CN115786770B - Rare earth-calcium-nickel hydrogen storage alloy and preparation method thereof - Google Patents
Rare earth-calcium-nickel hydrogen storage alloy and preparation method thereof Download PDFInfo
- Publication number
- CN115786770B CN115786770B CN202211632411.3A CN202211632411A CN115786770B CN 115786770 B CN115786770 B CN 115786770B CN 202211632411 A CN202211632411 A CN 202211632411A CN 115786770 B CN115786770 B CN 115786770B
- Authority
- CN
- China
- Prior art keywords
- hydrogen storage
- calcium
- rare earth
- storage alloy
- nickel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000001257 hydrogen Substances 0.000 title claims abstract description 107
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 107
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 239000000956 alloy Substances 0.000 title claims abstract description 77
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 76
- 238000003860 storage Methods 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 64
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- 238000000137 annealing Methods 0.000 claims description 13
- 238000003723 Smelting Methods 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 abstract description 8
- 229910052777 Praseodymium Inorganic materials 0.000 abstract description 6
- 229910052802 copper Inorganic materials 0.000 abstract description 6
- 229910052720 vanadium Inorganic materials 0.000 abstract description 6
- 239000011575 calcium Substances 0.000 description 47
- 239000011572 manganese Substances 0.000 description 45
- 238000010521 absorption reaction Methods 0.000 description 22
- 230000015572 biosynthetic process Effects 0.000 description 9
- 150000004678 hydrides Chemical class 0.000 description 9
- 230000014759 maintenance of location Effects 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052727 yttrium Inorganic materials 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052754 neon Inorganic materials 0.000 description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- LENJPRSQISBMDN-UHFFFAOYSA-N [Y].[Ce] Chemical compound [Y].[Ce] LENJPRSQISBMDN-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical group [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a rare earth-calcium-nickel hydrogen storage alloy and a preparation method thereof. The rare earth-calcium-nickel hydrogen storage alloy has the following composition: la aREbYcCadNixMnyAlz Q; wherein ,0.1≤a≤0.7,0≤b≤0.45,0.05≤c≤0.5,0.1≤d≤0.6,a+b+c+d＝1;4.3≤x≤4.95,0≤y≤0.4,0≤z≤0.4,0.05≤y+z≤0.65,0≤t≤0.2,4.8≤x+y+z+t≤5.2; wherein RE is selected from one or more of Ce, sm, nd and Pr; wherein Q is selected from one or more of Cu, sn, V, ti, zr, cr, zn, mo and Si. The rare earth-calcium-nickel hydrogen storage alloy has excellent cycle stability.
Description
Technical Field
The invention relates to a rare earth-calcium-nickel hydrogen storage alloy and a preparation method thereof.
Background
Hydrogen energy is one of ideal substitutes for secondary clean energy, and the key of hydrogen energy development and application is the capability of economically producing and safely producing and storing hydrogen at high density. The hydrogen storage alloy material can reversibly absorb and release a large amount of hydrogen, and is an important material for developing and utilizing hydrogen energy.
Jiang Wanting et al, "influence of rare earth element on microstructure and electrochemical properties of R-Y-Ni series A 2B7 type magnesium-free hydrogen storage alloy" discloses a hydrogen storage alloy having a composition of La 0.037Y0.7Ni3.25Mn0.15Al0.1. The hydrogen storage alloy is A 2B7; the hydrogen absorption sides are all rare earth elements and do not contain calcium. The capacity retention of the hydrogen absorbing alloy after 100 weeks of cycling is only 85.72%.
Li Xinyu et al, "research on microstructure and electrochemical properties of rapid-setting hydrogen storage alloy La 0.8Ce0.2Ni4.65-xMn0.9Ti0.05(V0.3Fe0.4Al0.3)x" disclose a hydrogen storage alloy of composition La 0.8Ce0.2Ni4.65-xMn0.9Ti0.05(V0.3Fe0.4Al0.3)x, in which the capacity retention rate after 100 weeks of recycling is only 92.1% at maximum.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a rare earth-calcium-nickel-based hydrogen storage alloy having excellent cycle stability. Further, the rare earth-calcium-nickel hydrogen storage alloy has higher hydrogen absorption capacity. Further, the rare earth-calcium-nickel hydrogen storage alloy has lower enthalpy of hydride formation and hysteresis coefficient. Another object of the present invention is to provide a method for producing the above rare earth-calcium-nickel based hydrogen storage alloy.
