CN101824566B - Rare earth-based hydrogen storage alloy for metal hydride heat pump and preparation method thereof - Google Patents
Rare earth-based hydrogen storage alloy for metal hydride heat pump and preparation method thereof Download PDFInfo
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- CN101824566B CN101824566B CN2009100105587A CN200910010558A CN101824566B CN 101824566 B CN101824566 B CN 101824566B CN 2009100105587 A CN2009100105587 A CN 2009100105587A CN 200910010558 A CN200910010558 A CN 200910010558A CN 101824566 B CN101824566 B CN 101824566B
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Abstract
The invention relates to a rare earth-based hydrogen storage alloy for a metal hydride heat pump and a preparation method thereof. The invention is characterized in that through adding elements such as Al, Mn, Cr, Fe, Cu in LaNi5 alloy, changing alloy stoichiometric ratio and the like, a new alloy is designed and is provided with a composition general formula of La (Ni3.8Al1.2-xMx) y, wherein M denotes Mn, Cr, Fe and Cu, x is more than or equal to 0.2 and is less than or equal to 0.6, and y is more than or equal to 0.94 and is less than or equal to 1.0. Elements on an A side exceed metering to enable a new phase to occur in the alloy. The rare earth-based hydrogen storage alloy is smelted by using a nonconsumable vacuum arc furnace, and the annealing heat treatment conditions are that a sample is annealed for 6h at 1323K in a vacuum condition and is rapidly cooled. The Invention has the advantages that the alloy production method is simple, the alloy can be easily activated, the platform pressure is low, the hydrogen absorption and release lag factor is small, the hydrogen absorption and release dynamic performance and the powdering resistance are high, and the method is very suitable for the preparation of the rare earth-based hydrogen storage alloy for the metal hydride heat pump.
Description
Technical field
The present invention relates to a kind of lanthanon hydrogen storage alloy, a kind of metal hydride heat pump rare earth hydrogen storage alloy that is applicable to is provided, belong to the hydrogen storage alloy field.
Background technology
Along with the progress of expanding economy and society, people's living standard improves constantly, and uses the unit or the family of air-conditioning increasing.But the conventional air-conditioning energy consumption is big, and freonll-11 easily leaks as working medium, destroys atmospheric ozone layer, causes serious environmental problem, the infringement eubiosis.Therefore seek and develop new equivalent material and become various countries' question of common concern.Novel metal hydride heat pump air-conditioning system is considered to a kind of method with good development prospect, and its advantage is: can utilize the thermal source of low tastes such as used heat, sun power to drive heat pump work, and energy-conservation, environmental protection, friction, noiselessness, good reliability, operating temperature range is big.
The principle of work of metal hydride heat pump is to be working medium with hydrogen, with hydrogen storage alloy as energy converslon materials.The thermodynamic cycle system that forms by two kinds of different hydrogen storage alloys of equilibrium pressure under the uniform temp.Utilize their balance pressure reduction to drive flow hydrogen gas, two kinds of hydride are in respectively inhale hydrogen (heat release) and put hydrogen (heat absorption) state, thereby reach the intensification gain of heat or refrigerating purpose.
The performance requriements of metal hydride heat pump with hydrogen storage alloy had: alloy should possess higher suction hydrogen discharge reaction reversibility, good suction hydrogen desorption kinetics performance, sufficiently long suction and put hydrogen cycle life, significantly inhales the hydrogen discharge reaction heat effect and hydrogen hysteresis etc. is put in less suction.
Choosing suitable hydrogen storage alloy is one of key that realizes the metal hydride heat pump efficiency operation.Present most of metal hydride heat pump all adopts AB with hydrogen storage alloy
5System, also useful Ti is.But TiFe is the alloy existence activates difficulty, suction is put hydrogen and lagged behind greatly, shortcomings such as easy poisoning; TiMn is that the alloy capacity is less than normal.And AB
5Be that alloy has excellent comprehensive performances, especially its smooth pressure platform characteristic and good activation performance have simultaneously and inhale hydrogen desorption kinetics characteristic and stronger anti-poisoning ability faster.Therefore we adopt LaNi
5The method searching of carrying out alloying and change alloy metering ratio is more suitable for the hydrogen storage alloy that metal hydride heat pump is used.
Summary of the invention
The object of the present invention is to provide a kind of metal hydride heat pump lanthanon hydrogen storage alloy and preparation method thereof, this alloy have easy activation, hydrogen storage capability height, plateau pressure low, inhale that to put the hydrogen hysteresis factors little, have good suction hydrogen desorption kinetics performance and resistance to chalking energy simultaneously, be highly suitable for the metal hydride heat pump hydrogen storage alloy.
The invention provides a kind of metal hydride heat pump lanthanon hydrogen storage alloy, it is characterized in that this alloy composition (atom composition) is La (Ni
3.8Al
1.2-xM
x)
y, wherein M=Mn, Cr, Fe, Cu, 0.2≤x≤0.6,0.94≤y≤1.0.
Metal hydride heat pump lanthanon hydrogen storage alloy provided by the present invention is characterized in that working as y=1.0, during x=0.2, and M=Mn, Cr, Fe, Cu.
Metal hydride heat pump lanthanon hydrogen storage alloy provided by the present invention is characterized in that working as y=1.0, during M=Mn, and 0.2≤x≤0.6.
Metal hydride heat pump lanthanon hydrogen storage alloy provided by the present invention is characterized in that when y＜1.0 x=0.2, M=Mn.
Metal hydride heat pump lanthanon hydrogen storage alloy provided by the present invention is characterized in that when y=1.0 alloy is single CaCu
5The type hexagonal crystallographic texture.
Metal hydride heat pump lanthanon hydrogen storage alloy provided by the present invention is characterized in that the principal phase of described alloy is CaCu when y＜1.0
5The type hexagonal structure, but have a small amount of cenotype to exist.
The present invention also provides the preparation method of a kind of metal hydride heat pump with lanthanon hydrogen storage alloy: it is characterized in that process is as follows:
Preparation hydrogen storage alloy La (Ni
3.8Al
1.2-xM
x)
yThe button ingot carries out proportioning raw materials by chemical formula, because the fusing point of Mn is lower, volatilizees easily during melting, so Mn is that 4%～5% ratio is added in the weight percent of Mn when joining sample; Be smelted into alloy cast ingot then in non-consumable arc furnace, in order to guarantee the homogeneity of alloy, alloy is total to melt back 3 to 4 times, for anti-oxidation is all carried out under argon shield atmosphere.
Metal hydride heat pump of the present invention is with the preparation method of lanthanon hydrogen storage alloy: it is characterized in that the alloy sample for preparing annealing under 1323K under the vacuum state, annealing time is 6h, and is cold soon afterwards.
The activation of alloy and hydrogen storage property test experiments all carry out on the PCT tester of development voluntarily.Suction is put hydrogen PCT curve and is all adopted volumetry.Used hydrogen purity is 99.999%, the fluctuating temperature≤1K of reactor, and the precision of pressure transmitter is 0.1%FS.Take by weighing 1g left and right sides sample and put into the sample chamber, at room temperature vacuumized 30 minutes, the hydrogen that feeds 1.7MPa then under 286K makes itself and example reaction.It is sample to be heated to 433K vacuumized then 30 minutes that alloy is put the hydrogen process.Inhale repeatedly and put hydrogen and guarantee under differing temps, to carry out respectively after sample fully activates the hydrogen storage property test for 5 times.
The calculation formula of alloy hydrogen absorption and desorption reaction enthalpy change and reaction entropy variate adopts Van ' t Hoff formula:
(wherein, Δ H and Δ S are respectively standard enthalpy change amount and standard entropy variable).
The present invention has adopted multi-element alloyed mode, and Al and Mn, Cr, Cu, Fe add simultaneously can guarantee when reduce lagging behind that alloy has higher hydrogen storage capability and resistance to chalking energy preferably.On the other hand, rare earth of the present invention is AB
5Partly adopted A side element to exceed stoichiometric ratio during the design of type hydrogen storage alloy composition, this helps improving the resistance to chalking energy.
La (Ni of the present invention
3.8Al
1.2-xM
x)
yHydrogen storage alloy, activation easily, it is little to lag behind, and has good resistance to chalking energy and dynamic performance, and over-all properties is good, is highly suitable for the metal hydride heat pump hydrogen storage alloy.
