CN1664141A - Ferrotitaniums hydrogen storage alloy - Google Patents
Ferrotitaniums hydrogen storage alloy Download PDFInfo
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- CN1664141A CN1664141A CN 200510024595 CN200510024595A CN1664141A CN 1664141 A CN1664141 A CN 1664141A CN 200510024595 CN200510024595 CN 200510024595 CN 200510024595 A CN200510024595 A CN 200510024595A CN 1664141 A CN1664141 A CN 1664141A
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Abstract
the invention relates to an iron titanium alloy used to store hydrogen. The component is TiaFebCrcVdLeMf, in which L is one element of Ni, Co, Cu, Mo, M is one element of Al, Si, C and S, 1.0<=1.4, 0.7<=b<=1.0, 0.01<=c<=0.2, 0.01<=d<=0.5, 0.005<=e<=0.03, 0.005<=f<=0.03. Iron titanium alloy in this invention can be smelted in non-self-consumable vacuum arc melting furnace and vacuum medium-frequency induction furnace. The alloy has the properties of facilitation of activating, fine dynamic behavior, high capacity of hydrogen storage, low cost of alloy. The alloy is suitable for hydrogen resource of fuel battery.
Description
Technical field
The present invention relates to a kind of ferrotitanium hydrogen storage alloy, relate in particular to a kind of high hydrogen storage amount and low-cost ferrotianium series hydrogen storage alloy, belong to storage hydrogen energy source material technology field.
Background technology
Hydrogen energy source is a kind of ideal secondary energy.The Metal hydrogen-storing material is one of key of exploitation hydrogen energy source.Store hydrogen with metal hydride, not only the density of hydrogen can surpass the density of liquid hydrogen, and close with the density of solid-state hydrogen.In addition, also have many other advantages, as the high pressure of undesirable gas steel cylinder and the low temperature of liquid hydrogen, can use under normal temperature and normal pressure, security is good, can recycle or the like.
The TiFe alloy is typical case's representative of AB type hydrogen-storage alloy, and it is at first put forward in 1974 by the U.S. breadboard Reilly of state-run Brookhaven.GIFe has bigger reversible hydrogen adsorption and desorption amount at normal temperatures, and the decomposition pressure of hydride only is about ten normal atmosphere, near industrial practical application; In addition, this alloy system is that price is cheapest in the current ambient temperature hydrogen storage metal material, and two kinds of elements of Ti and Fe are abundant at occurring in nature content, are well suited for large-scale application in industry, are up-and-coming hydrogen-storage alloy series.The U.S. and Germany etc. have studied fuel cell hydrogen source exploitation electromobile on automobile.But activation of TiFe series hydrogen storage alloy and dynamic performance are relatively poor, and the storage hydrogen capacity still can not satisfy the needs that application request improves constantly.For addressing the above problem, the various countries investigator has done many work.People (J.Less-Common Met.1987 such as Hiroshi Nagai; Vol.134 P275) has studied the Ti-Fe-Mn series hydrogen storage alloy, and the storage hydrogen capacity reaches 218ml/g.T.Bratanich (Int.J.Hydrogen Energy1995; Vol.20, P353) mixed powder by compression TiFe powdered alloy or several alloys improves activation performance, uses the TiFe powder of pressure compression 0.1～0.2mm of 450Mpa, and the briquetting of formation just can activate down at 100 ℃.(Acta Metallurgica Sinica, 1999 such as Ma Jianxin; Vol.35, P805) research FeTi
1.3(Mm)
yThe hydrogen storage performance of alloy at room temperature just can activate without any activation treatment, but its hydrogen desorption capacity is lower.In recent years, along with the price of domestic and international raw material metal rises steadily, the development task of the higher and cheap hydrogen-storage alloy of storage hydrogen capacity relatively is particularly urgent concerning the practical application of hydrogen storage material.
Summary of the invention
The purpose of this invention is to provide a kind of ferrotitanium hydrogen storage alloy.
Another object of the present invention provides a kind of high hydrogen storage amount and low-cost ferrotianium series hydrogen storage alloy is used as the fuel cell hydrogen source alloy.
