CN101072889A - Catalyzed hydrogen desorption in mg-based hydrogen storage material and methods for production thereof - Google Patents
Catalyzed hydrogen desorption in mg-based hydrogen storage material and methods for production thereof Download PDFInfo
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- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0026—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof of one single metal or a rare earth metal; Treatment thereof
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- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
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- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
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Abstract
A magnesium-based hydrogen storage material including magnesium or a magnesium-based hydrogen storage alloy and a hydrogen desorption catalyst which is insoluble in said magnesium-based hydrogen storage alloy and is in the form of: 1) discrete dispersed regions of catalytic material in the bulk of said magnesium or magnesium-based hydrogen storage alloy; 2) discrete dispersed regions on the surface of particles of said magnesium or magnesium-based hydrogen storage alloy; 3) a continuous or semi-continuous layer of catalytic material on the surface of said magnesium or magnesium-based hydrogen storage alloy which is in bulk or particulate form; or 4) combinations thereof. Methods of producing the material are also disclosed.
Description
Technical field
The present invention relates generally to hydrogen storage material, more specifically relate to magnesium-base hydrogen storage material, wherein inhale by insoluble material catalytic hydrogenolysis in described magnesium-base hydrogen storage material.Described insoluble catalytic material can be following form: 1) discrete dispersive catalytic material zone in the hydrogen storage material block; 2) the discrete discrete areas on the hydrogen storage material particle surface; 3) at bulk or the lip-deep continuous or semicontinuous catalytic material layer of particulate state hydrogen storage material; Or 4) its combination.
Background technology
Growing energy requirement forces brainstrust to recognize such fact, it is traditional energy, such as coal, oil or Sweet natural gas is not inexhaustible, and perhaps their cost is all increasing always at least, and desirable way is to replace these traditional energies with hydrogen.
Hydrogen can for example replace hydrocarbon to be used as the fuel of oil engine.The oxycarbide, oxynitride and the oxysulfide that have formed when in the case, advantage has been to eliminate owing to the hydrocarbon burning are to atmospheric pollution.Hydrogen also can be used for to hydrogen-air-fuel battery provides fuel, to produce the required electric power of electro-motor.
One of problem that employing hydrogen faces is its storage and transportation.People have proposed many solutions:
Hydrogen under high pressure can be stored in the steel gas cylinder, but this method shortcoming need to be the container (in addition, storage power is low, approximately is 1 weight %) that danger is heavy, be difficult to carry.Hydrogen also can be stored in the low-temperature (low temperature) vessel, but this inevitable with adopt the relevant shortcoming of cryogenic liquid; Such as, for example, container cost is high and need handle with care." evaporation " loss of about 2-5% is arranged in addition, every day.
The another kind of method that stores hydrogen is that it is stored with hydride form, and hydride decomposes to supply with hydrogen between when appropriate then.As described in French Patent No.1529371, and iron-titanium hydride, lanthanum-nickel hydride, vanadium hydride and magnesium hydride have been adopted in this way.
Because the initial hydrogen of finding can store with the fine and close solid metal hydride form of safety, so the researchist is managing to prepare the hydrogen storage material with optimal performance always.Generally speaking, these researchists ideal material character of endeavouring to realize is: 1) high hydrogen storage ability; 2) light material; 3) suitable hydrogen absorption/desorption temperature; 4) suitable absorption/desorption pressures; 5) rapid absorption kinetics; With 6) absorption/desorption cycle life-span is long.Except these material characters, desirable material should be cheaply, make easily.
MgH
2-Mg system since have the highest weight percent (7.65 weight %) theoretical hydrogen storage ability and thereby the unit weight stored material have the highest theoretical energy density (2332Wh/Kg; Reilly﹠amp; Sandrock, Spektrum der Wissenschaft, in April, 1980,53), thus be can be used as in all the known metal hydride of reversible hydrogen storage system and the metal system only.
Although the price that this character and magnesium are lower makes MgH
2-Mg for transportation, for hydrogen-powered vehicle seemingly optimum hydrogen storage system, but its kinetics that people can't be satisfied with has stoped its application up to now.For example known pure magnesium can only hydrogenation under about 400 ℃ violent condition, and can only be extremely lentamente, hydrogenation by halves.The dehydrogenation rate of gained hydride also is unacceptable (Genossar﹠amp for hydrogen storage material; Rudman, Z.f.Phys.Chem., Neue Folge 116,215 (1979) and the document of wherein quoting).
And, filling/putting in the working cycle, the hydrogen storage ability of magnesium hydrogen storage material (magnesium reserve) weakens.This phenomenon can obtain by the progressively poisoning on surface explaining, surface poisoning causes that hydrogen can not be near the magnesium atom that be positioned at hydrogen storage material inside during charging into.
In order to discharge the hydrogen in traditional magnesium or magnesium/nickel hydrogen storage system, require to be higher than 250 ℃ temperature, the lot of energy supply is arranged simultaneously.Discharge the required gentle high-energy requirement of high-temperature water of hydrogen, the Motor vehicles that cause for example having oil engine can not be operated by these alloys separately.This is because energy that tail gas contained, under vantage (full and down), only is enough to satisfy oil engine to 50% of hydrogen requirement by magnesium or magnesium/nickelalloy.Therefore, Sheng Xia hydrogen demand must be met from another kind of hydride alloy.For example, this alloy can be titanium/iron hydride (a typical low temperature hydride hydrogen-storing material), and it can be at the temperature operation that is low to moderate below 0 ℃.The shortcoming of these low temperature hydride alloys is that hydrogen storage ability is low.
The past people have developed hydrogen storage material, and their hydrogen storage ability is higher, but therefrom discharging hydrogen will carry out up to about 250 ℃ temperature.U.S. Patent No. 4160014 has been described has formula Ti
[1-x]Zr
[x]Mn
[2-y-z]Cr
[y]V
[z]Hydrogen storage material, x=0.05-0.4 wherein, y=0-1, and z=0-0.4.In this alloy, can store up to about the hydrogen of 2 weight %.Except described hydrogen storage ability was low, the shortcoming of these alloys was that also the alloy price is high when using vanadium metal.
And U.S. Patent No. 4111689 discloses a kind of hydrogen storage alloy, and it contains the titanium of 31-46 weight %, iron and/or the manganese of the vanadium of 5-33 weight % and 36-53 weight %.Although the hydrogen storage ability of the described alloy of such alloy ratio U.S. Patent No. 4160014 (being hereby incorporated by) is big, their shortcoming is to need at least 250 ℃ temperature in order to discharge hydrogen fully.Up to about 100 ℃ temperature, can discharge about 80% hydrogen richness under the best circumstances.But, usually can only obtain owing to from hydride hydrogen-storing material, discharge the required heat of hydrogen, so need the height under high discharge ability, the especially low temperature to discharge ability in the industry usually in low temperature level.
With other metal or metal alloy, especially contain those metal alloy differences of titanium or lanthanum, magnesium is preferred for storage hydrogen, this is not only that the cost of material is low owing to it, and the most important thing is because its proportion as hydrogen storage material is low.But, generally speaking, because magnesium surface quick oxidation in air forms stable MgO and/or Mg (OH)
2Upper layer is so magnesium more is difficult to realize hydrogenation.
