CN110714139A - Rare earth-nickel-based hydrogen storage alloy material and preparation method thereof - Google Patents

Rare earth-nickel-based hydrogen storage alloy material and preparation method thereof Download PDF

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CN110714139A
CN110714139A CN201810774933.4A CN201810774933A CN110714139A CN 110714139 A CN110714139 A CN 110714139A CN 201810774933 A CN201810774933 A CN 201810774933A CN 110714139 A CN110714139 A CN 110714139A
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苑慧萍
刘彧儒
郭淼
蒋利军
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Beijing General Research Institute for Non Ferrous Metals
GRIMN Engineering Technology Research Institute Co Ltd
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    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
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    • C22C1/023—Alloys based on nickel
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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Abstract

A rare earth-nickel-based hydrogen storage alloy material and a preparation method thereof. The hydrogen storage alloy material has the chemical formula composition of C1‑x‑ ySmxYyNiz‑a‑bAlaDbWherein x is more than or equal to 0.2 and less than or equal to 0.8, y is more than or equal to 0 and less than or equal to 0.5, z is more than or equal to 3.4 and less than or equal to 3.6, a is more than or equal to 0.1 and less than or equal to 0.4, b is more than or equal to 0 and less than or equal to 0.15, C is one or more than two of La, Ce, Pr, Nd, Gd, Zr and Ti, and D is one or more than two of Co, Mn, Cu, V, Fe, Zn, W and Si. The preparation method comprises the following steps: preparing the pure metal block material according to the chemical formula composition; placing the prepared raw materials into a crucible of a vacuum induction furnace, baking, degassing, vacuumizing, and filling inert gas; and after the alloy is completely melted, refining, cooling and annealing the obtained alloy ingot. The alloy has high electrochemical capacity and stable circulationSex, rate discharge ability and lower plateau pressure.

Description

Rare earth-nickel-based hydrogen storage alloy material and preparation method thereof
Technical Field
The invention relates to a rare earth-nickel-based hydrogen storage alloy material and a preparation method thereofMethod, especially for preparing rare earth-nickel base A2B7A hydrogen storage alloy material and a preparation method thereof belong to the field of hydrogen storage alloy materials.
Background
The hydrogen storage alloy is a novel functional material, and has attracted great attention in the field of hydrogen energy. The nickel-hydrogen battery cathode is the most important application field of hydrogen storage alloy, and AB which is commercialized at present5Rare earth hydrogen storage alloy and AB3～3.8The rare earth magnesium-based hydrogen storage alloy has good comprehensive properties, but AB5The type alloy is limited by the crystal structure, the gaseous hydrogen storage amount is not more than 1.4 wt%, and the discharge capacity is low. And AB3～3.8The rare earth magnesium-based hydrogen storage alloy consists of AB2Type unit and AB5Crystal structure of stacked type units, although capacity is higher than AB5The alloy is high, but the cycling stability still needs to be improved, and simultaneously, because the vapor pressure of the Mg element is high, the components are difficult to control in the preparation process of the alloy, and the magnesium powder volatilized in the smelting process is easy to explode, so that potential safety hazards exist. According to previous studies, the alloy has AB containing no Mg element2Type unit and AB5The rare earth hydrogen storage alloy with the type unit laminated crystal structure has serious non-crystallization, poor circulation stability and low electrochemical capacity. The research finds that the rare earth AB2The ratio of the atomic radii of the type hydrogen storage alloy rA to rB is a main factor influencing hydrogen-induced amorphization, and when the ratio of the atomic radii is less than 1.37, amorphization is not easy to occur.
In the rare earth elements, Y is the element with the smallest atomic radius, and according to theoretical analysis, when the A side element contains Y, the alloy has better structural stability, and the hydrogen absorption non-crystallization degree is weaker and is far smaller than the alloy with larger A side atomic radius such as La and Ce. CN104532095B discloses a rare earth hydrogen storage alloy without Mg element, with a general formula of RExYyNiz-a-bMnaAlbWherein RE is one or more elements of La, Ce, Pr, Nd, Sm and Gd, x is more than 0, y is more than 1.5, x + y is 3, 11 is more than or equal to z and more than or equal to 9.5, 4.5 is more than or equal to a + b and more than 0, the alloy has better pressure-composition-isothermal characteristic, and the maximum hydrogen storage capacity can reach more than 1.36 wt.% under the common condition. However, the alloy contains a high content of Y elementAlthough the amorphization of the alloy is inhibited, studies have shown that the Y element has poor chalking resistance, and among all rare earth elements, the Y element has the greatest reactivity with oxygen and is most easily oxidized in an alkaline electrolyte, thus affecting the cycling stability of the alloy.
Disclosure of Invention
The invention aims to provide a rare earth-nickel base A2B7The alloy material for hydrogen storage has high electrochemical capacity, high circulation stability, high rate discharge capacity and low plateau pressure.
Another object of the present invention is to provide a method for preparing the hydrogen storage alloy material.
In order to achieve the purpose, the invention adopts the following technical scheme:
rare earth-nickel base A2B7The hydrogen storage alloy material has the chemical formula composition of C1-x- ySmxYyNiz-a-bAlaDbWherein x is more than or equal to 0.2 and less than or equal to 0.8, y is more than or equal to 0 and less than or equal to 0.5, z is more than or equal to 3.3 and less than or equal to 3.6, a is more than or equal to 0.1 and less than or equal to 0.4, b is more than or equal to 0 and less than or equal to 0.15, C is one or more than two of La, Ce, Pr, Nd, Gd, Zr and Ti, and D is one or more than two of Co, Mn, Cu, V, Fe, Zn, W and Si.
Wherein the crystal structure of the hydrogen storage alloy material is hexagonal Ce2Ni7Form (I) having a phase content greater than 85%.
The rare earth-nickel base A2B7The preparation method of the hydrogen storage alloy material comprises the following steps: mixing pure metal block material according to chemical formula, placing the mixed raw material into a vacuum induction furnace crucible, baking, degassing, vacuumizing to 1 x 10-2～5×10-4Pa, applying inert gas Ar with the pressure of 0.01-0.1 MPa as protective gas; smelting at 1400-1800 ℃, refining for 3-10 min after the alloy is completely melted, and cooling to obtain an alloy ingot; and turning over the alloy ingot and repeatedly smelting for 2-3 times.
On the rare earth-nickel base A2B7The preparation method of the hydrogen storage alloy material comprises placing the obtained alloy ingot in vacuum or chargingAnd (3) annealing in a container in an argon atmosphere at the annealing temperature of 900-1000 ℃ for 6-24 hours, and cooling in an ice-water mixture.
Wherein the metal purity of the pure metal block material is more than or equal to 99.0 wt.%.
The invention has the advantages that:
the invention reduces the rare earth-nickel base A2B7The Y content in the hydrogen storage alloy material reduces alloy pulverization and corrosion in electrolyte, and obviously improves the cycling stability of the alloy. The substitute element is mainly Sm, which can reduce pulverization and corrosion, and can further reduce plateau pressure of the alloy, reduce the dosage of Mn in the alloy and contribute to improving the self-discharge performance of the alloy.
In addition, the invention improves the hexagonal Ce in the alloy through the alloy smelting and heat treatment process2Ni7The phase content further improves the comprehensive electrochemical performance of the alloy.
Drawings
FIG. 1 is an XRD pattern of the hydrogen storage material of example 3.
FIG. 2 is a pressure-composition-isotherm (P-C-T) curve of the hydrogen storage material of example 6.
Detailed Description
The present invention is further illustrated by the following examples. The following examples are provided only for illustrating the present invention and are not intended to limit the scope of the present invention.
For examples 1-10 and comparative example 1, pure metal block materials were compounded according to the chemical formula composition of each alloy in table 1, the purity of the raw material metal was not less than 99.0 wt.%, the compounded raw materials were put into a crucible of a vacuum induction furnace to be baked and degassed, and the crucible was evacuated to 1 × 10-2～5×10-4Pa, applying inert gas Ar with the pressure of 0.01-0.1 MPa as protective gas, smelting at 1400-1800 ℃, refining for 3-5 min after the alloy is completely melted, cooling to obtain an alloy ingot, turning the alloy ingot over, and repeatedly smelting for 3 times.
And placing the obtained alloy ingot in a vacuum or argon-filled container, annealing at 900-1000 ℃ for 6-24 hours, and cooling in an ice-water mixture.
For comparative example 2, a pure metal block material was compounded according to the alloy formula composition in table 1, the metal purity of the material was not less than 99.0 wt.%, the compounded material was put into a vacuum induction furnace crucible to bake out gas, and the crucible was evacuated to 1 × 10-2～5×10-4Pa, applying inert gas Ar with the pressure of 0.01-0.1 MPa as protective gas, smelting at 1400-1800 ℃, and after the alloy is completely melted, refining for 3-5 min and then rapidly solidifying. The linear speed of the rapid-hardening copper roller is 3.5 m/s. And placing the obtained alloy ingot in a vacuum or argon-filled container, and annealing at 1000 ℃ for 24 hours.
The heat-treated hydrogen storage alloy is mechanically crushed, ground and sieved, wherein powder with a size smaller than 400 meshes is used for an X-ray powder diffraction test. Cu Kalpha rays are adopted, the power is 40kV multiplied by 300mA, the step length is 0.02 degrees, the step length is 1s, and the 2 theta angle range is 10-90 degrees. FIG. 1 is an X-ray diffraction pattern of the hydrogen storage material of example 3. The X-ray diffraction result shows that the hydrogen storage material is mainly composed of hexagonal Ce2Ni7A structural phase, and a small amount of CaCu5Type phase, PuNi3Form phase and CesCo19A molding phase. Table 2 shows the results of the X-ray diffraction Rietveld analysis of the hydrogen storage material of example 3, including phase structure, lattice parameters, unit cell volume and mass percent of each phase.
Table 2 parameters of the phases contained in example 3 and the respective phase examples
Figure BDA0001730111400000031
Grinding the heat-treated hydrogen storage alloy ingot into powder, and taking the hydrogen storage alloy powder with the particle size of 160-200 meshes. 200mg of hydrogen storage alloy powder and 800mg of nickel carbonyl powder are accurately weighed, are uniformly mixed and are cold-pressed for 10min under the pressure of 16MPa to prepare an electrode slice with phi of 16mm multiplied by 1mm, and the electrode slice is placed in the middle of folded foam nickel to be cold-pressed and formed and then is connected with a nickel strap in a spot welding manner. The testing device is an open H-shaped glass three-electrode testing systemThe auxiliary electrode is [ Ni (OH) ]2/NiOOH]The electrode, the negative electrode are hydrogen storage alloy electrode, and the reference electrode is [ Hg/HgO ]]The electrode and electrolyte are 6mol/L KOH alkali solution, and the test temperature is kept at 298K by a constant-temperature water bath.
The alloy electrode was left to stand for 24h at open circuit to ensure adequate wetting and then was charged at 60mA · g-1Charging at constant current for 480min, standing for 10min, and charging at 60mA · g-1Constant current discharging with cut-off potential of-0.6V, standing for 10min, and sequentially circulating to reach maximum discharge capacity Cmax. The alloy is 1200mA g-1Discharging at constant current until cut-off potential is-0.6V to obtain discharge capacity C1200Standing for 10min, and adding 60mA · g-1Discharging at constant current until cut-off potential is-0.6V to obtain discharge capacity C60High rate capability HRD1200＝C1200/(C1200+C60)×100％。
Figure BDA0001730111400000041
The cycling stability of the alloy was tested using a sandwich electrode with the positive electrode being [ Ni (OH)2/NiOOH]The negative electrode is a hydrogen storage alloy electrode, and the electrolyte is 6mol/LKOH solution. The test method comprises the following steps: 300mA · g-1Charging at constant current for 90min, standing for 10min, and then charging at 300mA · g-1Discharging at constant current, stopping at-1.0V, standing for 10min, and sequentially circulating. Under the charge-discharge system, the ratio of the residual capacity to the maximum discharge capacity at 300 cycles of the charge-discharge cycle is S300。
The pressure-composition-isotherm (P-C-T) curve of the hydrogen storage material was measured at 298K using the Siever method. The maximum hydrogen storage capacity and plateau pressure of the material at 3MPa were measured.
The test results are shown in Table 1. Compared with comparative example 1, the alloy is added with a proper amount of Sm element, so that the circulation stability is obviously improved, and the plateau pressure is reduced. Example 6 in comparison to comparative example 2, using ingot casting in combination with a heat treatment process, hexagonal Ce in the alloy2Ni7The phase content is obviously increased, and the high-rate discharge performance of the alloy is obviously improved.

