CN1031836C - Activation method of hydrogen-storage material - Google Patents
Activation method of hydrogen-storage material Download PDFInfo
- Publication number
- CN1031836C CN1031836C CN 92109903 CN92109903A CN1031836C CN 1031836 C CN1031836 C CN 1031836C CN 92109903 CN92109903 CN 92109903 CN 92109903 A CN92109903 A CN 92109903A CN 1031836 C CN1031836 C CN 1031836C
- Authority
- CN
- China
- Prior art keywords
- hydrogen
- hydrogen storage
- storage material
- storage materials
- activated
- 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.)
- Expired - Fee Related
Links
- 239000011232 storage material Substances 0.000 title claims abstract description 35
- 230000004913 activation Effects 0.000 title claims description 17
- 238000000034 method Methods 0.000 title abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 79
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 79
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 69
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 12
- 239000000956 alloy Substances 0.000 claims abstract description 12
- 238000000498 ball milling Methods 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims abstract description 3
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 3
- 150000002431 hydrogen Chemical group 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000007796 conventional method Methods 0.000 abstract description 2
- 238000005086 pumping Methods 0.000 abstract description 2
- 230000003213 activating effect Effects 0.000 abstract 1
- 229910001325 element alloy Inorganic materials 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- 238000002360 preparation 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
- 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
- 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 Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Hydrogen, Water And Hydrids (AREA)
Abstract
The present invention relates to a process for activating hydrogen storage materials. The process comprises: metals or alloys, which are difficult to activate, are pulverized and put in a ball mill together with hydrogen storage alloys which are easy to activate, the ball mill is pumped into rough vacuum, Ar gas is led into the ball mill, and then ball milling is carried out for 0.5 to 2 hours to form a pseudo dual-element alloy; a container containing hydrogen storage materials under ordinary pressure is pumped into rough vacuum, and then hydrogen is led into the container, the hydrogen is absorbed by the hydrogen storage materials until the hydrogen storage materials are saturated, and thus, the hydrogen storage materials are activated. The present invention has the advantages of simple method, easy preparation and no need of heating and pumping into high vacuum, the propertied of the hydrogen storage materials after being activated are in accordance with the properties of the hydrogen storage materials activated by a conventional method, and the present invention has an important significance for engineering application.
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 together with other characteristic (as to the temperature effective of the selection absorption of hydrogen, equilibrium pressure, inhale the heat effect of putting hydrogen etc.) constituted the application foundation of hydrogen storage material.But, the ability that hydrogen storage material must just have reversibly, inhale hydrogen in large quantities and put hydrogen through " activation ", without activation, hydrogen storage material can't use, thereby whether 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 the hydrogen of tens normal atmosphere (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 the storage hydrogen density that can reach far away with usual method (low temperature is liquefaction storage hydrogen down, heavy and unsafe steel cylinder storage hydrogen), V must 4-500 ℃ repeatedly fill high pressure H
2-evacuation or be heated under ultrahigh vacuum(HHV) just can make it have to inhale and put Hydrogen Energy power, i.e. " activation " more than 900 ℃.After the activation, V at room temperature can inhale hydrogen apace, in large quantities and put hydrogen, TiFe and for example, and not only hydrogen storage property is good for it, and inexpensive, but it is very not easily-activated, needs between room temperature and 350 ℃ the hydrogen one that fills repeatedly to vacuumize.Activation brings a lot of troubles to practicality under several Baidu, all needs as design, selection, sealing and the valve of container, instrument etc. high temperature resistant, in some cases even be difficult to solution.So, be to activate 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
5Weight be the weight of the pseudobinary system alloy that behind ball milling, forms, require M
1-x(LaNi
5)
xX 〉=0.001, the pseudobinary system alloy packed under normal pressure uses the container of hydrogen storage material, take out the hydrogen that fills after the black vacuum with 4MPa, through 24-48 hour, 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; Hydrogen storage amount is big, service temperature near room temperature, suitable reaction heat is arranged; The pressure platform district that hydrogen is put in permanent angry suction 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, and speed for hydrogen absorbing and releasing is fast; Anti-O
2, strong, the good thermal conductances of poisoning capability such as CO, water vapour, resistance to chalking can be good, alloying element commonly used has Al, Co, Mn, Cr, Zr etc.
The present invention's embodiment:
Embodiment 1
Adopt metal V (vanadium), press V
0.999(LaNi
5)
0.001Proportioning, spongy V and LaNi
5It is little right to insert ball mill ball milling 1 together, 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 (refer to can reversibly emit hydrogen amount), and good dynamic characteristic arranged, do not change the suction hydrogen balance characteristic of V, but improved anti-poisoning characteristic and anti-efflorescence characteristic.
Embodiment 2
Adopt TiFe, by (TiFe)
0.97, (LaNi
5)
0.08Proportioning, ball milling 0.5 hour, the same usefulness of operating 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 (as anti-poisoning, Anti-efflorescence etc.), be significantly improved, the difficult hydrogen storage material that activates can be reversibly inhaled in a large number put hydrogen, Use significant to engineering.
Claims (1)
1. the activation of a hydrogen storage material is characterized in that 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, the pseudobinary system alloy M that behind ball milling, forms
1-x(LaNi
5)
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 hour, make inhale hydrogen reach saturated, LaNi
5Weight be the weight of the pseudobinary system 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 CN1084581A (en) | 1994-03-30 |
| CN1031836C true 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) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105132741B (en) * | 2015-09-25 | 2017-03-22 | 钢铁研究总院 | Rear earth-ferrotitanium hydrogen storage alloy for wind power storage |
| 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
Also Published As
| Publication number | Publication date |
|---|---|
| CN1084581A (en) | 1994-03-30 |
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