Description of drawings
Fig. 1 is La (Ni of the present invention
3.8Al
1.2-xM
x)
yThe XRD diffracting spectrum of alloy;
Fig. 2 is LaNi of the present invention
3.8Al
1.0Cu
0.2The PCT curve of alloy;
Fig. 3 is LaNi of the present invention
3.8Al
1.0Cr
0.2The PCT curve of alloy;
Fig. 4 is LaNi of the present invention
3.8Al
1.0Fe
0.2The PCT curve of alloy;
Fig. 5 is LaNi of the present invention
3.8Al
1.0Mn
0.2The PCT curve of alloy;
Fig. 6 is LaNi of the present invention
3.8Al
0.8Mn
0.4The PCT curve of alloy;
Fig. 7 is LaNi of the present invention
3.8Al
0.6Mn
0.6The PCT curve of alloy;
Fig. 8 is La (Ni of the present invention
3.8Al
1.0Mn
0.2)
0.98The PCT curve of alloy;
Fig. 9 is La (Ni of the present invention
3.8Al
1.0Mn
0.2)
0.94The PCT curve of alloy.
Embodiment
The metal hydride heat pump of the present invention preparation method and the heat-treat condition of lanthanon hydrogen storage alloy: preparation hydrogen storage alloy La (Ni
3.8Al
1.2-xM
x)
yThe button ingot carries out proportioning raw materials by chemical formula, because the fusing point of Mn is lower, volatilizees easily during melting, so Mn is that 4%～5% ratio is added in the weight percent of Mn when joining sample; Be smelted into alloy cast ingot then in non-consumable arc furnace, in order to guarantee the homogeneity of alloy, alloy is total to melt back 3 to 4 times, for anti-oxidation is all carried out under argon shield atmosphere.The alloy sample for preparing is annealed under 1323K under vacuum state, and annealing time is 6h, and is cold soon afterwards.
The activation of alloy and hydrogen storage property test experiments all carry out on the PCT tester of development voluntarily.Suction is put hydrogen PCT curve and is all adopted volumetry.Used hydrogen purity is 99.999%, the fluctuating temperature≤1K of reactor, and the precision of pressure transmitter is 0.1%FS.Take by weighing 1g left and right sides sample and put into the sample chamber, at room temperature vacuumized 30 minutes, the hydrogen that feeds 1.7MPa then under 286K makes itself and example reaction.It is sample to be heated to 433K vacuumized then 30 minutes that alloy is put the hydrogen process.Inhale repeatedly and put hydrogen and guarantee under differing temps, to carry out respectively after sample fully activates the hydrogen storage property test for 5 times.
Preparation and test hydrogen storage alloy LaNi
3.8Al
1.0Cu
0.2Alloy.Preparation method, heat-treat condition and activation method are as mentioned above.
Test result: LaNi
3.8Al
1.0Cu
0.2Alloy needs just can begin to inhale hydrogen rapidly the incubation period about process 1100s following of above-mentioned activation condition, and once just can finish reactivation process.The hydride hydrogen storage amount that forms under 286K is 4.70.Suction hydrogen balance pressure at 433K is 100kPa, and putting hydrogen balance pressure is 93kPa, and lag coefficient is very little, and it is all very fast to inhale hydrogen desorption kinetics speed, is 90% needs 40s that 1.2MPa, temperature reach maximum hydrogen during for 433K at initial hydrogen pressure.Suction is put the hydrogen enthalpy change and is respectively-49.45KJ/Mol and 49.87KJ/Mol.Reaction enthalpy, suction hydrogen desorption plateau pressure and suction hydrogen desorption kinetics performance all are fit to the metal hydride heat pump hydrogen storage alloy.