The technical aim is achieved through the following technical scheme.
In one aspect, the present invention provides a rare earth-calcium-nickel based hydrogen storage alloy having the composition shown below:
LaaREbYcCadNixMnyAlzQt
Wherein a, b, c, d, x, y, z and t represent the molar parts of La, RE, Y, ca, ni, mn, al and Q, respectively;
Wherein the method comprises the steps of ,0.1≤a≤0.7,0≤b≤0.45,0.05≤c≤0.5,0.1≤d≤0.6,a+b+c+d＝1;4.3≤x≤4.95,0≤y≤0.4,0≤z≤0.4,0.05≤y+z≤0.65,0≤t≤0.2,4.8≤x+y+z+t≤5.2;
Wherein RE is selected from one or more of Ce, sm, nd and Pr;
wherein Q is selected from one or more of Cu, sn, V, ti, zr, cr, zn, mo and Si.
The rare earth-calcium-nickel-based hydrogen storage alloy according to the present invention preferably, RE contains one or more of Ce, sm, or Nd.
The rare earth-calcium-nickel-based hydrogen storage alloy according to the present invention preferably, RE further includes Pr.
The rare earth-calcium-nickel-based hydrogen storage alloy according to the present invention preferably has RE of Pr and Ce, and the molar ratio of Pr to Ce is 1 (1-3).
The rare earth-calcium-nickel-based hydrogen storage alloy according to the present invention preferably has 4.7.ltoreq.x.ltoreq.4.9.
The rare earth-calcium-nickel-based hydrogen storage alloy according to the present invention preferably has 0.05.ltoreq.z.ltoreq. 0.3,0.1.ltoreq.y+z.ltoreq.0.5.
The rare earth-calcium-nickel-based hydrogen storage alloy according to the present invention preferably has 0.1.ltoreq.b.ltoreq.0.4.
Preferably, Q is selected from one or more of V, ti and Cu, and t is more than or equal to 0.01 and less than or equal to 0.15.
The rare earth-calcium-nickel-based hydrogen storage alloy according to the present invention preferably has a composition as one of:
La0.4Y0.3Ca0.3Ni4.8Mn0.1Al0.1；
La0.3Y0.3Ca0.4Ni4.7Mn0.1Al0.2；
La0.4Y0.4Ca0.2Ni4.7Mn0.2Al0.1；
La0.6Y0.2Ca0.2Ni4.7Mn0.1Al0.1V0.1；
La0.2Ce0.35Y0.1Ca0.35Ni4.45Mn0.3Al0.25；
La0.25Ce0.2Y0.1Ca0.45Ni4.7Mn0.15Al0.05V0.1；
La0.4Ce0.2Y0.2Ca0.2Ni4.8Mn0.1Al0.1；
La0.3Ce0.3Y0.2Ca0.2Ni4.7Mn0.1Al0.1Ti0.1；
La0.3Ce0.2Y0.2Ca0.3Ni4.8Mn0.1Al0.1；
La0.3Ce0.25Y0.2Ca0.25Ni4.7Mn0.15Al0.15；
La0.4Ce0.1Y0.3Ca0.2Ni4.8Mn0.2；
La0.4Ce0.2Y0.2Ca0.2Ni4.7Mn0.15Al0.15；
La0.3Ce0.2Y0.3Ca0.2Ni4.6Mn0.2Al0.2；
La0.3Ce0.3Y0.2Ca0.2Ni4.8Mn0.1Al0.1；
La0.35Ce0.25Y0.2Ca0.2Ni4.85Al0.15；
La0.4Ce0.2Y0.2Ca0.2Ni4.8Mn0.05Al0.15；
La0.2Ce0.2Y0.3Ca0.3Ni4.8Mn0.1Al0.1；
La0.4Sm0.2Y0.2Ca0.2Ni4.8 Mn0.05Al0.15；
La0.3Nd0.2Y0.2Ca0.3Ni4.7Mn0.2Cu0.1；
La0.2Pr0.1Ce0.2Y0.3Ca0.2Ni4.7Al0.3。
On the other hand, the invention provides a preparation method of the rare earth-calcium-nickel hydrogen storage alloy, which comprises the following steps:
(1) Smelting a metal raw material in an inert atmosphere to obtain a master alloy; wherein the smelting temperature is 1100-1600 ℃ and the smelting pressure is 0.01-0.1 MPa;
(2) Annealing the master alloy in an inert atmosphere to obtain a rare earth-calcium-nickel hydrogen storage alloy; wherein the annealing pressure is 0.01-0.1 MPa, the annealing temperature is 800-1200 ℃, and the annealing time is 10-25 h.
The rare earth-calcium-nickel hydrogen storage alloy is AB 5 type hydrogen storage alloy. The calcium element on the A side is replaced by La and Y in proper proportion, and the nickel element on the B side is replaced by Al and/or Mn in proper proportion, so that the cycle stability and the hydrogen storage amount of the rare earth-calcium-nickel hydrogen storage alloy can be improved, the service life is prolonged, and the formation enthalpy of the hydride is reduced. According to the preferred scheme of the invention, the adoption of RE element to replace part Y can further improve the cycle stability and hydrogen storage amount of the rare earth-calcium-nickel hydrogen storage alloy. The invention discovers that the combination of Al and Mn has more excellent effects on improving the cycle stability and the hydrogen storage amount of the rare earth-calcium-nickel hydrogen storage alloy.
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.
< Rare earth-calcium-Nickel-based Hydrogen absorbing alloy >
The rare earth-calcium-nickel-based hydrogen storage alloy of the present invention has the composition shown below:
LaaREbYcCadNixMnyAlzQt。
The rare earth-calcium-nickel hydrogen storage alloy is AB 5 type hydrogen storage alloy. Preferably, the rare earth-calcium-nickel-based hydrogen storage alloy of the present invention does not contain Mg, fe or Co. According to one embodiment of the present invention, the rare earth-calcium-nickel-based hydrogen storage alloy of the present invention contains no other components except unavoidable impurities.
La represents lanthanum. a represents the mole fraction of La. A is more than or equal to 0.1 and less than or equal to 0.7; preferably, a is more than or equal to 0.2 and less than or equal to 0.5; more preferably, 0.3.ltoreq.a.ltoreq.0.4.
RE is one or more selected from Ce, sm, nd and Pr. Preferably, M comprises one or more of Ce, sm or Nd. In certain embodiments, the RE further comprises Pr. According to one embodiment of the invention, RE is selected from one of the elemental compositions shown below: (1) Ce; (2) Sm; (3) Nd; (4) Ce and Pr. The RE element and Y can be matched to further improve the cycle stability and the hydrogen absorption amount of the rare earth-calcium-nickel hydrogen storage alloy.
B represents the mole fraction of RE element. B is more than or equal to 0 and less than or equal to 0.45. In some embodiments b=0. In other embodiments, 0.1.ltoreq.b.ltoreq.0.35; preferably, b is more than or equal to 0.2 and less than or equal to 0.3; more preferably, 0.2.ltoreq.b.ltoreq.0.25. The use amount of the RE element can improve the hydrogen absorption amount and the cycle stability of the rare earth-calcium-nickel hydrogen storage alloy.
In certain embodiments, RE is Pr and Ce. The mol ratio of Pr to Ce can be 1 (1-3); preferably 1 (1.5-2.5); more preferably 1:2.
Y represents yttrium cerium element. c represents the molar fraction of Y. C is more than or equal to 0.05 and less than or equal to 0.5; preferably, 0.1.ltoreq.c.ltoreq.0.4. In some embodiments, 0.2.ltoreq.c.ltoreq.0.5; preferably, 0.3.ltoreq.c.ltoreq.0.4. In other embodiments, 0.1.ltoreq.c.ltoreq.0.3; more preferably, 0.1.ltoreq.c.ltoreq.0.2. The adoption of proper amount of Y to replace Ca can improve the hydrogen absorption amount and the circulation stability of the rare earth-calcium-nickel hydrogen storage alloy and reduce the formation enthalpy of the hydride.
Ca represents a calcium element. d represents the mole fraction of Ca. D is more than or equal to 0.1 and less than or equal to 0.6; preferably, d is more than or equal to 0.2 and less than or equal to 0.5; more preferably, 0.2.ltoreq.d.ltoreq.0.3. Thus being beneficial to improving the cycle stability and the hydrogen absorption amount of the rare earth-calcium-nickel hydrogen storage alloy.
