CN1266296C - Nano composite amorphous magnesium-base hydrogen-storing material and its prepn - Google Patents
Nano composite amorphous magnesium-base hydrogen-storing material and its prepn Download PDFInfo
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- CN1266296C CN1266296C CNB021447047A CN02144704A CN1266296C CN 1266296 C CN1266296 C CN 1266296C CN B021447047 A CNB021447047 A CN B021447047A CN 02144704 A CN02144704 A CN 02144704A CN 1266296 C CN1266296 C CN 1266296C
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- hydrogen
- ball milling
- amorphous
- alloy
- storage material
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- 239000000463 material Substances 0.000 title claims description 7
- 239000002114 nanocomposite Substances 0.000 title 1
- 239000001257 hydrogen Substances 0.000 claims abstract description 62
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 62
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 59
- 238000000498 ball milling Methods 0.000 claims abstract description 16
- 239000011232 storage material Substances 0.000 claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 13
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 9
- 230000003197 catalytic effect Effects 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 13
- 239000000956 alloy Substances 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000011159 matrix material Substances 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 238000005266 casting Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 238000010791 quenching Methods 0.000 claims description 4
- 230000000171 quenching effect Effects 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 230000006698 induction Effects 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 238000003860 storage Methods 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 3
- 238000007599 discharging Methods 0.000 abstract description 2
- 239000012300 argon atmosphere Substances 0.000 abstract 1
- 238000003795 desorption Methods 0.000 description 10
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000005300 metallic glass Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Images
Classifications
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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
- Y02E60/10—Energy storage using batteries
-
- 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
- Y02E60/32—Hydrogen storage
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- Hydrogen, Water And Hydrids (AREA)
- Powder Metallurgy (AREA)
Abstract
The present invention relates to a Mg-based nanometer/amorphous composite hydrogen-storage material which is characterized in that an amorphous catalytic phase Zr<0.9>Ti<0.1>(Ni<0.57>Mn<0.28>V<0.1>Co<0.05>)<2.1> prepared by ball milling in an argon atmosphere is mixed with Mg powder, and then a catalytic reaction ball milling method is used for preparing the Mg-based nanometer/amorphous composite hydrogen-storage material by ball milling in a high-purity hydrogen atmosphere, wherein the quantity of the catalytic phase Zr<0.9>Ti<0.1>(Ni<0.57>Mn<0.28>V<0.1>Co<0.05>)<2.1> is from 10 to 50 wt%. The present invention keeps the high hydrogen-storage capacity of Mg and simultaneously and greatly improves the hydrogen absorbing and discharging dynamic property of the Mg.
Description
Technical field:
The present invention relates to hydrogen storage material, a kind of novel Mg+xwt.% amorphous Zr is provided especially
0.9Ti
0.1(Ni
0.57Mn
0.28V
0.1Co
0.05)
2.1Nanometer/amorphous composite hydrogen storage material.
Background technology:
Mg is acknowledged as the hydrogen storage material that has development prospect most owing to have high hydrogen storage capability (7.6wt.%) and cheap price.But its suction put the hydrogen working temperature higher (～673K), the hydrogenation dynamic performance is relatively poor, has seriously restricted its practical application exploitation.Manyly studies show that Mg is carried out high-energy ball milling with some metal or alloy additives can improve the dynamic performance that hydrogen is put in its suction.The selection of additive plays an important role to the improvement of the performance of Mg.The additive of selecting for use at present mostly is LaNi
5, Mg
2Ni, ZrFe
1.4Cr
0.6Or Ni, Fe, Co etc., and select the less of amorphous alloy for use.On behalf of hydrogenation equilibrated pressure platform, the non-crystalline state hydrogen storage material in the PCT curve disappear, and hydrogen is that solid solution enters in the non-crystaline amorphous metal, and does not have new hydride to generate.But a large amount of short range orders that exist in amorphous phase can be regarded as extreme defective, become the position that hydrogen atom can occupy, so non-crystalline areas has vital role for the improvement of material hydrogenation dynamic performance.Nearest studies show that, carries out ball milling (claiming catalytic reacting ball milling again) and can promote solid-solid/liquid/gas reactions in reaction atmosphere, at the direct synthesizing hydrogenated thing of room temperature.Therefore adopting new additive and Mg to carry out catalytic reacting ball milling is the important channel of improving the hydrogenation property of Mg.
The technology contents of invention:
The object of the present invention is to provide a kind of Mg base nanometer/amorphous composite hydrogen storage material, in the high hydrogen storage capability that keeps Mg, improve the suction hydrogen desorption kinetics performance of Mg significantly.
