CN102351142B - Reversible hydrogen storage method based on magnetostriction - Google Patents
Reversible hydrogen storage method based on magnetostriction Download PDFInfo
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- CN102351142B CN102351142B CN201110196477A CN201110196477A CN102351142B CN 102351142 B CN102351142 B CN 102351142B CN 201110196477 A CN201110196477 A CN 201110196477A CN 201110196477 A CN201110196477 A CN 201110196477A CN 102351142 B CN102351142 B CN 102351142B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
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Abstract
The invention discloses a reversible hydrogen storage method based on magnetostriction. A hydrogen storage material has a multilayer sandwich structure. A surface layer of the sandwich structure is a catalyst film capable of decomposing molecule hydrogen H2 into atom hydrogen; a second layer is a pure Mg film or a mg base multiple low alloy film; and a third layer is magnetostriction material film. Alternative second layers and third layers are arranged from outside to inside; and magnetic field with variable direction and intensity is loaded on the multilayer sandwich structure. The invention employs an applied magnetic field to control a hydrogen storage and hydrogen release process of Mg and alloy thereof. Under effect of the magnetic field, the magnetostriction material film generatesa magnetostriction effect in order to generate stress sigma in Mg and alloy film thereof and change crystal lattice constant or even crystal structure of the Mg and alloy film thereof, reduce hydrogen storage and hydrogen release temperatures of the Mg and alloy thereof and accelerate reaction speed. The method of the invention is easily controlled, has a reversible process and can substantially reduce hydrogen storage and hydrogen release temperatures (less than 100 DEG C or even reaching a room temperature) of a hydrogen cell, lower energy consumption and increase efficiency.
Description
One, technical field
The present invention relates to the solid-state hydrogen storage technology of new energy field, particularly utilize the hydrogen storage material of Mg and Mg alloy firm.
Two, background technology
Hydrogen is the energy carrier of rich hope of following green clean energy system.With respect to traditional fossil energy material, hydrogen has significant advantage, such as high-energy-density (142MJ.kg
-1), abundant source (all containing hydrogen) like water, biomass, organic substance etc., in light weight, the little grade of environmental influence (because water is unique reaction product).Yet the hydrogen storage system of exploitation volume compact remains a challenge aspect Science and Technology.No matter store the hydrogen of molecularity, be gaseous state or liquid state, all needs very high pressure or extremely low temperature, sees it is not economical from energy point of view.Current, the research and development trend of hydrogen storage technology is that storing hydrogen with atomic condition is in solid-state metal or complicated hydrogenate.Wasserstoffatoms occupies the interstitial site of acceptor metal lattice usually.In theory, solid-state storage hydrogen can obtain the high-energy-density of unit volume or unit mass hydrogen storage system, store up simultaneously hydrogen with release the hydrogen process can be in room temperature and atmospheric environment reversible carrying out.
Mg is a metal hydrogen storage material the most likely, and it is cheap, and is rich in mineral resources.Mg is through forming MgH with H-H reaction
2, its unit system storage Hydrogen Energy metric density is up to 7.6wt.%.Yet owing to receive Chu Qing and release H-H reaction associated hot mechanics and kinetic factor limits, the speed of block Mg and gaseous state H-H reaction is extremely low, when the hydrogen balance dividing potential drop is 1 normal atmosphere, and MgH
2Divide and explain that hydrogen needs 300 ° of C at least.At present, solid-state hydrogen storage technology mainly concentrates on three-dimensional hydrogen storage structure, and existing different routes reduce the kinetic barrier of releasing H-H reaction, for example utilizes mechanical alloying technology refinement MgH
2Crystal grain, the diffusion length of reduction Wasserstoffatoms; Add suitable catalyzer.Also have certain methods to be used for changing the thermodynamic behaviour of Mg-H system, for example reduce three dimensional particles size, alloying, polynary transition metal hydride etc., be reduced to 100 ° below the C but be difficult to release the hydrogen temperature.In the recent period, the research of two-dimensional film structure hydrogen storage property gets into people's the visual field.Compare with the conventional three-dimensional hydrogen storage structure, film has controllable structure system property, is the ideal system of research storage hydrogen mechanism.The research in this field has obtained some breakthroughs, and stress is considered to cause that the Mg-H thin film system releases the essential reason that the hydrogen temperature reduces significantly.