In the present invention, a+b+c+d=1.
Ni represents a nickel element. x represents the mole fraction of Ni. X is more than or equal to 4.3 and less than or equal to 4.95; preferably, x is more than or equal to 4.4 and less than or equal to 4.9; more preferably, 4.7.ltoreq.x.ltoreq.4.9; most preferably, 4.8.ltoreq.x.ltoreq.4.85. Too low a content of nickel may cause a decrease in the hydrogen absorption amount and cycle stability of the rare earth-calcium-nickel based hydrogen storage alloy.
Al represents an aluminum element. z represents the mole fraction of Al. Z is more than or equal to 0 and less than or equal to 0.4. In certain embodiments, z=0. In other embodiments, 0.05.ltoreq.z.ltoreq.0.3; preferably, 0.1.ltoreq.z.ltoreq.0.2; more preferably, 0.1.ltoreq.z.ltoreq.0.15. Al is adopted to replace part of Ni, and is matched with elements on the hydrogen absorption side of the rare earth-calcium-nickel hydrogen storage alloy, so that the hydrogen absorption amount and the cycle stability of the rare earth-calcium-nickel hydrogen storage alloy can be improved.
Mn represents a manganese element. y represents the mole fraction of Mn. Y is more than or equal to 0 and less than or equal to 0.4. In certain embodiments, y=0. In other embodiments, 0.05.ltoreq.y.ltoreq.0.3; preferably, 0.1.ltoreq.y.ltoreq.0.2. According to one embodiment of the invention, 0.05.ltoreq.y.ltoreq.0.1. Mn is adopted to replace part of Ni, and is matched with elements on the hydrogen absorption side of the rare earth-calcium-nickel hydrogen storage alloy, so that the hydrogen absorption amount and the cycle stability of the rare earth-calcium-nickel hydrogen storage alloy can be improved. Mn and Al are combined to further improve the hydrogen absorption amount and the cycle stability of the rare earth-calcium-nickel hydrogen storage alloy.
In the invention, y+z is more than or equal to 0.05 and less than or equal to 0.65; preferably, 0.1.ltoreq.y+z.ltoreq.0.55; more preferably, 0.15.ltoreq.y+z.ltoreq.0.3; most preferably, 0.15.ltoreq.y+z.ltoreq.0.2.
Q is selected from one or more of Cu, sn, V, ti, zr, cr, zn, mo and Si; preferably, Q is selected from one or more of Cu, V, ti; more preferably, Q is selected from one of V or Cu.
T represents the molar fraction of Q. T is more than or equal to 0 and less than or equal to 0.2. In certain embodiments, t=0. In other embodiments, 0.05.ltoreq.t.ltoreq.0.15; preferably, t is more than or equal to 0.05 and less than or equal to 0.1.
In the invention, x+y+z+t is more than or equal to 4.8 and less than or equal to 5.2; preferably, 4.9.ltoreq.x+y+z+t.ltoreq.5.1; more preferably, 5.ltoreq.x+y+z+t.ltoreq.5.1. Thus, the hydrogen storage amount and the cycle stability of the rare earth-calcium-nickel hydrogen storage alloy can be improved.