The invention provides a kind of Mg base nanometer/amorphous composite hydrogen storage material, it is characterized in that: this composite hydrogen storage material is by Mg and catalysis amorphous Zr mutually
0.9Ti
0.1(Ni
0.57Mn
0.28V
0.1Co
0.05)
2.1Alloy powder is formed, and the crystal grain of Mg reaches nanoscale, catalysis phase amorphous Zr
0.9Ti
0.1(Ni
0.57Mn
0.28V
0.1Co
0.05)
2.1Alloy is evenly distributed on nano particle in the matrix of Mg, Zr
0.9Ti
0.1(Ni
0.57Mn
0.28V
0.1Co
0.05)
2.1Content be 10～50wt.%.
The present invention also provides the preparation method of above-mentioned Mg base nanometer/amorphous composite hydrogen storage material; it is characterized in that: the quality proportion speed by alloy designs takes by weighing each constituent element pure metal Zr; Ti, Ni, Mn; V; Co, purity is all more than 99%, in vacuum induction furnace after the melting under argon shield casting ingot-forming; then ingot casting is carried out fast quenching and handle, again the alloy behind the fast quenching is prepared into non-crystalline state Zr with high energy ball mill ball milling under high-purity argon gas atmosphere
0.9Ti
0.1(Ni
0.57Mn
0.28V
0.1Co
0.05)
2.1Alloy powder, ratio of grinding media to material are 10～100: 1, and the ball milling time is 6～20 hours;
Non-crystalline state Zr with 100 purpose Mg powder and above-mentioned preparation
0.9Ti
0.1(Ni
0.57Mn
0.28V
0.1Co
0.05)
2.1Alloy powder mixes, and adopts catalytic reacting ball milling to be prepared into nanometer/amorphous composite hydrogen storage material, and ratio of grinding media to material is 10～100: 1; The ball milling time is 1～5 hour; Filling hydrogen pressure is 0.5～2.0MPa; Filled hydrogen once in per 15～40 minutes.
The present invention adopts the Mg+ amorphous Zr of catalytic reacting ball milling method preparation
0.9Ti
0.1(Ni
0.57Mn
0.28V
0.1Co
0.05)
2.1Nanometer/amorphous composite hydrogen storage material confirms that through scanning electron microscope, transmission electron microscope observing the grain-size of Mg reaches nanoscale, catalysis phase non-crystalline state Zr
0.9Ti
0.1(Ni
0.57Mn
0.28V
0.1Co
0.05)
2.1Be evenly distributed on nano-scale particle in the matrix of Mg.Zr in the catalysis mutually, Ti, Ni, Mn, V, Co is neither to generate intermetallic compound with Mg, and its Heat stability is good, reaches to inhale to put in the catalytic reacting ball milling process all to keep non-crystalline state in the hydrogen working cycle.Catalysis only plays katalysis mutually, does not influence the hydrogenation equilibrium response of Mg.Sample of the present invention need not activation, directly carries out dynamic performance and measures temperature range: 120～350 ℃, and pressure range: 0.5～2.0Mpa.
Performance index: hydrogen storage capability 3.5～4.2wt.%;
Hydrogen-absorption speed: inhaled hydrogen in 1 minute for 160～350 ℃ and reach 95% of maximum hydrogen separately;
Hydrogen discharging rate: put hydrogen in 5 minutes for 350 ℃ and reach 95% of maximum hydrogen desorption capacity;
Cycle life: 100 times performance does not have obvious decay.
In addition, this matrix material has excellent low temperature, low pressure hydrogen sucking function.At 160 ℃, under 0.5～2.0MPa hydrogen pressure, inhale hydrogen in 5 minutes and can reach 90% of saturation value.This matrix material has the excellent comprehensive hydrogenation property.
The present invention has the following advantages:
1. preparation technology is easy and simple to handle, realizes in-situ activation in material preparation.
2. the Heat stability is good of catalysis phase has guaranteed the katalysis that it is stable.
3. this matrix material has the excellent comprehensive hydrogen storage property, has excellent dynamic performance in the higher hydrogen storage capability of maintenance, still has higher hydrogen-absorption speed under low-temp low-pressure.
Description of drawings:
Fig. 1 is put the pattern after the hydrogen circulation for embodiment 1 inhales;
Fig. 2 is that embodiment 1 inhales the hydrogen desorption kinetics curve;
Fig. 3 is put the pattern after the hydrogen circulation for embodiment 2 inhales;
Fig. 4 is that embodiment 2 inhales the hydrogen desorption kinetics curve;
Fig. 5 is put the pattern after the hydrogen circulation for embodiment 3 inhales;
Fig. 6 is that embodiment 3 inhales the hydrogen desorption kinetics curve.
Embodiment:
Embodiment 1.
Catalysis phase Zr
0.9Ti
0.1(Ni
0.57Mn
0.28V
0.1Co
0.05)
2.1When addition was 30wt.%, hydrogen-storage amount reached 4wt.%; Can reach 3.8wt.% at 350 ℃ of following 1 minute suction hydrogen, hydrogen desorption capacity reached 3.4wt.% in 2 minutes; At 160 ℃, under the 1.0Mpa hydrogen pressure, inhaled hydrogen and can reach 3wt.% in 5 minutes; Put the hydrogen cycle performance through 100 suctions and do not have obvious decay.Its suction put after the hydrogen circulation pattern as shown in Figure 1, inhale hydrogen desorption kinetics curve such as Fig. 2.
Embodiment 2.
Catalysis phase Zr
0.9Ti
0.1(Ni
0.57Mn
0.28V
0.1Co
0.05)
2.1When addition was 40wt.%, hydrogen-storage amount was 4.2wt.%; Can reach 3.2wt.% at 120 ℃ of following 1 minute hydrogens, reach 3.66wt.% at 350 ℃ of following 2 minutes hydrogen desorption capacities; At 160 ℃, under the 0.5Mpa hydrogen pressure, inhaled hydrogen and can reach 2.8wt.% in 5 minutes; Put the hydrogen cycle performance through 100 suctions and do not have obvious decay.Its suction put after the hydrogen circulation pattern as shown in Figure 3, inhale hydrogen desorption kinetics curve such as Fig. 4.
Embodiment 3.
Catalysis phase Zr
0.9Ti
0.1(Ni
0.57Mn
0.28V
0.1Co
0.05)
2.1When addition was 50wt.%, hydrogen-storage amount was 3.5wt.%; 160～350 ℃ of following 1 minute hydrogens 95% of hydrogen that can reach capacity reaches 90% of saturation value at 350 ℃ of following 2 minutes hydrogen desorption capacities; Put the hydrogen cycle performance through 100 suctions and do not have obvious decay.Its suction put after the hydrogen circulation pattern as shown in Figure 5, inhale hydrogen kinetic curve such as Fig. 6.
Claims (1)
1, the preparation method of a kind of Mg base nanometer/amorphous composite hydrogen storage material, this composite hydrogen storage material is by Mg and catalysis amorphous Zr mutually
0.9Ti
0.1(Ni
0.57Mn
0.28V
0.1Co
0.05)
2.1Alloy powder is formed, and the crystal grain of Mg reaches nanoscale, catalysis phase amorphous Zr
0.9Ti
0.1(Ni
0.57Mn
0.28V
0.1Co
0.05)
2.1Alloy is evenly distributed on nano particle in the matrix of Mg, Zr
0.9Ti
0.1(Ni
0.57Mn
0.28V
0.1Co
0.05)
2.1Content be 30～50wt.%; it is characterized in that: the quality proportion speed by alloy designs takes by weighing each constituent element pure metal Zr; Ti, Ni, Mn; V; Co, purity is all more than 99%, in vacuum induction furnace after the melting under argon shield casting ingot-forming; then ingot casting is carried out fast quenching and handle, again the alloy behind the fast quenching is prepared into non-crystalline state Zr with high energy ball mill ball milling under high-purity argon gas atmosphere
0.9Ti
0.1(Ni
0.57Mn
0.28V
0.1Co
0.05)
2.1Alloy powder, ratio of grinding media to material are 10～100: 1, and the ball milling time is 6～20 hours;
Non-crystalline state Zr with 100 purpose Mg powder and above-mentioned preparation
0.9Ti
0.1(Ni
0.57Mn
0.28V
0.1Co
0.05)
2.1Alloy powder mixes, and adopts catalytic reacting ball milling to be prepared into nanometer/amorphous composite hydrogen storage material, and ratio of grinding media to material is 10～100: 1; The ball milling time is 1～5 hour; Filling hydrogen pressure is 0.5～2.0MPa; Filled hydrogen once in per 15～40 minutes.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021447047A CN1266296C (en) | 2002-12-06 | 2002-12-06 | Nano composite amorphous magnesium-base hydrogen-storing material and its prepn |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021447047A CN1266296C (en) | 2002-12-06 | 2002-12-06 | Nano composite amorphous magnesium-base hydrogen-storing material and its prepn |
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| Publication Number | Publication Date |
|---|---|
| CN1506482A CN1506482A (en) | 2004-06-23 |
| CN1266296C true CN1266296C (en) | 2006-07-26 |
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ID=34232069
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021447047A Expired - Fee Related CN1266296C (en) | 2002-12-06 | 2002-12-06 | Nano composite amorphous magnesium-base hydrogen-storing material and its prepn |
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| Country | Link |
|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9234264B2 (en) | 2004-12-07 | 2016-01-12 | Hydrexia Pty Limited | Magnesium alloys for hydrogen storage |
-
2002
- 2002-12-06 CN CNB021447047A patent/CN1266296C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9234264B2 (en) | 2004-12-07 | 2016-01-12 | Hydrexia Pty Limited | Magnesium alloys for hydrogen storage |
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| Publication number | Publication date |
|---|---|
| CN1506482A (en) | 2004-06-23 |
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