So-called magnetostrictive effect is meant ferro-magnetic when being magnetized by foreign field, because the interaction of externally-applied magnetic field and material internal magnetic domain magnetic moment causes that its volume and length are with the phenomenon that changes.Magnetostrictive effect can be through alloying constituent the change of selection, thermal annealing, cold working and magneticstrength control.The material that magnetostrictive effect takes place is more, mainly contains transition metal such as nickel, iron, cobalt and aluminium class alloy and ambrose alloy ferro-cobalt oxygen pottery etc., and its magnetostriction coefficient is about 10
-5Magnitude.High-magnetostriction coefficient (>=10
-3Magnitude) material also is developed, like terbium ferrous metal compound-TbFe
2, TbFe
3, Tb
xDy
1-xFe
2With noncrystal magnetostriction materials-like metallic glass Fe
81Si
3.5B
13.5C
2Deng.
Three, summary of the invention
The purpose of this invention is to provide a kind of MS reversible hydrogen storage material that can realize at a lower temperature.
Hydrogen storage material of the present invention has the Dagwood structure, and the top layer of sandwich structure is with molecular hydrogen H
2Be decomposed into the catalyst film of atomic hydrogen H; The second layer is pure Mg film or Mg Quito unit low-alloy film; The 3rd layer is the magnetostriction materials film; The alternative second layer and three-layer thin-film are inwardly arranged successively.On the Dagwood structure, be added with the magnetic field of direction and intensity variable.
The present invention controls the storage hydrogen of Mg and alloy thereof and releases the hydrogen process through externally-applied magnetic field.Utilize the magnetostriction materials film to issue magnetisation and cause flex effect at the action of a magnetic field; In Mg and alloy firm thereof, produce stress σ; Change its lattice parameter even change crystalline structure; Form metastable state Mg base hydride, reduce Mg and alloy thereof storage hydrogen and release the hydrogen temperature, accelerate storage hydrogen and release H-H reaction speed.Through changing the size and Orientation of externally-applied magnetic field; Can change the size and Orientation of stress σ in Mg and the alloy firm thereof; Cause the expansion of Mg in the hydrogen storage system and alloy firm lattice thereof, or release the contraction of Mg hydrogenate lattice in the hydrogen system, reach reversible hydrogen storage and the purpose of releasing hydrogen.
The present invention controls simply, and process is reversible; Can reduce hydrogen battery storage hydrogen significantly and release hydrogen temperature (, even reaching room temperature), reduce Mg and alloy firm thereof storage hydrogen and release the H-H reaction energy consumption, raise the efficiency less than 100 ° of C.
Four, description of drawings
Fig. 1 is the Dagwood structural representation of hydrogen storage material of the present invention;
Fig. 2 is storage hydrogen of the present invention, release hydrogen principle of work synoptic diagram.
Five, embodiment
The present invention constitutes a storage hydrogen/release hydrogen system by hydrogen storage material and externally-applied magnetic field, and this system has the Dagwood structure, and wherein: the top layer is with molecular hydrogen H
2Be decomposed into the catalyst film 1 of atomic hydrogen H, like pure Pt, pure Pd, Pt alloy or Pd alloy firm, thickness is about 5 ~ 50nm; The second layer is a pure Mg film or Mg base low-alloy film 2, and thickness is about 5 ~ 500nm, and the alloying element of Mg Quito unit low-alloy film can be a kind of among Nb, Ti, V, the Ni or several, and the alloy total content is 0 ~ 20wt.%; The 3rd layer is magnetostriction materials film 3, and thickness is about 5 ~ 500nm, can be transition metal such as nickel, iron, cobalt or aluminium class alloy, also can be ambrose alloy ferro-cobalt oxygen pottery, terbium ferrous metal compound-TbFe
2, TbFe
3Or Tb
xDy
1-xFe
2, can also be noncrystal magnetostriction materials Fe
81Si
3.5B
13.5C
2Deng; The alternative second layer and three-layer thin-film are inwardly arranged successively.On the Dagwood structure, be added with the magnetic field of direction and variable size, magnetic field is made up of the both sides that two permanent magnet opposite sex are opposite to the Dagwood structure mutually.
The formation of Dagwood film is at silicon or surface preoxidizing silicon substrate surface deposition one deck catalyst film 1; Deposit pure Mg or Mg base low-alloy film 2 again; Deposit magnetostriction materials film 3 again; Repeated deposition Mg or Mg base low-alloy film 2, magnetostriction materials film 3 to X time (X is number modulation period, by the total film thickness decision); And then deposit pure Mg or Mg base low-alloy film 2; The deposited catalyst film 1 again; Etch away silicon chip, obtain MS storage hydrogen Dagwood structure.
The principle of work of MS hydrogen storage structure is: hydrogen molecule H
2Under catalyst film 1 effect, resolve into Wasserstoffatoms H fast and get into catalyst film 1.Externally-applied magnetic field causes 3 elongations of magnetostriction materials film; In Mg or Mg base low-alloy film 2, produce tensile stress sigma; Cause Mg or Mg base low-alloy film 2 lattice dilatations even change crystalline structure, change thermodynamics of reactions and kinetic barrier, under the elastic stress effect, accelerate the diffusion of Wasserstoffatoms H at Mg or Mg base low-alloy film 2 interstitial voids; Form metastable state Mg base hydride, reach the purpose of lesser temps storage hydrogen.Magnetostriction materials film 3 also can be used as Wasserstoffatoms H and gets into one of passage of Mg or Mg base low-alloy film 2.Change the size and the direction in magnetic field; Cause that magnetostriction materials film 3 shrinks, in Mg or Mg base low-alloy film 2, produce stress-σ, cause the contraction of metastable state Mg base hydride lattice even change its crystalline structure; Reduction system thermodynamic stability; Under the elastic stress effect, the Wasserstoffatoms in the metastable state Mg base hydride is extruded Mg or Mg base low-alloy film 2, recombine into molecular hydrogen and overflow, accomplish lesser temps and release hydrogen.
Claims (8)
1. MS reversible hydrogen storage material, it has the Dagwood structure, it is characterized in that: the top layer of sandwich structure is for molecular hydrogen H
2Be decomposed into the catalyst film (1) of atomic hydrogen H; The second layer is pure Mg film or Mg Quito unit low-alloy film (2); The 3rd layer is magnetostriction materials film (3); The alternative second layer and three-layer thin-film are inwardly arranged successively; On the Dagwood structure, be added with the magnetic field of direction and intensity variable.
2. MS reversible hydrogen storage material according to claim 1 is characterized in that: said catalyst film (1) is pure Pt, pure Pd, Pt alloy or Pd alloy firm, and thickness is 5-50nm.
3. MS reversible hydrogen storage material according to claim 1; It is characterized in that: said pure Mg film or Mg Quito unit low-alloy film (2) thickness are 5 ~ 500nm; The alloying element of Mg Quito unit low-alloy film is a kind of among Nb, Ti, V, the Ni or several, and the alloy total content is 0 ~ 20wt.%.
4. MS reversible hydrogen storage material according to claim 1 is characterized in that: said magnetostriction materials film (3) thickness is 5 ~ 500nm.
5. according to claim 1 or 4 described MS reversible hydrogen storage material, it is characterized in that: magnetostriction materials film (3) is transiting metal nickel, iron, cobalt or aluminium class alloy.
6. according to claim 1 or 4 described MS reversible hydrogen storage material, it is characterized in that: magnetostriction materials film (3) is ambrose alloy ferro-cobalt oxygen pottery, terbium ferrous metal compound-TbFe
2, TbFe
3Or Tb
xDy
1-xFe
2
7. according to claim 1 or 4 described MS reversible hydrogen storage material, it is characterized in that: magnetostriction materials film (3) is noncrystal magnetostriction materials Fe
81Si
3.5B
13.5C
2
8. MS reversible hydrogen storage material according to claim 1 is characterized in that: said magnetic field is made up of the both sides that two permanent magnet opposite sex are opposite to the Dagwood structure mutually.
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