CN1270818C - Method for improving activation performance of hydrogen-storage alloy - Google Patents
Method for improving activation performance of hydrogen-storage alloy Download PDFInfo
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- CN1270818C CN1270818C CNB2003101080749A CN200310108074A CN1270818C CN 1270818 C CN1270818 C CN 1270818C CN B2003101080749 A CNB2003101080749 A CN B2003101080749A CN 200310108074 A CN200310108074 A CN 200310108074A CN 1270818 C CN1270818 C CN 1270818C
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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 a method for improving the activation performance of hydrogen storage alloy, which comprises: after hydrogen storage alloy powder and a small amount of ZnO are mixed, ball milling is carried out under the protection of inert gas. Hydrogen storage alloy comprises AB2(TiMn2), AB(TiFe), AB5(LaNi5), A2B(Mg2Ni) and BCC phase (Ti-V base) alloy. The method has the advantage of simple preparation. The activation performance of the obtained alloy powder is largely improved. The present invention has significance to the practical application of hydrogen storage alloy.
Description
Technical field:
The present invention relates to a kind of method of improving the hydrogen bearing alloy activity function.The alloyed powder of described method preparation has good activity function.
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 bearing 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 bearing alloy and releasing hydrogen gas, otherwise, when hydrogen and hydrogen bearing alloy constituted hydride, hydrogen just was stored in wherein with the form of solid-state bond.
Hydrogen bearing alloy can not absorb hydrogen in initial conditions; this is to stop hydrogen to enter oxide layer (the Jea-Han Jung of alloy substrate owing to can form one deck usually on the surface of alloy; et al.; J.Alloys Comp226 (1995) 166-169); so before inhaling hydrogen; hydrogen bearing alloy all will carry out activation processing (S.Bouaricha, et al., J.Alloys Comp.325 (2001) 245-251).Generally speaking, the activation fully of hydrogen bearing alloy will be passed through following step: (1) high pressure low temperature is inhaled hydrogen down; (2) vacuumize under the state high temperature and catch up with hydrogen; (3) the hydrogen circulation is put in suction repeatedly.Hydrogen bearing alloy must activate this characteristic and determine hydrogen storage vessel must satisfy the pressure and temperature condition of alloy activation before inhaling hydrogen.From application point of view, if can reduce the activation condition of alloy, the cost of hydrogen storage vessel also can reduce so.Desirable activation condition should be: at normal temperatures, the required hydrogen pressure of alloy activation should be lower than it and inhale the equilibrium pressure of putting hydrogen after activation fully.Like this, what the requirement of withstand voltage of hydrogen storage vessel was played a decisive role is not the activation condition of alloy just, but the suction of activation back alloy is put the hydrogen platform and pressed.Oelerich etc. had once reported metal oxide (TiO
2, V
2O
5Deng) to the improvement effect (W.Oelerich of Mg-base alloy activity function, T.Klassen, R.Bormann, J.Alloys Comp 315 (2001) 237-242), yet they do not report the influence of which oxide to other hydrogen bearing alloy activity function, do not report the influence of relevant ZnO to the hydrogen bearing alloy activity function yet.
Summary of the invention:
Purpose of the present invention is intended to work out a kind of method of improving the hydrogen bearing alloy activity function.This method makes hydrogen bearing alloy that good activity function be arranged under the situation that does not change hydrogen storage capability.This transports its scale at hydrogen, the hydrogen supply source of fuel cell, and fields such as the purification of hydrogen are widely used significant.
Alloy of the present invention can prepare by the following method, and each sample is crushed to average grain diameter about 50 μ m in air.With alloyed powder and mass fraction is that ball milling was 0.5～10 hour under inert gas conditions after 0.5%～10% ZnO mixed.The rotating speed of ball grinder is 200～1000 rev/mins.The mass ratio of ball-milling medium and alloyed powder is 10: 1～20: 1.Described ZnO powder or be common ZnO powder or be nano level ZnO powder.Described hydrogen bearing alloy is a broad sense, is AB
2, AB, AB
5, A
2A kind of in the mutually multiple hydrogen bearing alloy of the BCC of B or Ti-V base, as TiMn
1.25Cr
0.25, TiFe, LaNi
5, Mg
2A kind of among Ni or the Ti-32V-8Mn-10Cr.
Description of drawings:
Fig. 1 is the activity function curve (a) of Ti-32V-8Mn-10Cr alloyed powder, not and the ZnO mixing and ball milling, (b), after 10% ZnO mixing and ball milling.Test condition is pressure P=3MPa, temperature T=293K.
Fig. 2 is the ESEM picture after the nano-ZnO mixing and ball milling of TiFe alloyed powder and 3%.
Fig. 3 is TiMn
1.25Cr
0.25With the ESEM picture after 2% the nano-ZnO mixing and ball milling.