Task of the present invention is achieved in that
A kind of ferrotitanium hydrogen storage alloy is characterized in that composed as follows: Ti
aFe
bCr
cV
dL
eM
f, in the formula, L is that (Ni, Co, Cu, Mo) a kind of element in, M are (Al, Si, C, S) a kind of element in, 1.0≤a≤1.4,0.7≤b≤1.0,0.01≤c≤0.2,0.01≤d≤0.5,0.005≤e≤0.03,0.005≤f≤0.03.
As e=0 and f=0, when e=0 or f=0, the composition of ferrotitanium hydrogen storage alloy of the present invention is respectively: Ti
aFe
bCr
cV
d, Ti
aFe
bCr
cV
dM
f, Ti
aFe
bCr
cV
dL
e
Ferrotitanium hydrogen storage alloy of the present invention can prepare like this: at first can take by weighing 10～50 by hundred parts of ratios of the determined weight of alloy formula and restrain or 10～20 kilograms, the purity of testing used metal simple-substance raw material is all more than 99%.Melting in non-consumable arc furnace or vacuum medium frequency induction furnace is respectively then all carried out under argon shield atmosphere for anti-oxidation during melting.When adopting the non-consumable arc furnace melting, even for guaranteeing the hydrogen-storage alloy composition, need stand up melting 3～4 times.
The present invention has adopted multi-element alloyed.After the polynary replacement, the decomposition pressure of the hydride of TiFe base alloy drops to several normal atmosphere from ten normal atmosphere, makes the suction of this alloy put the hydrogen pressure condition and further relaxes.Because the replacement of these multicomponent alloy elements and the interaction between them, and second being distributed in mutually on the TiFe matrix of their formed multiple small and disperseds, make ferrotitanium hydrogen storage alloy of the present invention not only have higher storage hydrogen capacity, and under relatively mild condition, just being easy to activation, dynamic performance also improves.
Ferrotianium of the present invention has on the other hand adopted A side element to exceed stoichiometric ratio when being the design of AB type hydrogen-storage alloy composition, help on matrix, forming the second phase β-Ti (FeCrV) that can inhale hydrogen of more disperse, thereby improved the activation and the dynamic performance of alloy.
Ferrotianium of the present invention is that AB type hydrogen-storage alloy not only has higher storage hydrogen capacity, easily-activated and dynamic performance good, and with low cost.Be very suitable for alloy as hydrogen reservoir, hydrogen purification device and fuel cell fuel tank.Particularly at home and abroad the price of raw material metal rises steadily today, stores special its superiority to the large-scale application of hydrogen storage material that shows of the higher and cheap ferrotitanium hydrogen storage alloy of hydrogen capacity relatively.
Embodiment
After now embodiments of the invention being described in.
Embodiment one
Hydrogen-storage alloy Ti
1.09Fe
0.95Cr
0.04V
0.03Mo
0.02Take by weighing 30 grams by hundred parts of ratios of the determined weight of alloy formula, the purity of testing used metal simple-substance raw material is all more than 99%.In non-consumable arc furnace, under argon shield atmosphere, carry out then.For guaranteeing that alloying constituent is even, stand up melting 3～4 times.Get 5 gram sample machineries and be crushed to 50～100 orders, in the stainless reaction vessel of again sample being packed into.Activation vacuumized under 80 ℃ 1 hour, fed the hydrogen of 4Mpa then, just can activate through 5～30 minutes, inhaled repeatedly to put hydrogen and just can activate fully for 4 times.The hydrogen storage amount that records alloy is 234ml/g, and hydrogen desorption capacity is 218ml/g.
Embodiment two
Hydrogen-storage alloy Ti
1.06Fe
0.94Cr
0.03V
0.03Si
0.01Take by weighing 30 grams by hundred parts of ratios of the determined weight of alloy formula, the purity of testing used metal simple-substance raw material is all more than 99%.In non-consumable arc furnace, under argon shield atmosphere, carry out then.For guaranteeing that alloying constituent is even, stand up melting 3～4 times.Get 5 gram sample machineries and be crushed to 50～100 orders, in the stainless reaction vessel of again sample being packed into.Activation vacuumized under 80 ℃ 1 hour, fed the hydrogen of 4Mpa then, just can activate through 5～30 minutes, inhaled repeatedly to put hydrogen and just can activate fully for 4 times.The hydrogen storage amount that records alloy is 242ml/g, and hydrogen desorption capacity is 221ml/g.
Embodiment three
To ferrotianium is AB type hydrogen-storage alloy, takes by weighing 20 grams by hundred parts of ratios of the determined weight of alloy formula, and the purity of testing used metal simple-substance raw material is all more than 99%.In non-consumable arc furnace, under argon shield atmosphere, carry out then.For guaranteeing that alloying constituent is even, stand up melting 3～4 times.Get 5 gram sample machineries and be crushed to 50～100 orders, in the stainless reaction vessel of again sample being packed into.Activation vacuumized under 80 ℃ 1 hour, fed the hydrogen of 4Mpa then, just can activate through 5～30 minutes, inhaled repeatedly to put hydrogen and just can activate fully for several times.Recording the hydrogen storage amount of ferrotitanium hydrogen storage alloy and the data of hydrogen desorption capacity is listed in the table below.
| Alloying constituent | Hydrogen storage amount (ml/g) | Hydrogen desorption capacity (ml/g) |
| ????Ti 1.04Fe 0.92Cr 0.06V 0.01 | ????224 | ????212 |
| ????Ti 1.08Fe 0.95Cr 0.02V 0.03Ni 0.02Al 0.01 | ????245 | ????227 |
| ????Ti 1.08Fe 0.9Cr 0.04V 0.06Co 0.02Si 0.01 | ????256 | ????232 |
| ????Ti 1.06Fe 0.88Cr 0.05V 0.05Ni 0.02Sn 0.01 | ????249 | ????226 |
| ????Ti 1.06Fe 0.93Cr 0.03V 0.02Cu 0.02Sn 0.01 | ????251 | ????238 |
| ????Ti 1.15Fe 0.85Cr 0.07V 0.15Mo 0.02C 0.01 | ????247 | ????183 |
Embodiment four
By alloy designs prescription Ti
1.05Fe
0.9Cr
0.04V
0.04Cu
0.01Al
0.01Hundred parts of ratios of determined weight take by weighing 15 kilograms, and the purity of testing used metal simple-substance raw material is all more than 99%, and wherein V substitutes with VFe (weight ratio of V and Fe is 4: 1).Frequently under argon shield atmosphere, carry out melting in the induction furnace in a vacuum, be cast in the water cooled mo(u)ld of water flowing and cool off.The hydrogen-storage alloy sample is through mechanical disintegration to 50～100 orders, in the stainless reaction vessel of again sample being packed into.Activation vacuumized under 80 ℃ 1 hour, fed the hydrogen of 4Mpa then, just can activate through 5～30 minutes, inhaled repeatedly to put hydrogen and just can activate fully for 3 times.The hydrogen storage amount of this alloy is 248ml/g, and hydrogen desorption capacity is 230ml/g.
Embodiment five
Hydrogen-storage alloy Ti
1.3Fe
0.85Cr
0.04V
0.25Ni
0.01Si
0.005Take by weighing 50 grams by hundred parts of ratios of the determined weight of alloy formula, the purity of testing used metal simple-substance raw material is all more than 99%.In non-consumable arc furnace, under argon shield atmosphere, carry out then.For guaranteeing that alloying constituent is even, stand up melting 3～4 times.Get 5 gram sample machineries and be crushed to 50～100 orders, in the stainless reaction vessel of again sample being packed into.Activation vacuumized under 80 ℃ 1 hour, fed the hydrogen of 4Mpa then, just can activate through 5～30 minutes, repeated to inhale to put hydrogen and just can activate fully for 2 times.The hydrogen storage amount that records this alloy is 203ml/g, and hydrogen desorption capacity is 165ml/g.
Embodiment six
Hydrogen-storage alloy Ti
1.4Fe
0.85Cr
0.04V
0.35Co
0.01Sn
0.005Take by weighing 50 grams by hundred parts of ratios of the determined weight of alloy formula, the purity of testing used metal simple-substance raw material is all more than 99%.In non-consumable arc furnace, under argon shield atmosphere, carry out then.For guaranteeing that alloying constituent is even, stand up melting 3～4 times.Get 5 gram sample machineries and be crushed to 50～100 orders, in the stainless reaction vessel of again sample being packed into.Activation vacuumized under 80 ℃ 1 hour, fed the hydrogen of 4Mpa then, just can activate through 5～30 minutes, repeated to inhale to put hydrogen and just can activate fully for 2 times.The hydrogen storage amount that records this alloy is 183ml/g, and hydrogen desorption capacity is 139ml/g.
Claims (10)
1. a ferrotitanium hydrogen storage alloy is characterized in that composed as follows: Ti
aFe
bCr
cV
dL
eM
f, in the formula, L is that (Ni, Co, Cu, Mo) a kind of element in, M are (Al, Si, Sn, C, S) a kind of element in, 1.0≤a≤1.4,0.7≤b≤1.0,0.01≤c≤0.2,0.01≤d≤0.5,0.005≤e≤0.03,0.005≤f≤0.03.
2. by the described ferrotitanium hydrogen storage alloy of claim 1, it is characterized in that in the alloy composition when L for (Ni, when Cu, a kind of element in Co), M is (Al, Si, Sn) a kind of element in.
3. by the described ferrotitanium hydrogen storage alloy of claim 1, it is characterized in that in the alloy composition that when L was the Mo element, M was (C, S) a kind of element in.
4. by the described ferrotitanium hydrogen storage alloy of claim 1, it is characterized in that e=0 and f=0 in the alloy composition.
5. by the described ferrotitanium hydrogen storage alloy of claim 1, it is characterized in that e=0 or f=0 in the alloy composition.
6. by the described ferrotitanium hydrogen storage alloy of claim 1, it is characterized in that 1.0≤a in the alloy composition≤1.1,0.85≤b≤0.95,0.03≤c≤0.1,0.03≤d≤0.1.
7. by the described ferrotitanium hydrogen storage alloy of claim 1, it is characterized in that 0.01≤e in the alloy composition≤0.02,0.005≤f≤0.01.
8. by the described ferrotitanium hydrogen storage alloy of claim 1, it is characterized in that alloy composition is Ti
1.3Fe
0.85Cr
0.04V
0.25Ni
0.01Si
0.005
9. by the described ferrotitanium hydrogen storage alloy of claim 1, it is characterized in that alloy composition is Ti
1.4Fe
0.85Cr
0.04V
0.35Co
0.01Sn
0.005
10. by the described ferrotitanium hydrogen storage alloy of claim 1, it is characterized in that the vanadium in the alloy composition substitutes with vanadium iron.
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| CNB2005100245955A CN1317409C (en) | 2005-03-24 | 2005-03-24 | Ferrotitaniums hydrogen storage alloy |
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| CN1317409C CN1317409C (en) | 2007-05-23 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102383068A (en) * | 2011-10-09 | 2012-03-21 | 上海大学 | Amorphous state hydrogen absorption alloy having mechanical property and preparation method thereof |
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|---|---|---|---|---|
| CN86101527A (en) * | 1986-07-18 | 1988-01-27 | 上海工业大学 | Ti fexcry-based hydrogen-storage metal |
| JPH09237630A (en) * | 1996-02-29 | 1997-09-09 | Matsushita Electric Ind Co Ltd | Active material and positive electrode for alkali storage battery |
| JP2001266931A (en) * | 2000-03-23 | 2001-09-28 | Sanyo Electric Co Ltd | Nickel-hydrogen storage battery |
| JP2002030374A (en) * | 2000-07-11 | 2002-01-31 | Masuo Okada | Hydrogen storage alloy and its production method |
| CN1160814C (en) * | 2002-03-28 | 2004-08-04 | 刘华福 | Hydrogen storage alloy material for high temperature nickel-hydrogen cell and preparing method |
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| CN102383068A (en) * | 2011-10-09 | 2012-03-21 | 上海大学 | Amorphous state hydrogen absorption alloy having mechanical property and preparation method thereof |
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