Claims (4)

1. A rare earth-nickel based hydrogen storage alloy material is characterized in that the hydrogen storage alloy material has a chemical formula composition of C1-x- ySmxYyNiz-a-bAlaDbWherein x is more than or equal to 0.2 and less than or equal to 0.8, y is more than or equal to 0 and less than or equal to 0.5, z is more than or equal to 3.4 and less than or equal to 3.6, a is more than or equal to 0.1 and less than or equal to 0.4, b is more than or equal to 0 and less than or equal to 0.15, C is one or more than two of La, Ce, Pr, Nd, Gd, Zr and Ti, and D is one or more than two of Co, Mn, Cu, V, Fe, Zn, W and Si.
2. The rare earth-nickel-based hydrogen storage alloy material of claim 1, wherein the crystal structure of the hydrogen storage alloy material is hexagonal Ce2Ni7Form (I) having a phase content greater than 85%.
3. A method for preparing a rare earth-nickel based hydrogen occluding alloy material as claimed in claim 1 or 2, wherein the pure metal block material is prepared according to the chemical formula composition, the prepared raw material is put into a crucible of a vacuum induction furnace for baking and degassing, and the crucible is vacuumized to 1 x 10-2～5×10-4Pa, applying inert gas Ar with the pressure of 0.01-0.1 MPa as protective gas; smelting at 1400-1800 ℃, refining for 3-10 min after the alloy is completely melted, and cooling to obtain an alloy ingot; and turning over the alloy ingot and repeatedly smelting for 2-3 times.
4. The method for preparing a rare earth-nickel-based hydrogen storage alloy material according to claim 3, wherein the obtained alloy ingot is placed in a container in vacuum or filled with argon atmosphere, annealed at 900-1000 ℃ for 6-24 hours, and cooled in an ice-water mixture.
CN201810774933.4A 2018-07-13 2018-07-13 Rare earth-nickel-based hydrogen storage alloy material and preparation method thereof Pending CN110714139A (en)