Mg+H
2→MgH
2
These layers have suppressed the decomposition of hydrogen molecule, and to the absorption of the hydrogen atom that generates and hydrogen atom from the diffusion of particle surface to magnesium hydrogen storage material main body.
In recent years, people have carried out big quantity research, by with single external metal such as aluminium (Douglass, Metall.Tran.6a, 2179[1975]), indium (Mintz, Gavra; Hadari, J.Inorg.Nucl.Chem.40,765[1978]) or iron (Welter﹠amp; Rudman, Scripta Metallurgica 16,285[1982]), with various external metals (German Offenlegungsschriften 2846672 and 2846673) or with intermetallic compound such as Mg
2Ni or Mg
2Cu (Wiswall, Top Appl.Phys.29,201[1978] and Genossar﹠amp; Rudman, op.cit) and LaNi
5Magnesium is mixed (Tanguy etc., Mater.Res.Bull.11,1441[1976]) or alloying improves the hydrogenation ability of magnesium.
Although these effort have improved kinetics really to a certain extent, still do not remove some basic deficiencies from resulting system.The preliminary hydrogenation of magnesium of external metal or intermetallic compound of having mixed still requires violent reaction conditions, and only after repeatedly hydrogenation and dehydrogenation cycle, system dynamics just satisfactory and reversible hydrogen content just uprises.In order to improve kinetic property, also must have the external metal of suitable per-cent or valuable intermetallic compound.In addition, the hydrogen storage ability of these systems is generally well below MgH
2Theoretical expected value.
Known, by adding the material that can help to destroy stable magnesium oxide, also can improve the storage hydrogen quality of magnesium and magnesium alloy.For example, this alloy is Mg
2Ni, wherein Ni seems to have formed unsettled oxide compound.In this alloy, the thermodynamics detected result shows, is filling the air surface reaction Mg on the nickel inclusion metallic
2Ni+O
2→ 2MgO+Ni, this reaction pair hydrogen decomposition-absorption reaction plays katalysis.Reference can be A.Seiler etc., the 73,1980,193rd page of Journal ofLess-Common Metals and after.
Hydrogen decomposition-absorption reaction on the magnesium surface is carried out catalytic a kind of possibility also be to form two phase alloys, wherein one is hydride organizer (former) mutually, and another is catalyzer mutually.Therefore, the known magnesium that has adopted electronickelling is as hydrogen storage material, referring to F.G.Eisenberg etc., Journal of Less-Common Metals 74,1980, the 323rd page and after.But, adhere to and be distributed in the process of magnesium surface at nickel, run into problem.
In order under the condition that forms separately equilibrium phase, to obtain catalyzer phase that is extremely fine and close, good adhesion, knownly can adopt magnesium (forming phase) and magnesium copper (Mg as hydride
2Cu) eutectic mixture is used to store hydrogen, referring to J.Genossar etc., Zeitschrift furPhysikalische Chemie Neue Folge 116,1979, the 215th page and after.But, can not satisfy all high requests by this hydrogen storage ability that contains the material unit volume of magnesium granules acquisition, reason is the magnesium copper amount that this eutectic mixture needs.
The scientist in this field has studied various materials, assert that storage hydrogen needs special crystalline structure, referring to for example " Hydrogen Storage in Metal Hydride ", ScientificAmerican, Vol.242, No.2, pp.118-129, in February, 1980.Find that by adopting inhomogeneous material promptly unordered hydrogen storage material can solve many shortcomings of prior art material.For example, the U.S. Patent No. 4265720 of Guenter Winstel, " StorageMaterials for Hydrogen " described the storage hydrogen body of non-crystalline silicon or thin crystal silicon.Described silicon preferably is positioned on the substrate and film suitable catalyst combination.
The open Japanese patent application No.55-167401 of Matsumato etc., " HydrogenStorage Material " discloses two elements or element hydrogen storage material with at least 50 volume % non-crystal structures.First kind of element is selected from Ca, Mg, Ti, Zr, Hf, V, Nb, Ta, Y and lanthanide, and second kind of element is selected from Al, Cr, Fe, Co, Ni, Cu, Mn and Si.Can choose wantonly and have the element that is selected from B, C, P and Ge.According to the instruction of No.55-167401,, need amorphous structure in order to overcome the unfavorable high desorption temperature feature problem of most of crystal system.High desorption temperature (for example, being higher than 150 ℃) has seriously limited the possible purposes of this system.
According to Matsumoto etc., the material desorb at a lower temperature with at least 50% non-crystal structure is to small part hydrogen, and this is because the same with the situation of crystalline material, and the bound energy of each atom is also inhomogeneous but wide distribution range is arranged.
Matsumoto etc. have described the material with at least 50% non-crystal structure.Although Matsumoto etc. do not provide any further instruction of relational term " amorphous " meaning, about 20 or following maximum short range order are being contained in the definition that this term is generally acknowledged on science.
Because lag-effect curve unfairness (non-flat) is inappropriate, part solution so Matsumato etc. adopt the non-crystal structure material in order to obtain better desorption kinetic.The other problem of in the crystal hydrogen storage material, finding, especially in when temperature can be low with hydrogen storage ability, still exist.
But, if make full use of the advantage of the modification of the steady hydrogen storage material of unordered Jie, can obtain better to store up the hydrogen result, that is, have extended cycle life, physical strength is good, absorption/desorption temperature and pressure is low, reversibility and anti-chemical poisoning.In the U.S. Patent No. 4431561 of Stanford R.Ovshinsky etc., in " Hydrogen Storage Materials and Method ofMaking the Same ", the be situated between modification of steady hydrogen storage material of disordered structure has been described.As described in the document, the thermokinetics that the it is characterized by chemical modification unordered hydrogen storage material of steady constitutional features that is situated between can customize to have all required storage hydrogen character of commercial applications on a large scale.The hydrogen storage material of modification can be prepared to have than the bigger hydrogen storage ability of single-phase crystal host material.In these are material modified, can customize the bonding strength between hydrogen and the storage site, providing widely, thereby obtain required absorption and desorption characteristic in conjunction with possibility.Thermodynamics with chemical modification unordered hydrogen storage material of steady structure that is situated between, the density in its catalytic activity site obviously increase improving storage hydrogen kinetics, and anti-toxic increases.
Be combined in the synergistic combination effect of the selected properties-correcting agent in the selected host matrix, the structure and the chemical modification that make stable certain mass of chemistry, physics and electronic structure and degree are provided, and the structure that is suitable for Chu Qing.
The skeleton that is used for the modification hydrogen storage material is the lightweight host matrix.Host matrix is undertaken structurally-modified by the modifying element of choosing, so that the disordered material with topochemistry environment to be provided, described topochemistry environment has been realized required storage hydrogen character.