Specific examples of the rare earth-calcium-nickel-based hydrogen storage alloy of the present invention include, but are not limited to, compositions represented by one of the following formulas:
La0.4Y0.3Ca0.3Ni4.8Mn0.1Al0.1；
La0.3Y0.3Ca0.4Ni4.7Mn0.1Al0.2；
La0.4Y0.4Ca0.2Ni4.7Mn0.2Al0.1；
La0.6Y0.2Ca0.2Ni4.7Mn0.1Al0.1V0.1；
La0.2Ce0.35Y0.1Ca0.35Ni4.45Mn0.3Al0.25；
La0.25Ce0.2Y0.1Ca0.45Ni4.7Mn0.15Al0.05V0.1；
La0.4Ce0.2Y0.2Ca0.2Ni4.8Mn0.1Al0.1；
La0.3Ce0.3Y0.2Ca0.2Ni4.7Mn0.1Al0.1Ti0.1；
La0.3Ce0.2Y0.2Ca0.3Ni4.8Mn0.1Al0.1；
La0.3Ce0.25Y0.2Ca0.25Ni4.7Mn0.15Al0.15；
La0.4Ce0.1Y0.3Ca0.2Ni4.8Mn0.2；
La0.4Ce0.2Y0.2Ca0.2Ni4.7Mn0.15Al0.15；
La0.3Ce0.2Y0.3Ca0.2Ni4.6Mn0.2Al0.2；
La0.3Ce0.3Y0.2Ca0.2Ni4.8Mn0.1Al0.1；
La0.35Ce0.25Y0.2Ca0.2Ni4.85Al0.15；
La0.4Ce0.2Y0.2Ca0.2Ni4.8Mn0.05Al0.15；
La0.2Ce0.2Y0.3Ca0.3Ni4.8Mn0.1Al0.1；
La0.4Sm0.2Y0.2Ca0.2Ni4.8 Mn0.05Al0.15；
La0.3Nd0.2Y0.2Ca0.3Ni4.7Mn0.2Cu0.1；
La0.2Pr0.1Ce0.2Y0.3Ca0.2Ni4.7Al0.3。
The rare earth-calcium-nickel hydrogen storage alloy has higher hydrogen storage amount and cycle stability. According to the preferred technical scheme of the invention, the rare earth-calcium-nickel hydrogen storage alloy has lower enthalpy of hydride formation and hysteresis coefficient.
The rare earth-calcium-nickel hydrogen storage alloy of the invention has the maximum hydrogen absorption amount of more than or equal to 1.63wt% at 40 ℃; preferably, the maximum hydrogen absorption is greater than or equal to 1.65wt%; more preferably, the maximum hydrogen absorption amount is 1.67 to 1.69wt%. The capacity retention rate of the circulating 100 weeks is more than or equal to 99.3 percent; preferably, the capacity retention rate of 100 weeks of circulation is more than or equal to 99.6%; more preferably, the capacity retention rate of 100 weeks of circulation is greater than or equal to 99.7%.
< Method for producing rare earth-calcium-Nickel-based Hydrogen absorbing alloy >
The preparation method of the rare earth-calcium-nickel hydrogen storage alloy comprises the following steps: (1) Smelting a metal raw material in an inert atmosphere to obtain a master alloy; (2) Annealing the master alloy in inert atmosphere to obtain the rare earth-calcium-nickel hydrogen storage alloy.
In the step (1), the metal La, the metal RE, the metal Y, and the metal Ca in the metal raw material are metal raw materials from which surface oxides are removed. The metal feedstock may be placed in a smelting vessel for smelting. The smelting vessel may be a crucible, such as an alumina crucible. The inert atmosphere may be selected from one or more of nitrogen, neon, argon. According to one embodiment of the invention, the inert atmosphere is an argon atmosphere. The smelting temperature can be 1100-1600 ℃; preferably 1200-1500 ℃; more preferably 1300 to 1400 ℃. The smelting pressure can be 0.01-0.1 MPa; preferably 0.02-0.08 MPa; more preferably 0.03 to 0.06MPa.
In the step (2), the inert atmosphere may be selected from one or more of nitrogen, neon and argon. According to one embodiment of the invention, the inert atmosphere is an argon atmosphere. The annealing temperature can be 800-1200 ℃; preferably 900 to 1100 ℃; more preferably 1000 to 1100 ℃. The annealing pressure can be 0.01-0.1 MPa; preferably 0.02-0.08 MPa; more preferably 0.03 to 0.06MPa. The annealing time can be 10-25 h; preferably 13 to 20 hours; more preferably 15 to 18 hours.
Examples 1 to 20 and comparative examples 1 to 6
Polishing the metal La, the metal RE, the metal Y and the metal Ca to remove oxides on the surface, and respectively obtaining the treated metal La, the treated metal RE, the treated metal Y and the treated metal Ca.
The metal raw materials for forming the rare earth-calcium-nickel-based hydrogen storage alloy shown in table 1 were placed in an alumina crucible. The metal raw material placed in the alumina crucible was melted under an argon atmosphere at a pressure of 0.05MPa and a temperature of 1400 ℃ to form a master alloy. And (3) annealing the master alloy for 18 hours under the argon atmosphere and under the conditions that the pressure is 0.05MPa and the temperature is 1000 ℃ to obtain the rare earth-calcium-nickel hydrogen storage alloy.
