CN113106296B - Rare earth metal hydride hydrogen storage alloy suitable for solid-state hydrogen storage and preparation method thereof - Google Patents
Rare earth metal hydride hydrogen storage alloy suitable for solid-state hydrogen storage and preparation method thereof Download PDFInfo
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- 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
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- 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
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- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
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- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C2202/00—Physical properties
- C22C2202/04—Hydrogen absorbing
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
Abstract
The invention discloses a rare earth metal hydride hydrogen storage alloy suitable for solid-state hydrogen storage, which has a chemical general formula of R1‑x‑yMgxAyNiz‑w‑vBwCvThe hydrogen absorption and desorption device has the advantages of easy activation, high hydrogen absorption and desorption speed and moderate hydrogen absorption and desorption platform pressure, can be suitable for low-pressure solid hydrogen storage equipment and hydrogenation stations, and has the advantages of high safety, high volume hydrogen storage density and low cost; the invention also provides a preparation method of the hydrogen storage alloy, the hydrogen storage alloy is prepared through the steps of material preparation, smelting and heat treatment in sequence, the method is simple, the process is easy to control, and the hydrogen storage alloy with a corresponding phase structure can be prepared, so that the hydrogen storage performance of the obtained alloy is ensured, and the hydrogen storage alloy is convenient for industrial production and application. The invention is suitable for preparing the rare earth metal hydride hydrogen storage alloy for solid-state hydrogen storage.
Description
Technical Field
The invention belongs to the field of new energy materials, and relates to a rare earth metal hydride hydrogen storage alloy suitable for solid-state hydrogen storage and a preparation method thereof.
Background
With the continuous development of the economy of all countries in the world, the demand of energy is more and more. In order to solve the contradiction between economic development and energy demand, clean new energy sources must be searched to maintain the sustainable development of economy. Hydrogen energy, which is a clean and pollution-free secondary energy with high combustion value and abundant reserves, is meeting the demand of current social development for energy, so that hydrogen energy is receiving more and more attention, and industries related to the hydrogen energy are rapidly developed in recent years.
The popularization and promotion of hydrogen energy sources cannot leave the storage and transportation of hydrogen. The hydrogen has small density, is easy to leak, and has wide explosion range after being mixed with air, and the like, and is greatly limited in the storage and transportation process. Therefore, how to efficiently and conveniently store and transport hydrogen becomes a key link for promoting the development of a hydrogen energy system. Hydrogen storage materials currently being developed and studied mainly include the following classes: metal hydride hydrogen storage materials, complex hydrogen storage materials, organic liquid hydrogen storage materials, porous solid adsorption hydrogen storage materials and the like. Among them, the rare earth metal hydride hydrogen storage material is still the most promising hydrogen storage material with relatively high capacity under mild conditions.
In the existing different series of metal hydride hydrogen storage alloys, the Mg series alloy hydrogen storage capacity has the most advantages, but the hydrogen absorption and desorption temperature is too high, the dynamic performance is delayed, and the large-scale application of the alloy is restricted. The TiFe alloy is low in manufacturing cost and high in hydrogen storage capacity, but is difficult to activate and easy to poison. AB5The hydrogen storage alloy is easy to activate, has high hydrogen absorbing and releasing speed and small lag, but has low hydrogen storage capacity. The hydrogen storage capacity of the rare earth magnesium nickel hydrogen storage alloy developed in recent years is higher than that of AB5The hydrogen storage alloy has the advantages of easy activation, high hydrogen absorption and desorption platform pressure, strong regulation and control and good application prospect. The rare earth magnesium nickel hydrogen storage alloy is a hydrogen storage alloy with superlattice structure, and is formed from (A)2B4]And [ AB ]5]The subunits are formed by stacking along axis c at a certain ratio and can be divided into AB3Type (1:1), A2B7Type (1:2), A5B19Types (1:3) and AB4Type (1: 4). In the preparation process of the rare earth magnesium nickel hydrogen storage alloy, besides the superlattice structure, AB with a non-superlattice structure also exists2And AB5A type phase. Researches show that a certain interaction exists among different phase structures in the rare earth magnesium nickel hydrogen storage alloy, wherein AB is5The phase structure has high hydrogen absorbing and releasing pressure and certain catalytic effect, and can absorb hydrogenCan improve the hydrogen absorption and desorption rate of the alloy, so that the alloy is prepared into AB5The rare earth magnesium nickel series alloy with the multiphase composite of the type phase structure and the superlattice phase structure has important significance for improving the hydrogen absorption and desorption performance of the rare earth magnesium nickel series hydrogen storage alloy to a certain degree. How to effectively control the preparation with AB5The rare earth magnesium nickel hydrogen storage alloy with the multiphase composite of the type phase structure and the superlattice phase structure simultaneously considers the hydrogen storage performances of the hydrogen storage alloy, such as hydrogen absorption and desorption platform pressure, hydrogen storage capacity and the like, has simple process steps, short time consumption and meets the requirement of industrial scale, and becomes a technical problem to be solved urgently at present.
