CN1049529A - Hydrogen storage material - Google Patents
Hydrogen storage material Download PDFInfo
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- CN1049529A CN1049529A CN 90107922 CN90107922A CN1049529A CN 1049529 A CN1049529 A CN 1049529A CN 90107922 CN90107922 CN 90107922 CN 90107922 A CN90107922 A CN 90107922A CN 1049529 A CN1049529 A CN 1049529A
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Abstract
The present invention relates to a kind of Ti-Mn is hydrogen storage material, and by the content that improves Fe in the alloy, the content that reduces V, the composition that obtains (wt%) is: Ti20～26, Zr8.3～13.8, Mn47～60, Cr3.1～9.4, V2.6～6.1, Fe2.7～6.7.The maximum hydrogen storage amount of this alloy can reach 2.12wt%, and decomposition pressure is 0.5～1.6MPa under the room temperature, is the high and cheap hydrogen-storage alloy of a kind of hydrogen storage amount height, decomposition pressure.
Description
The present invention relates to a kind of Ti-Mn is hydrogen storage material, be applicable to fields such as purifying hydrogen of hydrogen, heat pump, hydrogen compressor, it requires the hydrogen storage amount of alloy big, generally want 2wt% just to have good practicality, simultaneously, also should there be sufficiently high decomposition pressure (0.5～1.0MPa is advisable under the room temperature) could satisfy the needs that use preferably.
The clear 59-208037 of Japanese Patent Application Laid-Open discloses a kind of hexa-atomic hydrogen-storage alloy, and composition is Ti
0.8Zr
0.2(Mn
0.8Fe
0.04V
0.15Al
0.01)
1.7, its hydrogen storage amount is 1.8wt%, plateau pressure is extremely low, 30 ℃ of decomposition pressures only are 1atm(0.1MPa).The spy opens the alloy Ti that clear 53-48011 mentions
0.8Zr
0.2Mn
1.6Cr
0.2V
0.2Hydrogen storage amount is 243ml/g(2.1wt%) but (20 ℃) decomposition pressure 0.1～0.4MPa under the room temperature, these two kinds of alloys are because V content is higher, thereby price is more expensive.The spy opens the alloy that clear 61-41741 provides and is made up of Ti, Al, Mn, Cr, Cu, Zr, and (30 ℃) put the higher 0.7～1MPa of being of hydrogen pressure under the room temperature, but hydrogen storage amount only is 1.80wt%.
Purpose of the present invention will obtain a kind of hydrogen storage amount height, the hydrogen-storage alloy that decomposition pressure obviously improves and reduces cost significantly exactly.
For achieving the above object, the present invention is achieved in that the content by suitable interpolation Fe substitutes V, and the content of V is reduced, the composition (wt%) that obtains alloy is: Ti20～26, Zr8.3～13.8, Mn47～60, Cr3.1～9.4, V2.6～6.1, Fe2.7～6.7.
The best composition (wt%) of this alloy is Ti23, Zr11, Mn53, Cr6.5, V3.2, Fe3.3.
Table 1 adopts the composition scope of multi-form expression for hydrogen-storage alloy of the present invention.
Fig. 1 is the decomposition pressure curve of the present invention and comparative example under the room temperature, and H/M represents to inhale the number that hydrogen atom is arranged in the atoms metal, has shown the size of alloy hydrogen storage amount.
Among the present invention,, increased the lattice parameter of alloy, helped the suction hydrogen of alloy owing to added metal Fe; Owing to the minimizing of V content, can improve the homogeneity of alloy, make the crystallization of metal have MgZn
2Due to effective suction hydrogen phase Laves of type increases mutually.There is the Fe of adding that system capacity is changed again, the stability of metal hydride is reduced greatly, caused the raising of decomposition pressure.Owing to add cheap Fe, replace expensive metal V simultaneously, cost of alloy is reduced significantly.
Effect below in conjunction with each alloying element is further described the present invention.
Absorb this physical chemical process of hydrogen for dissolving metal, two kinds of possibilities of heat absorption and heat release are arranged, and from the thermodynamics viewpoint analysis, the metal with thermopositive reaction just has big hydrogen storage amount, because after dissolving in hydrogen the total system energy is reduced, dissolving absorbs just can be proceeded.A few limited in periodictable ability is possible, as Ti, Zr, V, but these all can not be separately use as hydrogen-absorbing material, and must be hydrogen rationally cooperates by different requirements with the strong element with a little less than the avidity of metal avidity, just can obtain to have the alloy of required hydrogen storage property.
