CN103668070A - Magnesium-base hydrogen storage film and preparation method thereof - Google Patents

Magnesium-base hydrogen storage film and preparation method thereof Download PDF

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Publication number
CN103668070A
CN103668070A CN201310652616.2A CN201310652616A CN103668070A CN 103668070 A CN103668070 A CN 103668070A CN 201310652616 A CN201310652616 A CN 201310652616A CN 103668070 A CN103668070 A CN 103668070A
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hydrogen
layer
bearing
base
base hydrogen
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程宇婷
卓之久
郑兴才
方章建
陶磊明
周欢欢
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Zhongying Changjiang International New Energy Investment Co Ltd
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Zhongying Changjiang International New Energy Investment Co Ltd
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Priority to PCT/CN2014/090449 priority patent/WO2015081781A1/en
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005—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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/087—Oxides of copper or solid solutions thereof
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/20—Metallic material, boron or silicon on organic substrates
    • C23C14/205—Metallic material, boron or silicon on organic substrates by cathodic sputtering
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage

Abstract

The present invention discloses a magnesium-base hydrogen storage film and a preparation method thereof. The film has five layers of structures, wherein the middle is a magnesium-base hydrogen storage layer, both surfaces of the magnesium-base hydrogen storage layer are respectively compounded with a diffusion layer, and the outer surfaces of the diffusion layers are respectively compounded with a catalysis layer. The method comprises: wrapping tin foil on a substrate, coating an easily-soluble organic matter on the tin foil in a rotation manner, and standing until the organic matter is subjected to complete curing film forming; adopting a physical deposition method to sequentially depositing the three targets to obtain a film material; taking the film material and the substrate material, placing into the corresponding organic solvent to soak; and carrying out a microwave heat treatment on the film material after the easily-soluble organic matter is completely dissolved to obtain the magnesium-base hydrogen storage film material. The magnesium-base hydrogen storage film can perform reversible hydrogen absorption and discharge at a low temperature, wherein hydrogen absorption can be performed at a room temperature, the hydrogen storage mass fraction can be 6.5 wt%, hydrogen discharge within a short time can be performed at a temperature of 100 DEG C under a pressure of 1 MPa, and hydrogen storage and discharge efficiency is significantly improved.

Description

Mg-base hydrogen-bearing film and preparation method thereof
Technical field
The present invention relates to a kind of film for storage power, refer to particularly a kind of Mg-base hydrogen-bearing film and preparation method thereof.
Background technology
The substitute energy of fossil oil has been subjected to increasing concern, society, government, enterprise and scientific research institution all progressively recognize its importance, and Hydrogen Energy as one can constantly regenerate, safe, the clean alternative energy, from the angle of safety, convenience and energy density, consider, thereby hydrogen storage material is more prone to utilize metal adsorption hydrogen to form a metal hydride solid not easy to explode.USDOE has been released about the correlative study task to low temperature hydrogen storage and Chu Qing carbon material.Use hydrogen energy source fuel cell as the power of automobile, require the hydrogen storage capability of hydrogen storage system to reach 6.5wt% or 60kg/m 3, and the once formation of hydrogen storage system will be over 350 miles.
Hydride hydrogen-storing, some transition metal, alloy, intermetallic compound are due to its special reason such as crystalline network, and under certain condition, hydrogen atom, than being easier to enter in the tetrahedron or octahedral interstice of metal lattice, forms metal hydride.Its storage hydrogen volume density is large, can reach 100kg/m 3, but quality is larger, and the condition when putting hydrogen is harsh, thereby cost is higher.So develop one not only light but also cheap, putting hydrogen process does not need too high temperature, and can repeatedly circulate that to inhale the material of putting hydrogen be very necessary.
Magnesium is a kind of good hydrogen storage material, can inhale and put hydrogen under certain conditions, but will be widely used, and hydrogen condition is put in the suction of its harshness, high storage hydrogen cost allows people hang back to it.Research finds, has three kinds of effective meanss can change its severe condition:
1, add catalyzing metal layer, make hydrogen more easily be decomposed into hydrogen atom;
2, reduce the particle size of magnesium, such as nanostructure can significantly increase the hydrogenation rate of magnesium, we can think that specific surface area increases, and accelerates the hydrogenation reaction rate of MAGNESIUM METAL and hydrogen atom;
3, the alloy of magnesium and other element (such as Ni etc.) can further change the thermokinetics performance of inhaling hydrogen discharge reaction.
So study, a kind ofly can meet above 3 conditions simultaneously, and use cheaply, resourceful starting material are prepared hydrogen storage material, are very significant.
