CN115710664B - Cobalt-containing Y-Mg-Ni-based hydrogen storage alloy and preparation method thereof - Google Patents
Cobalt-containing Y-Mg-Ni-based hydrogen storage alloy and preparation method thereof Download PDFInfo
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 122
- 239000000956 alloy Substances 0.000 title claims abstract description 122
- 239000001257 hydrogen Substances 0.000 title claims abstract description 61
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 61
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000003860 storage Methods 0.000 title claims abstract description 24
- 229910019083 Mg-Ni Inorganic materials 0.000 title claims abstract description 20
- 229910019403 Mg—Ni Inorganic materials 0.000 title claims abstract description 20
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 18
- 239000010941 cobalt Substances 0.000 title claims abstract description 18
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 37
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 35
- 238000010521 absorption reaction Methods 0.000 claims abstract description 23
- 230000014759 maintenance of location Effects 0.000 claims abstract description 14
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 3
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 48
- 238000005245 sintering Methods 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 22
- 230000001681 protective effect Effects 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 18
- 239000010935 stainless steel Substances 0.000 claims description 14
- 229910001220 stainless steel Inorganic materials 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 238000003825 pressing Methods 0.000 claims description 12
- 238000007873 sieving Methods 0.000 claims description 11
- 238000003723 Smelting Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 6
- 239000002245 particle Substances 0.000 claims 1
- 230000001351 cycling effect Effects 0.000 abstract description 3
- 239000011232 storage material Substances 0.000 abstract description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 48
- 229910052786 argon Inorganic materials 0.000 description 24
- 239000000203 mixture Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 13
- 230000006698 induction Effects 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 238000003991 Rietveld refinement Methods 0.000 description 2
- 238000005280 amorphization Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000004453 electron probe microanalysis Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910001068 laves phase Inorganic materials 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Y02E60/10—Energy storage using batteries
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Abstract
The invention relates to the field of hydrogen storage materials, in particular to a cobalt-containing Y-Mg-Ni-based hydrogen storage alloy and a preparation method thereof, wherein the chemical formula of the alloy is Y 1‑a‑b Mg a D b Ni x Co y E z Wherein D is one or more of rare earth elements and Ca except Y, E is one or more of Al, mn, fe, mo, V, zn, sn elements, a is more than or equal to 0.3 and less than or equal to 0.6,0 and b is more than or equal to 0.10,1.7 and less than or equal to x+y+z is more than or equal to 2,0.85 and less than or equal to 1.95,0 and z is more than or equal to 0.15. Comprises a space group F-43m (Y, mg, D) (Ni, co, E) 2 The phase and space group is R-3m (Y, mg, D) (Ni, co, E) 3 And (3) phase (C). The maximum hydrogen absorption capacity and the cycling stability of the alloy can be obviously increased by adding Co element, the maximum hydrogen absorption capacity can reach more than 2wt%, and the capacity retention rate in the first 5 weeks can reach more than 95%.
Description
Technical Field
The invention relates to the field of hydrogen storage materials, in particular to a cobalt-containing Y-Mg-Ni-based hydrogen storage alloy and a preparation method thereof.
Background
Rare earth system AB 2 The hydrogen storage alloy has a higher AB than the conventional one 5 The alloy has larger theoretical hydrogen storage amount, but the alloy is easy to generate hydrogen-induced amorphization and hydrogen-induced disproportionation in the process of hydrogen absorption and desorption, and generates amorphous phase and stable hydride which are unfavorable for reversible hydrogen absorption and desorption, such as LaH 2 、YH 2 And YH 3 Etc. hydrogen storage capacity during circulationThe amount decays severely.
