to claim 3, wherein the pressure in the sintering heat treatment is 0.07 to 0.12MPa, preferably 0.08 to 0.11 MPa.
CN202210092926.2A 2022-01-26 2022-01-26 MgCu 4 Sn type hydrogen storage alloy and preparation method thereof Active CN114457260B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210092926.2A CN114457260B (en) 2022-01-26 2022-01-26 MgCu 4 Sn type hydrogen storage alloy and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210092926.2A CN114457260B (en) 2022-01-26 2022-01-26 MgCu 4 Sn type hydrogen storage alloy and preparation method thereof

Publications (2)

Publication Number Publication Date
CN114457260A true CN114457260A (en) 2022-05-10
CN114457260B CN114457260B (en) 2022-12-06

Family

ID=81410775

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210092926.2A Active CN114457260B (en) 2022-01-26 2022-01-26 MgCu 4 Sn type hydrogen storage alloy and preparation method thereof

Country Status (1)

Country Link
CN (1) CN114457260B (en)

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

Also Published As

Publication number Publication date
CN114457260B (en) 2022-12-06

Similar Documents

Publication Publication Date Title
CN111636012B (en) La-Mg-Ni series hydrogen storage material and preparation method thereof
Puszkiel et al. Thermodynamic and kinetic studies of Mg–Fe–H after mechanical milling followed by sintering
Zhao et al. Characterization and improvement of electrochemical properties of Pr5Co19-type single-phase La0. 84Mg0. 16Ni3. 80 alloy
CN113148947B (en) Rare earth alloy hydrogen storage material and preparation method thereof
KR101904499B1 (en) PROCESS FOR PRODUCTION OF (RARE EARTH)-Mg-Ni-BASED HYDROGEN STORAGE ALLOY
CN112779439A (en) Hydrogen storage material doped with V and capable of improving performance of ZrCo hydrogen storage alloy and preparation method of hydrogen storage material
US9859556B2 (en) Hydrogen absorption alloy powder, negative electrode, and nickel-hydrogen secondary cell
Zhang et al. Preparation and hydrogen storage properties of single-phase Ce2Ni7-type La–Sm–Y–Ni based hydrogen storage alloy
CN108172817B (en) Single-phase Gd2Co7Rare earth magnesium-nickel hydrogen storage alloy, preparation method and application thereof
CN112899548A (en) Yttrium-zirconium-iron-aluminum alloy material, preparation method and application
CN110241350B (en) Copper-containing cobalt-boron hydrogen storage material and preparation method and application thereof
CN114457260B (en) MgCu 4 Sn type hydrogen storage alloy and preparation method thereof
CN115074578B (en) Y-Mg-Ni-based hydrogen storage alloy and preparation method thereof
CN112708801B (en) Single-phase PuNi3Preparation method of type superlattice La-Y-Ni hydrogen storage alloy
CN113862536B (en) Mg-Al-Y-based hydrogen storage material and preparation method thereof
CN113881880A (en) High-capacity Gd-Mg-Ni-based composite hydrogen storage material doped with fluoride and preparation method thereof
CN106756355B (en) Fuel cell stores hydrogen intermediate alloy, hydrogen storage material and preparation method with Mg-Sn-Ni ternary
Zhu et al. Function mechanism of Fe in improving cycle stability and plateau characteristics of AB5-type hydrogen storage alloys
CN115710664B (en) Cobalt-containing Y-Mg-Ni-based hydrogen storage alloy and preparation method thereof
JP7439316B1 (en) Hydrogen storage alloy powder for nickel metal hydride battery negative electrode
CN115852273B (en) Preparation method of nanocrystalline magnesium-based hydrogen storage alloy
CN115595491B (en) Design and preparation method of ZrCo-based multi-element intermetallic compound with weak hydrogen absorption and desorption lattice distortion
WO2022250093A1 (en) High-entropy hydrogen storage alloy, negative electrode for alkaline storage batteries, and alkaline storage battery
CN116200627B (en) Long-cycle life pure-phase 2H-A2B7 hydrogen storage alloy electrode material and preparation method thereof
CN114672740B (en) Yttrium-iron-based hydrogen storage alloy, 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
GR01 Patent grant
GR01 Patent grant