Another advantage of the host matrix of descriptions such as Ovshinsky is that it can carry out modification with the modifying element of basic continuous variable percentage range.This ability makes host matrix to handle the hydrogen storage material that has the character that is suitable for special applications with customization or manufacturing by properties-correcting agent.These are different with the single-phase host's crystalline material of polycomponent, and generally speaking, latter's available stoichiometric ratio scope is extremely limited.So, can not and structurally-modifiedly carry out successive range control to the chemistry of the thermodynamics and kinetics of this crystalline material.
Another advantage of these unordered hydrogen storage materials is that their anti-toxic are stronger.As previously mentioned, the catalytic activity site density of these materials is bigger.Therefore, can sacrifice a certain amount of described site, but still have a large amount of avtive spots of not poisoning to remain to continue the storage hydrogen kinetics that provides required owing to the influence of poisonous species.
Another advantage of these disordered materials is that they can be designed to have the mechanically flexible bigger than single phase crystalline material.Therefore, these disordered materials can bear bigger distortion in expansion and contraction process, make that mechanical stability is bigger in the absorption and desorption circulation.
A shortcoming of these disordered materials is over some Mg base alloys and is difficult to preparation.Especially those do not form the material of solution in melt.In addition, the most promising material (that is mg-based material) extremely is difficult to make block form.That is to say, do not have the block technology of preparing although the thin film sputtering technology can prepare a small amount of these disordered alloys.
Then, at twentieth century the mid-80, two study group have developed the mechanical alloying technology and have prepared the unordered magnesium alloy hydrogen storage material of block.Find mechanical alloying be convenient to have the element of remarkable different vapour pressure and fusing point (such as, Mg and Fe or Ti etc.) realize alloying, especially when not having stable intermetallic phase.Find that routine techniques is not suitable for this purpose such as induction fusing.
First group of these two study group is French scientist troop, and they have studied the mechanical alloying and the storage hydrogen character thereof of Mg-Ni system material." PhaseCharacterization and Hydrogen Diffusion Study in the Mg-Ni-HSystem " referring to Senegas etc., Journal of the Less-Common Metals, Vol.129,1987, pp.317-326 (the binary mechanical alloy of Mg and Ni, Ni binding capacity are 0,10,25 and 55 weight %); With " Hydriding and Dehydriding Characteristicsof Mechanically Alloyed Mixtures Mg-xwt.%Ni (x=5; 10; 25and 55) " such as Song, Journal of the Less-Common Metals, Vol.131,1987, pp.71-79 (the binary mechanical alloy of Mg and Ni, Ni binding capacity are 5,10,25 and 55 weight %).
Second group of these two study group is Russian scientist troop, and they have studied the storage hydrogen character of the binary mechanical alloy of magnesium and other metal.Referring to " MechanicalAlloys of Ma gnesium-New Materials For Hydrogen Energy " such as Ivanov, Doklady Physical Chemistry (English edition), Vol.286:1-3,1986, pp.55-57, (the binary mechanical alloy of Mg and Ni, Ce, Nb, Ti, Fe, Co, Si and C); And Ivanov etc. " Magnesium Mechanical Alloys for HydrogenStorage ", Journal of the Less-Common Metals, vol.131,1987, pp.25-29 (the binary mechanical alloy of Mg and Ni, Fe, Co, Nb and Ti); With " Hydriding Properties of Mechanical Alloys of Mg-Ni " such as Stepanov, Journal of the Less-Common Metals, vol.131,1987, pp.89-97 (the binary mechanical alloy of Mg-Ni system).See also the cooperation work of France and Russian study group in addition, Konstanchuk etc. " The Hydriding Properties of aMechanical Alloy with Composition Mg-25%Fe ", Journal of theLess-Common Metals, vol.131,1987, pp.181-189 (the binary mechanical alloy of Mg and 25 weight %Fe).
Afterwards, early stage in the twentieth century later stage eighties and the nineties, the storage hydrogen character of the mechanical alloy of magnesium and metal oxide had been studied by Bulgarian scientist group (cooperating with described Russian scientist group sometimes).Referring to Khrussanova etc., " Hydriding Kineticsof Mixtures Containing Some 3d-Transition Metal Oxides andMagnesium ", Zeitschriftfur Physikalische Chemie Neue Folge, Munchen, vol.164,1989, pp.1261-1266 (compares Mg and TiO
2, V
2O
5And Cr
2O
3Binary mixture and mechanical alloy); With " Surface Compositionof Mg-TiO2 Mixtures for Hydrogen Storage; Prepared by DifferentMethods " such as Peshev, Materials Research Bulletin, vol.24,1989, pp.207-212 (relatively conventional mixture and the mechanical alloy of Mg and TiO2).See also " On the Hydriding of a Mechanically Alloyed Mg (90%)-V205 (10%) Mixture " such as Khrussanova equally, International Journal ofHydrogen Energy, vol.15, No.11,1990, pp.799-805 (has studied Mg and V
2O
5The storage hydrogen character of binary mechanical alloy); With Khrussanova etc., " Hydridingof Mechanically Alloyed Mixtures of Magnesium With MnO
2, Fe
2O
3And NiO ", Materials Research Bulletin, vol.26,1991, pp.561-567 (has studied Mg and MnO
2, Fe
2O
3Storage hydrogen character with the binary mechanical alloy of NiO).At last, see also " The Effect of the d-ElectronConcentration on the Absorption Capacity of Some Systems forHydrogen Storage " such as Khrussanova, Materials Research Bulletin, vol.26,1991, pp.1291-1298 (studied the influence of d electron density to material storage hydrogen character, described material comprises the mechanical alloy of Mg and 3-d metal oxide); With " A MossbauerStudy of a Hydrided Mechanically Alloyed Mixture of Magnesiumand Iron (III) Oxide " such as Mitov, Materials Research Bulletin, vol.27,1992, pp.905-910 (has studied Mg and Fe
2O
3The storage hydrogen character of binary mechanical alloy).
Recently, the storage hydrogen character of some mechanical alloy of Mg and other metal has been studied by Chinese science man group.Referring to Yang etc., " The Thermal Stability of AmorphousHydride Mg50Ni50H54 and Mg30Ni70H45 ", Zeitschrift furPhysikalische Chemie, Munchen, vol.183,1994, pp.141-147 (has studied mechanical alloy Mg
50Ni
50And Mg
30Ni
70Storage hydrogen character); With " Electrochemical Behavior of Some Mechanically AlloyedMg-Ni-based Amorphous Hydrogen Storage Alloys " such as Lei, Zeitschriftfur Physikalische Chemie, Munchen, vol.183,1994, pp.379-384 (having studied electrochemistry [that is Ni-MH the battery ,] character of some mechanical alloy of Mg-Ni and Co, Si, Al and Co-Si).