The results of the current stage of research generally suggest AB 2 The structural stability of the shape alloy is closely related to the atomic radius ratio on the A, B side, when the atomic radius ratio on the A side and the B side (R A /R B ) Above 1.37, hydrogen induced amorphization of the alloy may occur. Atomic radius of rare earth element YAnd the relative atomic mass (88.91) is smaller than other rare earth elements, so that the atomic radius ratio of the alloy can be reduced, and the mass hydrogen storage density of the alloy can be improved. But YNi 2 The alloy can only form crystalline Y after absorbing hydrogen 0.95 Ni 2 H 2.6 The hydrogen absorption amount was only 1.27wt%, and after further increasing the hydrogen absorption amount, the alloy was amorphized. By partially substituting the alloy with an element having a smaller atomic radius than Y and an element having a larger atomic radius than the B-side Ni element, the structural stability of the alloy can be significantly improved. Partial substitution of rare earth RNi with Mg 2 (r=la, pr, nd, sm, Y) alloys, which form C15b type Laves phases that are structurally stable and capable of reversibly absorbing and releasing hydrogen, but form rmgn 4 The actual hydrogen storage capacity of the alloy is still lower by about 1.1-1.3wt%, limiting the further applications of the alloy.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a Y-Mg-Ni-based hydrogen storage alloy with high hydrogen storage capacity and good structural stability and a preparation method thereof, and the preparation method specifically comprises the following steps:
a cobalt-containing Y-Mg-Ni-based hydrogen storage alloy has a chemical formula of Y 1-a-b Mg a D b Ni x Co y E z Wherein D is one or more of rare earth elements and Ca except Y, E is one or more of Al, mn, fe, mo, V, zn, sn elements, a is more than or equal to 0.3 and less than or equal to 0.6,0 and b is more than or equal to 0.10,1.7 and less than or equal to x+y+z is more than or equal to 2,0.85 and less than or equal to 1.95,0 and z is more than or equal to 0.15. Specifically, a may be 0.3, 0.4, 0.45, 0.5, 0.55, 0.6, or the like; the b may be 0, 0.02, 0.04, 0.06, 0.08, 0.10, or the like; the value of x+y+z may be 1.7, 1.75, 1.8, 1.85, 19, 1.95, or 1.99, etc.; the y may be 0.85, 0.95, 1, 1.2, 1.4, 1.6, 1.8, 1.85, 1.95, etc.; the z may be 0, 0.01, 0.02, 0.04, 0.06, 0.08, 0.10, 0.12, 0.15, or the like.
Preferably, the composition comprises (Y, mg, D) (Ni, co, E) with space group F-43m 2 The phase and space group is R-3m (Y, mg, D) (Ni, co, E) 3 Phases in which (Y, mg, D) (Ni, co, E) 2 The phase content is more than or equal to 50wt.% and less than or equal to 10wt.% of (Y, mg, D) (Ni, co, E) 3 The phase content is less than or equal to 50wt.%. Specifically, (Y, mg, D) (Ni, co, E) 2 The phase content may be 50wt.%, 55wt.%, 60wt.%, 65wt.%, 70wt.%, 80wt.%, etc.; said (Y, mg, D) (Ni, co, E) 3 The phase content may be 10wt.%, 20wt.%, 30wt.%, 35wt.%, 40wt.%, 45wt.%, 50wt.%, etc.
Preferably, the alloy contains less than or equal to 10wt.% of a hetero-phase, Y 2 O 3 、Y、YNi、Mg 2 Ni, and the like.
Preferably, the maximum hydrogen absorption capacity of the alloy is more than or equal to 1.8wt.%, and the capacity retention rate in the first five weeks is more than or equal to 90%. Specifically, the maximum hydrogen absorption capacity of the alloy may be 1.8wt.%, 1.85wt.%, 1.9wt.%, 2.0wt.%, etc.; the capacity retention for the first five weeks may be 90%, 92%, 94%, 95%, 96%, etc., as detailed in the examples.
A preparation method of a Y-Mg-Ni-based hydrogen storage alloy containing cobalt comprises the following steps:
(1) Proportioning metal raw materials Y, D, ni, co, E in proportion, and smelting to prepare an as-cast alloy ingot;
(2) Crushing an as-cast alloy ingot in a protective gas atmosphere, and sieving to obtain as-cast alloy powder;
(3) Mixing the as-cast alloy powder and the Mg powder in a protective gas atmosphere according to a proportion, and cold-pressing the uniformly mixed metal powder into an alloy sheet under a certain pressure;
(4) Sintering the alloy sheet at high temperature, and then cooling to obtain a cobalt-containing Y-Mg-Ni-based hydrogen storage alloy finished product.
