CN1473948A - High hydrogen storage titanium and vanadium base hydrogen storage alloy - Google Patents

High hydrogen storage titanium and vanadium base hydrogen storage alloy Download PDF

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Publication number
CN1473948A
CN1473948A CNA03141849XA CN03141849A CN1473948A CN 1473948 A CN1473948 A CN 1473948A CN A03141849X A CNA03141849X A CN A03141849XA CN 03141849 A CN03141849 A CN 03141849A CN 1473948 A CN1473948 A CN 1473948A
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alloy
hydrogen
hydrogen storage
phase
bcc
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CN1207412C (en
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余学斌
吴铸
黄太仲
陈金舟
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Shanghai Institute of Microsystem and Information Technology of CAS
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Shanghai Institute of Microsystem and Information Technology of CAS
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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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

The present invention relates to a kind of Ti-V based BCC phase alloy with high hydrogen storage capacity. The alloy is Ti100-x-y-zVxMnyMz, where x is 15-50, y is 5-30, z is 5-30, x+y+z is 50-80, and M is one or two of Cr, Fe and RE. The alloy is one single BCC solid solution phase structure or one two-phase structure with BCC phase and included partial C14 Laves phase. The production of the alloy includes one annealing process at 800-1500 deg.c for 0.5-50 hr. The alloy has a maximum hydrogen storage capacity of 3.8-4.2 wt%, hydrogen releasing capacity of 2.5-3 wt% below 100 deg.c. The alloy has simple production process and wide application range in hydrogen storage and transportation, negative pole material of Ni-H battery, hydrogen storage bottle for fuel cell, etc.