Hydrogen storage alloy need to have one to hydrogen, have the element of powerful adsorptive power and can be combined into a compound state with hydrogen molecule.Hydrogen storage alloy mainly comprises: rare earth metal, titanium system, zinc system and magnesium system, or classified in several atomic ratios of above-mentioned chief component element: AB, A 2b, AB 2, AB 5, A xb, AB x(A is the combination element of hydrogen, and B is the element with katalysis or other special role).Between magnesium-base metal, compound is a kind of typical alloy, and magnesium is combined with the second element as substrate, have or even multiple element combine.Between magnesium-base metal compound main with Ni, Ti, V and Cu etc. in conjunction with being used as hydrogen storage material.
Catalytic material (simultaneously possessing corrosion proof function) with inhale the also stage in continuous test all always of amalgamation mode put hydrogen material, conventionally two kinds of methods that adopt are: wet chemistry method and mechanical ball milling method, adopting presoma add-ins is transistion metal compound or element state transition metal powders.Although feasible with aforesaid method, catalyst system but has problems at aspects such as composition formation or catalysis phase composite structures.Wet chemistry method easily causes actual hydrogen-storage amount to reduce and when adding organic ligand, in heat-processed, whole catalyst system is vulnerable to hydrocarbon polymer impact pollution hydrogen source; In mechanical milling process, be difficult to obtain desirable catalysis phase composite structure, there is no the good hydrogen dynamic performance that stores.
Physical deposition method has its unique advantage, and can make simply Catalytic Layer reach nano level, and also can obtain nano level Magnuminium, and this method be simple and easy to do, has characteristic cheaply, for preparing hydrogen storage material, be a kind of still good selection.And draw by a series of checking, the hydrogen storage property of catalyzer and hydrogen storage material reduces and significantly improves with its size, when the particle size of hydrogen storage material reaches nano level, its hydrogen discharging temperature significantly reduces, and has effectively improved the hydrogen storage property of hydrogen storage material.But due to the characteristic of film itself, if do not remove substrate, its effective hydrogen-storage amount is very low so, and even less than 1%.Although the thickness of film has very large advantage on storage hydrogen mass ratio, also just because sputtered film has caused its effective hydrogen-storage amount low, the shortcoming such as cycle index is few.General magnesium-base hydrogen storage material is in order to improve storage hydrogen efficiency, the material that need to wherein have catalysis and diffusion function, thereby can be sooner and store more efficiently hydrogen, but required metallic substance is more, just more difficult when preparing target so, and easily cause target to mix inhomogeneous problem, also caused final effective hydrogen-storage amount low, and will store H-H reaction material, catalytic material, diffusion material layering sputter, will avoid these problems, make each material effectively bring into play its function, and can significantly improve the actual hydrogen-storage amount of material.
Microwave thermal facture, generally be common in and process inorganic non-metallic or high molecular polymer, but after carrying out a series of condition setting, discovery is for metal alloy, the particularly lifting of the catalytic effect of metal catalyst, microwave thermal facture also has significant effect, can strengthen the interaction between Catalytic Layer and responding layer, thereby significantly improves the catalytic effect of metal catalyst.And in order to make performance between the needed Catalytic Layer of hydrogen storage material, diffusion layer and responding layer better store up hydrogen effect, select can strengthen storing up the interaction between layers of hydrogen thin-film material by microwave thermal facture.
At present, also not about by the report of physical deposition method and microwave thermal facture combination treatment.
Summary of the invention
Technical problem to be solved by this invention will provide a kind of nano Mg base storage hydrogen film exactly, it inhales the temperature of reaction of putting in hydrogen process and the storage hydrogen massfraction that improves Magnuminium by reduction, can significantly improve hydrogen discharging speed at a lower temperature, thereby improve storage hydrogen efficiency.
The present invention also provides a kind of preparation method of Mg-base hydrogen-bearing film, the method is by physical deposition method and the microwave thermal facture required nano Mg base storage hydrogen film of preparation that organically combines, advantage in conjunction with two kinds of methods, not only improve surface-area, the saving material of material, and can improve storage hydrogen efficiency, significantly improve its hydrogen storage property.
For solving the problems of the technologies described above, the invention provides a kind of Mg-base hydrogen-bearing film, this film has five-layer structure, in the middle of it, is Mg-base hydrogen-bearing layer, and described Mg-base hydrogen-bearing layer two sides is compounded with respectively diffusion layer, and described diffusion layer outside is compounded with respectively Catalytic Layer; Wherein,
Described Catalytic Layer is any one or a few in transition metal, metal oxide and the intermetallic compound with catalytic activity;
The chemical composition of described diffusion layer is the alloy of Fe or Fe and Li, and all the other are inevitable impurity;
The chemical composition of described Mg-base hydrogen-bearing layer is any one or a few in Mg, Mg alloy and Mg coordination compound.
Further, described transition metal is any one or a few in Pd, La, Zr, Ce, Pt, V, Ti, Ni, Cr and Y, and described metal oxide is ZnO, CuO and TiO 2in any one or a few, described intermetallic compound is ZrV 2, LaNi 5, FeTi, Ti xv yand Zr xpd yin any one or a few.
Again further, the parts by weight proportioning in described Fe and Li alloy is: Fe ︰ Li=1 ︰ 1～4.
Again further, described Mg alloy is any one or a few in the alloy of Mg and Al, Li, Ni, Ce, La; Described Mg coordination compound is Mg xni y, Mg xla y, Mg xpa y, Mg xal yni, Mg xv ytiz, Mg xli yti z, Mg xli yni zand Mg xal yni zin any one or a few.
Again further, in described Mg-base hydrogen-bearing layer, Mg content is more than or equal to 60%.
Again further, the thickness of described Catalytic Layer is that the thickness of 1～10nm, diffusion layer is that the thickness of 1～10nm, Mg-base hydrogen-bearing layer is 10～50nm.
Again further, the Thickness Ratio of described Catalytic Layer and Mg-base hydrogen-bearing layer is 1 ︰ 10～20; The Thickness Ratio of described diffusion layer and Mg-base hydrogen-bearing layer is 1 ︰ 10～20.
The present invention also provides a kind of preparation method of Mg-base hydrogen-bearing film, comprises the following steps:
1) tinfoil paper is wrapped on substrate, processable organism is rotated and is coated on tinfoil paper under the rotating speed of 2500～4500rpm, standing its complete film-forming for the treatment of, makes base material;
2) by described proportioning, take Catalytic Layer, diffusion layer and the required raw material of Mg-base hydrogen-bearing layer, and be prepared into target;
3) by physical deposition method, above-mentioned three kinds of targets are deposited on the prepared base material of step 1) by described level, obtain thin-film material, this thin-film material is followed successively by Catalytic Layer, diffusion layer, Mg-base hydrogen-bearing layer, diffusion layer and Catalytic Layer;
4) after this thin-film material is taken off together with base material, rub after tinfoil paper, put into corresponding organic solvent and soak 20～120s, after processable organism dissolves completely, take tinfoil paper away;
5) centrifugal 20～60min under 10000～25000rpm rotating speed by this thin-film material and organic solution, elimination upper solution after layering, add again processable organism residual on corresponding organic solvent washing thin-film material, continue centrifugal, and then elimination upper solution, this process that circulates repeatedly 2～5 times;
6) this thin-film material is placed under vacuum room temperature environment and is dried, remove the debris on it; Pass into again hydrogen, and microwave thermal is processed 2～10min under 250～350 ℃ of conditions, finally in hydrogen environment, is cooled to room temperature, obtains Mg-base hydrogen-bearing thin-film material.
As preferred version, in described step 1), processable organism is any one or a few in polyimide, polyethylene terephthalate, polymethyl acrylic acid and photoresist material.
As preferred version, in described step 5), pass into after hydrogen, air pressure remains 2.0～3.0kPa, and microwave power is 150～250W.
Beneficial effect of the present invention is:
1, in the present invention, use processable organism (polymethylmethacrylate (PMMA), polyimide (PI), polyethylene terephthalate (PET), photoresist material) as the substrate of magnetron sputtering, this kind of organism has and is soluble in some organic characteristic, thereby can simply substrate be peeled off to target as sputter film, and avoid the impacts such as film comes off, and then can improve effective storage hydrogen quality of hydrogen storage material.The thin-film material preparing is processed by microwave thermal again, Catalytic Layer particle is combined with diffusion layer and Chu Qing layer better, therefore can improve the interaction of storage hydrogen phase with its diffusion internal layer, the Catalytic Layer of hydrogen storage material, the better magnesium-base hydrogen storage material of the acquisition higher while catalytic performance of activity.
2, to prepare Mg-base hydrogen-bearing film be Catalytic Layer, diffusion layer, Mg-base hydrogen-bearing layer (core layer with storage hydrogen function), diffusion layer and five such layer film materials of Catalytic Layer in the present invention.This five-layer structure can accelerate to inhale the speed of hydrogen.Wherein: the Catalytic Layer on top layer has stoped the oxidation of responding layer magnesium-base metal effectively, and can accelerate hydrogen and be decomposed into hydrogen atom; Diffusion layer Fe metallic element can promote the diffusion of hydrogen atom, and the absorption to hydrogen can be strengthened in the surface of Li, further helps the diffusion of hydrogen atom, thereby can improve the hydrogen storage property of responding layer magnesium base film.