Preferably, the screen used in the screening operation in the step (2) is a 200-500 mesh screen, specifically 500 mesh, 400 mesh, 350 mesh, 250 mesh, 200 mesh, etc., preferably 300 mesh.
Preferably, the granularity of the Mg powder in the step (3) is less than 200 mesh, and may specifically be 250 mesh, 300 mesh, 400 mesh, etc.; the Mg powder is added in a burn-out amount of 1wt.% to 10 wt.%.
Preferably, the pressure of the cold pressing in the step (3) is 5MPa to 10MPa, specifically, 5MPa, 6MPa, 7MPa, 8MPa, 9MPa, 10MPa, etc.
Preferably, the sintering operation in the step (4) is as follows: the alloy sheet is placed in a stainless steel tank, the alloy sheet is separated from the stainless steel tank body by a tantalum foil, and then the stainless steel tank is placed in a muffle furnace for sintering.
Preferably, the sintering procedure in the step (4) is as follows: firstly, raising the temperature from room temperature to 500-600 ℃ (the specific temperature can be 500 ℃, 520 ℃, 550 ℃, 580 ℃, 600 ℃ or the like), and preserving the temperature for 5-10 hours (the specific temperature can be 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours or the like); then heating to 700-800 ℃ (the specific temperature can be 700 ℃, 720 ℃, 750 ℃, 780 ℃ or 800 ℃ and the like), and preserving heat for 5-10 hours (the specific temperature can be preserved for 5 hours, 6 hours, 7 hours, 8 hours, 9 hours or 10 hours and the like); finally cooling to 500-600 ℃ (the specific temperature can be 500 ℃, 520 ℃, 550 ℃, 580 ℃, 600 ℃ or the like), preserving heat for 50-80 hours (the specific temperature can be 50 hours, 55 hours, 60 hours, 65 hours, 70 hours or 80 hours or the like), and cooling to room temperature along with the furnace.
The invention has the beneficial effects that:
the invention increases the content of Co element in the Y-Mg-Ni based alloy, and can increase the content of (Y, mg, D) (Ni, co, E) in the alloy 3 The content of the phase increases (Y, mg, D) (Ni, co, E) 2 The unit cell volume of the phase increases the maximum hydrogen absorption capacity and cycling stability of the alloy significantly. The preparation method of blending and sintering the alloy powder and the Mg powder can lead the prepared alloy components to be more uniform and generate more (Y, mg and D) (Ni, co and E) 3 And the phase improves the hydrogen storage performance of the alloy. The maximum hydrogen absorption capacity of the cobalt-containing Y-Mg-Ni-based alloy prepared by the method disclosed by the invention can reach more than 2wt%, and the capacity retention rate in the first 5 weeks can reach more than 95%.
Drawings
FIG. 1 is an EPMA back-scattered electron image of the alloy prepared in example 1;
FIG. 2 is an EPMA back-scattered electron image of the alloy prepared in comparative example 1;
FIG. 3 is XRD patterns of the alloys prepared in example 1 and comparative example 1;
FIG. 4 is a graph showing the first-week hydrogen absorption kinetics of the alloys prepared in example 1 and comparative example 1.
Detailed Description
The invention will be described in detail below with reference to the drawings and the detailed description. The embodiments shown below do not limit the inventive content described in the claims in any way. The whole contents of the constitution shown in the following examples are not limited to the solution of the invention described in the claims.