The specific embodiment:
The invention will be further described below by instantiation:
Example 1: with after the nano-ZnO of 1% (mass fraction) mixes, ball milling is 30 minutes under 500 rev/mins rotating speed with 5g Ti-32V-8Mn-10Cr alloyed powder.The mass ratio of ball-milling medium and alloyed powder is 10: 1.Exposing 30 days in air after, the gained alloyed powder carries out the activity function test.Its activity function curve such as Fig. 1 can see, do not have modification to expose this alloyed powder after 30 days under the condition of P=3MPa and T=293K, and hydrogen is less than 0.5% after 120 minutes, and hydrogen can reach about 3.8% under the alloyed powder the same terms after the modification.
Example 2: with 5g LaNi
5Alloyed powder is with after 5% common ZnO mixes, and ball milling is 1 hour under 600 rev/mins rotating speed.The mass ratio of ball-milling medium and alloyed powder is 15: 1.Exposing 30 days in air after, the gained alloyed powder carries out the activity function test.Alloyed powder after the modification is compared with the alloyed powder that does not have modification, and its activity function improves greatly.
Example 3: with after 3% nano-ZnO mixes, ball milling is 3 hours under 200 rev/mins rotating speed with 10g TiFe alloyed powder.The mass ratio of ball-milling medium and alloyed powder is 18: 1.ESEM picture such as Fig. 2 of gained alloyed powder.White particle small among the figure is nano-ZnO, and it is mounted in the alloyed powder.Exposing 30 days in air after, the gained alloyed powder carries out the activity function test.Alloyed powder after the modification is compared with the alloyed powder that does not have modification, and its activity function improves greatly.
Example 4: with 5g TiMn
1.25Cr
0.25Alloyed powder is with after 2% nano-ZnO mixes, and ball milling is 2 hours under 300 rev/mins rotating speed.The mass ratio of ball-milling medium and alloyed powder is 15: 1.ESEM picture such as Fig. 3 of gained alloyed powder.White particle small among the figure is nano-ZnO, also is mounted in the alloyed powder.Exposing 30 days in air after, the gained alloyed powder carries out the activity function test.Alloyed powder after the modification is compared with the alloyed powder that does not have modification, and its activity function improves greatly.
Example 5: with 5g Mg
2The Ni alloyed powder is with after 10% common ZnO mixes, and ball milling is 5 hours under 600 rev/mins rotating speed.The mass ratio of ball-milling medium and alloyed powder is 16: 1.Exposing 30 days in air after, the gained alloyed powder carries out the activity function test.Alloyed powder after the modification is compared with the alloyed powder that does not have modification, and its activity function improves greatly.
Claims (4)
1. method of improving the hydrogen bearing alloy activity function; it is characterized in that with hydrogen storing alloy powder and mass fraction being that 0.5%～10% ZnO powder mixes the back carry out ball milling under inert gas shielding; the ball milling time is 0.5～10 hour, and the ball grinder rotating speed is 200～1000 rev/mins.
2. by the described method of improving the hydrogen bearing alloy activity function of claim 1, it is characterized in that described ZnO powder or for common ZnO powder or be nano level ZnO powder.
3. by claim 1 or the 2 described methods of improving the hydrogen bearing alloy activity function, it is characterized in that described hydrogen bearing alloy is TiMn
1.25Cr
0.25, TiFe, LaNi
5, Mg
2A kind of in the BCC phase alloy of Ni or Ti-V base.
4. by claim 1 or the 2 described methods of improving the hydrogen bearing alloy activity function, the mass ratio of ball-milling medium and alloyed powder is 10: 1～20: 1 when it is characterized in that ball milling.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101080749A CN1270818C (en) | 2003-10-21 | 2003-10-21 | Method for improving activation performance of hydrogen-storage alloy |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101080749A CN1270818C (en) | 2003-10-21 | 2003-10-21 | Method for improving activation performance of hydrogen-storage alloy |
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| CN1528508A CN1528508A (en) | 2004-09-15 |
| CN1270818C true CN1270818C (en) | 2006-08-23 |
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| CNB2003101080749A Expired - Fee Related CN1270818C (en) | 2003-10-21 | 2003-10-21 | Method for improving activation performance of hydrogen-storage alloy |
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| CN101899591B (en) * | 2010-07-06 | 2011-12-21 | 上海纳米技术及应用国家工程研究中心有限公司 | Superlattice hydrogen storage alloy material for nickel hydrogen battery and preparation method thereof |
| CN106811616B (en) * | 2017-02-21 | 2018-08-21 | 淄博君行电源技术有限公司 | Capacitive Ni-MH power cell Zinc oxide-base hydrogen-storage alloy |
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2003
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