Embodiment 2
Be with the difference of embodiment 1: preparation and test hydrogen storage alloy LaNi
3.8Al
1.0Cr
0.2
Test result: LaNi
3.8Al
1.0Cr
0.2Alloy needs just can begin to inhale hydrogen rapidly the incubation period about process 120s following of above-mentioned activation condition, and once just can finish reactivation process.The hydride hydrogen storage amount that forms under 286K is 4.86.Suction hydrogen balance pressure at 433K is 56kPa, and putting hydrogen balance pressure is 53kPa, and lag coefficient is very little, and it is all very fast to inhale hydrogen desorption kinetics speed, is 90% needs 30s that 1.2MPa, temperature reach maximum hydrogen during for 433K at initial hydrogen pressure.Suction is put the hydrogen enthalpy change and is respectively-52.69KJ/Mol and 53.21KJ/Mol.Reaction enthalpy, suction hydrogen desorption plateau pressure and suction hydrogen desorption kinetics performance all are fit to the metal hydride heat pump hydrogen storage alloy.
Embodiment 3
Be with the difference of embodiment 1: preparation and test hydrogen storage alloy LaNi
3.8Al
1.0Fe
0.2
Test result: LaNi
3.8Al
1.0Fe
0.2Alloy needs just can begin to inhale hydrogen rapidly the incubation period about process 750s following of above-mentioned activation condition, and once just can finish reactivation process.The hydride hydrogen storage amount that forms under 286K is 4.83.Suction hydrogen balance pressure at 433K is 83kPa, and putting hydrogen balance pressure is 80kPa, and lag coefficient is very little, and it is all very fast to inhale hydrogen desorption kinetics speed, is 90% needs 35s that 1.2MPa, temperature reach maximum hydrogen during for 433K at initial hydrogen pressure.Suction is put the hydrogen enthalpy change and is respectively-50.02KJ/Mol and 50.43KJ/Mol.Reaction enthalpy, suction hydrogen desorption plateau pressure and suction hydrogen desorption kinetics performance all are fit to the metal hydride heat pump hydrogen storage alloy.
Embodiment 4
Be with the difference of embodiment 1: preparation and test hydrogen storage alloy LaNi
3.8Al
1.0Mn
0.2
Test result: alloy needs just can finish the suction H-H reaction rapidly in 450s in case it begins to inhale hydrogen, and once just can finish reactivation process through just beginning to inhale rapidly hydrogen the incubation period about 2500s following of above-mentioned activation condition.The hydride hydrogen storage amount that forms under 286K is 5.07.Suction hydrogen balance pressure at 433K is 43kPa, and putting hydrogen balance pressure is 41kPa, and lag coefficient is very little, and it is all very fast to inhale hydrogen desorption kinetics speed, is 90% needs 26s that 1.2MPa, temperature reach maximum hydrogen during for 433K at initial hydrogen pressure.Suction is put the hydrogen enthalpy change and is respectively-53.39KJ/Mol and 53.57KJ/Mol.Reaction enthalpy, suction hydrogen desorption plateau pressure and suction hydrogen desorption kinetics performance all are fit to the metal hydride heat pump hydrogen storage alloy.
Embodiment 5
Be with the difference of embodiment 1: preparation and test hydrogen storage alloy LaNi
3.8Al
0.8Mn
0.4
Test result: alloy needs just can finish the suction H-H reaction rapidly in 350s in case it begins to inhale hydrogen, and once just can finish reactivation process through just beginning to inhale rapidly hydrogen the incubation period about 1500s following of above-mentioned activation condition.The hydride hydrogen storage amount that forms under 286K is 5.27.Suction hydrogen balance pressure at 433K is 60kPa, and putting hydrogen balance pressure is 54kPa, and lag coefficient is very little, and it is all very fast to inhale hydrogen desorption kinetics speed, is 90% needs 26s that 1.2MPa, temperature reach maximum hydrogen during for 433K at initial hydrogen pressure.Suction is put the hydrogen enthalpy change and is respectively-50.45KJ/Mol and 51.87KJ/Mol.Reaction enthalpy, suction hydrogen desorption plateau pressure and suction hydrogen desorption kinetics performance all are fit to the metal hydride heat pump hydrogen storage alloy.