Example 1
Pure metal raw material with purity not less than 99.5wt% is processed according to a molecular formula Y 0.7 Ni 0.1 Co 1.8 Proportioning, preparing an as-cast alloy ingot by induction smelting in an argon protective atmosphere, mechanically crushing and sieving with a 300-mesh sieve under the argon protective atmosphere, and obtaining Y 0.7 Ni 0.1 Co 1.8 The alloy powder and the Mg powder smaller than 200 meshes are mixed according to the stoichiometric ratio Y 0.7 Mg 0.3 Ni 0.1 Co 1.8 The mixture was thoroughly mixed in an argon glove box, and 1wt.% to 10wt.% of a burn-out amount was added to the Mg powder. Cold pressing the alloy powder into alloy sheet under 5-10 MPa, and separating the alloy sheet from the tank with tantalum foil. Placing the stainless steel tank in a muffle furnace for sintering, wherein the specific sintering procedure is as follows: raising the temperature to 500-600 ℃ from room temperature, and preserving the heat for 5-10h; heating to 700-800 ℃, and preserving heat for 5-10h; cooling to 500-600 deg.c, maintaining for 50-80 hr, and cooling to room temperature with furnace.
Comparative example 1
Pure metal raw material with purity not less than 99.5wt% is processed according to a molecular formula Y 0.7 Ni 1.9 Proportioning, preparing an as-cast alloy ingot by induction smelting in an argon protective atmosphere, mechanically crushing and sieving with a 300-mesh sieve under the argon protective atmosphere, and obtaining Y 0.7 Ni 1.9 Alloy powder and less than200-mesh Mg powder according to stoichiometric ratio Y 0.7 Mg 0.3 Ni 1.9 The mixture was thoroughly mixed in an argon glove box, and 1wt.% to 10wt.% of a burn-out amount was added to the Mg powder. Cold pressing the alloy powder into alloy sheet under 5-10 MPa, and separating the alloy sheet from the tank with tantalum foil. Placing the stainless steel tank in a muffle furnace for sintering, wherein the specific sintering procedure is as follows: raising the temperature to 500-600 ℃ from room temperature, and preserving the heat for 5-10h; heating to 700-800 ℃, and preserving heat for 5-10h; cooling to 500-600 deg.c, maintaining for 50-80 hr, and cooling to room temperature with furnace.
The hydrogen occluding alloys of example 1 and comparative example 1 obtained were polished on 400, 600, 800, 1200, 1500, 2000, 3000 mesh sandpaper in this order, and then subjected to micro-domain phase composition analysis using an electronic probe of the equipment model JXA-8230, as shown in fig. 1 and 2. As can be seen from the figure, example 1 shows dark gray areas (points 1 to 5) and light gray areas (points 6 to 15) in two phases, and comparative example 1 shows a single phase (points 1 to 3), wherein points 4 to 9 show voids left after sintering of the alloy. The composition of the dark gray region of example 1 was obtained by averaging the compositions of the different points of each region 0.67 Mg 0.33 (Ni,Co) 2.18 The light gray area component is Y (Ni, co) 3.16 Comparative example 1 Main phase component Y 0.70 Mg 0.30 Ni 2.12 . The above results show that example 1 is mainly composed of (Y, mg) (Ni, co) 2 And Y (Ni, co) 3 Two-phase composition, comparative example 1 was made of (Y, mg) Ni 2 Is the main phase.
Mechanically crushing the obtained hydrogen storage alloy after removing oxide skin, selecting powder smaller than 400 meshes for X-ray powder diffraction test, using Cu K alpha rays, scanning in a stepping way with the power of 40kV multiplied by 150mA and the step length of 0.02 DEG and the 2 theta range of 10 DEG-90 DEG, and carrying out Retvield refinement on the obtained XRD data by using Fullprof software to obtain the phase composition of the alloy. FIG. 3 shows XRD patterns of example 1 and comparative example 1, and Rietveld refinement results, unit cell parameters and placements are shown in Table 1. It can be seen that the small amounts of Y and Y were removed in example 1 and comparative example 1 2 O 3 Comparative example 2 contains (Y, mg) Ni alone except for the impurity phase 2 Phase, except (Y, mg) (Ni, co) in example 1 2 Y (Ni, co) outside the phase 3 The phase increases significantly.
