CN1084581A - A kind of activation method of hydrogen storage material - Google Patents
A kind of activation method of hydrogen storage material Download PDFInfo
- Publication number
- CN1084581A CN1084581A CN 92109903 CN92109903A CN1084581A CN 1084581 A CN1084581 A CN 1084581A CN 92109903 CN92109903 CN 92109903 CN 92109903 A CN92109903 A CN 92109903A CN 1084581 A CN1084581 A CN 1084581A
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- CN
- China
- Prior art keywords
- hydrogen
- storage material
- hydrogen storage
- activation
- alloy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 78
- 239000001257 hydrogen Substances 0.000 title claims abstract description 78
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000011232 storage material Substances 0.000 title claims abstract description 34
- 230000004913 activation Effects 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title abstract description 11
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 12
- 239000000956 alloy Substances 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 3
- 150000002431 hydrogen Chemical group 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 229910002335 LaNi5 Inorganic materials 0.000 claims 2
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000005086 pumping Methods 0.000 abstract description 2
- 238000003672 processing method Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 150000004678 hydrides Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 238000006253 efflorescence Methods 0.000 description 2
- 206010037844 rash Diseases 0.000 description 2
- 229910018007 MmNi Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- -1 without activation Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Hydrogen, Water And Hydrids (AREA)
Abstract
Present method relates to a kind of activation of hydrogen storage material, its processing method is that difficult activatory metal or alloy is pulverized, put into ball mill with easily-activated hydrogen-storage alloy, take out and fill after the black vacuum with Ar balloon mill 0.5～2 hour, form pseudo-two mischmetals, under normal pressure, pack into the container of hydrogen storage material, fill with hydrogen after taking out black vacuum, at room temperature through 24～48 hours, make and inhale hydrogen to saturated, promptly hydrogen storage material is activated, its advantage: method is simple, make easily, need not add gentle pumping high vacuum, the performance after the activation of the performance after the activation and ordinary method is consistent, uses significant to engineering.
Description
The present invention relates to a kind of activation method of hydrogen storage material.
The fundamental characteristics of hydrogen storage material is can be reversibly, a large amount of absorption hydrogen and put hydrogen, this fundamental characteristics has constituted the application foundation of hydrogen storage material together with other characteristic (as to the selection absorption of hydrogen, the temperature effective of equilibrium pressure, the heat effect that hydrogen is put in suction etc.), but, hydrogen storage material must pass through the ability that " activation " just has reversibly, inhales hydrogen in large quantities and put hydrogen, without activation, hydrogen storage material can't use, whether thereby to be easy to activate be one of major requirement to hydrogen storage material.
Some hydrogen storage material is easy to activation, as LaNi
5, MmNi
5(Mm is a mishmetal), as long as they are placed tens big hydrogen of pressing (several MPa), at room temperature keep dozens of minutes just passable to several hrs, and most hydrogen storage material, as the very excellent TiFe of hydrogen storage property, V etc., activate all very difficult.The hydrogen density that V inhales behind the hydrogen reaches 10.5 * 10
22H-atom/cm
2, first of hydrogen storage material, be higher than far away with usual method (utmost point low temperature down liquefaction storage hydrogen (the storage hydrogen density is 4.2 * 10
22H-afom/cm
3, heavy and unsafe steel cylinder storage hydrogen) and the storage hydrogen density that can reach, but must press H at 4～500 ℃ of high pressure that fill repeatedly
2-evacuation or be heated under ultrahigh vacuum(HHV) just can make it have the Hydrogen Energy power of putting of inhaling more than 900 ℃, i.e. " activation ".After the activation, V at room temperature can inhale hydrogen apace, in large quantities and put hydrogen, TiFe and for example, not only hydrogen storage property is good for it, and inexpensive, but it is very not easily-activated, need between room temperature and 350 ℃ repeatedly fill hydrogen-vacuumize.Activation brings a lot of troubles to practicality under several Baidu, as design, selection, the sealing of container, and valve, instrument etc. all needs high temperature resistant, in some cases even be difficult to solution.So, be carry out the thenization under the special ideal situation in room temperature to the requirement activation easily of hydrogen storage material.
For solving the activation of hydrogen storage material, the invention provides a kind of difficulty activation hydrogen storage material that makes at room temperature can activate, become the method for easily-activated hydrogen-storage alloy, utilize this simple operations of mechanical ball milling, with the method for adding a small amount of easily-activated hydrogen-storage alloy, effectively solved the activation problem of hydrogen storage material.
Technical scheme of the present invention is achieved in that its method is difficulty is activated hydrogen storage material (metal or alloy) to be ground into＜particle of 5mm, with easily-activated hydrogen-storage alloy LaNi
5Insert ball mill together, take out the Ar gas that fills after the black vacuum with 0.05MPa, ball milling 0.5～2 hour, LaNi
5The r amount is the pseudobinary alloy that forms behind ball milling, M
1-x(LaNi
5)
xX 〉=0.001 pseudobinary alloy packed under normal pressure use the container of hydrogen storage material, take out the hydrogen that fills after the black vacuum with 4MPa, through 24～48 hours, can inhale hydrogen under the room temperature to saturated, this moment, hydrogen storage material was activated.
The primary feature of hydrogen storage material is promptly to inhale hydrogen and put hydrogen in a large number, and companion's have a heat effect, and hydrogen storage material generates hydride and heat content after adding hydrogen, and the result is suction hydrogen, heat release; Otherwise put hydrogen, heat absorption.The direction that reaction is carried out depends on temperature and pressure.If there is second kind of hydride to form mutually in the reaction process, add hydrogen as β phase hydride and produce the γ phase, the result inhales hydrogen, heat release, otherwise also sets up, and is to put hydrogen, heat absorption.Hydrogen is present in the interstitial site of hydrogen storage material with atomic form in hydride, forms to have the phase of a fixed structure, and inhaling hydrogen or putting hydrogen all is phase transition process.In certain temperature, hydrogen storage material and H
2Reaction has equilibrium pressure to exist, and the heat effect of reaction and balance pressure following temperature sharply change, and has constituted the basis that hydrogen storage material is used.Requirement is to hydrogen storage material: activation easily; Hydrogen storage amount is big, service temperature near room temperature, suitable reaction heat is arranged; Constant temperature inhales that the pressure platform district put hydrogen is wide, and pressure is 0.1～0.5MPa near room temperature, and it is little with the equilibrium pressure difference of putting hydrogen to inhale hydrogen; Speed for hydrogen absorbing and releasing is fast; Anti-O
2, poisoning capability such as CO, water vapor is strong; Good thermal conductance, resistance to chalking can be good, and alloying element commonly used has Al, Co, Mn, Cr, Zr etc.
The present invention's embodiment:
Example 1
Adopt metal V(vanadium), press V
0.999(LaNi
5)
0.001Proportioning, spongy V and LaNi
5Inserted the ball mill ball milling together 1 hour, in air, put into the hydrogen storage material container, at room temperature pass to 0.4MPa hydrogen after 24 hours, V inhales hydrogen and reaches 196ml/g(and refer to the hydrogen amount that can reversibly emit), and good dynamic characteristic arranged, do not change the suction hydrogen balance characteristic of V, but improved anti-poisoning characteristic and anti-efflorescence characteristic.
Example 2
Adopt TiFe, by (TiFe)
0.97, (LaNi
5)
0.03Proportioning, ball milling 0.5 hour, operate the same with last example, 48 hours are postactivated, the reversible hydrogen adsorption and desorption amount reaches 158ml/g.
Advantage of the present invention: the activation of hydrogen storage material is simple and easy to do, need not add gentle pumping high vacuum, performance after the activation is with consistent with the performance after the conventional method activation, some characteristic (such as anti-poisoning, anti-efflorescence etc.), be significantly improved, the difficult hydrogen storage material that activates can reversibly be inhaled in a large number put hydrogen, use significant to engineering.
Claims (2)
1, a kind of activation of hydrogen storage material, it is characterized in that difficulty is activated hydrogen storage material (metal or alloy) to be ground into＜particle of 5mm, insert ball mill with easily-activated hydrogen-storage alloy LaNi5, take out the Ar gas that fills after the black vacuum with 0.05MPa, ball milling 0.5～2 hour forms pseudobinary system alloy M behind ball milling
1-x(LaNi5)
x, pseudo-two mischmetals are packed under normal pressure use the container of hydrogen storage material, take out the hydrogen that fills after the black vacuum with 4MPa, at room temperature through 24～48 hours, make and inhale hydrogen and reach saturated.
2, by the activation of the described hydrogen storage material of claim 1, it is characterized in that LaNi
5Amount be the pseudobinary alloy that behind ball milling, forms, require M
1-x(LaNi
5)
xX 〉=0.001.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92109903 CN1031836C (en) | 1992-09-22 | 1992-09-22 | Activation method of hydrogen-storage material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92109903 CN1031836C (en) | 1992-09-22 | 1992-09-22 | Activation method of hydrogen-storage material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1084581A true CN1084581A (en) | 1994-03-30 |
| CN1031836C CN1031836C (en) | 1996-05-22 |
Family
ID=4944454
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92109903 Expired - Fee Related CN1031836C (en) | 1992-09-22 | 1992-09-22 | Activation method of hydrogen-storage material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1031836C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105132741A (en) * | 2015-09-25 | 2015-12-09 | 钢铁研究总院 | Rear earth-ferrotitanium hydrogen storage alloy for wind power storage and preparation method thereof |
| CN115090885A (en) * | 2022-06-22 | 2022-09-23 | 海南天宇科技集团有限公司 | Method for improving solid-state gold storage performance of titanium-based zirconium-based alloy by using activation method |
-
1992
- 1992-09-22 CN CN 92109903 patent/CN1031836C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105132741A (en) * | 2015-09-25 | 2015-12-09 | 钢铁研究总院 | Rear earth-ferrotitanium hydrogen storage alloy for wind power storage and preparation method thereof |
| CN115090885A (en) * | 2022-06-22 | 2022-09-23 | 海南天宇科技集团有限公司 | Method for improving solid-state gold storage performance of titanium-based zirconium-based alloy by using activation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1031836C (en) | 1996-05-22 |
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| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |