CN1222631C - Modified titanium-manganese base hydrogen storage alloy - Google Patents
Modified titanium-manganese base hydrogen storage alloy Download PDFInfo
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- CN1222631C CN1222631C CNB021112134A CN02111213A CN1222631C CN 1222631 C CN1222631 C CN 1222631C CN B021112134 A CNB021112134 A CN B021112134A CN 02111213 A CN02111213 A CN 02111213A CN 1222631 C CN1222631 C CN 1222631C
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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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The present invention relates to modified titanium-manganese base hydrogen storing alloy which belongs to the field of hydrogen storing alloy. The present invention is characterized in that three modified elements comprising V, Fe and Cr are added to TiMn2 alloy so as to design a new alloy ingredient with the general formula of TiFe<x>V<y>Cr<z>Mn<(2-x-y-z)>, wherein x is more than or equal to 0 and is less than or equal to 0.15, and x preferably ranges from 0.05 to 0.1; y is more than or equal to 0 and is less than or equal to 0.30, and y preferably ranges from 0.10 to 0.25; z is more than or equal to 0 and is less than or equal to 0.10, and z preferably ranges from 0.05 to 0.08; three kinds of elements of Fe, Cr and V or any two kinds of the elements of Fe, Cr and V are used for simultaneously replacing the Mn element in the TiMn2 alloy. Due to the introduction of new elements of Fe, Cr and V, new phases exist in the alloy. Therefore, the hydrogen-absorbing maximum atom ratio (H/M) of new alloy reaches 3.0; compared with the hydrogen-absorbing amount of unmodified TiMn2, a hydrogen-absorbing amount is obviously increased, and a hydrogen storing amount can be more than 2%. The present invention is possible to be used as the hydrogen storing material of large-scale hydrogen sources for the application of the hydrogen sources in fuel cells, etc.
Description
Technical field
The present invention relates to the composition design of a class store hydrogen alloy.Or rather, the present invention passes through at TiMn
2Add V, Fe, three kinds of modifying elements of Cr in the alloy, improve the hydrogen-storage amount of alloy, thereby make this class material can be used as the hydrogen storage material of extensive hydrogen source.Belong to the hydrogen storage alloy field.
Background technology
Along with the development of fuel cell technology, fuel cell is just obtaining application more and more widely, and is the restriction that the development of the fuel cell of fuel has been subjected to its hydrogen source with hydrogen.In the various hydrogen sources of having developed, based on the various hydrogen sources of hydrogen storage alloy owing to its safety, efficiently just more and more obtain people's attention.
In the various hydrogen storage alloys of having developed, the titanium Mn series alloy is because it is easily-activated, cost is low, becomes the popular candidate alloy as the hydrogen storage alloy of hydrogen source gradually.TiMn
2Alloy is that the representative in the titanium Mn series alloy is formed, the about 1.5wt% of its storage hydrogen mass ratio.Yet, TiMn
2Alloy still has its shortcoming as a kind of promising hydrogen storage alloy.For example: still lower (the Waterstrat R M of its hydrogen-storage amount, Das B N, Beck PA.Trans.TMS-AIME, 1962,224:512), and hydrogen difficulty (Gamo T is put in suction under the normal temperature, MoriwakiY, Yanagihara N et al.Int.J.Hydrogen Energy, 1985,10:39), in order further to improve the hydrogen-storage amount and the normal temperature hydrogen storage property of this hydrogen storage alloy, preceding West Germany Benz company (Bemauer O, Topler J, Noreus D et al.Int.Hydrogen Energy, 1989,14:187) utilize Zr to replace the part titanium elements, improved its hydrogen-storage amount, but plateau pressure raises.U.S. Carnegie-Mellon university with Cu and Mo replace part Mn element as negative material (Pebler A, Gullbransen EA.Electrochem.Technol., 1966,4:211), but the normal temperature hydrogen storage property is relatively poor.
Summary of the invention
The present invention attempts by at TiMn
2Add V, Fe, three kinds of modifying elements of Cr in the alloy, improved the hydrogen-storage amount of alloy, improved activation condition, it is more suitable for as extensive with the hydrogen source under the hydrogen condition.
The linkage force that V, Fe, three kinds of elements of Cr can be regulated metal and hydrogen, V, Cr are again good hydrogen storage materials simultaneously.The present invention by with V, Fe, three kinds of elements of Cr or wherein two kinds replace TiMn
2The part Mn element of alloy kind improves the linkage force of metal and hydrogen, has obviously improved the hydrogen-storage amount of alloy.V not only can store up hydrogen as important hydrogen storage element element, and is important alloy catalyst, because the introducing of V also is improved the activation performance of alloy, the initial activation pressure of alloy obviously reduces.Therefore, the present invention has designed a kind of hydrogen storage alloy of new component, has improved the hydrogen-storage amount of alloy, has improved activation condition.The design of components of the hydrogen storage alloy through modification provided by the invention is: TiFe
xV
yCr
zMn
(2-x-y-z).
Wherein the scope of x is: 0≤x≤0.15, recommended range are 0.05-0.1;
Wherein the scope of y is: 0≤y≤0.30, recommended range are 0.10-0.25;
Wherein the scope of z is: 0≤z≤0.10, recommended range are 0.05-0.08;
The modification titanium Mn series alloy that proposes among the present invention can prepare with common alloy method, specifically: (metal purity is the first metal of each component respective quality of weighing in proportion: Ti 〉=99%, Mn 〉=99%, V 〉=98%, Fe 〉=99%, Cr 〉=99%), complete melting is three～four times under Ar gas atmosphere, can obtain the alloy of respective components.In air, have satisfactory stability when this alloy does not activate, can under air atmosphere, pulverize, mechanical workout such as sieve and be difficult for taking place oxidation.
Respective alloy is got poplar after mechanical disintegration (80 orders sieve) in air, carry out pressure-component-temperature (PCT) test; Put in the hydrogen storage equipment in suction alloy is carried out the test that hydrogen is put in the suction under the different pressures.Measure the influence of temperature and hydrogen pressure to its hydrogen-storage amount.
Alloy sieves through 200 orders after pulverizing, and with X-ray diffractometer (XRD) alloy is carried out phase composite and measures, and sees Fig. 1, Fig. 2.The XRD test result proves: because the introducing of new element, the phase composite of alloy is by γ-TiMn
1-2Change γ-TiMn into
1-2With six side TiMn
5Coexistence mutually, the introducing of new element makes and has occurred new alloy phase in the alloy.
TiFe provided by the invention
xV
yCr
zMn
(2-x-y-z), composition in usually comprise two kinds of elements in V, Fe, three kinds of elements of Cr at least.Be X=0, Y, Z ≠ 0 then; Y=0, then X, Z ≠ 0; Z=0, then X, Y ≠ 0 replaces TiMn simultaneously
2Mn element in the alloy, or Fe, Cr, three kinds of elements of V replace TiMn simultaneously
2Mn element in the alloy.
The hydrogen-storage amount of this alloy surpasses TiMn
2Alloy can reach more than 2%, is expected to the hydrogen storage material as extensive hydrogen source, is applied in other aspects such as fuel cell.GIFe provided by the present invention
xV
yCr
zMn
(2-x-y-z)The absorption hydrogen amount is shown respectively and Fig. 4 and table 1 with the variation of temperature and pressure.
Description of drawings
Fig. 1 is TiMn
2The X-ray diffractogram of alloy.
Fig. 2 is TiFe
0.1V
0.2Mn
1.7The X-ray diffractogram of alloy.
Fig. 3 is alloy TiMn
2And TiFe
0.1V
0.2Mn
1.7Hydrogen curve ratio under 273K, X-coordinate is the atomic ratio of hydrogen and metal, ordinate zou is for inhaling hydrogen pressure, unit is normal atmosphere (atm).
Fig. 4 is TiFe
0.1V
0.2Mn
1.7The PCT curve of alloy; X-coordinate is the atomic ratio (H/M) of hydrogen and metal, and ordinate zou is for inhaling hydrogen pressure, and unit is normal atmosphere (atm).
Fig. 5 is TiFe
0.1Cr
0.05Mn
1.85The PCT curve of alloy; X-coordinate is the atomic ratio (H/M) of hydrogen and metal, and ordinate zou is for inhaling hydrogen pressure, and unit is normal atmosphere (atm).
Embodiment
Embodiment 1
Design component is TiFe
0.1V
0.2Mn
1.7Alloy and TiMn
2Alloy, take by weighing each element of respective quality, melting is three times under Ar gas atmosphere protection, obtains forming the alloy of uniform respective components, pulverizes, 80 orders sieve, and carry out X ray, PCT and hydrogen test.GIFe
0.1V
0.2Mn
1.7And TiMn
2X ray see Fig. 1 and Fig. 2.GIFe as seen from the figure
0.1V
0.2Mn
1.7With TiMn
2Compare TiFe
0.1V
0.2Mn
1.7New composition phase has appearred in the alloy; As seen from Figure 3: TiFe
0.1V
0.2Mn
1.7Hydrogen obviously increases, and initial activation pressure also decreases.
TiFe under table 1 different pressures
0.1V
0.2Mn
1.7Hydrogen
| Inhale hydrogen pressure Kg/Cm 2 | 30 | 40 | 50 | 40 |
| Hydrogen desorption capacity ml/g | 181.4 | 193.9 | 219.8 | 194.6 |
Pressure is to the influence of alloy hydrogen absorption and desorption: measure the different alloy hydrogen desorption capacities under the hydrogen pressures of inhaling, can be got by table one, with the rising of inhaling hydrogen pressure, the alloy hydrogen desorption capacity increases, and TiFe is described
0.1V
0.2The hydrogen of Mn increases with the rising of pressure.
Temperature is to TiFe
0.1V
0.2Mn
1.7The suction influence of putting hydrogen, measure the PCT curve of alloy, its PCT curve is seen Fig. 4.Can be got by the PCT curve, the amount of alloy hydrogen absorption and desorption reduces with the rising of temperature, and inhales that to put the hydrogen curve also more and more approaching with the rising of temperature, illustrates that in use the use temperature that suitably raises can reach higher utilization ratio.
Embodiment 2
Design component is TiFe
0.1Cr
0.05Mn
1.85Alloy, melting is four times under Ar gas atmosphere protection, obtains forming the alloy of uniform respective components, pulverizes, 80 orders sieve, and carry out the PCT test.Test result is seen Fig. 5.All the other are with embodiment 1.
Design component is TiFe
0.09V
0.16Cr
0.07Mn
1.68Alloy, melting evenly and pulverize after the PCT test proves that it inhales the highest atomic ratio of hydrogen (H/M) and can reach 3.0, mass ratio about 2.0%.All the other are with embodiment 1.
Claims (4)
1. through the titanium-manganese base hydrogen storage alloy of modification, it is characterized in that the TiFe that consists of of alloy
xV
yCr
zMn
(2-x-y-z), wherein: 0≤x≤0.15; 0≤y≤0.30; 0≤z≤0.10; And contain at least two kinds in Fe, V, three kinds of modifying elements of Cr in the described hydrogen storage alloy.
2. the titanium-manganese base hydrogen storage alloy through modification according to claim 1 is characterized in that:
The x scope is 0.05---0.1;
The y scope is 0.10---0.25;
The z scope is 0.05---0.08.
3. the titanium-manganese base hydrogen storage alloy through modification according to claim 1 and 2, that it is characterized in that described alloy is γ-TiMn mutually
1-2With six side TiMn
5Coexistence mutually.
4. the titanium-manganese base hydrogen storage alloy through modification according to claim 1 and 2, the element purity that it is characterized in that component alloy are except that V 〉=98%, and all the other each element purity all 〉=99%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021112134A CN1222631C (en) | 2002-03-29 | 2002-03-29 | Modified titanium-manganese base hydrogen storage alloy |
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|---|---|---|---|
| CNB021112134A CN1222631C (en) | 2002-03-29 | 2002-03-29 | Modified titanium-manganese base hydrogen storage alloy |
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|---|---|
| CN1385546A CN1385546A (en) | 2002-12-18 |
| CN1222631C true CN1222631C (en) | 2005-10-12 |
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| CNB021112134A Expired - Fee Related CN1222631C (en) | 2002-03-29 | 2002-03-29 | Modified titanium-manganese base hydrogen storage alloy |
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Families Citing this family (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 |
| CN1307318C (en) * | 2004-09-10 | 2007-03-28 | 中国科学院上海微系统与信息技术研究所 | Titanium manganese hydrogen storage alloy modified by zirconium, iron and vanadium simultaneously |
| CN106602048B (en) * | 2017-03-02 | 2019-03-22 | 辽宁九夷能源科技有限公司 | A kind of resistance to deep discharge nickel-metal hydride battery and preparation method thereof |
| CN109097612B (en) * | 2018-09-21 | 2020-10-09 | 北京大学 | High-pressure hydrogen storage alloy for hydrogen storage and preparation method thereof |
| US20220275480A1 (en) * | 2019-08-05 | 2022-09-01 | Newsouth Innovations Pty Ltd | Method for making hydrogen storage alloys |
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