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Cited By (10)

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CN111118342A (en) * 2019-09-16 2020-05-08 包头稀土研究院 A2B7 type RE-Sm-Ni series hydrogen storage alloy, negative electrode, battery and preparation method
CN111118345A (en) * 2019-11-28 2020-05-08 包头稀土研究院 Multi-element samarium-nickel hydrogen storage material, negative electrode, battery and preparation method
CN111118341A (en) * 2019-09-16 2020-05-08 包头稀土研究院 Rare earth-samarium-nickel type hydrogen storage alloy, negative electrode, battery and preparation method
CN111471913A (en) * 2020-04-14 2020-07-31 包头稀土研究院 AB3 type rare earth-samarium-nickel hydrogen storage alloy, negative electrode, 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
CN111471892A (en) * 2020-04-14 2020-07-31 包头稀土研究院 A5B19Samarium-containing hydrogen storage alloy, battery and preparation method
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
CN112899548A (en) * 2021-01-20 2021-06-04 华南理工大学 Yttrium-zirconium-iron-aluminum alloy material, preparation method and application
CN115466880A (en) * 2022-08-31 2022-12-13 深圳市豪鹏科技股份有限公司 Low-temperature hydrogen storage alloy, preparation method, nickel-hydrogen alloy electrode and nickel-hydrogen battery
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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CN111118341B (en) * 2019-09-16 2021-08-06 包头稀土研究院 Rare earth-samarium-nickel type hydrogen storage alloy, negative electrode, battery and preparation method
CN111118341A (en) * 2019-09-16 2020-05-08 包头稀土研究院 Rare earth-samarium-nickel type hydrogen storage alloy, negative electrode, battery and preparation method
CN111118342B (en) * 2019-09-16 2021-08-06 包头稀土研究院 A2B7 type RE-Sm-Ni series hydrogen storage alloy, negative electrode, battery and preparation method
CN111118342A (en) * 2019-09-16 2020-05-08 包头稀土研究院 A2B7 type RE-Sm-Ni series hydrogen storage alloy, negative electrode, battery and preparation method
CN111118345A (en) * 2019-11-28 2020-05-08 包头稀土研究院 Multi-element samarium-nickel hydrogen storage material, negative electrode, 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
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
CN111471892B (en) * 2020-04-14 2021-06-04 包头稀土研究院 A5B19Samarium-containing hydrogen storage alloy, battery and preparation method
CN111471913B (en) * 2020-04-14 2021-07-13 包头稀土研究院 AB3 type rare earth-samarium-nickel hydrogen storage alloy, negative electrode, battery and preparation method
CN111471911B (en) * 2020-04-14 2021-07-16 包头稀土研究院 Doped AB3 type rare earth-samarium-nickel hydrogen storage alloy, battery and preparation method
CN111471892A (en) * 2020-04-14 2020-07-31 包头稀土研究院 A5B19Samarium-containing hydrogen storage alloy, battery and preparation method
CN111471913A (en) * 2020-04-14 2020-07-31 包头稀土研究院 AB3 type rare earth-samarium-nickel hydrogen storage alloy, negative electrode, battery and preparation method
CN112899548A (en) * 2021-01-20 2021-06-04 华南理工大学 Yttrium-zirconium-iron-aluminum alloy material, preparation method and application
CN115466880A (en) * 2022-08-31 2022-12-13 深圳市豪鹏科技股份有限公司 Low-temperature hydrogen storage alloy, preparation method, nickel-hydrogen alloy electrode and nickel-hydrogen battery
CN115466880B (en) * 2022-08-31 2023-07-11 深圳市豪鹏科技股份有限公司 Low-temperature hydrogen storage alloy, preparation method, nickel-hydrogen alloy electrode and nickel-hydrogen battery
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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