Embodiment 6
Be with the difference of embodiment 1: preparation and test hydrogen storage alloy LaNi
3.8Al
0.6Mn
0.6
Test result: alloy needs just can finish the suction H-H reaction rapidly in 230s in case it begins to inhale hydrogen, and once just can finish reactivation process through just beginning to inhale rapidly hydrogen the incubation period about 250s following of above-mentioned activation condition.The hydride hydrogen storage amount that forms under 286K is 5.46.Suction hydrogen balance pressure at 433K is 77kPa, and putting hydrogen balance pressure is 69kPa, and lag coefficient is very little, and it is all very fast to inhale hydrogen desorption kinetics speed, is 90% needs 30s that 1.2MPa, temperature reach maximum hydrogen during for 433K at initial hydrogen pressure.Suction is put the hydrogen enthalpy change and is respectively-49.35KJ/Mol and 50.81KJ/Mol.Reaction enthalpy, suction hydrogen desorption plateau pressure and suction hydrogen desorption kinetics performance all are fit to the metal hydride heat pump hydrogen storage alloy.
Embodiment 7
Be with the difference of embodiment 1: preparation and test hydrogen storage alloy La (Ni
3.8Al
1.0Mn
0.2)
0.98
Test result: alloy needs just can finish the suction H-H reaction rapidly in 500s in case it begins to inhale hydrogen, and once just can finish reactivation process through just beginning to inhale rapidly hydrogen the incubation period about 4300s following of above-mentioned activation condition.The hydride hydrogen storage amount that forms under 286K is 4.95.Suction hydrogen balance pressure at 433K is 57kPa, and putting hydrogen balance pressure is 50kPa, and lag coefficient is very little, and it is all very fast to inhale hydrogen desorption kinetics speed, is 90% needs 26s that 1.2MPa, temperature reach maximum hydrogen during for 433K at initial hydrogen pressure.Suction is put the hydrogen enthalpy change and is respectively-51.3KJ/Mol and 52.37KJ/Mol.After 13 circulations, this alloying pellet mean size is 40.66 μ m, has resistance to chalking energy preferably.Reaction enthalpy, suction hydrogen desorption plateau pressure and suction hydrogen desorption kinetics performance and good resistance to chalking can all be fit to the metal hydride heat pump hydrogen storage alloy.
Embodiment 8
Difference from Example 1 is: preparation and test hydrogen storage alloy La (Ni
3.8Al
1.0Mn
0.2)
0.94
Test result: alloy needs just can finish the suction H-H reaction rapidly in 400s in case it begins to inhale hydrogen, and once just can finish reactivation process through just beginning to inhale rapidly hydrogen the incubation period about 1950s following of above-mentioned activation condition.The hydride hydrogen storage amount that forms under 286K is 4.74.Suction hydrogen balance pressure at 433K is 48kPa, and putting hydrogen balance pressure is 45kPa, and lag coefficient is very little, and it is all very fast to inhale hydrogen desorption kinetics speed, is 90% needs 26s that 1.2MPa, temperature reach maximum hydrogen during for 433K at initial hydrogen pressure.Suction is put the hydrogen enthalpy change and is respectively-51.71KJ/Mol and 52.64KJ/Mol.After 13 circulations, this alloying pellet mean size is 46.87 μ m, has resistance to chalking energy preferably.Reaction enthalpy, suction hydrogen desorption plateau pressure and suction hydrogen desorption kinetics performance and good resistance to chalking can all be fit to the metal hydride heat pump hydrogen storage alloy.
Claims (2)
1. a metal hydride heat pump lanthanon hydrogen storage alloy is characterized in that described alloy composition is LaNi
3.8Al
1.0Mn
0.2
2. according to the described metal hydride heat pump lanthanon hydrogen storage alloy of claim 1, it is characterized in that alloy is single CaCu
5The type hexagonal crystallographic texture.
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| CN1338006A (en) * | 1999-01-29 | 2002-02-27 | 桑特库美国公司 | AB-type rare earth transition intermetallic compounds for the negative electrodes of rechargeable batteries |
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| CN1338006A (en) * | 1999-01-29 | 2002-02-27 | 桑特库美国公司 | AB-type rare earth transition intermetallic compounds for the negative electrodes of rechargeable batteries |
Non-Patent Citations (2)
| Title |
|---|
| JIANG Yuwei et al..Designing appropriate heat treatment temperature for LaNi3.8Al0.75Mn0.45 alloy.《RARE METALS》.2006,第25卷243-246. * |
| JP昭58-217655A 1983.12.17 |
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