Table 1 Rietveld refinement results for example 1 and comparative example 1
The hydrogen storage properties of the alloys were measured using a Sieverts apparatus. The testing method comprises the following steps: about 2g of alloy powder with 100-300 meshes is taken, vacuumized for 1-2 hours at 400 ℃, cooled to 25 ℃, and absorbed with hydrogen under 10MPa of initial hydrogen pressure, and the operation is repeated for 5 times. Capacity reached a maximum at the first week (fig. 4), capacity fade occurred mainly in the first 2 weeks, and capacity remained essentially stable after 5 weeks. The capacity retention rate of the alloy in the first five weeks was obtained using the maximum hydrogen absorption amount and the fifth week hydrogen absorption amount. The maximum hydrogen absorption of example 1 was 2.011wt%, and the capacity retention in the first 5 weeks was 96.36%. Whereas comparative example 1 had a maximum hydrogen absorption of 1.731wt%, the capacity retention of 74.52% in the first 5 weeks. It can be seen that the capacity and the cycling stability of the alloy are significantly increased after the Co element is used to replace Ni. The main reason is that Y (Ni, co) is increased after Co substitution 3 Compared with (Y, mg) (Ni, co) 2 The phase structure is more stable. Furthermore, it can be seen from Table 1 that Co is substituted (Y, mg) (Ni, co) 2 Unit cell volume of phase is higher than (Y, mg) Ni 2 The phase is larger, so that more H atoms can be accommodated, and the hydrogen absorption amount is higher.
Example 2
Pure metal raw material with purity not less than 99.5wt% is processed according to a molecular formula Y 0.7 Ni 0.3 Co 1.6 Proportioning, preparing an as-cast alloy ingot by induction smelting in an argon protective atmosphere, mechanically crushing and sieving with a 300-mesh sieve under the argon protective atmosphere, and obtaining Y 0.7 Ni 0.3 Co 1.6 The alloy powder and the Mg powder smaller than 200 meshes are mixed according to the stoichiometric ratio Y 0.7 Mg 0.3 Ni 0.3 Co 1.6 The mixture was thoroughly mixed in an argon glove box, and 1wt.% to 10wt.% of a burn-out amount was added to the Mg powder. Cold pressing the alloy powder into alloy sheet under 5-10 MPa, and separating the alloy sheet from the tank with tantalum foil. Placing stainless steel potSintering in a muffle furnace, wherein the specific sintering procedure is as follows: raising the temperature to 500-600 ℃ from room temperature, and preserving the heat for 5-10h; heating to 700-800 ℃, and preserving heat for 5-10h; cooling to 500-600 deg.c, maintaining for 50-80 hr, and cooling to room temperature with furnace.
The phase composition of the resulting alloy was (Y, mg) (Ni, co) tested according to the above method 2 The phase content was 78wt%, (Y, mg) (Ni, co) 3 The phase content was 15wt%. The maximum hydrogen absorption was 1.952wt%, and the capacity retention was 95.76% for the first 5 weeks.
Example 3
Pure metal raw material with purity not less than 99.5wt% is processed according to a molecular formula Y 0.6 Ni 0.5 Co 1.3 Proportioning, preparing an as-cast alloy ingot by induction smelting in an argon protective atmosphere, mechanically crushing and sieving with a 300-mesh sieve under the argon protective atmosphere, and obtaining Y 0.6 Ni 0.5 Co 1.3 The alloy powder and the Mg powder smaller than 200 meshes are mixed according to the stoichiometric ratio Y 0.6 Mg 0.4 Ni 0.5 Co 1.3 The mixture was thoroughly mixed in an argon glove box, and 1wt.% to 10wt.% of a burn-out amount was added to the Mg powder. Cold pressing the alloy powder into alloy sheet under 5-10 MPa, and separating the alloy sheet from the tank with tantalum foil. Placing the stainless steel tank in a muffle furnace for sintering, wherein the specific sintering procedure is as follows: raising the temperature to 500-600 ℃ from room temperature, and preserving the heat for 5-10h; heating to 700-800 ℃, and preserving heat for 5-10h; cooling to 500-600 deg.c, maintaining for 50-80 hr, and cooling to room temperature with furnace.
The phase composition of the resulting alloy was (Y, mg) (Ni, co) tested according to the above method 2 The phase content was 82wt%, (Y, mg) (Ni, co) 3 The phase content was 13% by weight. The maximum hydrogen absorption was 1.846wt%, and the capacity retention was 94.02% for the first 5 weeks.
Example 4
Pure metal raw material with purity not less than 99.5wt% is processed according to a molecular formula Y 0.55 La 0.1 Ni 0.85 Co 1.1 Proportioning, preparing an as-cast alloy ingot by induction smelting in an argon protective atmosphere, mechanically crushing and sieving with a 300-mesh sieve under the argon protective atmosphere, and obtaining Y 0.55 La 0.1 Ni 0.85 Co 1.1 The alloy powder and the Mg powder smaller than 200 meshes are mixed according to the stoichiometric ratio Y 0.55 La 0.1 Mg 0.35 Ni 0.85 Co 1.1 The mixture was thoroughly mixed in an argon glove box, and 1wt.% to 10wt.% of a burn-out amount was added to the Mg powder. Cold pressing the alloy powder into alloy sheet under 5-10 MPa, and separating the alloy sheet from the tank with tantalum foil. Placing the stainless steel tank in a muffle furnace for sintering, wherein the specific sintering procedure is as follows: raising the temperature to 500-600 ℃ from room temperature, and preserving the heat for 5-10h; heating to 700-800 ℃, and preserving heat for 5-10h; cooling to 500-600 deg.c, maintaining for 50-80 hr, and cooling to room temperature with furnace.
The phase composition of the resulting alloy was (Y, mg) (Ni, co) tested according to the above method 2 The phase content was 83wt%, (Y, mg) (Ni, co) 3 The phase content was 10wt%. The maximum hydrogen absorption was 1.817wt%, and the capacity retention in the first 5 weeks was 90.19%.
Example 5
Pure metal raw material with purity not less than 99.5wt% is processed according to a molecular formula Y 0.6 Ni 0.8 Co 1.0 Mn 0.05 Proportioning, preparing an as-cast alloy ingot by induction smelting in an argon protective atmosphere, mechanically crushing and sieving with a 300-mesh sieve under the argon protective atmosphere, and obtaining Y 0.6 Ni 0.8 Co 1.0 Mn 0.05 The alloy powder and the Mg powder smaller than 200 meshes are mixed according to the stoichiometric ratio Y 0.6 Mg 0.4 Ni 0.8 Co 1.0 Mn 0.05 The mixture was thoroughly mixed in an argon glove box, and 1wt.% to 10wt.% of a burn-out amount was added to the Mg powder. Cold pressing the alloy powder into alloy sheet under 5-10 MPa, and separating the alloy sheet from the tank with tantalum foil. Placing the stainless steel tank in a muffle furnace for sintering, wherein the specific sintering procedure is as follows: raising the temperature to 500-600 ℃ from room temperature, and preserving the heat for 5-10h; heating to 700-800 ℃, and preserving heat for 5-10h; cooling to 500-600 deg.c, maintaining for 50-80 hr, and cooling to room temperature with furnace.
The phase composition of the resulting alloy was (Y, mg) (Ni, co) tested according to the above method 2 The phase content was 80wt%, (Y, mg) (Ni, co) 3 The phase content was 14% by weight. Maximum hydrogen absorption of 1.803wt%, capacity retention for the first 5 weeks was 92.55%.
Example 6
Pure metal raw material with purity not less than 99.5wt% is processed according to a molecular formula Y 0.45 Ni 0.7 Co 1.2 Proportioning, preparing an as-cast alloy ingot by induction smelting in an argon protective atmosphere, mechanically crushing and sieving with a 300-mesh sieve under the argon protective atmosphere, and obtaining Y 0.45 Ni 0.7 Co 1.2 The alloy powder and the Mg powder smaller than 200 meshes are mixed according to the stoichiometric ratio Y 0.45 Mg 0.55 Ni 0.7 Co 1.2 The mixture was thoroughly mixed in an argon glove box, and 1wt.% to 10wt.% of a burn-out amount was added to the Mg powder. Cold pressing the alloy powder into alloy sheet under 5-10 MPa, and separating the alloy sheet from the tank with tantalum foil. Placing the stainless steel tank in a muffle furnace for sintering, wherein the specific sintering procedure is as follows: raising the temperature to 500-600 ℃ from room temperature, and preserving the heat for 5-10h; heating to 700-800 ℃, and preserving heat for 5-10h; cooling to 500-600 deg.c, maintaining for 50-80 hr, and cooling to room temperature with furnace.
The phase composition of the resulting alloy was (Y, mg) (Ni, co) tested according to the above method 2 Phase content 76wt%, (Y, mg) (Ni, co) 3 The phase content was 16% by weight. The maximum hydrogen absorption was 1.928wt%, and the capacity retention was 91.93% for the first 5 weeks.
Example 7
Pure metal raw material with purity not less than 99.5wt% is processed according to a molecular formula Y 0.3 La 0.1 Ni 0.65 Co 0.95 Proportioning, preparing an as-cast alloy ingot by induction smelting in an argon protective atmosphere, mechanically crushing and sieving with a 300-mesh sieve under the argon protective atmosphere, and obtaining Y 0.3 La 0.1 Ni 0.65 Co 0.95 The alloy powder and the Mg powder smaller than 200 meshes are mixed according to the stoichiometric ratio Y 0.3 La 0.1 Mg 0.6 Ni 0.65 Co 0.95 The mixture was thoroughly mixed in an argon glove box, and 1wt.% to 10wt.% of a burn-out amount was added to the Mg powder. Cold pressing the alloy powder into alloy sheet under 5-10 MPa, and separating the alloy sheet from the tank with tantalum foil. Placing stainless steel tank in muffle furnaceThe specific sintering procedure is as follows: raising the temperature to 500-600 ℃ from room temperature, and preserving the heat for 5-10h; heating to 700-800 ℃, and preserving heat for 5-10h; cooling to 500-600 deg.c, maintaining for 50-80 hr, and cooling to room temperature with furnace.
The phase composition of the resulting alloy was (Y, mg) (Ni, co) tested according to the above method 2 The phase content was 80wt%, (Y, mg) (Ni, co) 3 The phase content was 18% by weight. The maximum hydrogen absorption was 1.823wt%, and the capacity retention was 90.01% for the first 5 weeks.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. A cobalt-containing Y-Mg-Ni-based hydrogen storage alloy is characterized in that the chemical formula of the hydrogen storage alloy is Y 1-a- b Mg a D b Ni x Co y E z Wherein D is one or more of rare earth elements and Ca except Y, E is one or more of Al, mn, fe, mo, V, zn, sn elements, a is more than or equal to 0.3 and less than or equal to 0.6,0 and b is more than or equal to 0.10,1.7 and less than or equal to x+y+z is more than or equal to 2,1.6 and less than or equal to 1.95,0 and z is more than or equal to 0.15; the maximum hydrogen absorption capacity of the alloy is more than or equal to 1.8wt.%, and the capacity retention rate in the first five weeks is more than or equal to 90%.
2. The cobalt-containing Y-Mg-Ni-based hydrogen occluding alloy as recited in claim 1, wherein the alloy comprises (Y, mg, D) (Ni, co, E) having a space group of F-43m 2 The phase and space group is R-3m (Y, mg, D) (Ni, co, E) 3 Phases in which (Y, mg, D) (Ni, co, E) 2 The phase content is more than or equal to 50wt.% and is less than or equal to 10wt wt.% of (Y, mg, D) (Ni, co, E) 3 The phase content is less than or equal to 50wt.%.
3. The cobalt-containing Y-Mg-Ni-based hydrogen occluding alloy according to claim 1, wherein the alloy contains a hetero-phase of not more than 10wt.%, said hetero-phase being Y 2 O 3 、Y、YNi、Mg 2 One or more of Ni.
4. A method for producing a cobalt-containing Y-Mg-Ni-based hydrogen storage alloy according to any one of claims 1 to 3, comprising the steps of:
(1) Proportioning metal raw materials Y, D, ni, co, E in proportion, and smelting to prepare an as-cast alloy ingot;
(2) Crushing an as-cast alloy ingot in a protective gas atmosphere, and sieving to obtain as-cast alloy powder;
(3) Mixing the as-cast alloy powder and the Mg powder in a protective gas atmosphere according to a proportion, and cold-pressing the uniformly mixed metal powder into an alloy sheet under a certain pressure;
(4) Sintering the alloy sheet at high temperature, and then cooling to obtain a cobalt-containing Y-Mg-Ni-based hydrogen storage alloy finished product.
5. The method for producing a cobalt-containing Y-Mg-Ni-based hydrogen occluding alloy according to claim 4, wherein the sieve used in the sieving operation in the step (2) is a 500-200 mesh sieve.
6. The method for producing a cobalt-containing Y-Mg-Ni-based hydrogen storage alloy according to claim 4, wherein the particle size of Mg powder in said step (3) is less than 200 mesh, and said Mg powder is added with a burn-out amount of 1wt.% to 10wt%.
7. The method for producing a cobalt-containing Y-Mg-Ni-based hydrogen occluding alloy according to claim 4, wherein the pressure of the cold pressing in the step (3) is 5MPa to 10MPa.
8. The method for producing a cobalt-containing Y-Mg-Ni-based hydrogen storage alloy according to claim 4, wherein said sintering operation in said step (4) is: the alloy sheet is placed in a stainless steel tank, the alloy sheet is separated from the stainless steel tank body by a tantalum foil, and then the stainless steel tank is placed in a muffle furnace for sintering.
9. The method for producing a cobalt-containing Y-Mg-Ni-based hydrogen storage alloy according to claim 4, wherein said sintering process in said step (4) is: firstly, raising the temperature to 500-600 ℃ from room temperature, and preserving the heat for 5-10h; then heating to 700-800 ℃, and preserving heat for 5-10h; finally cooling to 500-600 ℃, preserving heat by 50-80h, and cooling to room temperature along with a furnace.
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| CN1194473A (en) * | 1997-03-24 | 1998-09-30 | 松下电器产业株式会社 | Alloy electrode for absorbing hydrogen |
| CN1219001A (en) * | 1997-11-28 | 1999-06-09 | 株式会社东芝 | Nickel-hydrogen secondary battery |
| CN111647773A (en) * | 2020-05-20 | 2020-09-11 | 有研工程技术研究院有限公司 | Rare earth hydrogen storage material and preparation method thereof |
| CN115074578A (en) * | 2022-06-07 | 2022-09-20 | 有研工程技术研究院有限公司 | Y-Mg-Ni-based hydrogen storage alloy and preparation method thereof |
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| CN1194473A (en) * | 1997-03-24 | 1998-09-30 | 松下电器产业株式会社 | Alloy electrode for absorbing hydrogen |
| CN1219001A (en) * | 1997-11-28 | 1999-06-09 | 株式会社东芝 | Nickel-hydrogen secondary battery |
| CN111647773A (en) * | 2020-05-20 | 2020-09-11 | 有研工程技术研究院有限公司 | Rare earth hydrogen storage material and preparation method thereof |
| CN115074578A (en) * | 2022-06-07 | 2022-09-20 | 有研工程技术研究院有限公司 | Y-Mg-Ni-based hydrogen storage alloy and preparation method thereof |
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Effective date of registration: 20231225 Address after: No.11, Xingke East Street, Yanqi Economic Development Zone, Huairou District, Beijing Patentee after: YOUYAN ENGINEERING TECHNOLOGY RESEARCH INSTITUTE Co.,Ltd. Patentee after: Youyan (Guangdong) new material technology Research Institute Address before: 101407 No. 11 Xingke East Street, Yanqi Economic Development Zone, Huairou District, Beijing Patentee before: YOUYAN ENGINEERING TECHNOLOGY RESEARCH INSTITUTE Co.,Ltd. |