Disclosure of Invention
In order to solve the above technical problems, the present invention aims to provide a rare earth metal hydride hydrogen storage alloy suitable for solid-state hydrogen storage, wherein the chemical formula of the hydrogen storage alloy is R1-x-yMgxAyNiz-w-vBwCvThe hydrogen absorption/desorption device has the advantages of easy activation, high hydrogen absorption/desorption speed, moderate hydrogen absorption/desorption platform pressure, high safety, high volume hydrogen storage density and low cost, and can be suitable for low-pressure solid hydrogen storage equipment and hydrogenation stations.
The invention also provides a preparation method of the rare earth metal hydride hydrogen storage alloy suitable for solid-state hydrogen storage, the hydrogen storage alloy is prepared through the steps of material preparation, smelting and heat treatment in sequence, the process is simple and easy to control, and the hydrogen storage alloy forming the corresponding phase structure can be prepared, so that the hydrogen storage performance of the obtained alloy is ensured, and the industrial production and application are facilitated.
The technical scheme provided by the invention is as follows:
a rare-earth metal hydride hydrogen storage alloy suitable for solid-state hydrogen storage has a chemical general formula R1-x-yMgxAyNiz-w-vBwCvWherein x, y, z, w and v represent molar ratio, x is more than or equal to 0.05 and less than or equal to 0.20, y is more than or equal to 0 and less than or equal to 0.50, z is more than 4.10 and less than or equal to 4.80, w is more than 0 and less than or equal to 0.15, and v is more than or equal to 0 and less than or equal to 0.05; in the formula: r is at least one element selected from the rare earth elements Pr, Nd, Sm, Gd and Y, A is at least one element selected from the group consisting of La, Ce, Pr, Nd, Sm, Gd, Zr, Ti and V, B represents at least one element selected from the group consisting of Mn, Al and CoC represents at least one element selected from Mn, Al, Co, Si, Fe and Cu.
The invention prepares the low-pressure solid hydrogen storage alloy which can increase the hydrogen storage capacity of the alloy and improve the hydrogen absorption and desorption platform and the hydrogen absorption and desorption dynamic performance according to the difference of the atomic radius and the electronegativity of different elements and the coaction with atoms of transition metal elements; the hydrogen storage alloy provided by the invention has the advantages of high hydrogen storage capacity, moderate pressure of a hydrogen absorption and desorption platform, easy activation and high hydrogen absorption and desorption speed, and is suitable for solid hydrogen storage devices.
In the alloy composition expression of the invention, when x is more than 0.20, along with the increase of the content of Mg element in the alloy, AB in the alloy under the preparation method provided by the invention5The phase structure content is too low, the pressure of the alloy hydrogen absorption and release platform is low, and the circulation stability is poor; when x is less than 0.05, AB in the prepared alloy5The phase structure content is too high, and the hydrogen absorbing and releasing capacity of the hydrogen storage alloy is lower than 1.0 wt%.
The elements on the R side and the A side are main hydrogen absorption elements in the alloy, when the content of the element other than the R element in the A exceeds 0.5, for example, the La and the Ce elements can reduce the platform pressure of the hydrogen storage alloy, and the Zr, the Ti and the V elements can reduce the hydrogen storage capacity of the hydrogen storage alloy. In addition, the transition metal element in B is mainly used for regulating and controlling the hysteresis quality of the alloy hydrogen absorption and desorption platform, but when the content of Mn, Al and Co of B side elements exceeds 0.20, namely w + v is more than or equal to 0.20, the pressure of the prepared alloy platform is reduced; when v is more than 0.05, the hydrogen storage capacity of the alloy is obviously reduced. In addition, the structural composition of the alloy phase is controlled by the value of z under specific preparation conditions, and when z is less than or equal to 4.10, the non-superlattice structure AB exists in the prepared alloy under the preparation conditions2The phase content, the pressure of the alloy hydrogen absorption and desorption platform is reduced, and when z is more than 4.80, the non-superlattice AB in the prepared alloy5The content of the phase structure is too high, and the hydrogen storage capacity of the alloy is obviously reduced.