Described short distance or local order in the U.S. Patent No. 4520039 " Compositionally VariedMaterials and Method for Synthesizing the Materials " of Ovshinsky, this patent content is hereby incorporated by.This patent disclosure disordered material do not require any periodic local order, and how under this precision increases and can the local structure control of qualitative generation new phenomenon, will similar or dissimilar atom or atomic group carry out space and directed placement.In addition, this patent has been discussed used atom and need not to be limited in " d band " or " f band " atom, but can be any following atom: wherein, with the controlled aspect of local environmental interaction and/or Orbital Overlap physically, on the electronics or chemically have a critical role, thereby influence the physical properties of material, and thereby influence material function.The element of these materials is because the multidirectional of d track provides various in conjunction with possibility.The multidirectional of D track (" porcupine effect ") sharply increases density, and thereby active Chu Qing site is sharply increased.These technology provide the method for synthesizing at the simultaneously unordered novel material of a plurality of different aspects.
Ovshinsky proposed in the past, can obviously increase the surface site number by preparation amorphous film (wherein its main body and required surperficial similar than pure material).Ovshinsky also adopts multiple element to provide other bonding and local environment orderly, thereby makes material obtain required electrochemical properties.As Ovshinsky at Principles and Applications ofAmorphicity, Structural Change, and Optical InformationEncoding, described in the 42 Journal De Physique at C4-1096 (in October, 1981):
Non-crystalline state (amorphicity) is common name, is meant the X-ray diffraction sign that lacks long-range periodicity, is the insufficient description to material.In order to understand amorphous material, consider several important parameters: the bond number that chemical bonding type, local order form, promptly its ligancy and whole local environment (chemistry with how much) are to the influence of the structure of final variation.Non-crystalline state is not pile up to be determined by the atomic disorder of being used as hard sphere, neither be only by the represented non-crystalline solids of host of unordered embedding atom wherein.Amorphous material should be regarded as and comprise interactional matrix, and the electronic structure of this matrix is formed by free ability (free energy force), and amorphous material can specifically be limited by the chemical property and the ligancy of composed atom.Adopt multiple road element and various technology of preparing, normal relaxation that can the opposing reaction equilibrium conditions, and, because amorphous 3 D auto degree makes brand-new amorphous material-chemical modification material ...
In case understood non-crystalline state is to introduce the method for surface site in film, then can form " unordered ", and described unordered whole effects of having considered are such as the distance between porosity, topology, crystallite, site character and the site.Therefore, Ovshinsky and he begin to make up " unordered " material that required irregularity is customized in the group of ECD, rather than searching can produce the changes in material of the Ordered Materials with maximum sporadic surface bonds and surface imperfection.Referring to U.S. Patent No. 4623597, its open text is hereby incorporated by.
Term used herein " unordered " is meant the aggregatio mentium of used this term in the electrochemical electrode material and the document, such as described below:
Disordered semiconductor can exist with multiple structural state.This textural factor has constituted new variables, adopts this new variables, the physical properties of then described [material] ... can be controlled.And, structural disorder brought preparation to be in to be situated between steady state, considerably beyond the possibility of thermodynamic(al)equilibrium ultimate novel composition and mixture.Therefore, we are with following feature as further differentiation.In many unordered [materials], may control the short range order parameter, and thereby realize the rapid variation of these material physical properties comprising the new ligancy that forces element ...
S.R.Ovshinsky, The Shape of Disorder, 32 Journal ofNon-Crystalline Solids, 22,1979 (having added the emphasis diacritics).
Ovshinsky is at The Chemical Basis of Amorphicity:Structureand Function, 26:8-9 Rev.Roum.Phys, and 893-903 (1981) has further explained " short range order " of these disordered materials:
Short range order does not obtain preserving ... in fact, when crystal symmetry is destroyed, just can not keep identical short range order.Reason is the field of force control of short range order by electronic orbit, so must be different substantially at corresponding crystalline state and the environment in the non-crystalline solids.In other words, what determine material electrical property, chemical property and physical properties is the interaction of topochemistry key and its surrounding environment, and these are absolutely not with identical in crystalline material in amorphous material ... can be in amorphous material and can not be present in track relation in the three-dimensional space in crystalline material, be the basis of new geometrical shape, wherein many geometrical shapies are anti-crystalline in itself.Key distortion and knocking out may be to occur amorphous suitable reason in the single component material.But in order to fully understand non-crystalline state, it must be understood that inherent three-dimensional relationship in non-crystalline state, because these three-dimensional relationship have produced and the inconsistent inner topology of the translational symmetry of crystal lattice just .... this fact importantly in non-crystalline state, promptly can prepare infinite many materials, even can prepare the similar substantially material of those chemical constitutions without any crystalline state counterpart (crystalline counterpart).These atoms in space and energy relationship can non-crystalline state can be fully different with crystalline form, even their chemical element can be identical ...
Based on these principles of above-mentioned disordered material, prepared extremely effectively electrochemical hydrogen storage negative electrode material of three races.The back is called these negative electrode material families separately and together " two-way (Ovonic) ".Gang is La-Ni
5The type negative electrode material, it carries out great modification such as Ce, Pr and Nd and other metal such as Mn, Al and Co and becomes unordered multi-component alloys, i.e. " two-way " by adding rare earth element recently.Second family is a Ti-Ni type negative electrode material, it is introduced and exploitation by transferee of the present invention, and carry out great modification such as Zr and V and other metal-modified element such as Mn, Cr, Al, Fe etc. and become unordered multi-component alloys, i.e. " two-way " by adding transition element.Three races is U.S. Patent No. 5506069,5616432 and 5554456 described unordered polycomponent MgNi type negative electrode materials (it openly is hereby incorporated by).
The principle that ' 597 patent is described based on Ovshinsky's is being authorized Sapru, and the U.S. Patent No. 4551400 of Fetcenko etc. (" ' 400 patents ") two-way Ti-V-Zr-Ni type active material is disclosed, this patent is hereby incorporated by.Described second family ovonic material reversibly forms hydride to store hydrogen.The all material that adopts in the patent of ' 400 has adopted the Ti-V-Ni composition, wherein has Ti, V and Ni at least and is selected from least a or multiple of Cr, Zr and Al.The normally heterogeneous polycrystalline material of the material of ' 400 patent, it can be including but not limited to having C
14And C
15One phase or heterogeneous Ti-V-Zr-Ni material of crystalline structure.In commonly assigned U.S. Patent No. 4728586 (" ' 586 patents "), Enhanced ChargeRetention Electrochemical Hydrogen Storage Alloys and anEnhanced Charge Retention Electrochemical Cell, in other two-way Ti-V-Zr-Ni alloy has been described, its disclosure is hereby incorporated by.
The figuratrix roughness at electrolytic etching of metal matter interface comes from the unordered essence of material, as described in the commonly assigned U.S. Patent No. 4716088 of Reichman, Venkatesan, Fetcenko, Jeffries, Stahl and Bennet, this patent is hereby incorporated by.Because all components, with and many alloys with mutually, in whole metal, exist, so the cracks that they also form in surface and metal/electrolyte interface exists.Therefore, the figuratrix roughness has been described the crystal physics and the interaction of chemical property in alkaline environment mutually of host metal and alloy and alloy.Microcosmic chemistry, physics and the crystallographic parameter of each phase in the alloy material storing hydrogen, very important on definite its macroscopical electrochemical properties.