The maximum hydrogen absorption is obtained according to the P-C-T curve measured by Sieverts device at 40 deg.C of rare earth-calcium-nickel hydrogen storage alloy.
The hysteresis coefficient and the enthalpy of hydride formation are obtained according to the P-C-T curve and calculated by a formula.
The capacity retention at 100 weeks of cycling was measured using the following method:
(1) Dehydrogenating the activated sample: vacuumizing for 1h at the normal temperature of 30 ℃ to ensure that the sample is completely dehydrogenated.
(2) The sample is dehydrogenated and then subjected to a first hydrogen absorption cycle: and (3) filling hydrogen with a certain hydrogen pressure, recording the change of the hydrogen absorption amount of the sample along with the time until the hydrogen absorption amount is not changed, and recording the hydrogen absorption amount as the first hydrogen absorption amount C 1 of the sample.
(3) And (3) repeating the steps 1 and 2 to complete the alloy for a plurality of times, and recording the hydrogen absorption quantity C n (n represents the cycle times) of each cycle.
(4) The cycle n-week capacity retention (S n)：Sn＝(Cn/C1) x 100% was calculated according to the formula.
TABLE 1
The hydrogen absorbing side of comparative examples 1 to 4 did not contain yttrium, and both of the hydrogen storage amount and the capacity retention after 100 weeks of cycle were lower than those of the rare earth-calcium-nickel-based hydrogen storage alloy of the present invention, and the enthalpy of hydride formation was higher than that of the rare earth-calcium-nickel-based hydrogen storage alloy of the present invention. The yttrium can effectively improve the hydrogen storage amount and the cycle stability of the rare earth-calcium-nickel hydrogen storage alloy and reduce the enthalpy of hydride formation.
The molar fraction of the non-hydrogen-absorbing element in comparative example 5 is too large, and the hydrogen storage capacity, the cycle stability, the enthalpy of hydride formation, and the like of the hydrogen storage alloy are reduced.
The content of Ni in comparative example 6 is too small, which results in a decrease in the hydrogen storage amount and cycle stability of the hydrogen storage alloy and an increase in the enthalpy of hydride formation.
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 (2)
1. A rare earth-calcium-nickel-based hydrogen storage alloy, characterized in that the rare earth-calcium-nickel-based hydrogen storage alloy has a composition of one of the following:
La0.4Y0.3Ca0.3Ni4.8Mn0.1Al0.1；
La0.4Ce0.2Y0.2Ca0.2Ni4.8Mn0.1Al0.1；
La0.3Ce0.2Y0.2Ca0.3Ni4.8Mn0.1Al0.1；
La0.4Ce0.1Y0.3Ca0.2Ni4.8Mn0.2；
La0.3Ce0.3Y0.2Ca0.2Ni4.8Mn0.1Al0.1；
La0.35Ce0.25Y0.2Ca0.2Ni4.85Al0.15；
La0.4Ce0.2Y0.2Ca0.2Ni4.8Mn0.05Al0.15；
La0.2Ce0.2Y0.3Ca0.3Ni4.8Mn0.1Al0.1；
La0.4Sm0.2Y0.2Ca0.2Ni4.8Mn0.05Al0.15。
2. The method for producing a rare earth-calcium-nickel-based hydrogen storage alloy according to claim 1, comprising the steps of:
(1) Smelting a metal raw material in an inert atmosphere to obtain a master alloy; wherein the smelting temperature is 1100-1600 ℃ and the smelting pressure is 0.01-0.1 MPa;
(2) Annealing the master alloy in an inert atmosphere to obtain a rare earth-calcium-nickel hydrogen storage alloy; wherein the annealing pressure is 0.01-0.1 MPa, the annealing temperature is 800-1200 ℃, and the annealing time is 10-25 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211632411.3A CN115786770B (en) | 2022-12-19 | 2022-12-19 | Rare earth-calcium-nickel hydrogen storage alloy and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211632411.3A CN115786770B (en) | 2022-12-19 | 2022-12-19 | Rare earth-calcium-nickel hydrogen storage alloy and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115786770A CN115786770A (en) | 2023-03-14 |
| CN115786770B true CN115786770B (en) | 2024-04-26 |
Family
ID=85425699
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211632411.3A Active CN115786770B (en) | 2022-12-19 | 2022-12-19 | Rare earth-calcium-nickel hydrogen storage alloy and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115786770B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1165542A (en) * | 1995-08-31 | 1997-11-19 | 三德金属工业株式会社 | Rare earth metal-nickel-base hydrogen absorbing alloy, process for preparing the same, and negative electrode for nickel-hydrogen secondary battery |
| CN101589491A (en) * | 2007-07-24 | 2009-11-25 | 松下电器产业株式会社 | Negative-electrode material for nickel hydrogen battery, method of treating the same, and nickel hydrogen battery |
| CN110023523A (en) * | 2016-12-26 | 2019-07-16 | 三井金属矿业株式会社 | Hydrogen bearing alloy |
| CN112159993A (en) * | 2020-09-24 | 2021-01-01 | 赣州有色冶金研究所 | Yttrium-containing mixed rare earth metal, rare earth hydrogen storage alloy and preparation method thereof |
-
2022
- 2022-12-19 CN CN202211632411.3A patent/CN115786770B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1165542A (en) * | 1995-08-31 | 1997-11-19 | 三德金属工业株式会社 | Rare earth metal-nickel-base hydrogen absorbing alloy, process for preparing the same, and negative electrode for nickel-hydrogen secondary battery |
| CN101589491A (en) * | 2007-07-24 | 2009-11-25 | 松下电器产业株式会社 | Negative-electrode material for nickel hydrogen battery, method of treating the same, and nickel hydrogen battery |
| CN110023523A (en) * | 2016-12-26 | 2019-07-16 | 三井金属矿业株式会社 | Hydrogen bearing alloy |
| CN112159993A (en) * | 2020-09-24 | 2021-01-01 | 赣州有色冶金研究所 | Yttrium-containing mixed rare earth metal, rare earth hydrogen storage alloy and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115786770A (en) | 2023-03-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7935305B2 (en) | Hydrogen storage alloy, production method therefor and nickel-hydrogen secondary battery-use cathode | |
| JP5119551B2 (en) | Hydrogen storage alloy, method for producing the same, and secondary battery | |
| JP5449989B2 (en) | Hydrogen storage alloy, method for producing the same, and hydrogen storage device | |
| CN115786770B (en) | Rare earth-calcium-nickel hydrogen storage alloy and preparation method thereof | |
| CN115074578B (en) | Y-Mg-Ni-based hydrogen storage alloy and preparation method thereof | |
| JP3845057B2 (en) | Hydrogen storage alloy and heat treatment method of hydrogen storage alloy | |
| JP3493516B2 (en) | Hydrogen storage alloy and method for producing the same | |
| JPS59143036A (en) | Ternary alloy of rare earth element for occluding hydrogen | |
| CN115807180A (en) | Hydrogen storage alloy containing yttrium and its preparation process | |
| CN115992319B (en) | Rare earth hydrogen storage alloy and preparation method thereof | |
| CN114686772B (en) | Rare earth-iron-based alloy material, and preparation method and application thereof | |
| CN114672740B (en) | Yttrium-iron-based hydrogen storage alloy, battery and preparation method | |
| CN114672721B (en) | Non-stoichiometric rare earth-iron-based hydrogen storage alloy and preparation method and application thereof | |
| JP3114677B2 (en) | Hydrogen storage alloy and method for producing the same | |
| CN115710664B (en) | Cobalt-containing Y-Mg-Ni-based hydrogen storage alloy and preparation method thereof | |
| JPH06228687A (en) | Hydrogen storage alloy and its production | |
| JP3930638B2 (en) | Hydrogen storage alloy and method for producing the same | |
| CN117363948A (en) | Hydrogen storage alloy, preparation method thereof and application of titanium | |
| JP3670506B2 (en) | Hydrogen or hydrogen isotope storage material | |
| JP3984802B2 (en) | Hydrogen storage alloy | |
| CN115948678A (en) | AB5 type hydrogen storage alloy, preparation method and application of Ce and Al | |
| CN117286386A (en) | Rare earth phase precipitation strengthening high-entropy alloy and preparation method thereof | |
| JP2662436B2 (en) | Method for improving characteristics of metal material for hydrogen storage | |
| CN117385258A (en) | Aluminum-containing hydrogen storage alloy, preparation method thereof and application of calcium element | |
| JP4462909B2 (en) | Hydrogen storage alloy |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |