CN114703400B - A 5 B 19 Rare earth-yttrium-nickel hydrogen storage alloy, battery and preparation method - Google Patents

A 5 B 19 Rare earth-yttrium-nickel hydrogen storage alloy, battery and preparation method Download PDF

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CN114703400B
CN114703400B CN202210433973.9A CN202210433973A CN114703400B CN 114703400 B CN114703400 B CN 114703400B CN 202210433973 A CN202210433973 A CN 202210433973A CN 114703400 B CN114703400 B CN 114703400B
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王利
张旭
李金�
李宝犬
徐津
赵玉园
周淑娟
熊玮
闫慧忠
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Ruike Rare Earth Metallurgy and Functional Materials National Engineering Research Center Co Ltd
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Abstract

The invention discloses A 5 B 19 Rare earth-yttrium-nickel hydrogen storage alloy, battery and preparation method thereof. The A is 5 B 19 Rare earth-yttrium-nickel based hydrogen storage alloy having RE x Y 3‑x Ni y M z Is composed of the following components: wherein Y is yttrium element, ni is nickel element, RE is one or more selected from La, ce, pr, nd, sm and Gd elements; m is selected from one or more of Mn, al, cu, fe and Co elements; wherein x, 3-x, Y, z represent molar coefficients of RE, Y, ni and M, respectively; wherein 0.75<x≤1.2；0.55<z is less than or equal to 1.4, and y+z is less than or equal to 11.0 and less than or equal to 12.0; the phase structure of the hydrogen storage alloy is single-phase A 5 B 19 Super-stack chopping structure consisting of only AB 5 Subcell and AB 2 Stacking subcells; wherein AB 5 The average length of the c-axis of the subcell is
Figure DDA0003612089960000011
Figure DDA0003612089960000012
AB 2 The average length of the c-axis of the subcell is
Figure DDA0003612089960000013
The hydrogen storage alloy of the present invention has a single phase A 5 B 19 Super pile structure.

Description

A 5 B 19 Rare earth-yttrium-nickel hydrogen storage alloy, battery and preparation method
Technical Field
The invention relates to A 5 B 19 Rare earth-yttrium-nickel hydrogen storage alloy, battery and preparation method thereof.
Background
On the one hand, la-Mg-Ni-based hydrogen storage alloys have received attention because of their high discharge capacity. However, an important problem of the La-Mg-Ni alloy is industrialization problem, mainly because the alloy contains magnesium element with low melting point and is extremely volatile, the alloy composition is difficult to control by using the traditional vacuum induction melting method, and the volatilized magnesium powder is easy to cause explosion, so that the alloy is difficult to form large-scale production, and therefore, the development of the high-capacity hydrogen storage alloy without magnesium element has important significance.
On the other hand, la-Mg-Ni based hydrogen storage alloy is composed of a certain number of [ AB ] 5 ]And [ AB 2 ]Super-stacked structural alloys with subunits stacked in the c-axis direction. La-Mg-Ni based hydrogen storage alloys are classified into different types due to the number of stacked subunits: AB (AB) 3 A is a 2 B 7 Form A and A 5 B 19 Type (2). Each type of super-stacked structure is based on its inclusion [ A ] 2 B 4 ]The subunit types are different and are classified into type 2H and type 3R. It has also been found that the effect between the phases of different super-stacks can affect the electrochemical properties of the alloy, and that the complex phase structure of the alloy makes it difficult to determine the phase characteristics of a particular super-stack, and also the effect on the electrochemical properties of the alloy. CN108493436a discloses a 2H type a 5 B 19 La-M-Mg-Ni based quaternary hydrogen storage alloy electrode material with super-stacking structure and chemical composition of La x M y Mg z Ni r Wherein, x, y, z, r is the atomic ratio, and x is more than or equal to 0.6 and less than or equal to 0.7, y is more than or equal to 0.1 and less than or equal to 0.2, z is more than or equal to 0.1 and less than or equal to 0.20, and r is more than or equal to 3.70 and less than or equal to 3.85; m is one of rare earth elements Pr, nd, sm or Gd. The hydrogen storage alloy electrode material contains metal element Mg and has 2H type A 5 B 19 Alloy material of super-stacking structure.
Therefore, research and experiments show that La-Y-Ni series hydrogen storage alloy without magnesium element has good activation performance, multiplying power discharge capacity and charge-discharge or hydrogen absorption-discharge cycling stability.
For example, CN104532062A discloses a yttrium-nickel rare earth hydrogen storage alloy of the formula RE x Y y Ni z-a-b Mn a Al b RE is one or more elements in La, ce, pr, nd, sm, gd; x is x>0，y≥0.5，x+y＝3；12.5≥z≥11；5.5≥a+b>0.CN104152749A discloses A added with zirconium and titanium 5 B 19 RE is one or more elements in La, ce, pr, nd, sm, gd; m is one or more elements in Cu, fe, co, sn, V, W; x is x>0，y≥0.5，x+y＝3；12.5≥z≥14；4≥a+b>0，3.5≥c≥0，2.5≥A+B>0. The hydrogen storage alloy contains no Mg element and is A 5 B 19 But still not a single phase super-stacked structure.
In addition, it has been found that La-Y-Ni based hydrogen storage alloys are similar to La-Mg-Ni alloys, and are also generally of a multi-phase structure, including AB 3 、A 2 B 7 、A 5 B 19 、AB 5 The phase composition has a great influence on the electrochemical performance of the phase. At present, the research is more that A 2 B 7 La-Y-Ni hydrogen storage alloy and reports that single phase A can be prepared 2 B 7 La-Y-Ni based hydrogen storage alloy. However, no single phase A is known at present 5 B 19 Reports of rare earth-yttrium-nickel based hydrogen storage alloys.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a 5 B 19 Rare earth-yttrium-nickel hydrogen storage alloy, its phase structure is single phase A 5 B 19 Super-stack chopping structure consisting of only AB 5 Subcell and AB 2 The subcells are stacked. Further, AB 5 The average length of the c-axis of the subcell is
Figure BDA0003612089940000021
AB 2 The average length of the c-axis of the subcell is
Figure BDA0003612089940000022
Another object of the present invention is to provide a method for producing the above hydrogen storage alloy. It is still another object of the present invention to provide a battery. The invention adopts the following technical scheme to realize the aim. />
In one aspect, the present invention provides a 5 B 19 A rare earth-yttrium-nickel-based hydrogen storage alloy having a composition represented by formula (1):
RE x Y 3-x Ni y M z (1)
wherein Y is yttrium element, ni is nickel element, RE is one or more selected from La, ce, pr, nd, sm and Gd elements; m is selected from one or more of Mn, al, cu, fe and Co elements;
wherein x, 3-x, Y, z represent molar coefficients of RE, Y, ni and M, respectively;
wherein x is more than 0.75 and less than or equal to 1.2;0.55< z < 1.4 and 11.0 < y+z < 12.0;
the phase structure of the hydrogen storage alloy is single-phase A 5 B 19 Super-stack chopping structure consisting of only AB 5 Subcell and AB 2 Stacking subcells; wherein AB 5 The average length of the c-axis of the subcell is
Figure BDA0003612089940000031
AB 2 The average length of the c-axis of the subcell is +.>
Figure BDA0003612089940000032
Figure BDA0003612089940000033
The hydrogen occluding alloy according to the present invention preferably does not contain A in the phase structure of the hydrogen occluding alloy 2 B 7 Form and AB 5 Type (2).
In the hydrogen occluding alloy according to the present invention, it is preferable that the hydrogen occluding alloy is subjected to X-ray diffraction measurement using Cu-K alpha as a ray source, and in an X-ray diffraction pattern produced by using diffraction angle 2 theta as a horizontal axis, unit of diffraction angle 2 theta is DEG and detection intensity as a vertical axis, the intensity of the strongest diffraction peak in the range of 35 DEG.ltoreq.2 theta.ltoreq.37 DEG is regarded as I A The intensity of the strongest diffraction peak in the range of 31 DEG.ltoreq.2θ.ltoreq.34° is taken as I B ，I A And I B The ratio of (2) satisfies the following relation:
0.87≤I A /I B ≤2.67。
according to the hydrogen occluding alloy of the present invention, preferably, the hydrogen occluding alloy does not contain Mg, zr, and Ti elements.
The hydrogen occluding alloy according to the present invention preferably has a composition represented by one of the following formulas:
LaY 2 Ni 10.6 Mn 0.5 Al 0.3 ，
La 0.9 Ce 0.1 Y 2 Ni 10.2 Mn 0.8 ，
La 0.6 Pr 0.1 Nd 0.1 Y 2.2 Ni 10.6 Mn 0.5 Al 0.5 ，
LaSm 0.1 Y 1.9 Ni 10.6 Mn 0.5 Fe 0.1 ，
LaY 2 Ni 11 Mn 0.5 Co 0.3 ，
La 0.9 Gd 0.3 Y 1.8 Ni 10.6 Mn 0.5 Al 0.3 ，
LaY 2 Ni 10.6 MnCu 0.4 ，
La 0.8 Nd 0.2 Y 2 Ni 10.6 Mn 0.6 ，
La 0.8 Pr 0.2 Y 2 Ni 10.8 Mn 0.6 or (b)
LaNd 0.1 Sm 0.1 Y 2 Ni 10.4 Mn 0.6 Co 0.5 。
In another aspect, the present invention also provides A as described above 5 B 19 The preparation method of the rare earth-yttrium-nickel hydrogen storage alloy comprises the following steps:
preparing a raw material according to a composition represented by formula (1); preparing an alloy sheet by using an intermediate frequency induction smelting-rapid quenching process; placing the alloy sheet into a heat treatment device for sectional heat treatment, and naturally cooling to obtain A 5 B 19 Rare earth-yttrium-nickel based hydrogen storage alloy;
wherein the sectional heat treatment comprises: raising the temperature from room temperature to 680-720 ℃ at a first heating rate of 9-16 ℃/min, raising the temperature to 830-870 ℃ at a second heating rate of 4.5-8 ℃/min, and preserving the temperature for 20-40 min; then heating to 935-960 ℃ at a third heating rate of 4.5-8 ℃/min, and preserving heat for 20-40 min; then the temperature is raised to 1030-1150 ℃ at a fourth heating rate of 1-3 ℃/min, and the temperature is kept for 20-23 h.
According to the preparation method of the invention, preferably, the intermediate frequency induction smelting-rapid quenching process comprises the following steps: putting the raw materials into a smelting furnace, vacuumizing to an absolute vacuum degree of below 5Pa, and filling inert gas until the relative vacuum degree is 0.05-0.06 MPa for smelting protection; heating to fully melt the raw materials, refining for 2-4 min, and cooling the molten liquid by a rotary copper roller with cooling water to obtain an alloy sheet; wherein the linear speed of the rotating copper roller is 3-5 m/s.
According to the production method of the present invention, preferably, the thickness of the alloy sheet is 0.15 to 1.0mm.
According to the preparation method of the present invention, preferably, before the sectional heat treatment, the heat treatment apparatus is evacuated to an absolute vacuum degree of 0.2Pa or less, and then an inert gas of 0.045 to 0.055MPa is introduced.
In yet another aspect, the present invention also provides a battery comprising A as described above 5 B 19 Rare earth-yttrium-nickel based hydrogen storage alloys.
A of the invention 5 B 19 The phase structure of the hydrogen storage alloy is single phase A 5 B 19 Super-stack chopping structure consisting of only AB 5 Subcell and AB 2 Stacking subcells; AB (AB) 5 The average length of the c-axis of the subcell is
Figure BDA0003612089940000051
AB 2 The average length of the c-axis of the subcell is +.>
Figure BDA0003612089940000052
Further, the phase structure of the hydrogen storage alloy does not contain A 2 B 7 Form and AB 5 Type (2). The invention can obtain single-phase A by controlling the temperature rising rate of the sectional heat treatment, the temperature of the sectional heat treatment and the sectional heat preservation time 5 B 19 Hydrogen storage alloy of super-stack-chopped structure. In addition, the invention can be beneficial to single-phase A by controlling the thickness of the alloy sheet 5 B 19 And (5) forming a model.
Drawings
FIG. 1 shows the result A of example 4 of the present invention 5 B 19 XRD diffraction pattern of rare earth-yttrium-nickel hydrogen storage alloy.
FIG. 2 is an XRD diffraction pattern of the rare earth-yttrium-nickel-based hydrogen storage alloy obtained in comparative example 1-1.
Detailed Description
The present invention will be further described with reference to specific examples, but the scope of the present invention is not limited thereto.
In the present invention, the absolute vacuum represents the actual pressure in the container. The relative vacuum represents the difference between the pressure of the container and 1 normal atmospheric pressure. The inert gas includes nitrogen or argon, etc.
< Hydrogen absorbing alloy >
A of the invention 5 B 19 The rare earth-yttrium-nickel-based hydrogen storage alloy has a composition represented by formula (1):
RE x Y 3-x Ni y M z (1)
the hydrogen storage alloy of the present invention is free of metal elements Mg, zr, and Ti. Preferably, the hydrogen occluding alloy of the present invention does not add any additional components other than some unavoidable impurities.
RE is selected from one or more of La, ce, pr, nd, sm and Gd elements. In certain embodiments, RE is selected from one of La, ce, pr, nd, sm and Gd elements. In other embodiments, RE is selected from two of La, ce, pr, nd, sm and Gd elements. In still other embodiments, RE is selected from three of La, ce, pr, nd, sm and Gd elements.
Preferably, RE contains La. In certain embodiments, RE contains La, and La is 50 to 100 mole%, preferably 60 to 100 mole%, more preferably 65 to 100 mole% of the total moles of RE. In certain specific embodiments, RE is a combination of La and Ce. In other specific embodiments, RE is a combination of La and Gd. In still other specific embodiments, RE is a combination of La, pr, and Nd. In yet other specific embodiments, RE is a combination of La, nd, and Sm.
x represents the molar coefficient of RE, 0.75< x.ltoreq.1.2, preferably 0.8.ltoreq.x.ltoreq.1.2; more preferably, 0.85.ltoreq.x.ltoreq.1.2.
In the present invention, Y is yttrium element. 3-x represents the molar coefficient of Y.
In the present invention, M is selected from one or more of Mn, al, cu, fe and Co elements. Preferably, M is selected from one or two of Mn, al, cu, fe and Co elements. More preferably, M contains Mn.
In certain embodiments, M contains Mn, and Mn is 50 to 100 mole%, preferably 53 to 100 mole%, more preferably 54 to 100 mole% of the total moles of M.
In certain embodiments, M is Mn. In other specific embodiments, M is a combination of Mn and Al. In still other specific embodiments, M is a combination of Mn and Fe. In still other specific embodiments, M is a combination of Mn and Co. In other still specific embodiments, M is a combination of Mn and Cu.
z represents the molar coefficient of the element M. Z is less than or equal to 0.55 and less than or equal to 1.4; preferably, 0.6.ltoreq.z.ltoreq.1.4; more preferably, 0.65.ltoreq.z.ltoreq.1.4.
In the present invention, ni represents nickel element. y represents the molar coefficient of Ni, and y+z is 11.0.ltoreq.y.ltoreq.12.0.
The invention finds that such a chemical composition is more advantageous for obtaining single phase A 5 B 19 Super pile structure.
The phase structure of the rare earth-yttrium-nickel hydrogen storage alloy is single phase A 5 B 19 Super-stack structure, the phase structure of the hydrogen storage alloy does not contain A 2 B 7 Form and AB 5 Type (2). The single phase A 5 B 19 The super-stack chopping structure is composed of AB only 5 Subcell and AB 2 The subcells are stacked. Wherein AB 5 The average length of the c-axis of the subcell is
Figure BDA0003612089940000071
Preferably is
Figure BDA0003612089940000072
Figure BDA0003612089940000073
More preferably +.>
Figure BDA0003612089940000074
Wherein AB 2 The average length of the c-axis of the subcell is +.>
Figure BDA0003612089940000075
Preferably +.>
Figure BDA0003612089940000076
More preferably +.>
Figure BDA0003612089940000077
Figure BDA0003612089940000078
Such a structure is advantageous for forming single phase a 5 B 19 A super-stack chopping structure; in addition, the structure can provide a certain direction guide for further researching the electrochemical performance of the hydrogen storage alloy.
In the invention, the Maid software is used for carrying out Rietveld refinement on the XRD diffraction pattern to obtain AB 5 Subcell and AB 2 The average length of the c-axis of the subcell.
In the present invention, the hydrogen storage alloy is subjected to X-ray diffraction measurement using Cu-K alpha as a ray source, and in an X-ray diffraction pattern produced by taking the diffraction angle 2 theta as the horizontal axis, the unit of the diffraction angle 2 theta as DEG and the detection intensity as the vertical axis, the intensity of the strongest diffraction peak in the range of 35 DEG to 2 theta to 37 DEG is regarded as I A The intensity of the strongest diffraction peak in the range of 31 DEG.ltoreq.2θ.ltoreq.34° is taken as I B ，I A And I B The ratio of (2) satisfies the following relation: i is more than or equal to 0.87 A /I B And is less than or equal to 2.67. Preferably, I A And I B The ratio of (2) satisfies the following relation: i is more than or equal to 0.87 A /I B Less than or equal to 2.45. More preferably, I A And I B The ratio of (2) satisfies the following relation: i is not less than 0.92 A /I B Less than or equal to 2.45. This facilitates the formation of A 5 B 19 Rare earth-yttrium-nickel based hydrogen storage alloys.
A of the invention 5 B 19 Specific examples of rare earth-yttrium-nickel based hydrogen storage alloys include, but are not limited to, alloys represented by one of the following formulas:
LaY 2 Ni 10.6 Mn 0.5 Al 0.3 ，
La 0.9 Ce 0.1 Y 2 Ni 10.2 Mn 0.8 ，
La 0.6 Pr 0.1 Nd 0.1 Y 2.2 Ni 10.6 Mn 0.5 Al 0.5 ，
LaSm 0.1 Y 1.9 Ni 10.6 Mn 0.5 Fe 0.1 ，
LaY 2 Ni 11 Mn 0.5 Co 0.3 ，
La 0.9 Gd 0.3 Y 1.8 Ni 10.6 Mn 0.5 Al 0.3 ，
LaY 2 Ni 10.6 MnCu 0.4 ，
La 0.8 Nd 0.2 Y 2 Ni 10.6 Mn 0.6 ，
La 0.8 Pr 0.2 Y 2 Ni 10.8 Mn 0.6 or (b)
LaNd 0.1 Sm 0.1 Y 2 Ni 10.4 Mn 0.6 Co 0.5 。
< preparation method >
The preparation of the hydrogen storage alloy of the invention comprises the following steps: (1) a preparation step of an alloy sheet; (2) a step of sectional heat treatment. The following is a detailed description.
Preparation step of alloy sheet
Meeting the composition of RE x Y 3-x Ni y M z Is prepared; and preparing the alloy sheet by using an intermediate frequency induction smelting-rapid quenching process. RE (RE) x Y 3-x Ni y M z The specific components of (a) are detailed in the above description, and are not described in detail herein.
The intermediate frequency induction smelting-rapid quenching process comprises the following steps: putting the raw materials into a smelting furnace, vacuumizing to an absolute vacuum degree of below 5Pa, and filling inert gas until the relative vacuum degree is 0.05-0.06 MPa for smelting protection; heating to fully melt the raw materials, refining for 2-4 min, and cooling the molten liquid by a rotary copper roller with cooling water to obtain an alloy sheet; wherein the linear speed of the rotating copper roller is 3-5 m/s.
In certain embodiments, the raw materials are placed into an alumina crucible and then into a melting furnace, and the melting furnace is evacuated.
In some embodiments, the alloy sheet is prepared by heating to a temperature at which the raw materials are completely melted, refining in this state for 2 to 4 minutes, and pouring the molten liquid onto a rotating copper roll through which cooling water is passed. And taking out the alloy sheet for standby after the alloy sheet is cooled to room temperature.
In the present invention, the thickness of the alloy sheet is 0.15 to 1.0mm, preferably 0.15 to 0.65mm, more preferably 0.2 to 0.55mm, still more preferably 0.2 to 0.45mm. The present invention has found that this facilitates the formation of single phase A 5 B 19 Hydrogen storage alloy of super-stacking structure.
Stage heat treatment step
The alloy sheet is first placed in a heat treatment apparatus. Before the sectional heat treatment, the heat treatment device is vacuumized until the absolute vacuum degree is below 0.2Pa, preferably to below 0.15Pa, more preferably to below 0.1 Pa; then, an inert gas of 0.045 to 0.055MPa, preferably 0.047 to 0.055MPa, more preferably 0.05 to 0.055MPa is introduced.
And placing the alloy sheet into a heat treatment device for sectional heat treatment. The invention discovers that the single-phase A can be obtained only by adopting the sectional heat treatment under the specific conditions 5 B 19 Super pile structure. If the heat treatment conditions are not suitable, single phase A cannot be obtained 5 B 19 Super pile structure. Therefore, the heat treatment conditions are very important for the phase structure and are not a routine choice in the art.
In the present invention, the heat treatment apparatus may be a heat treatment vacuum furnace.
The sectional heat treatment includes: raising the temperature from room temperature to a first temperature at a first temperature raising rate, raising the temperature to a second temperature at a second temperature raising rate, and preserving heat for a first time; then heating to a third temperature at a third heating rate, and preserving heat for a second time; and then heating to a fourth temperature at a fourth heating rate, and preserving heat for a third time.
The first heating rate may be 9 to 16 deg.c/min, preferably 9.5 to 15.5 deg.c/min, more preferably 10 to 15.5 deg.c/min. The first temperature may be 680 to 720 ℃, preferably 690 to 720 ℃, more preferably 695 to 710 ℃.
The second heating rate may be 4.5 to 8 ℃/min, preferably 5 to 8 ℃/min, more preferably 5 to 7 ℃/min. The second temperature may be 830 to 870 ℃, preferably 840 to 860 ℃, more preferably 845 to 855 ℃. The first time of incubation may be 20 to 40 minutes, preferably 25 to 40 minutes, more preferably 25 to 35 minutes.
The third heating rate may be 4.5 to 8 ℃/min, preferably 5 to 8 ℃/min, more preferably 5.5 to 7.5 ℃/min. The third temperature may be 935 to 960 ℃, preferably 940 to 955 ℃, more preferably 945 to 955 ℃. The second time of incubation may be 20 to 40 minutes, preferably 25 to 40 minutes, more preferably 25 to 35 minutes.
The fourth heating rate may be 1 to 3℃per minute, preferably 1 to 2.5℃per minute, more preferably 1 to 2℃per minute. The fourth temperature may be 1030 to 1150 ℃, preferably 1040 to 1150 ℃, more preferably 1040 to 1120 ℃. The third time of incubation may be 20 to 23 hours, preferably 20 to 22.5 hours, more preferably 20 to 22 hours.
In the invention, the product is naturally cooled to room temperature (15-40 ℃). Such a heat treatment is advantageous in obtaining single phase A 5 B 19 Super heap of chop structure, AB therein 5 The average length of the c-axis of the subcell is within a specific range, AB 2 The average length of the c-axis of the subcell is within a specific range.
According to one embodiment of the present invention, the composition satisfies the formula RE x Y 3-x Ni y M z The raw materials of the alloy sheet are prepared, and an alloy sheet with the thickness of 0.2-0.3 mm is prepared by using an intermediate frequency induction smelting-rapid quenching process. Placing the alloy sheet into a heat treatment device, vacuumizing the heat treatment device until the absolute vacuum degree is below 0.2Pa, and then filling inert gas of 0.045-0.055 MPa. Then 9.5-15.5 ℃/minThe first heating rate is raised to 690-720 ℃ from room temperature, then raised to 840-860 ℃ at the second heating rate of 5-8 ℃/min, and the temperature is kept for 20-40 min; then heating to 940-955 ℃ at a third heating rate of 5-8 ℃/min, and preserving heat for 20-40 min; then the temperature is raised to 1040-1150 ℃ at a fourth heating rate of 1-2.5 ℃/min, and the temperature is kept for 20-23 h. Naturally cooling to 30-40 ℃.
< Battery >
The battery of the invention comprises A as described above 5 B 19 Rare earth-yttrium-nickel based hydrogen storage alloys.
< analytical methods >
XRD diffractometry: measured using a PANalytical XPERT-PRO powder diffractometer.
Examples 1 to 13
According to the formulation of table 1, a rare earth-yttrium-nickel based hydrogen storage alloy was prepared as follows:
and preparing the raw materials into alloy sheets with the thickness of 0.2-0.3 mm under the protection of argon by adopting an intermediate frequency induction smelting-rapid quenching process.
And placing the prepared alloy sheet into a heat treatment vacuum furnace for sectional heat treatment. Before heat treatment, vacuumizing a heat treatment furnace until the absolute vacuum degree is below 0.1Pa, then filling argon with the pressure of 0.05MPa for protection, raising the temperature from room temperature to a first temperature T1 at a first temperature raising rate of V1, raising the temperature to a second temperature T2 at a second temperature raising rate of V2, and preserving the heat for 30min; continuously heating to a third temperature T3 at a third heating rate of V3, and preserving heat for 30min; and then heating to a fourth temperature T4 at a fourth heating rate of V4, preserving heat, recording a third time of heat preservation as T3, and naturally cooling to room temperature to obtain the hydrogen storage alloy.
The above hydrogen storage alloys were ground respectively and then sieved through a 200 mesh sieve to obtain alloy powder, XRD testing was first conducted (XRD diffraction patterns of the hydrogen storage alloys obtained in example 4 are shown in FIG. 1, XRD diffraction patterns of examples 1-3 and 5 to 13 are not shown), and I was calculated from the collected data A /I B And carrying out Rietveld refinement on the XRD diffraction pattern by using Maud software to obtain AB 5 C-axis average length and AB of subcell 2 The average length of the c-axis of the subcell is shown in table 2. As can be seen from Table 2, the present inventionThe obtained hydrogen storage alloy is composed of A 5 B 19 Of the type consisting of AB only 5 Subcell and AB 2 Single phase a formed by subcell 5 B 19 Super stack structure.
Comparative examples 1 to 1
Comparative example 1-1 differs from example 1 in the heat treatment. Comparative example 1-1 an alloy flake was obtained by an intermediate frequency induction melting-rapid quenching process, and the alloy flake was annealed at 750 ℃ for 8 hours to obtain a hydrogen storage alloy. Grinding the above hydrogen storage alloy, sieving with 200 mesh sieve to obtain alloy powder, XRD testing, and calculating I according to the collected data A /I B As shown in table 2. As can be seen from FIG. 2, the alloy sheet obtained in comparative example 1-1 has a multi-phase structure with a major phase A 5 B 19 Phase, also contains A 2 B 7 Phase and AB 5 And (3) phase (C).
Comparative examples 1 to 2
Comparative examples 1-2 differ from example 1 in that the staged heat treatment is different. In the comparative example 1-2, the temperature is raised from room temperature to a first temperature T1 at a first temperature raising rate of V1, and then raised to a second temperature T2 at a second temperature raising rate of V2, and the temperature is kept for 30min; then heating to a third temperature T3 at a third heating rate of V3, and preserving heat for 20h; and finally, naturally cooling to room temperature to obtain the hydrogen storage alloy. XRD testing (XRD pattern not shown) was first performed and I was calculated from the data collected A /I B As shown in table 2. The hydrogen occluding alloy obtained in comparative examples 1-2 has a multi-phase structure with a main phase A 5 B 19 Phase, also contains A 2 B 7 Phase and AB 5 And (3) phase (C).
TABLE 1
Figure BDA0003612089940000131
TABLE 2
Figure BDA0003612089940000141
Note that: in tables 1 and 2, example 1 represents example 1, and so on. Example 1-1 represents comparative example 1-1, and so on.
The present invention is not limited to the above-described embodiments, and any modifications, improvements, substitutions, and the like, which may occur to those skilled in the art, fall within the scope of the present invention without departing from the spirit of the invention.

Claims (9)

1. A, A 5 B 19 A rare earth-yttrium-nickel-based hydrogen storage alloy characterized by having a composition represented by formula (1):
RE x Y 3-x Ni y M z (1)
wherein Y is yttrium element, ni is nickel element, RE is one or more selected from La, ce, pr, nd, sm and Gd elements; m is selected from one or more of Mn, al, cu, fe and Co elements;
wherein x, 3-x, Y, z represent molar coefficients of RE, Y, ni and M, respectively;
wherein x is more than 0.75 and less than or equal to 1.2;0.55< z < 1.4 and 11.0 < y+z < 12.0;
the phase structure of the hydrogen storage alloy is single-phase A 5 B 19 Super-stack chopping structure consisting of only AB 5 Subcell and AB 2 Stacking subcells; wherein AB 5 The average length of the c-axis of the subcell is
Figure FDA0004089891580000011
AB 2 The average length of the c-axis of the subcell is +.>
Figure FDA0004089891580000013
Figure FDA0004089891580000012
Performing an X-ray diffraction measurement on the hydrogen storage alloy by using Cu-K alpha as a ray source, wherein in an X-ray diffraction pattern manufactured by using a diffraction angle 2 theta as a horizontal axis, a unit of the diffraction angle 2 theta is DEG, and a detection intensity as a vertical axis, the strongest diffraction is within a range of 35 DEG 2 theta to 37 DEGPeak intensity as I A The intensity of the strongest diffraction peak in the range of 31 DEG.ltoreq.2θ.ltoreq.34° is taken as I B ，I A And I B The ratio of (2) satisfies the following relation:
0.87≤I A /I B ≤2.67。
2. the hydrogen occluding alloy of claim 1 wherein the phase structure of the hydrogen occluding alloy is free of a 2 B 7 Form and AB 5 Type (2).
3. The hydrogen occluding alloy of claim 1 wherein the hydrogen occluding alloy is free of Mg, zr and Ti elements.
4. A hydrogen occluding alloy as recited in any one of claims 1 to 3, having a composition represented by one of the following formulas:
LaY 2 Ni 10.6 Mn 0.5 Al 0.3 ，
La 0.9 Ce 0.1 Y 2 Ni 10.2 Mn 0.8 ，
La 0.6 Pr 0.1 Nd 0.1 Y 2.2 Ni 10.6 Mn 0.5 Al 0.5 ，
LaSm 0.1 Y 1.9 Ni 10.6 Mn 0.5 Fe 0.1 ，
LaY 2 Ni 11 Mn 0.5 Co 0.3 ，
La 0.9 Gd 0.3 Y 1.8 Ni 10.6 Mn 0.5 Al 0.3 ，
LaY 2 Ni 10.6 MnCu 0.4 ，
La 0.8 Nd 0.2 Y 2 Ni 10.6 Mn 0.6 ，
La 0.8 Pr 0.2 Y 2 Ni 10.8 Mn 0.6 or (b)
LaNd 0.1 Sm 0.1 Y 2 Ni 10.4 Mn 0.6 Co 0.5 。
5. A according to any one of claims 1 to 4 5 B 19 The preparation method of the rare earth-yttrium-nickel hydrogen storage alloy is characterized by comprising the following steps:
preparing a raw material according to a composition represented by formula (1); preparing an alloy sheet by using an intermediate frequency induction smelting-rapid quenching process; placing the alloy sheet into a heat treatment device for sectional heat treatment, and naturally cooling to obtain A 5 B 19 Rare earth-yttrium-nickel based hydrogen storage alloy;
wherein the sectional heat treatment comprises: raising the temperature from room temperature to 680-720 ℃ at a first heating rate of 9-16 ℃/min, raising the temperature to 830-870 ℃ at a second heating rate of 4.5-8 ℃/min, and preserving the temperature for 20-40 min; then heating to 935-960 ℃ at a third heating rate of 4.5-8 ℃/min, and preserving heat for 20-40 min; then the temperature is raised to 1030-1150 ℃ at a fourth heating rate of 1-3 ℃/min, and the temperature is kept for 20-23 h.
6. The method of claim 5, wherein the medium frequency induction melting-rapid quenching process comprises the steps of: putting the raw materials into a smelting furnace, vacuumizing to an absolute vacuum degree of below 5Pa, and filling inert gas until the relative vacuum degree is 0.05-0.06 MPa for smelting protection; heating to fully melt the raw materials, refining for 2-4 min, and cooling the molten liquid by a rotary copper roller with cooling water to obtain an alloy sheet; wherein the linear speed of the rotating copper roller is 3-5 m/s.
7. The method according to claim 6, wherein the thickness of the alloy sheet is 0.15 to 1.0mm.
8. The method according to any one of claims 5 to 7, wherein the heat treatment apparatus is evacuated to an absolute vacuum of 0.2Pa or less before the stepwise heat treatment, and then an inert gas of 0.045 to 0.055MPa is introduced.
9. A battery comprising the following claimsA as described in any one of 1 to 4 5 B 19 Rare earth-yttrium-nickel based hydrogen storage alloys.
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CN115261675B (en) * 2022-07-20 2022-12-23 华南理工大学 Single-phase or multi-phase AB 4 La-Y-Ni based superlattice hydrogen storage alloy and preparation method thereof
CN116024459A (en) * 2022-12-08 2023-04-28 有研工程技术研究院有限公司 Superlattice rare earth hydrogen storage material and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106086569A (en) * 2016-08-22 2016-11-09 河南理工大学 Multiphase Mg-RE-Ni hydrogen storage alloy and application thereof
CN111471893A (en) * 2020-04-14 2020-07-31 包头稀土研究院 Doped A5B19 type gadolinium-containing hydrogen storage alloy, electrode, battery and preparation method thereof
CN111471895A (en) * 2020-04-14 2020-07-31 包头稀土研究院 Hydrogen storage alloy containing gadolinium and nickel, cathode, battery and preparation method
CN111471911A (en) * 2020-04-14 2020-07-31 包头稀土研究院 Doped AB3 type rare earth-samarium-nickel hydrogen storage alloy, battery and preparation method

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5171114B2 (en) * 2007-05-30 2013-03-27 三洋電機株式会社 Hydrogen storage alloy for alkaline storage battery, method for producing the same, and alkaline storage battery
JP5577672B2 (en) * 2009-10-23 2014-08-27 株式会社Ｇｓユアサ Hydrogen storage alloy electrode and nickel metal hydride battery using the same
CN104195372B (en) * 2014-05-23 2016-09-28 四会市达博文实业有限公司 One uses for nickel-hydrogen battery many phase hydrogen storage alloys of RE-Mg-Ni system and preparation method thereof
CN104518204B (en) * 2014-08-28 2018-05-04 包头稀土研究院 A kind of rare earth-yttrium-nickel base hydrogen storage alloy and the secondary cell containing the hydrogen bearing alloy
CN104513915B (en) * 2014-08-28 2017-05-03 包头稀土研究院 Zirconium and titanium-doped AB3 type rare earth-yttrium-nickel family hydrogen storage alloy
CN104152749B (en) * 2014-08-28 2017-05-03 包头稀土研究院 A5B19 type rare earth-yttrium-nickel system hydrogen storage alloy added with zirconium and titanium elements
CN110317974B (en) * 2014-08-28 2021-02-05 包头稀土研究院 Yttrium-nickel rare earth hydrogen storage alloy
CN104513925B (en) * 2014-08-28 2017-05-03 包头稀土研究院 Yttrium-nickel rare earth family hydrogen storage alloy, and secondary battery containing hydrogen storage alloy
CN104532095B (en) * 2014-08-28 2017-01-25 包头稀土研究院 Yttrium-nickel rare earth-based hydrogen storage alloy
CN107275626B (en) * 2017-05-22 2019-11-22 燕山大学 A kind of single-phase AB4Type superlattice hydrogen storage alloy electrode material and preparation method thereof
CN108172807B (en) * 2018-01-10 2020-04-28 包头中科轩达新能源科技有限公司 Multi-element single-phase A5B19Superlattice hydrogen storage alloy electrode material and preparation method thereof
CN108493436B (en) * 2018-03-09 2021-01-08 燕山大学 2H-type A5B19 super-stacking structure lanthanum-M-magnesium-nickel-based quaternary hydrogen storage alloy electrode material and preparation method thereof
CN109825740B (en) * 2019-01-28 2020-09-04 燕山大学 Hydrogen storage alloy, preparation method thereof, hydrogen storage alloy electrode and nickel-metal hydride battery
CN111411262B (en) * 2020-04-14 2021-09-14 包头稀土研究院 A5B19 type gadolinium-containing hydrogen storage alloy, negative electrode and preparation method
CN111471894B (en) * 2020-04-14 2021-09-10 包头稀土研究院 Doped A5B19 type samarium-containing hydrogen storage alloy, battery and preparation method
CN113106296B (en) * 2021-04-13 2022-07-01 包头中科轩达新能源科技有限公司 Rare earth metal hydride hydrogen storage alloy suitable for solid-state hydrogen storage and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106086569A (en) * 2016-08-22 2016-11-09 河南理工大学 Multiphase Mg-RE-Ni hydrogen storage alloy and application thereof
CN111471893A (en) * 2020-04-14 2020-07-31 包头稀土研究院 Doped A5B19 type gadolinium-containing hydrogen storage alloy, electrode, battery and preparation method thereof
CN111471895A (en) * 2020-04-14 2020-07-31 包头稀土研究院 Hydrogen storage alloy containing gadolinium and nickel, cathode, battery and preparation method
CN111471911A (en) * 2020-04-14 2020-07-31 包头稀土研究院 Doped AB3 type rare earth-samarium-nickel hydrogen storage alloy, battery and preparation method

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