As a limitation of the invention, the crystal structure of the hydrogen storage alloy is a superlattice single-phase structure, or AB5Phase structure and superlattice single phaseA phase structure of composition, the superlattice single-phase structure comprises A2B7Type A5B19Type and AB4Type superlattice phase structure.
As a further limitation of the invention, the hydrogen storage alloy has a crystal structure consisting of AB5In the phase structure consisting of a phase structure and a superlattice single-phase structure, AB5The phase structure content is 15-70 wt%; preferably, AB5The phase structure content is 30-40 wt%.
The invention also provides a preparation method of the rare earth hydrogen storage alloy suitable for low-pressure solid hydrogen storage, which is sequentially carried out according to the following steps:
(1) ingredients
Selecting a metal simple substance or an alloy compound as a raw material, and batching according to the chemical composition of the alloy, wherein the volatilization loss in preparation is considered, and the volatilization amount of corresponding elements is supplemented and increased in batching;
(2) melting
Preparing an as-cast alloy by adopting an induction smelting method, vacuumizing a furnace chamber to be lower than 0.06MPa before smelting, introducing high-purity argon to be 0.01-0.04 MPa, adding metal Mg in a secondary feeding manner, casting the alloy into a water-cooled ingot mold, and cooling to obtain an alloy ingot;
(3) thermal treatment
And sealing the alloy ingot, then loading the alloy ingot into a vacuum annealing furnace, filling inert gas into the furnace, and then carrying out heat treatment to obtain the final hydrogen storage alloy.
As a limitation of the present invention:
in the step (one), the heat treatment is carried out according to the following steps:
the first stage, raising the temperature from room temperature to 300 ℃, and keeping the temperature for 0.5 h;
in the second stage, raising the temperature from 300 ℃ to 600 ℃, and keeping the temperature for 1 h;
in the third stage, the temperature is raised from 600 ℃ to 800-900 ℃, and the temperature is kept for 5-10 h;
and step four, cooling to room temperature along with the furnace.
In the second step (3), the inert gas is nitrogen or helium.
And (III) in the step (3), the pressure of the inert gas is 0-0.04 MPa.
As a further limitation of the preparation method of the rare earth metal hydride hydrogen storage alloy suitable for solid-state hydrogen storage, the temperature rise rate of the first stage is 5-10 ℃/min; the temperature rise rate of the second stage is 5-10 ℃/min; and the temperature rise rate of the third stage is 2-5 ℃/min.
In the preparation process of the invention, because the melting points of metals such as Mg, Mn, Al and the like are low and the metals are easy to volatilize in the smelting process, the metals need to be added in an overdosing manner during the material preparation so as to ensure that the alloy obtained by smelting is in a preset proportion range. Before the smelting is started, the smelting device is vacuumized and high-purity argon gas with certain pressure is introduced to reduce the content of non-metal impurities in the alloy, so that the hydrogen storage capacity of the alloy is improved. Because metal Mg in the superlattice structure is very volatile in the smelting process, the metal Mg is added in a secondary feeding mode, the loss of magnesium is reduced, the stable alloy components are ensured, and all elements are uniformly distributed, so that the composition of alloy elements is ensured, and the phase structure of the alloy after subsequent annealing is ensured.
The prepared as-cast alloy is annealed to eliminate lattice defect of hydrogen storing alloy, reduce internal stress of alloy, raise hydrogen storing capacity and hydrogen absorbing and releasing platform pressure of hydrogen storing alloy, reduce hysteresis and raise the As-cast alloy AB2The phase non-superlattice phase structure is converted into a superlattice phase structure through peritectic reaction, and meanwhile, the composition of an alloy phase structure is guaranteed. Wherein, in the first stage of heating and heat-preserving annealing process in the heat treatment process, the heat treatment temperature is the non-oxidation preheating stage of the annealing process, and simultaneously, certain stress is eliminated in the alloy; in the second stage of temperature rise and heat preservation annealing process, AB in the as-cast hydrogen storage alloy2The phase structure dissociates into corresponding chemical particles; in the third stage of temperature raising and maintaining process, the dissociated reactant chemical particles enter the alloy continuously to form non-superlattice phase structure AB5And the phase structure forms a superlattice phase structure with a certain content through peritectic reaction.
The preparation method of the invention is taken as a whole, each step is closely related, the reversible hydrogen absorption and desorption capacity of the hydrogen storage alloy is more than 1.0 wt% under the condition of 25 ℃, the hydrogen can be absorbed and desorbed within 5min to more than 80% of the maximum capacity, and the pressure of the hydrogen desorption platform is more than 0.5 MPa.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the technical progress that:
1. the preparation method provided by the invention is simple and stable in operation and equipment, easy in control of process conditions, simple in method and convenient for industrial production and application.
2. The hydrogen storage alloy provided by the invention has the advantages of easiness in activation, high hydrogen absorption and desorption speed, moderate hydrogen absorption and desorption platform pressure and the like, can be suitable for 1-5 MPa low-pressure solid hydrogen storage equipment and 35-70 MPa hydrogen storage devices of mobile and hydrogenation stations, and has the advantages of high safety, high volume hydrogen storage density and low cost.
The invention is suitable for preparing the low-pressure solid hydrogen storage alloy.
The present invention will be described in further detail with reference to specific examples.
Drawings
FIG. 1 is a structural view of XRD of a hydrogen occluding alloy prepared in example 1 of the present invention;
FIG. 2 is a XRD structural view of a hydrogen occluding alloy prepared in example 2 of the present invention;
FIG. 3 is a XRD structural view of a hydrogen occluding alloy prepared in example 3 of the present invention;
FIG. 4 is a XRD structural view of a hydrogen occluding alloy prepared in example 4 of the present invention;
FIG. 5 is a XRD structural view of a hydrogen occluding alloy prepared in example 5 of the present invention;
FIG. 6 is an XRD structural view of a hydrogen occluding alloy prepared in example 6 of the present invention;
FIG. 7 is a P-C-T diagram of a hydrogen occluding alloy prepared in example 1 of the present invention;
FIG. 8 is a P-C-T graph of a hydrogen occluding alloy prepared in example 2 of the present invention;
FIG. 9 is a P-C-T graph of a hydrogen occluding alloy prepared in example 3 of the present invention;
FIG. 10 is a P-C-T graph of a hydrogen occluding alloy prepared in example 4 of the present invention;
FIG. 11 is a P-C-T graph of a hydrogen occluding alloy prepared in example 5 of the present invention;
FIG. 12 is a P-C-T graph of a hydrogen occluding alloy prepared in example 6 of the present invention;
FIG. 13 is a hydrogen absorption/desorption graph of hydrogen storage alloys prepared in examples 1 to 6 of the present invention.
Detailed Description
The reagents used in the following examples can be purchased from commercially available reagents, unless otherwise specified, and the preparation methods and the test methods used in the following examples can be performed by conventional methods, unless otherwise specified.
Example 1
The embodiment provides a rare earth metal hydride hydrogen storage alloy suitable for solid-state hydrogen storage, which comprises the following components: sm0.92Mg0.08Ni4.11Co0.13Al0.06The preparation method comprises the following steps in sequence:
(11) preparing materials: metals Sm, Mg, Ni, Co and Al are selected as raw materials, the materials are mixed according to the chemical composition of the alloy in the embodiment, and the volatilization loss in preparation is considered, so that the volatilization amount of corresponding elements is supplemented and increased in mixing;
(12) smelting: preparing as-cast alloy by adopting an induction smelting method, vacuumizing a furnace chamber to 0.08MPa before smelting, and introducing high-purity argon to 0.01 MPa; smelting the raw materials to be completely alloyed, overturning for multiple times in the smelting process to ensure the uniformity of the alloy, wherein the metal Mg is added in a secondary feeding mode, finally casting the alloy into a water-cooled ingot mold, and cooling to obtain an alloy ingot;
(13) and (3) heat treatment: sealing the cast alloy ingot (alloy ingot) obtained in the step, then putting the alloy ingot into a vacuum annealing furnace, filling argon to 0MPa, and then carrying out heat treatment to obtain the final hydrogen storage alloy;
in this step, the heat treatment is carried out in the following order:
in the first stage, the temperature is raised from room temperature to 300 ℃ at the heating rate of 5 ℃/min, and the temperature is kept for 0.5 h;
in the second stage, the temperature is raised from 300 ℃ to 600 ℃ at the heating rate of 7 ℃/min, and the temperature is kept for 1 h;
in the third stage, the temperature is raised from 600 ℃ to 800 ℃ according to the temperature raising rate of 5 ℃/min, and the temperature is kept for 8 hours;
and step four, cooling to room temperature along with the furnace.
The hydrogen absorbing alloy ingot obtained in this example was pulverized and ground into powder by a mechanical mill, and the powder of the alloy having a particle size of 37 μm or less was analyzed by X-ray diffraction (XRD), as shown in FIG. 1. The analysis of the result shows that the alloy phase structure is formed by AB5Type (52 wt.%) phase structure, 3R type AB4(5 wt.%) phase structure, 2H form a5B19Phase structure of form (21 wt.%) and 3R form a5B19Type (22 wt.%) phase structure.
Example 2
The embodiment provides a rare earth metal hydride hydrogen storage alloy suitable for solid-state hydrogen storage, which comprises the following components: nd (neodymium)0.60Ce0.10Ti0.10Mg0.20Ni3.92Co0.05Si0.05The preparation method comprises the following steps in sequence:
(21) preparing materials: selecting Nd, Ti, Mg, Ni, Co, Si and Ce as raw materials, batching according to the alloy chemical composition of the embodiment, and supplementing and increasing the volatilization amount of corresponding elements in batching considering volatilization loss in preparation;
(22) smelting: preparing as-cast alloy by adopting an induction smelting method, vacuumizing a furnace chamber to 0.08MPa before smelting, and introducing high-purity argon to 0.04 MPa; smelting the raw materials to be completely alloyed, overturning for multiple times in the smelting process to ensure the uniformity of the alloy, wherein the metal Mg is added in a secondary feeding mode, finally casting the alloy into a water-cooled ingot mold, and cooling to obtain an alloy ingot;
(23) and (3) heat treatment: sealing the cast alloy ingot (alloy ingot) obtained in the step, putting the alloy ingot into a vacuum annealing furnace, filling helium to 0.04MPa, and then carrying out heat treatment to obtain the final hydrogen storage alloy;
in this step, the heat treatment is carried out in the following order:
in the first stage, the temperature is raised to 300 ℃ from room temperature according to the heating rate of 7 ℃/min, and the temperature is kept for 0.5 h;
in the second stage, the temperature is raised from 300 ℃ to 600 ℃ according to the temperature raising rate of 5 ℃/min, and the temperature is kept for 1 h;
in the third stage, according to the heating rate of 2 ℃/min, the temperature is raised from 600 ℃ to 900 ℃, and the temperature is kept for 5 hours;
and step four, cooling to room temperature along with the furnace.
The hydrogen absorbing alloy ingot obtained in this example was pulverized and ground into powder by a mechanical mill, and the powder of the alloy having a particle size of 37 μm or less was analyzed by X-ray diffraction (XRD), as shown in FIG. 2. The analysis of the result shows that the alloy phase structure is formed by AB5Form (15 wt.%) phase structure, 2H form a2B7Phase structure of form (26 wt.%), 3R form a2B7Type (44 wt.%) phase structure and 3R type a5B19Type (15 wt.%) phase structure.
Example 3
The embodiment provides a rare earth metal hydride hydrogen storage alloy suitable for solid-state hydrogen storage, which comprises the following components: y is0.65Sm0.15La0.10Mg0.10Ni3.90Co0.10Al0.05Mn0.05The preparation method comprises the following steps in sequence:
(31) preparing materials: selecting metals Y, Sm, La, Mg, Ni, Co, Al and Mn as raw materials, batching according to the alloy chemical composition of the embodiment, considering volatilization loss in preparation, and supplementing and increasing volatilization amount of corresponding elements during batching;
(32) smelting: preparing as-cast alloy by adopting an induction smelting method, vacuumizing a furnace chamber to 0.08MPa before smelting, and introducing high-purity argon to 0.02 MPa; smelting the raw materials to be completely alloyed, overturning for multiple times in the smelting process to ensure the uniformity of the alloy, wherein the metal Mg is added in a secondary feeding mode, finally casting the alloy into a water-cooled ingot mold, and cooling to obtain an alloy ingot;
(33) and (3) heat treatment: sealing the cast alloy ingot (alloy ingot) obtained in the step, then putting the alloy ingot into a vacuum annealing furnace, filling argon to 0.04MPa, and then carrying out heat treatment to obtain the final hydrogen storage alloy;
in this step, the heat treatment is carried out in the following order:
in the first stage, the temperature is increased from room temperature to 300 ℃ at the heating rate of 10 ℃/min, and the temperature is kept for 0.5 h;
in the second stage, the temperature is raised from 300 ℃ to 600 ℃ according to the heating rate of 10 ℃/min, and the temperature is kept for 1 h;
in the third stage, according to the heating rate of 3 ℃/min, the temperature is raised from 600 ℃ to 850 ℃, and the temperature is kept for 7 h;
and step four, cooling to room temperature along with the furnace.
The hydrogen-absorbing alloy ingot obtained in this example was pulverized and ground into powder by a mechanical mill, and the powder of the alloy having a particle size of 37 μm or less was analyzed by X-ray diffraction (XRD), as shown in FIG. 3. Analysis shows that the alloy phase structure is AB5Form (18 wt.%) phase structure, 2H form a5B19Phase structure of form (59 wt.%) and 3R form a5B19Type (21 wt.%) phase structure.
Example 4
The embodiment provides a rare earth metal hydride hydrogen storage alloy suitable for solid-state hydrogen storage, which comprises the following components: pr (Pr) of0.72Y0.05La0.10Ce0.05Mg0.08Ni4.0Co0.10Fe0.05The preparation method comprises the following steps in sequence:
(41) preparing materials: selecting metals Pr, Y, La, Ce, Mg, Ni, Co and Fe as raw materials, and batching according to the alloy chemical composition of the embodiment, wherein the volatilization loss in preparation is considered, and the volatilization amount of corresponding elements is supplemented and increased in batching;
(42) smelting: preparing as-cast alloy by adopting an induction smelting method, vacuumizing a furnace chamber to 0.08MPa before smelting, and introducing high-purity argon to 0.04 MPa; smelting the raw materials to be completely alloyed, overturning for multiple times in the smelting process to ensure the uniformity of the alloy, wherein the metal Mg is added in a secondary feeding mode, finally casting the alloy into a water-cooled ingot mold, and cooling to obtain an alloy ingot;
(43) and (3) heat treatment: sealing the cast alloy ingot (alloy ingot) obtained in the step, putting the alloy ingot into a vacuum annealing furnace, filling helium to 0.04MPa, and then carrying out heat treatment to obtain the final hydrogen storage alloy;
in this step, the heat treatment is carried out in the following order:
in the first stage, the temperature is raised from room temperature to 300 ℃ at the heating rate of 8 ℃/min, and the temperature is kept for 0.5 h;
in the second stage, the temperature is raised from 300 ℃ to 600 ℃ according to the temperature raising rate of 5 ℃/min, and the temperature is kept for 1 h;
in the third stage, according to the heating rate of 5 ℃/min, the temperature is increased from 600 ℃ to 900 ℃, and the temperature is kept for 10 h;
and in the fourth stage, cooling the mixture to room temperature along with the furnace.
The hydrogen-absorbing alloy ingot produced in this example was mechanically crushed and ground into powder, and the powder of the alloy having a particle size of 37 μm or less was subjected to X-ray diffraction (XRD) analysis, as shown in fig. 4. The analysis of the result shows that the alloy phase structure is A5B19Form (35 wt.%) phase structure, 2H form a5B19Type (42 wt.%) phase structure and 3R type a5B19Type (23 wt.%) phase structure.
Example 5
The embodiment provides a rare earth metal hydride hydrogen storage alloy suitable for solid-state hydrogen storage, which comprises the following components: gd (Gd)0.62V0.20Mg0.18Ni4.82Al0.08The preparation method comprises the following steps in sequence:
(51) preparing materials: selecting metals Gd, V, Mg, Ni and Al as raw materials, batching according to the alloy chemical composition of the embodiment, considering volatilization loss in preparation, and supplementing and increasing the volatilization amount of corresponding elements during batching;
(52) smelting: an as-cast alloy is prepared by an induction melting method. Before smelting, vacuumizing a furnace chamber to 0.08MPa, and introducing high-purity argon to 0.04 MPa; smelting the raw materials to be completely alloyed, overturning for multiple times in the smelting process to ensure the uniformity of the alloy, wherein the metal Mg is added in a secondary feeding mode, finally casting the alloy into a water-cooled ingot mold, and cooling to obtain an alloy ingot;
(53) and (3) heat treatment: sealing the cast alloy ingot (alloy ingot) obtained in the step, then putting the alloy ingot into a vacuum annealing furnace, filling argon to 0.04MPa, and then carrying out heat treatment to obtain the final hydrogen storage alloy;
in this step, the heat treatment is carried out in the following order:
in the first stage, the temperature is raised from room temperature to 300 ℃ at the heating rate of 5 ℃/min, and the temperature is kept for 0.5 h;
in the second stage, the temperature is raised from 300 ℃ to 600 ℃ according to the heating rate of 10 ℃/min, and the temperature is kept for 1 h;
in the third stage, according to the heating rate of 2 ℃/min, heating from 600 ℃ to 800 ℃, and preserving heat for 5 hours;
and step four, cooling to room temperature along with the furnace.
The hydrogen-absorbing alloy ingot obtained in this example was pulverized and ground into powder by a mechanical mill, and the powder of the alloy having a particle size of 37 μm or less was analyzed by X-ray diffraction (XRD), as shown in FIG. 5. The analysis of the result shows that the alloy phase structure is AB5Form (60 wt.%) phase structure, 2H form a5B19Phase structure of form (18 wt.%) and 3R form a5B19Type (22 wt.%) phase structure.
Example 6
The embodiment provides a rare earth metal hydride hydrogen storage alloy suitable for solid-state hydrogen storage, which comprises the following components: sm0.95Mg0.05Ni4.2Co0.10Cu0.05The preparation method comprises the following steps in sequence:
(61) preparing materials: metals Sm, Mg, Ni, Co and Cu are selected as raw materials, the alloy is proportioned according to the chemical composition of the alloy in the embodiment, and the volatilization loss in preparation is considered, so that the volatilization amount of corresponding elements is supplemented and increased in proportioning;
(62) smelting: preparing as-cast alloy by adopting an induction smelting method, vacuumizing a furnace chamber to 0.08MPa before smelting, and introducing high-purity argon to 0.04 MPa; smelting the raw materials to be completely alloyed, overturning for multiple times in the smelting process to ensure the uniformity of the alloy, wherein the metal Mg is added in a secondary feeding mode, finally casting the alloy into a water-cooled ingot mold, and cooling to obtain an alloy ingot;
(63) and (3) heat treatment: sealing the cast alloy ingot (alloy ingot) obtained in the step, putting the alloy ingot into a vacuum annealing furnace, and then filling argon or helium inert gas atmosphere to 0.04MPa for heat treatment to obtain the final hydrogen storage alloy;
in this step, the heat treatment is carried out in the following order:
in the first stage, the temperature is increased from room temperature to 300 ℃ at the heating rate of 9 ℃/min, and the temperature is kept for 0.5 h;
in the second stage, the temperature is raised from 300 ℃ to 600 ℃ according to the heating rate of 8 ℃/min, and the temperature is kept for 1 h;
in the third stage, according to the heating rate of 3 ℃/min, the temperature is raised from 600 ℃ to 870 ℃, and the temperature is kept for 8 hours;
and step four, cooling to room temperature along with the furnace.
The hydrogen-absorbing alloy ingot produced in this example was mechanically crushed and ground to obtain a powder, and the powder of the alloy having a particle size of 37 μm or less was analyzed by X-ray diffraction (XRD), as shown in FIG. 6. The analysis of the result shows that the alloy phase structure is AB5Form (70 wt.%) phase structure, 2H form a5B19Phase structure of form (10 wt.%), 3R form a5B19Form (3 wt.%) phase structure, 2H form a2B7Form (4 wt.%) phase structure, 3R form a2B7Type (13 wt.%) phase structure.
Example 7 Performance testing
The hydrogen storage alloys prepared in examples 1 to 6 were used as samples, and after crushing the samples into particles of 100 μm, hydrogen storage performance was measured, and hydrogen absorption/desorption P-C-T curves and hydrogen absorption/desorption performance of the samples at different temperatures were measured, and the results are shown in fig. 7 to 13 and table 1.
As can be seen from fig. 7 to 12, the maximum hydrogen storage capacities of the hydrogen storage alloys prepared in examples 1, 2, 3, 4, 5 and 6 at 25 ℃ were 1.34 wt.%, 1.35 wt.%, 1.10 wt.%, 1.12 wt.%, 1.15 wt.% and 1.10 wt.%, respectively, and the hydrogen storage capacities were all 1.0 wt.% or more.
The pressure of the hydrogen discharging platform of the alloy reaches 0.75MPa, 0.61MPa, 1.40MPa, 1.98MPa, 3.35MPa and 3.53MPa respectively, and the pressure is more than 0.5 MPa; the hydrogen absorption and desorption hysteresis factors are respectively 0.10, 0.41, 0.37, 0.45, 0.23 and 0.22, and are all below 0.5.
As can be seen from FIG. 13, the hydrogen absorption and desorption amounts of the hydrogen occluding alloys prepared in examples 1 to 6 were maximized within 2min at the respective test temperatures.
The test results show that the hydrogen storage alloy prepared in the embodiments 1 to 6 is suitable for low-pressure solid hydrogen storage devices and 35 to 70MPa hydrogenation stations.
TABLE 1 chemical formula of alloy and hydrogen storage property of each example
The embodiments 1 to 6 are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and those skilled in the art may make modifications or changes to the equivalent embodiments by using the above technical contents as a teaching. However, simple modifications, equivalent changes and modifications of the above embodiments may be made without departing from the technical spirit of the claims of the present invention, and the scope of the claims of the present invention may be protected.
Claims (5)
1. A rare earth metal hydride hydrogen storage alloy suitable for solid-state hydrogen storage is characterized in that the chemical general formula of the hydrogen storage alloy is R x-y1-Mg x A y Ni z-w-v B w C v In the formula (I), the reaction is carried out,x、y、z、w、vexpressed as a molar ratio, 0.05 ≦x≤0.20，0≤y≤0.50，4.10＜z≤4.80，0＜w≤0.15，0≤vLess than or equal to 0.05; in the formula: r is selected from at least one element of rare earth Pr, Nd, Sm, Gd and Y, A is selected from at least one element of La, Ce, Pr, Nd, Sm, Gd, Zr, Ti and V, B represents at least one element selected from Mn, Al and Co, C represents at least one element selected from Mn, Al, Co, Si, Fe and Cu;
the preparation method of the rare earth metal hydride hydrogen storage alloy suitable for solid-state hydrogen storage is sequentially carried out according to the following steps:
(1) ingredients
Selecting a metal simple substance or an alloy compound as a raw material, and batching according to the chemical composition of the alloy, wherein the volatilization loss in preparation is considered, and the volatilization amount of corresponding elements is supplemented and increased in batching;
(2) melting
Preparing an as-cast alloy by adopting an induction smelting method, vacuumizing a furnace chamber to be lower than 0.06MPa before smelting, introducing high-purity argon to be 0.01-0.04 MPa, adding metal Mg in a secondary feeding manner, casting the alloy into a water-cooled ingot mold, and cooling to obtain an alloy ingot;
(3) thermal treatment
Sealing the alloy cast ingot, then loading the alloy cast ingot into a vacuum annealing furnace, filling inert gas into the vacuum annealing furnace, and then carrying out heat treatment to obtain a final hydrogen storage alloy;
the heat treatment is carried out according to the following stages in sequence:
in the first stage, the temperature is increased from room temperature to 300 ℃, the temperature increase rate is 5-10 ℃/min, and the temperature is kept for 0.5 h;
in the second stage, raising the temperature from 300 ℃ to 600 ℃, wherein the temperature raising rate is 5-10 ℃/min, and keeping the temperature for 1 h;
in the third stage, the temperature is raised from 600 ℃ to 800-900 ℃, the temperature raising rate is 2-5 ℃/min, and the temperature is kept for 5-10 h;
and step four, cooling to room temperature along with the furnace.
2. The rare-earth metal hydride hydrogen storage alloy as claimed in claim 1, wherein the crystal structure of the alloy is a single phase superlattice structure or AB structure5A phase structure consisting of a phase structure and a superlattice single-phase structure including A2B7Type A5B19Type and AB4Type superlattice phase structure.
3. According to claim 1The rare earth metal hydride hydrogen storage alloy suitable for solid-state hydrogen storage is characterized in that the crystal structure of the hydrogen storage alloy is AB5In the phase structure consisting of a phase structure and a superlattice single-phase structure, AB5The phase structure content is 15-70 wt%.
4. The rare earth metal hydride hydrogen storage alloy as claimed in claim 1, wherein: in the step (3), the inert gas is nitrogen or helium.
5. The rare earth metal hydride hydrogen storage alloy as claimed in any one of claims 1 to 4, wherein: in the step (3), the pressure of the inert gas is 0-0.04 MPa.
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| CN115074578B (en) * | 2022-06-07 | 2023-04-07 | 有研工程技术研究院有限公司 | Y-Mg-Ni-based hydrogen storage alloy and preparation method thereof |
| CN115948678A (en) * | 2022-12-19 | 2023-04-11 | 包头稀土研究院 | AB5 type hydrogen storage alloy, preparation method and application of Ce and Al |
| CN115961177A (en) * | 2023-02-03 | 2023-04-14 | 包头中科轩达新能源科技有限公司 | High-power long-life hydrogen storage alloy with superlattice structure and preparation method thereof |
| CN116043064A (en) * | 2023-02-03 | 2023-05-02 | 包头中科轩达新能源科技有限公司 | Low-cost long-life pure phase 2H type A 2 B 7 Hydrogen storage alloy electrode material and preparation method thereof |
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