In hydrogen storage material of the present invention, Ti20～26Wt%, because Ti is a kind of strong suction hydrogen agent, thermopositive reaction can form TiH
2Storage hydrogen reaches 4wt%, but absorb the hydrogen condition harshness and (inhale hydrogen down for 400 ℃, put hydrogen for 600 ℃) therefore can not use separately, must with other with the hydrogen avidity a little less than element match, reduce the stability of hydride, experiment draws Ti content and is advisable at 20～26wt%, and Ti content is lower than the hydrogen storage amount that 20wt% then influences alloy, very stable greater than the hydride that 26wt% forms, so decomposition pressure is low.
Zr is similar to the fundamental characteristics of Ti, also is strong suction hydrogen agent, and thermopositive reaction can form ZrH
2, hydrogen storage amount reaches 2.2wt%, because the adding of Zr can obtain to suppress the effect of alloy powderization, this point is for hydrogen-storage alloy, is that alloy causes and closes importantly for Ti-Mn especially, and the adding of Zr increases lattice parameter, hydrogen increases, but decomposition pressure reduces, and hydrogen desorption capacity descends, so too high Zr can make the homogeneity of alloy and crystallinity degenerate, effectively alloy phase reduces, hydrogen reduces, if Zr content≤8wt%, then Zr is just ineffective.In order to reach the inhibition efflorescence, increase sucking/placing hydrogen amount and hydrogen-releasing rate, the 8.3～13.8Wt% that is chosen as of Zr is advisable.
V is similar to the effect of Ti, Zr, also is the agent of a kind of strong suction hydrogen, and thermopositive reaction forms VH
2, storage hydrogen can reach 3.8wt%, and its acceptance condition is than Ti and Zr gentleness, and its adding can improve the decomposition pressure and the hydrogen of alloy, but owing to costing an arm and a leg of V should not be used more, so the scope of the V of the present invention's selection is lower, is 2.6～6.1wt%.
Mn is the very strong element of a kind of activity, the reaction of it and hydrogen is decided according to the height of system capacity, an amount of Mn can make the activity of alloy increase, even also can activate at ambient temperature, and along with the increase decomposition pressure of Mn content increases, but hydrogen sharply descends during the Mn too high levels, does not even inhale hydrogen, and experiment draws Mn content must be for best between 47～60wt%.
Cr is an endothermic metal with the H reaction separately, and hydrogen is very little, but it matches with Mn and can play the hysteresis quality that hydrogen is put in the improvement suction, platform property is improved, improve resistance of oxidation, too high levels influences hydrogen, therefore the broken difficulty of alloy selects content to be advisable at 3.1～9.4wt%.
Fe and H-H reaction are the heat absorption metal, inhale hydrogen seldom, but after in multicomponent alloy, adding a spot of Fe,, can improve hydrogen because lattice parameter is increased, reduce simultaneously the stability of alloy hydride greatly, the present invention is compared with the contrast experiment, only need to add the Fe content of 3.3wt%, decomposition pressure is promptly brought up to 0.5～1.1MPa from 0.1～0.4MPa, but will influence hydrogen as Fe content 〉=5wt%, and≤1.7wt% do not reach due effect.
The hydrogen storage material Ti that composition range according to the present invention obtains
0.8Zr
0.2Mn
1.6Cr
0.2V
0.1Fe
0.1, through the x-ray diffraction analysis, the result shows: its resultative construction belongs to hexagonal system MgZn
2Type, its effective alloy phase belongs to intermetallic compound Laves phase.
In addition,, therefore in smelting process, can adopt the V-Fe alloy form to add in the alloy, cost be reduced, and have very high practicality in actual applications owing to contain V and Fe element simultaneously in the alloy ingredient of the present invention.
Compared with prior art, the present invention is owing to adopted the proportioning of suitable alloying element, can obtain the ideal hydrogen storage property, guaranteed that alloy has sufficiently high hydrogen storage amount (under 〉=2.0wt%) the prerequisite, decomposition pressure under the room temperature improves significantly, and maximum value has reached 0.5～1.6MPa.The more important thing is overcome hydrogen storage amount height in the prior art, decomposition pressure is just low, and decomposition pressure height, the contradiction that hydrogen storage amount is low has again obtained the good hydrogen storage material of a kind of over-all properties.Because alloy of the present invention is used V and Fe instead the V-Fe alloy adds and V measures reduction, can make cost of alloy reduce about 40% simultaneously.The alloy of the present invention that makes has fabulous practicality, is particularly suitable for aspects such as purifying hydrogen of hydrogen, heat pump and hydrogen compressor.
Introduce embodiments of the invention below.
The composition of the embodiment of the invention 1,2,3 is as shown in table 2.Adopt the sponge Ti of purity 99% in the starting material, 99% sponge Zr, 99% electrolysis Mn, 99% Metal Cr and the V-Fe alloy that contains 48.9wt%V.Melting in non-consumable arc furnace, light is evacuated to 4 * 10
-4MmHg fills Ar gas shiled refining.In order to make alloying constituent even, need such melting several times repeatedly, treat that then the spindle in the water cooled copper mould is cooled to after the room temperature, take off ingot and the 10g that takes a sample, be crushed to≤particulate state of 10mm, carry out activation treatment in the stainless steel sample tube of packing into, after vacuumizing several minutes, feed the H of 99% purity
2Gas activates H to be inhaled immediately to the pressure of 5MPa
2After saturated, inhale and put H
2The test of amount and decomposition pressure.
By visible embodiments of the invention 1,2,3 its compositions of alloy of table 2 all within composition range of the present invention, the hydrogen that obtains all 〉=2.0wt%, and the decomposition pressure maximum under the room temperature can reach 0.5～1.6MPa, and higher its room temperature decomposition pressure of the content of Fe is just high as can be seen, corresponding hydrogen is just slightly smaller, on its these characteristics, its composition of the alloy of over-all properties the best such as embodiment 1.The contrast of the embodiment of the invention and comparative example contains the V height and Fe is lower than No. 4.5 alloys of composition range of the present invention, though its hydrogen is not low, but the room temperature decomposition pressure is too low, can not satisfy the requirement of use, No. 6 alloying constituents and the present invention are too far away partially, the effect of not inhaling hydrogen.
Claims (2)
1, a kind of hydrogen storage material is characterized in that: composition range (wt%) is: Ti20～26, Zr8.3～13.8, Mn47～60, Cr3.1～9.4, V2.6～6.1, Fe2.7～6.7.
2, hydrogen storage material according to claim 1 is characterized in that: optimal components scope (wt%) is: Ti23, Zr11, Mn53, Cr6.5, V3.2, Fe3.3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90107922 CN1016517B (en) | 1990-09-29 | 1990-09-29 | Hydrogen carrier materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90107922 CN1016517B (en) | 1990-09-29 | 1990-09-29 | Hydrogen carrier materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1049529A true CN1049529A (en) | 1991-02-27 |
| CN1016517B CN1016517B (en) | 1992-05-06 |
Family
ID=4880772
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 90107922 Expired CN1016517B (en) | 1990-09-29 | 1990-09-29 | Hydrogen carrier materials |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1016517B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100373665C (en) * | 2003-10-31 | 2008-03-05 | 中国科学院上海微系统与信息技术研究所 | Cathode material of nickel-hydrogen battery and preparationmethod |
| CN102443730A (en) * | 2010-10-13 | 2012-05-09 | 陈瑞凯 | Hydrogen storage alloy |
| CN114107776A (en) * | 2021-11-23 | 2022-03-01 | 厦门钨业股份有限公司 | Hydrogen storage alloy with high hydrogen storage capacity and preparation method thereof |
| CN114293086A (en) * | 2021-12-30 | 2022-04-08 | 江苏集萃安泰创明先进能源材料研究院有限公司 | Hydrogen storage high-entropy alloy and preparation method thereof |
-
1990
- 1990-09-29 CN CN 90107922 patent/CN1016517B/en not_active Expired
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100373665C (en) * | 2003-10-31 | 2008-03-05 | 中国科学院上海微系统与信息技术研究所 | Cathode material of nickel-hydrogen battery and preparationmethod |
| CN102443730A (en) * | 2010-10-13 | 2012-05-09 | 陈瑞凯 | Hydrogen storage alloy |
| CN114107776A (en) * | 2021-11-23 | 2022-03-01 | 厦门钨业股份有限公司 | Hydrogen storage alloy with high hydrogen storage capacity and preparation method thereof |
| CN114107776B (en) * | 2021-11-23 | 2022-04-22 | 厦门钨业股份有限公司 | Hydrogen storage alloy with high hydrogen storage capacity and preparation method thereof |
| CN114293086A (en) * | 2021-12-30 | 2022-04-08 | 江苏集萃安泰创明先进能源材料研究院有限公司 | Hydrogen storage high-entropy alloy and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1016517B (en) | 1992-05-06 |
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