Except the physical essence of its uneven surface, have been found that V-Ti-Zr-Ni type alloy often reaches stable state surface condition and particle size.The concentration that this stable state surface condition is characterised in that metallic nickel is higher.These observationss and remove titanium oxide and Zirconium oxide from the surface with higher rate by precipitation and much lower nickel dissolution rate consistent.The nickel concentration beguine on final surface is formed desired height according to the main body of negative hydrogen-storage electrode.The nickel of metallic state has electroconductibility and catalytic, and gives the surface with these character.Catalytic and electroconductibility height when therefore, the greater concn insulation oxide is contained on this surface of surface ratio of negative hydrogen-storage electrode.
Negative electrode surface has conduction and catalyst component---metallic nickel, and electrochemical charge and exoelectrical reaction step are being carried out catalysis and promoted in the quick reorganization of gas and the metal hydride alloy interaction.
At last, in U.S. Patent No. 5616432 (" ' 432 patents "), the contriver of Ovonic BatteryCompany has prepared the Mg-Ni-Co-Mn alloy similar with the base alloy of composite hydrogen storage material of the present invention.The hydrogen storage ability of these alloys is limited in about 2.7 weight %, does not have the hydrogen desorb from this alloy that stores in the time of 30 ℃.The PCT curve (Reference numeral △) of ' 432 patent thin film alloys that Fig. 1 has drawn and the PCT curve (Reference numeral ◆) of composite hydrogen storage material of the present invention.Can find that composite for hydrogen storage of the present invention absorbs the hydrogen more than 4 weight %, hydrogen can be 30 ℃ of desorbs even more noteworthy.
The present invention adopts insoluble catalytic material to utilize katalysis to promote hydrogen absorption/desorb in purer Mg material, and by adding the desorption temperature of some grain growth inhibitors reduction high capacity Mg sills.
Summary of the invention
The invention provides magnesium-base hydrogen storage material, comprise magnesium or Mg base hydrogen bearing alloy; With desorption catalyzer insoluble in described Mg base hydrogen bearing alloy and that have following form: 1) the discrete dispersive catalytic material district in described magnesium or Mg base hydrogen bearing alloy; 2) in the discrete dispersive zone of described magnesium or Mg base hydrogen bearing alloy particle surface soil; 3) continuous or semicontinuous catalytic material layer on the described magnesium of block form or particle form or Mg base hydrogen bearing alloy surface; Or 4) its combination.Preferably, described Mg base hydrogen bearing alloy comprises at least 80 atom % magnesium and can comprise aluminium.Preferably, the desorption catalyzer comprises iron, and may further include one or more elements that are selected from B, Cu, Pd, V, Ni, C, Mn, Zr, Rb, Nb, Ti, U and Sc.
The present invention further comprises the method for preparing magnesium-base hydrogen storage material.A kind of described method comprises a) mixes the powder of described magnesium or Mg base hydrogen bearing alloy and described desorption catalyst fines; B) mixed powder is pressed into base substrate; And c) the temperature sintering between 450 ℃-600 ℃/described base substrate of annealing.Preferred sintering/annealing was carried out 10 hours at least.
Another kind of described method comprises a) to prepare the powder of described magnesium or Mg base hydrogen bearing alloy and the melt of described desorption catalyst fines in protective atmosphere; B) stir described melt, with the insoluble powder suspension of guaranteeing the desorption catalyzer in molten magnesium or Mg base hydrogen bearing alloy; And c) melt of the quick described stirring of Quench makes that the insoluble powder of suspension of desorption catalyzer is well distributed in solidified magnesium or Mg base hydrogen bearing alloy.
Another kind method comprises: a) with the powder mixes of the powder and the described desorption catalyzer of described magnesium or Mg base hydrogen bearing alloy; And b) in masher, makes this mixture mechanical alloying, make the powder particle of described desorption catalyzer be embedded in the surface of the powder particle of described at least magnesium or Mg base hydrogen bearing alloy.Preferably in the ma process of described mixture, adopt heptane and carbon dust as grinding aid.
Another kind method comprises: bulk or particulate state magnesium or Mg base hydrogen bearing alloy a) are provided; And b) applies or do not have electropaining by vapour deposition, electrolysis and cover deposition successive or semi-continuous catalytic material layer on described bulk or particulate state magnesium or Mg base hydrogen bearing alloy surface.Preferred described coating is by the described catalytic material preparation of evaporation, and it is thick to be about 100 .
Catalyzer can distribute in many ways by the combination of above-mentioned technology.Bulk or particulate state magnesium or Mg base hydrogen bearing alloy can be by following preparations: the melt that a) forms described magnesium or Mg base hydrogen bearing alloy; And b) makes described magnesium or the quick Quench of Mg base hydrogen bearing alloy by the quick Quench method of integral body.The whole Quench method fast of available comprises melt-spinning, centrifugal atomizing, gas atomization or water atomization.
Description of drawings
Fig. 1 is the back scattering mode scanning electron photomicrograph (SEM) of hydrogen storage material of the present invention, and this material prepared in the temperature sintering that is higher than 500 ℃ by the compacting pure metal powder and under vacuum in 22 hours;
Fig. 2 is the X ray diffracting spectrum of the material of Fig. 1;
Fig. 3 is pressure-concentration-isothermal (PCT) curve of the material of Fig. 1 240 ℃ of measurements;
Fig. 4 is hydrogen percent absorption and the time relation curve (that is, uptake rate) of the material of Fig. 1 in differing temps;
Fig. 5 is that the material of Fig. 1 is at 240 ℃ desorption per-cent and time relation curve (that is desorption rate);
Fig. 6 has the composition identical with Fig. 1 but respectively at the PCT curve of 570 ℃ and 600 ℃ sintering/annealed samples;
Fig. 7 is the SEM back scattering Photomicrograph according to another material of the present invention, and the material of this material and Fig. 1 has same composition but passes through prepared by mechanical alloy;
Fig. 8 is the XRD figure spectrum of the material of Fig. 7;
Fig. 9 is that the material of Fig. 7 is at the PCT of 240 ℃ of measurements curve;
Figure 10 is the PCT absorption curve of the material of Fig. 7 240 ℃, 210 ℃, 180 ℃ and 150 ℃;
Figure 11 is the section SEM back scattering Photomicrograph of melt-spinning Mg-Al alloy band extremely uniformly that is used to prepare material of the present invention;
Figure 12 is a hydrogen storage material according to the present invention at 150 ℃ PCT curve, and this material adopts the material preparation of Figure 11, flattens and coat in both sides the iron of 100 through mechanical alloying, on expansible nickel substrate;
Figure 13 has compared Fig. 1,7 and 12 material maximum reversible hydrogen storage ability in each temperature;
The section SEM Photomicrograph of Figure 14 ingot casting, described ingot casting by the required metal element powder of the composition that will prepare Fig. 1 material carry out induction fusing and casting and simultaneously this melt of continuously stirring so that insoluble material suspends prepares;
Figure 15 is the microtexture synoptic diagram by the hydrogen storag powder powder material of various working method preparations of the present invention.
Embodiment
The present invention finds extremely low iron and/or other element of solubleness in Mg or Mg base alloy, has suppressed the grain growing of Mg or Mg base crystallite in this alloy, and catalysis is carried out in the desorb from described Mg material to hydrogen.Therefore, the invention provides magnesium-base hydrogen storage material, wherein desorption is by largely insoluble iron in described magnesium-base hydrogen storage material and/or other element catalysis.Insoluble catalytic material can be following form: 1) the discrete dispersive catalytic material district in described hydrogen storage material block; 2) the discrete dispersive zone on described hydrogen storage material particle surface; 3) at bulk or the lip-deep continuous or semicontinuous catalytic material layer of particulate state hydrogen storage material; Or 4) its combination.Catalytic material can add in alloying process by express Quench method; Perhaps add by the mechanical alloying method.Catalytic material also can be applied to the Magnuminium surface such as hot evaporation, magnetic sputter or plating or electroless process by method.
In Mg, almost there is not the element of solid solubility can be used as crystal growth inhibitor/desorb catalyzer.Concrete candidate's element comprises Fe (solubleness is 0.00043 atom %), Rb (solubleness is less than 0.05 atom %), Nb, Ti, V and u.In addition, in magnesium, have partial solid solubility element can as and the part of the intermetallic compound of above-mentioned element, suppress material to form the crystal boundary microcrystalline growth.Candidate's element comprises Mn (solubleness in Mg is 0.99 atom %) and Zr (solubleness in Mg is 1.042 atom %).
In agate mortar-pestle, mix the starting material of forming by pure metal powder magnesium (99.8%, 325 order), aluminium (99.5%, 325 order), iron (99.9+%, 10 microns) and other trace ingredients.Prepared 10 kinds of different compositions, its weight percent is formed as shown in table 1.Adopting the quenching punching block that the blended powder is pressed into diameter is that 1cm, length are the spherolite of 1cm.The spherolite of compacting is placed silica tube, under vacuum in the temperature sintering 22 hours that is higher than 500 ℃.
Table I, chemical constitution (all numerals are weight percents)
| Alloy Number | Mg | Al | Fe | B | Cu | Pd | V | Ni | C | Sc |
| MM-1 | 88.8 | 2.7 | 8.5 | - | - | - | - | - | - | - |
| MM-2 | 87 | 3 | 9 | 1 | - | - | - | - | - | - |
| MM-3 | 86 | 3 | 9 | 2 | - | - | - | - | - | - |
| MM-4 | 86 | 3 | 9 | - | 2 | - | - | - | - | - |
| MM-5 | 87 | 3 | 6 | - | 4 | - | - | - | - | - |
| MM-6 | 87 | 3 | 8 | - | - | 2 | - | - | - | - |
| MM-7 | 87 | 3 | 8 | - | - | - | 2 | - | - | - |
| MM-8 | 87 | - | 9 | - | - | - | - | 4 | - | - |
| MM-9 | 87 | - | 9 | - | - | - | - | - | 4 | - |
| MM-10 | 87 | 3 | 7 | - | - | - | - | - | - | 3 |
Fig. 1 is the back scattering mode scanning electron photomicrograph (SEM) at 500 ℃ of sintering/annealed MM-1 sample.This SEM shows phase segregation and the Al that is embedded with Fe in main Mg matrix
5Fe
2Intermetallic compound.Fe is big approximate number micron with rich Fe diameter mutually, near about 10-20 micron.Fig. 2 is the X ray diffracting spectrum of the sample that writes down on Rigaku Mini Flex.Clear find coexisting in mutually Fe and FeAl at main Mg.
Fig. 3 is pressure-concentration-thermoisopleth (PCT) curve of same material 240 ℃ of measurements.Can find to have very flat plateau pressure in about 1800 holders.Whole absorption/desorb is a reversible, and maximum absorption/desorption ability is 5 weight % hydrogen.Fig. 4 shows hydrogen percent absorption and the time relation curve (that is, uptake rate) of MM-1 alloy material in differing temps.As shown in Figure 4, along with temperature increases, absorption dynamics increases.Can find equally, if absorption temperature is too high, maximum storage ability drop (referring to 270 ℃ example).Therefore, seem to find the optimal absorption temperature to be based on balance between kinetics and the storage power.For the MM-1 material, we find that the optimal absorption temperature is about 240 ℃.When the maximum hydrogen supply pressure was 120-150PSI, 90% hydrogen was absorbed with interior at 2 hours.When the hydrogen transmission pressure was higher, the absorption process time further shortened.Fig. 5 has drawn MM-1 at 240 ℃ desorption per-cent and time relation curve (that is desorption rate).In this temperature, 90% hydrogen is discharging within an hour.
Method change sintering/annealing temperature by embodiment 1 has prepared another MM-1 material.Fig. 6 shows respectively the PCT curve at 570 ℃ and 600 ℃ sintering/annealed samples.Although the PCT at the material of PCT of 570 ℃ of sintering/annealed material (500 ℃ of sintering/annealing) and embodiment 1 does not almost have deviation, provide at the prolongation platform at high pressure place slightly at 600 ℃ of sintering/annealed material.
Mechanical alloying (MA) powder that has prepared MM-1 by the mixture of pure element magnesium (99.8%, 325 order), aluminium (99.5%, 325 order) and iron (99.9+%, 10 microns).In the masher that Cr-steel abrading-ball is housed, grind.Ma process carries out under argon atmospher, adds 1% graphite and heptane in case material lumps on the masher wall.Usually the ball milling time is 2 hours.Fig. 7 is the SEM back scattering Photomicrograph of this sample.This figure shows serious phase segregation in material.Fe and Al powder have been filled in 1 (the bright contrast district on the photo), zone, and zone 2 (center is than dark areas) all are magnesium.Fig. 8 is the XRD figure spectrum of sample, shows that this technology does not form product between any amorphous metal.The MA-MM-1 powder is forced on the expansible nickel metal substrate, coats the iron of 100 then in both sides as surface catalyst.
Fig. 9 is that MA-MM-1 is at the PCT of 240 ℃ of measurements curve.Because Mg-stores mutually and the distance variable between the Fe-catalysis mutually, thus pressure platform than the height of agglomerating MM-1, this pressure platform demonstrates the dynamics range of variation.Maximum hydrogen storage ability rises to 5.7% from 5.0%, and hydrogen is 240 ℃ of complete desorbs.Figure 10 is the MA-MM1-1 sample at the PCT absorption curve of 240 ℃, 210 ℃, 180 ℃ and 150 ℃.Plateau pressure increases and increases along with temperature.Consider to expect this phenomenon from thermal equilibrium.But maximum hydrogen storage ability descends and descends along with temperature.This feature and the thermal balance model of getting along well adapt.We believe that this abnormal phenomena is owing to the influence of temperature to absorption dynamics.Also promptly, this PCT analyzes within concrete time limitation and carries out the complete hydrogen storage ability in the time of therefore may having underestimated low temperature.If have the longer time to can be used for reaching balance, when these low temperature, may obtain the maximum capacity higher so than observed value.