Description

Titanium-the V-Based Hydrogen Storage Alloy of high hydrogen storage
Technical field
The present invention relates to a kind of novel titanium one vanadium (Ti-V) base hydrogenous alloy, this alloy has good activation performance and high hydrogen storage capability, is storage and transportation, nickel-hydrogen battery negative pole material and the fuel cell ideal material that stores up aspects such as hydrogen bottle as hydrogen.
Background technology
Hydride hydrogen-storing is the important means of hydrogen storage.Its principle is the reversible reaction of being undertaken by between hydrogen and the hydrogen storage alloy, realize the storage and the release of hydrogen, be that the external world is when having the heat transferred metal hydride, it just is decomposed into hydrogen storage alloy and releasing hydrogen gas, otherwise, when hydrogen and hydrogen storage alloy constituted hydride, hydrogen just was stored in wherein with the form of solid-state bond.With carrying hydrogen following characteristics are arranged with the hydrogen storage material storage:
(1) volume hydrogen-storage density height
(2) do not need high pressure vessel and heat-insulated container
(3) security is good, does not have explosion hazard
(4) can obtain high-purity hydrogen
Hydrogen storage alloy can be divided into Ti system (with TiMn usually by main difference of inhaling protium in all kinds of alloys 2With TiFe be representative), Mg is (with Mg 2Ni is representative), rare earth is (with LaNi 5Be representative) and V be solid solution hydrogen storage alloy.The hydrogen storage capability of Ti system and rare earth-based alloy, is inhaled and is put the hydrogen requirement more than 200 ℃ though there is the hydrogen-storage amount about 3% in Mg system less than 2% (weight percent, below identical), and this has limited their application.
Ti-V as a new generation is a solid solution alloy, because of its bigger hydrogen (greater than 3%), inhales the hydrogen desorption kinetics performance preferably, relatively is hopeful to be used for hydrogen storage and conveying.But the hydrogen platform identity is put in the suction of limited hydrogen desorption capacity (usually only being half of hydrogen) and difference and harsh activation condition is the subject matter [T.Mouri of such alloy practical application of restriction, H.Iba, Mater.Sci.Engng A, 329-331 (2002) 346-350], [Kei Nomura, Etsuo Akiba, J.Alloys Comp., 231 (1995) 513-517].
Iba in 1997 etc. have reported that at first the Ti-V-Mn alloy that comprises C14 Laves phase and BCC solid solution phase has 2.1% hydrogen desorption capacity [H.Iba, E.Akiba, J.Alloys Comp.253 (1997) 21-24.].The Ti of the annealed processing of report such as Cho subsequently 0.16Zr 0.05Cr 0.22V 0.57The maximum of BCC phase alloy and effectively hydrogen-storage amount be respectively 3.55% and 2.14%[S.W.Cho, C.S.Han, C.N.Park, E.Akiba, J.Alloys Comp.298 (1999) 244.].One piece of patent (patent No.: 6419764) also reported V of the nearest U.S. 68Ti 10Cr 20Ni 1.0Mn 1.0The BCC phase alloy has that activation characteristic and smooth suction are put the hydrogen platform preferably.Yet in these above reports, the hydrogen of alloy is still less than 3.6%, and the content of V is higher simultaneously, because the price of V is relatively expensive, has in fact also limited the practical application of these alloys.
Summary of the invention
Purpose of the present invention aims to provide the hydrogen storage alloy that a class has higher hydrogen storage capability and better activation performance, to overcome Ti-V base hydrogenous alloy the deficiencies in the prior art.Make that this hydrogen storage alloy can be in the mass-producing transportation of hydrogen, the hydrogen supply source of fuel cell, nickel metal hydride battery, fields such as the purification of hydrogen are widely used.
The molecular formula of alloy composition of the present invention is Ti 100-x-y-zV xMn yM z, wherein 15≤x≤50,5≤y≤30,5≤z≤30,50≤x+y+z≤80 (z is atomic percentage conc for x, y).M is at least Cr, Fe, Ni, one or both elements among the Re (rare earth).
Alloy of the present invention can be by common smelting method for preparing, and method is as follows: purity all takes by weighing in proportion at 99.5% above simple substance element.Melting under the argon shield in the magnetic levitation high frequency furnace.In order to guarantee the homogeneity of alloy, the alloy melting 3 to 4 times of overturning repeatedly because the fusing point of Mn is lower, is volatilized during melting easily, so add certain weight when joining sample in proportion.Melting gained sample carries out anneal under 800 ℃～1500 ℃.Annealing time 0.5-50 hour.
The maximum hydrogen of alloy provided by the invention is 3.8～4.2wt%, is 2.5～3gwt% at the hydrogen desorption capacity below 100 ℃, and the alloy that provides forms the two phase structure that single BCC solid solution phase or BCC comprise portion C 14Laves phase mutually.In the storage and the transportation of hydrogen, the aspects such as storage hydrogen bottle that nickel-hydrogen battery negative pole material and combustion rice battery are used are widely used, and production technique is simple.
Description of drawings
Fig. 1 is X-diffraction (a) and the scanning electron microscope analysis (b) of alloy Ti-25Cr-5Mn-20V-2La.
Fig. 2 is put the hydrogen curve for alloy Ti-25Cr-5Mn-20V-2La at 333K.
Fig. 3 be alloy Ti-40V-25Mn-5Ni at 293K, the hydrogen during 3MPa is curve over time.
Fig. 4 is X-diffraction (a) and the scanning electron microscope analysis (b) of alloy Ti-20V-25Mn-25Cr.
Embodiment
The invention will be further described below by the specific embodiment description: but the present invention only limits to by no means
Embodiment;
Embodiment 1: the design alloy component is Ti-25Cr-5Mn-20V-2La, tests raw materials used purity all more than 99.5%, joins and gets 50 gram samples melt backs 4 times on high frequency magnetic levitation melting stove, and is even to guarantee alloy.Anneal under argon shield then, annealing conditions be 1000 ℃ following 10 hours.Fig. 1 is respectively the X-diffraction and the scanning electron microscope analysis result of this alloy.Can see that this alloy is single BCC solid solution phase.Get 3 gram Mechanical Crushing to 80 orders and inhale and put the hydrogen test, Fig. 2 is put the hydrogen curve for this alloy, and as can be seen, the maximum hydrogen and the hydrogen desorption capacity of this alloy are respectively 4.0% and 2.5%.
Embodiment 2: the design alloy component is Ti-40V-25Mn-5Ni, tests raw materials used purity all more than 99.5%, joins and gets 50 gram samples melt backs 4 times on high frequency magnetic levitation melting stove, and is even to guarantee alloy.Anneal under argon shield then, annealing conditions be 1200 ℃ following 0.5 hour.The X-diffraction shows that with the scanning electron microscope result this alloy forms single BCC mutually.Get 3 gram Mechanical Crushing to 80 orders and carry out the hydrogen storage property test, suction hydrogen curve such as Fig. 3 of this alloy, as can be seen, the maximum hydrogen of this alloy is 4.2%,
Embodiment 3: the design alloy component is Ti-20V-25Mn-25Cr, tests raw materials used purity all more than 99.5%, joins and gets 50 gram samples melt backs 4 times on high frequency magnetic levitation melting stove.Fig. 4 is respectively the X-diffraction and the scanning electron microscope analysis result of this alloy.Can see that this alloy comprises portion C 14 Laves phase two phase structures for the BCC solid solution phase.Get 3 gram Mechanical Crushing to 80 orders and carry out the hydrogen storage property test, the result shows that the maximum hydrogen of this alloy and effective hydrogen desorption capacity are respectively 3.85% and 2.6%.
Embodiment 4: the design alloy component is Ti-30V-25Mn-5Cr-5Fe, tests raw materials used purity all more than 99.5%.Join and get 50 gram samples melt backs 4 times on high frequency magnetic levitation melting stove, even to guarantee alloy.Get sample segment 950 ℃ of anneal 24 hours under argon shield.X-diffraction and scanning electron microscope analysis result show this alloy be single BCC mutually.Get 3 gram sample machineries and be crushed to 80 orders and carry out the hydrogen storage property test, the result show the maximum hydrogen of this alloy and effectively hydrogen desorption capacity be respectively 3.8% and 2.5%.
Embodiment 5: the design alloy component is Ti-35V-10Mn-20Cr-3Ni, tests raw materials used purity all more than 99.5%.Join and get 50 gram samples melt backs 3～4 times on high frequency magnetic levitation melting stove, even to guarantee alloy.Anneal under argon shield then, annealing conditions be 1500 ℃ following 5 minutes.Get 1 gram sample machinery and be crushed to 200 orders and carry out electrochemical property test, the result shows that the maximum discharge capacity of this alloy is 700mAh/g.

Claims (6)

1, a kind of Ti-V base hydrogenous alloy, the molecular formula that it is characterized in that alloy is Ti 100-x-y-zV xMn yM z, M is at least Cr, Fe, Ni, one or both elements among the Re, 15≤x in the formula≤50,5≤y≤30,5≤z≤30,50≤x+y+z≤80 (z is atomic percentage conc for x, y).
2, Ti-V base hydrogenous alloy according to claim 1 is characterized in that alloy forms the two phase structure that single BCC solid solution phase or BCC comprise portion C 14 Laves phases mutually.
3, according to claim 1 and 2 described Ti-V base hydrogenous alloys, it is characterized by alloy composition is Ti-25Cr-5Mn-20V-2La, and alloy forms single BCC solid solution phase.
4, according to claim 1 and 2 described Ti-V base hydrogenous alloys, it is characterized in that alloy composition is Ti-40V-25Mn-5Ni, alloy forms single BCC solid solution phase.
5, according to the Ti-V base hydrogenous alloy of claim 1 and 2, it is characterized in that this alloy composition is Ti-20V-25Mn-25Cr, alloy forms the BCC solid solution phase and comprises partly C14 Laves two phase structure.
6, Ti-V base hydrogenous alloy according to claim 1 is characterized in that this alloy composition is Ti-30V-25Mn-5Cr-5Fe or Ti-35V-10Mn-20Cr-3Ni.
CNB03141849XA 2003-07-25 2003-07-25 High hydrogen storage titanium and vanadium base hydrogen storage alloy Expired - Fee Related CN1207412C (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100482833C (en) * 2007-04-03 2009-04-29 中国科学院上海微系统与信息技术研究所 Surface catalyzed high activity magnesium-base hydrogen storing material and preparing method thereof
CN101435049B (en) * 2007-11-16 2010-11-10 北京有色金属研究总院 Rare earth Ce doping titanium-chromium-vanadium-manganese solid solution hydrogen occluding alloy
CN101994028B (en) * 2009-08-27 2012-12-26 北京有色金属研究总院 Solar energy thermal utilization vacuum pipe hydrogen absorption material and using method thereof
CN105088011A (en) * 2015-08-31 2015-11-25 攀钢集团攀枝花钢铁研究院有限公司 Titanium-based dual-phase hydrogen storing alloy and preparation method thereof
CN112961996A (en) * 2021-02-01 2021-06-15 中国科学院江西稀土研究院 Rare earth hydrogen storage alloy and preparation method and application thereof
CN114525440A (en) * 2022-01-27 2022-05-24 江苏理工学院 TiV-based multi-component complex phase alloy and preparation method thereof

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101251228B (en) * 2008-03-21 2010-06-09 石锋 Solid hydrogen-storing conveying apparatus

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100482833C (en) * 2007-04-03 2009-04-29 中国科学院上海微系统与信息技术研究所 Surface catalyzed high activity magnesium-base hydrogen storing material and preparing method thereof
CN101435049B (en) * 2007-11-16 2010-11-10 北京有色金属研究总院 Rare earth Ce doping titanium-chromium-vanadium-manganese solid solution hydrogen occluding alloy
CN101994028B (en) * 2009-08-27 2012-12-26 北京有色金属研究总院 Solar energy thermal utilization vacuum pipe hydrogen absorption material and using method thereof
CN105088011A (en) * 2015-08-31 2015-11-25 攀钢集团攀枝花钢铁研究院有限公司 Titanium-based dual-phase hydrogen storing alloy and preparation method thereof
CN105088011B (en) * 2015-08-31 2017-05-31 攀钢集团攀枝花钢铁研究院有限公司 Titanium-based two-phase hydrogen-storage alloy and preparation method thereof
CN112961996A (en) * 2021-02-01 2021-06-15 中国科学院江西稀土研究院 Rare earth hydrogen storage alloy and preparation method and application thereof
CN112961996B (en) * 2021-02-01 2022-05-03 中国科学院江西稀土研究院 Rare earth hydrogen storage alloy and preparation method and application thereof
CN114525440A (en) * 2022-01-27 2022-05-24 江苏理工学院 TiV-based multi-component complex phase alloy and preparation method thereof

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