CN1397659A - Non-crystal rare-earth and Mg base hydrogen bearing alloy and its preparing process - Google Patents
Non-crystal rare-earth and Mg base hydrogen bearing alloy and its preparing process Download PDFInfo
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- CN1397659A CN1397659A CN 02111382 CN02111382A CN1397659A CN 1397659 A CN1397659 A CN 1397659A CN 02111382 CN02111382 CN 02111382 CN 02111382 A CN02111382 A CN 02111382A CN 1397659 A CN1397659 A CN 1397659A
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 95
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 95
- 239000013078 crystal Substances 0.000 title claims abstract description 18
- 125000004435 hydrogen atom Chemical group [H]* 0.000 title claims abstract description 13
- 229910052761 rare earth metal Inorganic materials 0.000 title claims description 20
- 150000002910 rare earth metals Chemical class 0.000 title claims description 17
- 238000000034 method Methods 0.000 title claims description 12
- 239000001996 bearing alloy Substances 0.000 title claims description 10
- 230000008569 process Effects 0.000 title description 5
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 74
- 239000000956 alloy Substances 0.000 claims abstract description 74
- 239000000126 substance Substances 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 12
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 8
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 7
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 6
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 6
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 238000003860 storage Methods 0.000 claims description 38
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 25
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 238000000498 ball milling Methods 0.000 claims description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 10
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 238000005275 alloying Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 5
- -1 aromatic organic compounds Chemical class 0.000 claims description 5
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 3
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 3
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 claims description 3
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 claims description 3
- 229910001122 Mischmetal Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 229910000808 amorphous metal alloy Inorganic materials 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 70
- 238000000227 grinding Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000002635 aromatic organic solvent Substances 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 229910052726 zirconium Inorganic materials 0.000 abstract description 2
- 238000003723 Smelting Methods 0.000 abstract 1
- 238000010298 pulverizing process Methods 0.000 abstract 1
- 239000011777 magnesium Substances 0.000 description 60
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 26
- 229910052749 magnesium Inorganic materials 0.000 description 19
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 18
- 150000002431 hydrogen Chemical class 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 8
- 150000002894 organic compounds Chemical class 0.000 description 7
- 229910000990 Ni alloy Inorganic materials 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000002828 fuel tank Substances 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 229910005438 FeTi Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011232 storage material Substances 0.000 description 3
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000005551 mechanical alloying Methods 0.000 description 2
- 238000003701 mechanical milling Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229910000714 At alloy Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910003298 Ni-Ni Inorganic materials 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- 241000720974 Protium Species 0.000 description 1
- 241001417490 Sillaginidae Species 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003974 emollient agent Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- KHTIGPKSZNZLNJ-UHFFFAOYSA-N magnesium palladium Chemical compound [Mg].[Pd] KHTIGPKSZNZLNJ-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000005300 metallic glass Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- Powder Metallurgy (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
A non-crystal rare earth-Mg-bse alloy for bearing hydrogen has a chemical formula: Re1-xMxMg12-yNy, where x=0-0.5, y=0-3, Re is chosen from La, Ce, Pr, etc. M is chosen from Ca, Ti, V and Zr, and N is chosen from Ni, Co, Fe, etc. It is prepared through smelting its cystal alloy, pulverizing, mixing with aromatic organic solvent, ball grinding and removing solvent. Its advantages are high hydrogen-bearing power etc.
Description
Technical field
The present invention relates to a kind ofly be main component with magnesium and be that the Magnuminium ， And of submember relates to the structure that changes this alloy with cold process with the rare earth metal.
Background technology
Hydrogen Energy is reproducible desirable clear energy sources.At present, progressively applying such as fields such as vapour Trucks, power-assist Trucks, motor Trucks, mobile phone, communication, computer, pick up camera, power tool and military equipments with the fuel cell that hydrogen acts as a fuel, its hydrogen source is provided together that is storage, the transportation problem of hydrogen have become the task of top priority.Hydrogen storage material is safer and economical than technology such as present high pressure vessel, liquid hydrogen and methyl alcohol as Hydrogen Energy storage transmission carrier, is considered to hydrogen fuel cell and hydrogen engine one of fuel tank candidate material.So far, mainly be the hydrogen storage alloy that a class at room temperature can reversible hydrogen adsorption and desorption in the hydrogen storage material of practical application, as AB
5Rare earth system and the AB type and the AB of type
2The titanium alloy of type., the weight hydrogen-storage density of this class alloy is lower, only is 1.4～1.6% as the weight hydrogen-storage density of lanthanon hydrogen storage alloy, and the weight hydrogen-storage density of titanium base hydrogen storage alloy is 1.6～2.0%.Another kind of heavy body (higher 2～4 times than rare earth system and titanium alloy) hydrogen storage material is pure magnesium and Magnuminium, and wherein the maximum weight hydrogen-storage density of pure magnesium can reach 7.6%, but pure magnesium needs could inhale hydrogen usually under 320～400 ℃ of high temperature and 6.0MPa hydrogen pressure.In Magnuminium, hydrogen uptake condition demulcent the most is Mg
2The Ni alloy, under 200 ℃ and 1.4MPa can with H-H reaction, but its maximum storage hydrogen quantity only is 3.6%, no more than half of pure magnesium hydrogen-storage amount.Also have a class Magnuminium, they form intermetallic compound by rare earth element and magnesium, and typical composition has LnMg
12(Ln be among La, Ce, the Mm a kind of), Ln
2Mg
17(Ln is La or Ce) and Ce
5Mg
41The hydrogen-storage amount of this class Magnuminium is between pure magnesium and Mg
2Between the Ni, the weight hydrogen-storage density under 325 ℃ and 3.0MPa is 4.0～6.0%.All conventional preparations and the pure magnesium of handling without any modification and Magnuminium all are not inhale hydrogen or hydrogen is few at normal temperatures.
For the suction hydrogen discharging temperature that reduces pure magnesium and Magnuminium and improve its dynamic performance, various improvement technology have been proposed, wherein modal improvement project is an alloying, for example, to Mg
2The Ni alloy has been studied with Cr, Y, Zn, Ti, Mn, Al, Cu, Co, the various units of Fe and has usually partly been substituted Mg
2Ni among the Ni or Mg form ternary or multicomponent alloy, and the result is that hydrogen-storage amount reduces a lot, reduces seldom and inhale hydrogen discharging temperature; Another kind of improvement technology is in alloying, pure magnesium or Magnuminium is prepared into tiny nanocrystalline, provides a kind of mechanical alloying method to prepare ternary Mg as document [1]
1.9Ti
0.1Ni (Mg
2The Ni type) nanometer crystal alloy can and be inhaled hydrogen 3.2% in activation under 200 ℃ the lesser temps in 150 ℃ of next hours; Document [2-4] has proposed pure magnesium-graphite, pure magnesium-palladium blending aromatic organic solvent ball milling respectively and has prepared the nanocrystalline method of Mg, and the best result that these preparation methods obtain is to have 90% pure magnesium to be converted into hydride through 20 hours suction hydrogen process under 180 ℃ and the 6～7KPa hydrogen pressure; The another kind of complex-phase nano crystal alloy that document [5] provides is Mg-50wt%ZrFe
1.4Cr
0.6, this alloy is synthetic by the mechanical alloying method, and its weight hydrogen-storage density under 160～200 ℃ of temperature is 3.4%.But above-mentioned alloying or make the effect that nanocrystalline various improvement technology all fail to obtain to absorb under the room temperature a large amount of hydrogen.In addition, document [6] has been reported a kind of agglomerating multiphase alloy Mg-40wt%FeTi (Mn), this multiphase alloy by the pure magnesium of high temperature modification with normal temperature type FeTi (Mn) sintering, thereafter carry out pre-treatment under 400 ℃ of nitrogen atmosphere, so the multiphase alloy weight hydrogen-storage density at room temperature of preparation can reach 3.5%.Document [7] has reported that the Magnuminium that can inhale hydrogen under a kind of room temperature is MgH
2-5wt%V, this alloy adopt the preparation of mechanical ball milling method, and allow pure Mg suction hydrogen become MgH earlier
2, and then synthetic with pure vanadium ball milling, the hydrogen under its room temperature is weight 2.0wt%, although this alloy can at room temperature be inhaled hydrogen, its hydrogen only be pure magnesium when high temperature saturated hydrogen 26%.Being prepared into non-crystalline state also is to reduce to inhale the hydrogen temperature and improve the effective ways of inhaling hydrogen speed.Document [8] provides a kind of with Mg
2The Ni alloy mixes with 70wt%Ni and carries out ball milling and obtain a kind of amorphous Mg
2The Ni-Ni matrix material finds that its suction hydrogen speed is than as cast condition Mg
2The nanocrystalline M g of Ni alloy and ball milling
2The Ni alloy is much higher, can absorb the hydrogen of 2.4wt% under 30 ℃ and 3.0MPa hydrogen pressure, in this amorphous composite owing to added the Ni that do not inhale hydrogen in a large number, so the weight hydrogen-storage density reduces a lot.
Summary of the invention
The object of the present invention is to provide under a kind of room temperature and can absorb hydrogen storage alloy of a large amount of hydrogen and preparation method thereof.Hydrogen storage alloy of the present invention is a kind of amorphous binary or multielement rare earth-Magnuminium, the high advantage of hydrogen-storage amount that it had both kept the rare-earth and Mg base alloy of former crystalline structure to be had, having overcome former crystal alloy again must be in activation more than 300 ℃ and the shortcoming of inhaling hydrogen, owing at room temperature also can absorb a large amount of hydrogen, inhaling the hydrogen operation can carry out at ambient temperature, needn't be especially to the alloy heat temperature raising, therefore, the fuel tank or the storage hydrogen device that use this alloy to make are simple in structure, easy to operate, the saving energy, cost is low, is particularly suitable for using on hydrogen fuel cell or combustion hydrogen engine.
A kind of non-crystal rare-earht-Mg based hydrogen bearing alloy is characterized in that: the chemical formula of this hydrogen storage alloy is Re
1-xM
xMg
12-yN
y0≤x in the formula≤0.5,0≤y≤3, Re is a kind of among rare-earth metal La, Ce, Pr, Nd, Sm, cerium-rich mischmetal metal M m, the lanthanum rich norium Ml, M is a kind of among metal Ca, Ti, V, the Zr, and N is a kind of among metal Ni, Co, Fe, Mn, the Cu.
A kind of manufacture method of non-crystal rare-earht-Mg based hydrogen bearing alloy, it is characterized in that: predefined rare-earth and Mg base alloying constituent is made crystal alloy by melting, crystal alloy at room temperature is ground into less than 200 powder materials, place the ball mill ball milling to form non-crystal rare-earht-Mg based alloy with the aromatic organic compounds solvent powder again, promptly obtain solid amorphous attitude rare-earth and Mg base hydrogen bearing alloy except that after desolvating; Solvent is selected one or several in tetrahydrofuran (THF), naphthane, naphthalene, toluene, benzene, ethylbenzene, tetrahydrobenzene, hexanaphthene, methylcyclohexane, the En, perylene for use.
Alloy of the present invention is equivalent to CeMg before decrystallized
12(1:12 type) phase structure.Be that a class is inhaled protium to rare earth element Re part alternate M element in the above-mentioned chemical general formula, they are all light than Re, and it is favourable to improving the weight hydrogen-storage density therefore to substitute the back; Be a class transition metal to Mg part alternate N element in the chemical general formula, they substitute that to be decomposed into the reaction of hydrogen atom highly beneficial to improving alloy surface catalysis hydrogen molecule.
The preparation method of non-crystal rare-earht-Mg based alloy of the present invention, it is characterized in that being prepared into crystal alloy by the chemical formula composition of setting by the method for founding earlier, in ball mill, carry out ball milling until changing non-crystalline state into the aromatic organic compounds solvent then.Just a kind of mechanical mill process of mechanical milling process, it is crucial to the non-crystalline state that the rare-earth and Mg base alloy is converted into tiny high-specific surface area; And the existence of aromatic organic compounds solvent also is very important, and at first, the existence of organic compound has protected the alloy particle surface to avoid or few oxidated, thereby has guaranteed the active surface chemical state that alloy is fresh; Secondly, the existence of solution of organic compound has changed transmission ofenergy and the distribution in the process of lapping system, thereby makes alloying pellet can obtain tiny amorphous rather than nanocrystalline in the shorter time; At last, electronic migration has taken place in the alloying element of organic compound and rare-earth and Mg base alloy surface in mechanical milling process, and has therefore formed many new complex catalysis active centre at alloy surface.Alloy of the present invention is a kind of rare-earth and Mg base binary or multicomponent alloy; And selected organic compound solvent be a class can and this class alloy produce and move between electronics, thereby can on these alloy surfaces, form the strong solvent in complex catalysis active centre, solvent is selected one or several in tetrahydrofuran (THF), naphthane, naphthalene, toluene, benzene, ethylbenzene, tetrahydrobenzene, hexanaphthene, methylcyclohexane, the En, perylene for use.If alloy is to select pure magnesium or MgH for use
2+ Ni, then the grinding of carrying out under the organic solvent dipping owing to magnesium can only obtain the nanocrystalline amorphous that is difficult to obtain; If that select for use is Mg
2Ni or Mg+Ni alloy can obtain Mg though then grind the back
2The Ni amorphous, but, therefore can not in the grinding under the organic compound dipping, produce more complex catalysis active centre because of this alloy does not contain rare earth metal and some other useful elements, then can not get a large amount of effects of inhaling hydrogen under the room temperature, and because Mg
2The maximum hydrogen of Ni only is 3.6%, and unit weight hydrogen-storage density itself is just on the low side.Weight hydrogen-storage density under the room temperature of the then decrystallized back of alloy of the present invention high more person of the weight hydrogen-storage density of original crystal alloy when high temperature before decrystallized is also high more; The complex catalysis active centre that employed organic compound solvent can form during its preparation amorphous is many more, then the at room temperature absorbent hydrogen of amorphous of this solvent preparation is many more, the big more then grinding of the specific inductivity of fragrant aromatics organic compound back non-crystaline amorphous metal surface complex catalytic center is also just many more, tetrahydrofuran (THF) for example, naphthane, naphthalene, toluene, benzene, the specific inductivity of ethylbenzene and hexanaphthene is respectively 7.8,2.7,2.5,2.4,2.3,2.3 with 2.1, the action effect of these aromatic organic compounds is tetrahydrofuran (THF)＞naphthane＞naphthalene＞toluene＞benzene＞ethylbenzene＞hexanaphthene in proper order.Non-crystal rare-earht-Mg based hydrogen bearing alloy of the present invention is the hydrogen storage alloy that can absorb a large amount of hydrogen under the class room temperature, and its hydrogen under 25 ℃, 3.0MPa hydrogen pressure reaches 4.0～4.5%, and this value is (AB for the normal temperature type rare earth
5) 2～3 times of hydrogen storage alloy hydrogen, be titanium system (AB and AB
2) 2～3 times of hydrogen storage alloy hydrogen, and general Magnuminium is not inhale hydrogen under the normal temperature condition.
Compared with the prior art, alloy of the present invention has following outstanding advantage: the hydrogen storage alloy of (1) and normal temperature type (can inhale hydrogen under the room temperature) compares, and this hydrogen storage alloy at room temperature hydrogen will exceed 2～3 times; (2) compare with conventional magnesium of making or Magnuminium, hydrogen storage alloy of the present invention can at room temperature be inhaled hydrogen, and the former need inhale hydrogen under 200～400 ℃ high temperature, therefore simple in structure with the fuel tank or the storage hydrogen device of the making of this hydrogen storage alloy, operate also more convenient, the saving energy, cost is low; (3) with previous Mg-graphite, Mg-palladium, the Mg-50wt%ZrFe that releases
1.4Cr
0.6, Mg-40wt%FeTi (Mn) and MgH
2The nanocrystalline comparison of magnesium such as-50wt%V and other element or alloy preparation, the hydrogen of amorphous rare-earth and Mg base alloy of the present invention when room temperature is more, and preparation process is then simpler; (4) and Mg
2The composite amorphous alloy ratio of Ni-70wt%Ni; Amorphous rare-earth and Mg base alloy of the present invention not only room temperature hydrogen exceeds a lot, and does not have material (and the Mg that can not inhale hydrogen in the alloy
2Among the Ni-70wt%Ni, the Ni that does not inhale hydrogen occupied gross weight 70%), fuel tank of making or the storage hydrogen amount of thinking highly of are lighter, volume is littler, efficient is higher.
Embodiment
Embodiment 1:
A kind of non-crystal rare-earht-Mg based hydrogen bearing alloy, its chemical general formula are Re
1-xM
xMg
12-yN
y, make that Re is Ce in the formula, x=0, y=1, N are Ni, then constituting chemical formula is CeMg
11The Ni ternary alloy by the weight proportion of this chemical formula calculating Ce, Mg and Ni, is smelted in the vacuum induction furnace of argon shield is arranged, and the back casting ingot-forming finishes.In the starting material, Ce is the metal Cerium of purity 98% (weight percentage, together following), and Mg is the MAGNESIUM METAL of purity 99%, and Ni is the electrolytic nickel of purity 99.9%.Alloy pig is broken for fine powder in air, powder particle size is not more than 200 orders, with this fine powder ball grinder of packing into, put into Mo Qiu And by 30: 1 ratio of grinding media to material and add chemical pure tetrahydrofuran solvent, till submergence alloy powder and abrading-ball, carry out ball milling then, the ball mill speed of mainshaft is 225 rev/mins, and be 60 minutes each running period, running in wherein preceding 50 minutes, back stall in 10 minutes, preventing that continuous operation from causing the alloy powder temperature too high, behind 15 hours interrupted ball millings, alloy changes tiny amorphous into, material behind the ball milling is vacuumized, promptly obtain non-crystalline state CeMg behind the removal tetrahydrofuran (THF)
11The Ni hydrogen storage alloy.This hydrogen storage alloy can be inhaled hydrogen under room temperature and 3.0MPa hydrogen pressure, the hydrogen actual measurement is 4.2% in 3 hours.
Embodiment 2:
Preferred chemical formula Re
1-xM
xMg
12-yN
yIn, Re is Ce; X=0.2; M is Ca; Y=1; N is Ni, and promptly constituting chemical formula is Ce
0.8Ca
0.2Mg
11The quad alloy of Ni is pressed the weight proportion that chemical formula calculates Ce, Ca, Mg and Ni, smelts in the vacuum induction furnace of argon shield is arranged, and the back casting ingot-forming finishes.Ca is the calcium metal of purity 99% in the starting material, and other material purities are with embodiment 1, and with embodiment 1, alloy changes amorphous into behind 10 hours interrupted ball millings with the technology of organic solvent ball milling and solvent.The non-crystalline state Ce of preparation like this
0.8Ca
0.2Mg
11The Ni hydrogen storage alloy under room temperature and 3.0MPa in 2 hours hydrogen actual measurement be 4.5%.
Document [1]: J.Alloys and Compounds, 1999, Vol.282, pp286-290
Document [2]: J.Alloys and Compounds, 1996, Vol.232, pp218-223
Document [3]: J.Alloys and Compounds, 1997, Vol.253-254, pp34-37
Document [4]: J.Alloys and Compounds, 1999, Vol.293-295, pp564-568
Document [5]: J.Alloys and Compounds, 2000, Vol.297, pp240-243
Document [6]: J.Alloys and Compounds, 1992, Vol.184, pp1-9
Document [7]: J.Alloys and Compounds, 2000, Vol.305, pp239-245
Document [8]: J.Alloys and Compounds.1999.Vol.285.pp246-249
Claims (3)
1, a kind of non-crystal rare-earht-Mg based hydrogen bearing alloy is characterized in that: the chemical formula of this hydrogen storage alloy is Re
1-xM
xMg
12-yN
y, in the formula, 0≤x≤0.5; 0≤y≤3; Re is a kind of among rare-earth metal La, Ce, Pr, Nd, Sm, cerium-rich mischmetal metal M m, the lanthanum rich norium Ml; M is a kind of among metal Ca, Ti, V, the Zr; N is a kind of among metal Ni, Co, Fe, Mn, the Cu.
2, a kind of manufacture method of non-crystal rare-earht-Mg based hydrogen bearing alloy, it is characterized in that: predefined rare-earth and Mg base alloying constituent is made crystal alloy by melting, alloy at room temperature is ground into less than 200 powder materials, place the ball mill ball milling to form amorphous alloy with the aromatic organic compounds solvent powder again, promptly obtain solid amorphous attitude rare-earth and Mg base hydrogen bearing alloy except that after desolvating.
3, in accordance with the method for claim 2, it is characterized in that: solvent is selected one or several in tetrahydrofuran (THF), naphthane, naphthalene, toluene, benzene, ethylbenzene, tetrahydrobenzene, hexanaphthene, methylcyclohexane, the En, perylene for use.
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| CN1320671C (en) * | 2005-08-30 | 2007-06-06 | 包头稀土研究院 | Amorphous rear-earth-magnesium-Nickel series hydrogen storage electrode material and producing method thereof |
| CN101857947A (en) * | 2010-06-07 | 2010-10-13 | 安徽工业大学 | Amorphous magnesium-yttrium-transition metal hydrogen storage material and preparation method thereof |
| CN104846249A (en) * | 2015-05-11 | 2015-08-19 | 北京科技大学 | Rare earth-magnesium metal hydride high-temperature heat storage material for solar heat collection for power generation |
| CN105271113A (en) * | 2015-10-16 | 2016-01-27 | 安徽工业大学 | Composite hydrogen storage material and preparation method thereof |
| CN110512238A (en) * | 2019-09-26 | 2019-11-29 | 辽宁工程技术大学 | The electrochemistry fast preparation method of transition element amorphous alloy before a kind of Ni- |
| CN112921188A (en) * | 2019-12-05 | 2021-06-08 | 本田技研工业株式会社 | Magnesium powder anodes and electrochemical cells comprising such anodes |
| CN113699469A (en) * | 2021-08-27 | 2021-11-26 | 广东省国研科技研究中心有限公司 | High-thermal-stability magnesium-based amorphous micron hydrogen storage filament and preparation method thereof |
| CN114438386A (en) * | 2022-03-15 | 2022-05-06 | 北京氢冉新能源科技有限公司 | Magnesium-based hydrogen storage material doped with single metal element and preparation method thereof |
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2002
- 2002-04-10 CN CNB021113823A patent/CN1177075C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1320671C (en) * | 2005-08-30 | 2007-06-06 | 包头稀土研究院 | Amorphous rear-earth-magnesium-Nickel series hydrogen storage electrode material and producing method thereof |
| CN101857947A (en) * | 2010-06-07 | 2010-10-13 | 安徽工业大学 | Amorphous magnesium-yttrium-transition metal hydrogen storage material and preparation method thereof |
| CN104846249A (en) * | 2015-05-11 | 2015-08-19 | 北京科技大学 | Rare earth-magnesium metal hydride high-temperature heat storage material for solar heat collection for power generation |
| CN105271113A (en) * | 2015-10-16 | 2016-01-27 | 安徽工业大学 | Composite hydrogen storage material and preparation method thereof |
| CN110512238A (en) * | 2019-09-26 | 2019-11-29 | 辽宁工程技术大学 | The electrochemistry fast preparation method of transition element amorphous alloy before a kind of Ni- |
| CN112921188A (en) * | 2019-12-05 | 2021-06-08 | 本田技研工业株式会社 | Magnesium powder anodes and electrochemical cells comprising such anodes |
| CN112921188B (en) * | 2019-12-05 | 2023-10-13 | 本田技研工业株式会社 | Magnesium powder anode and electrochemical cell comprising such anode |
| CN113699469A (en) * | 2021-08-27 | 2021-11-26 | 广东省国研科技研究中心有限公司 | High-thermal-stability magnesium-based amorphous micron hydrogen storage filament and preparation method thereof |
| CN114438386A (en) * | 2022-03-15 | 2022-05-06 | 北京氢冉新能源科技有限公司 | Magnesium-based hydrogen storage material doped with single metal element and preparation method thereof |
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