To have the starting material that MM-1 design forms and place air-operated induction furnace, and adopt solvent (flux) with surface and isolated from atmosphere and prevent in addition from the excessive magnesium evaporation of metal liquid.To the excessive argon gas of crucible supply, as isolating coverture with the fusion proof metal oxidation.In crucible, after all the components fusion, melt is tilted to pour in the mould, slowly cool to room temperature.Adopt the composition of inductive couple plasma (ICP) analyzing and testing gained ingot casting, do not find the iron of trace.From then on the comparative example can find, conventional induction fusing technology can not be in conjunction with iron in the Mg block.
Above-mentioned Mg-Al ingot casting is placed rising pouring type melt spinning machine.After more than temperature is raised to fusing point, liquid is injected on the water-cooled copper runner, rotation forms long band.Figure 11 is the SEM back scattering Photomicrograph of this band section, demonstrates Mg-AL alloy very uniformly.Then, described band is cut into pieces, put into masher and carry out handling with embodiment 3 described identical MA.Then, the powder that grinds is pressed onto on the substrate of Ni expanding metal, and all coats the Fe of 100 on the two sides.
MS+MA-MM-1 demonstrates extraordinary desorption kinetics at a lower temperature.Figure 12 shows this sample at the PCT of 150 ℃ of measurements curve.Observed absorption/desorption pressures hysteresis phenomenon is because the measurement temperature is low.Yet, allow the people extremely rouse oneself at the desorb platform of 250 holders place.Figure 13 compares the maximum reversible hydrogen storage ability of three kinds of different process (that is, sintering, only MA, MS+MA) in differing temps.MS+MA technology has obtained minimum desorb starting temperature (90 ℃), but also because the uneven distribution of Fe phase thereby obtained minimum maximum reversible capacity.Only the sample of MA processing demonstrates maximum desorption temperature initial value (150 ℃), but has maximum reversible hydrogen storage ability.
To have the starting material that the MM-1 nominal forms and place air-operated induction furnace, and adopt solvent (flux) with melt surface and isolated from atmosphere and prevent in addition from the excessive magnesium evaporation of metal liquid.To the excessive argon gas of crucible supply, as isolating coverture with the fusion proof metal oxidation.Manually stirring molten alloy makes immiscible FeAl evenly float on a liquid mutually with Fe.The ladle of this liquid by argon shield tilted to pour in the water-cooled Quench mould, thereby Fe and FeAl are combined in the end article.Figure 14 is the section SEM Photomicrograph of gained ingot casting, demonstrates and be uniform-distribution with FeAl and Fe two second phases in the Mg host matrix.The size of Fe inclusion is about 1 micron.Icp analysis confirms to exist Fe and Al in ingot casting.Other whole Quench method fast such as melt-spinning, centrifugal atomizing, gas atomization, water atomization, is aided with the suitable stirring in liquid, such as secondary stirring coil, rare gas element bubbling, crucible rotating etc., can obtain similar results.Figure 15 is the microtexture synoptic diagram by the hydrogen storag powder powder material of various working method preparations of the present invention.All methods can both realize reversible hydrogen storage under the temperature more much lower than prior art.
The accompanying drawing of this specification sheets, discussion, description and embodiment only are illustrating of specific embodiments of the present invention, and do not mean that the restriction to its enforcement.Following claim comprises all Equivalents, defines scope of the present invention.
Claims (22)
1, magnesium-base hydrogen storage material comprises:
Magnesium or Mg base hydrogen bearing alloy; With
The desorption catalyzer,
Wherein said desorption catalyzer is insoluble to described Mg base hydrogen bearing alloy and has following form:
1) the discrete dispersive catalytic material district in described magnesium or Mg base hydrogen bearing alloy block;
2) the discrete dispersive zone on described magnesium or Mg base hydrogen bearing alloy particle surface;
3) at the described magnesium or the lip-deep continuous or semicontinuous catalytic material layer of Mg base hydrogen bearing alloy of block form or particle form; Or
4) its combination.
2, the magnesium-base hydrogen storage material of claim 1, wherein said Mg base hydrogen bearing alloy comprises the magnesium of at least 80 atom %.
3, the magnesium-base hydrogen storage material of claim 2, wherein said Mg base hydrogen bearing alloy also comprises aluminium.
4, the magnesium-base hydrogen storage material of claim 1, wherein said desorption catalyzer comprises iron.
5, the magnesium-base hydrogen storage material of claim 4, wherein said desorption catalyzer also comprises one or more elements that are selected from B, Cu, Pd, V, Ni, C, Mn, Zr, Rb, Nb, Ti, U and Sc.
6, the magnesium-base hydrogen storage material of claim 1, wherein said desorption catalyzer comprise the discrete dispersive catalytic material district in described magnesium or Mg base hydrogen bearing alloy block.
7, the magnesium-base hydrogen storage material of claim 6, wherein said magnesium-base hydrogen storage material is formed by the following step:
A) powder and the described desorption catalyst fines with described magnesium or Mg base hydrogen bearing alloy mixes;
B) mixed powder is pressed into base substrate; With
C) the temperature sintering between 450 ℃-600 ℃/described base substrate of annealing.
8, the magnesium-base hydrogen storage material of claim 7, wherein said sintering/annealing was carried out 10 hours at least.
9, the magnesium-base hydrogen storage material of claim 6, wherein said magnesium-base hydrogen storage material is formed by the following step:
A) in protective atmosphere, prepare the powder of described magnesium or Mg base hydrogen bearing alloy and the melt of described desorption catalyst fines;
B) stir described melt, with the insoluble powder suspension of guaranteeing described desorption catalyzer in molten magnesium or Mg base hydrogen bearing alloy;
C) melt of the quick described stirring of Quench makes that the insoluble powder of suspension of described desorption catalyzer is well distributed in solidified magnesium or Mg base hydrogen bearing alloy.
10, the magnesium-base hydrogen storage material of claim 1, wherein said desorption catalyzer comprises the discrete discrete areas on described magnesium or Mg base hydrogen bearing alloy particle surface.
11, the magnesium-base hydrogen storage material of claim 10, wherein said magnesium-base hydrogen storage material is formed by following steps:
A) with the powder mixes of the powder and the described desorption catalyzer of described magnesium or Mg base hydrogen bearing alloy; With
B) in masher, make this mixture mechanical alloying, make the powder particle of described desorption catalyzer be embedded in the surface of the powder particle of described at least magnesium or Mg base hydrogen bearing alloy.
12, the magnesium-base hydrogen storage material of claim 10 wherein adopts heptane and carbon dust as grinding aid in the ma process of described mixture.
13, the magnesium-base hydrogen storage material of claim 1, wherein said desorption catalyzer comprise at the magnesium of described block form or particle form or the lip-deep continuous or semicontinuous catalytic material layer of Mg base hydrogen bearing alloy.
14, the magnesium-base hydrogen storage material of claim 13, wherein said magnesium-base hydrogen storage material is formed by the following step:
A) provide bulk or particulate state magnesium or Mg base hydrogen bearing alloy; With
B) apply or do not have electropaining by vapour deposition, electrolysis and cover deposition successive or semi-continuous catalytic material layer on described bulk or particulate state magnesium or Mg base hydrogen bearing alloy surface.
15, the magnesium-base hydrogen storage material of claim 14, the wherein said step that deposits continuous or semicontinuous catalytic material layer on described bulk or particulate state magnesium or Mg base hydrogen bearing alloy surface comprises the evaporation of described catalytic material.
16, the magnesium-base hydrogen storage material of claim 13, the thickness of wherein said continuous or semicontinuous catalytic material layer are about 100 .
17, the magnesium-base hydrogen storage material of claim 14, the wherein said step that bulk or particulate state magnesium or Mg base hydrogen bearing alloy be provided comprises provides bulk or particulate state magnesium or Mg base hydrogen bearing alloy, has the desorption catalyzer that is arranged in the discrete discrete areas in described bulk or particulate state magnesium or the Mg base hydrogen bearing alloy.
18, the magnesium-base hydrogen storage material of claim 17, the wherein said step of bulk or particulate state magnesium or Mg base hydrogen bearing alloy that provides comprises:
A) with the powder mixes of the powder and the described desorption catalyzer of described magnesium or Mg base hydrogen bearing alloy;
B) described mixed powder is pressed into base substrate; With
C) the temperature sintering between 450 ℃-600 ℃/described base substrate of annealing.
19, the magnesium-base hydrogen storage material of claim 18, wherein said sintering/annealing was carried out 10 hours at least.
20, the magnesium-base hydrogen storage material of claim 17, the wherein said step of bulk or particulate state magnesium or Mg base hydrogen bearing alloy that provides comprises:
A) in protective atmosphere, prepare the powder of described magnesium or Mg base hydrogen bearing alloy and the melt of described desorption catalyst fines;
B) stir described melt, with the insoluble powder suspension of guaranteeing described desorption catalyzer in molten magnesium or Mg base hydrogen bearing alloy;
C) the quick described melt of Quench makes that the insoluble powder of suspension of described desorption catalyzer is well distributed in solidified magnesium or Mg base hydrogen bearing alloy.
21, the magnesium-base hydrogen storage material of claim 14, the wherein said step of bulk or particulate state magnesium or Mg base hydrogen bearing alloy that provides comprises:
A) melt of described magnesium of formation or Mg base hydrogen bearing alloy; With
B) make described magnesium or the quick Quench of Mg base hydrogen bearing alloy by the quick Quench method of integral body.
22, the magnesium-base hydrogen storage material of claim 21, the quick Quench method of wherein said integral body comprises melt-spinning, centrifugal atomizing, gas atomization or water atomization.
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| WO2012021996A1 (en) * | 2010-08-18 | 2012-02-23 | The Governors Of The University Of Alberta | Kinetic stabilization of magnesium hydride |
| US9045335B2 (en) | 2010-08-18 | 2015-06-02 | The Governors Of The University Of Alberta | Kinetic stabilization of magnesium hydride |
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| US2228781A (en) * | 1938-11-08 | 1941-01-14 | Magnesium Dev Corp | Process for the production of magnesium-zirconium alloys |
| DE3147839C2 (en) * | 1981-12-03 | 1983-12-22 | Kernforschungsanlage Jülich GmbH, 5170 Jülich | Magnesium-containing metal granules for storing hydrogen |
| US4765954A (en) * | 1985-09-30 | 1988-08-23 | Allied Corporation | Rapidly solidified high strength, corrosion resistant magnesium base metal alloys |
| DE69522471T2 (en) * | 1994-12-22 | 2002-05-29 | Energy Conversion Devices Inc | MAGNESIUM-BASED MECHANICAL ALLOY FOR THERMAL HYDROGEN STORAGE |
| JP3715743B2 (en) * | 1997-04-15 | 2005-11-16 | 株式会社神戸製鋼所 | Manufacturing method of Mg alloy member |
| US6830725B2 (en) * | 2003-04-01 | 2004-12-14 | Texaco Ovonic Battery Systems, Llc | Hydrogen storage alloys having a high porosity surface layer |
-
2003
- 2003-12-11 US US10/735,240 patent/US20050126663A1/en not_active Abandoned
-
2004
- 2004-12-02 JP JP2006543883A patent/JP2007522917A/en active Pending
- 2004-12-02 CN CNA2004800415945A patent/CN101072889A/en active Pending
- 2004-12-02 MX MXPA06006678A patent/MXPA06006678A/en active IP Right Grant
- 2004-12-02 CA CA002548093A patent/CA2548093A1/en not_active Abandoned
- 2004-12-02 KR KR1020067011441A patent/KR20060123300A/en not_active Application Discontinuation
- 2004-12-02 WO PCT/US2004/040227 patent/WO2005060547A2/en active Search and Examination
- 2004-12-02 EP EP04812679A patent/EP1691775A2/en not_active Withdrawn
-
2006
- 2006-07-06 NO NO20063136A patent/NO20063136L/en not_active Application Discontinuation
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| CN103256479A (en) * | 2012-02-15 | 2013-08-21 | 福特全球技术公司 | System and method for hydrogen storage |
| CN103256479B (en) * | 2012-02-15 | 2016-11-09 | 福特全球技术公司 | System and method for hydrogen storage |
| CN103663369A (en) * | 2012-09-12 | 2014-03-26 | 财团法人工业技术研究院 | Hydrogen storage composite and method of forming same |
| CN103663369B (en) * | 2012-09-12 | 2015-09-09 | 财团法人工业技术研究院 | Hydrogen storage composite and method of forming same |
| CN104988344A (en) * | 2015-06-23 | 2015-10-21 | 辽宁石化职业技术学院 | Method for preparing composite hydrogen storage materials |
| CN104988344B (en) * | 2015-06-23 | 2017-07-28 | 辽宁石化职业技术学院 | The preparation method of composite hydrogen storage material |
| CN105132838A (en) * | 2015-09-25 | 2015-12-09 | 广西大学 | Regulation method of Mg17Al12 hydrogenation |
| CN106614639A (en) * | 2016-12-26 | 2017-05-10 | 常熟市胜阳干燥剂贸易有限公司 | Broad-spectrum high-efficiency safe mildewproof material |
| CN107154481A (en) * | 2017-04-28 | 2017-09-12 | 内蒙古科技大学 | Ni MH battery hydrogen-storing alloy as electrode and preparation method thereof |
| CN107154481B (en) * | 2017-04-28 | 2020-05-19 | 内蒙古科技大学 | Hydrogen storage electrode alloy for Ni-MH battery and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1691775A2 (en) | 2006-08-23 |
| WO2005060547A3 (en) | 2007-05-10 |
| US20050126663A1 (en) | 2005-06-16 |
| CA2548093A1 (en) | 2005-07-07 |
| NO20063136L (en) | 2006-09-07 |
| MXPA06006678A (en) | 2007-02-02 |
| KR20060123300A (en) | 2006-12-01 |
| WO2005060547A2 (en) | 2005-07-07 |
| JP2007522917A (en) | 2007-08-16 |
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