3, in preparation method of the present invention, used physical deposition method, the method is compared with traditional ball milling method, it can make hydrogen fast decoupled under catalyst is hydrogen atom, then diffusion layer just can react more thoroughly with magnesium-base metal more fast and equably in addition, improves storage hydrogen efficiency.Empirical tests, hydrogen storage material particle diameter is less, and its hydrogen storage property is better, and physical deposition method can be controlled the thickness of every one deck, makes film hydrogen storage material have higher performance.
4, the present invention is after physical deposition film, by microwave thermal facture, magnesium-base metal thin-film material is processed again, make the interaction force between layers of Catalytic Layer, diffusion layer, responding layer stronger, composite structure is between layers finer and close, be conducive to the diffusion of hydrogen, and further inhale hydrogen discharge reaction with mg-based material.
5, the Mg-base hydrogen-bearing film in the present invention can carry out reversible hydrogen adsorption and desorption at low temperatures, inhale hydrogen and can carry out at normal temperatures, and storage hydrogen massfraction can reach 6.5wt%, and putting at short notice hydrogen can carry out at 1MPa, 100 ℃, stores hydrogen efficiency and significantly improves.
Accompanying drawing explanation
Fig. 1 is the structural representation of Mg-base hydrogen-bearing film of the present invention;
Fig. 2 be the nano Mg base storage hydrogen film of the Ti-Mg/Al/Fe-Ti material processing and do not process through microwave thermal through microwave thermal at 1MPa, temperature is respectively the suction hydrogen curve at 25 ℃, 100 ℃.
Fig. 3 is that the nano Mg base storage hydrogen film of Ti-Mg/Al/Fe-Ti is processed and through microwave thermal, do not processed and a kind of nanometer MgH through microwave thermal 2the Hydrogen desorption isotherms of the material that powder (30nm) is not processed through microwave thermal under 100 ℃, 1MPa.
In figure: Catalytic Layer 1, diffusion layer 2, Mg-base hydrogen-bearing layer 3.
Embodiment
In order to explain better the present invention, below in conjunction with specific embodiment, further illustrate main contents of the present invention, but content of the present invention is not only confined to following examples.
Embodiment 1
A preparation method for Mg-base hydrogen-bearing film, comprises the following steps:
1) tinfoil paper is wrapped on substrate, PMMA is rotated and is coated on tinfoil paper under the rotating speed of 4000rpm, after spin coating 45s, the complete film-forming of standing 24h, makes base material;
2) take Ti as the raw material of Catalytic Layer 1, take pure Fe as the raw material of diffusion layer 2, take Mg-Al alloy as the raw material of Mg-base hydrogen-bearing layer 3, wherein the weight part ratio of Mg-Al is 2 ︰ 1, and three kinds of raw materials are made respectively to corresponding target;
3) by adopting vacuum ionic electroplating technology (PVD) that above-mentioned three kinds of targets are deposited successively and obtain thin-film material, this thin-film material is followed successively by Catalytic Layer 1, diffusion layer 2, Mg-base hydrogen-bearing layer 3, diffusion layer 2 and Catalytic Layer 1; Wherein, the thickness of Catalytic Layer 1 is 10nm, and diffusion layer 2 thickness are 5nm, and the thickness of Mg-base hydrogen-bearing layer 3 is 20nm;
4) after thin-film material is taken off together with base material, rub after tinfoil paper, put into acetone soln and soak 90s, after PMMA dissolves completely, take tinfoil paper away;
5) thin-film material and organic solution are put into 50ml centrifuge tube, centrifugal 30min under 15000rpm rotating speed, after layering, elimination upper solution, then add residual PAMM on acetone soln washing thin-film material, continue centrifugal, and then elimination upper solution, this process that circulates repeatedly 2～5 times, after finally gained solid film material being dried under vacuum room temperature environment, the solid film material obtaining is put into and is vacuumized silica tube;
6) to being placed with in the vitreosil pipe of solid film material, pass into hydrogen, air pressure remains 2.5kPa, and at 300 ℃, microwave power is that 200W microwave thermal is processed 5min, and continues to pass into hydrogen, is cooled to room temperature.Finally take out prepared nanometer, obtain Mg-base hydrogen-bearing thin-film material.
Embodiment 2
A preparation method for Mg-base hydrogen-bearing film, comprises the following steps:
1) tinfoil paper is wrapped on substrate, PMMA is rotated and is coated on tinfoil paper under the rotating speed of 4000rpm, after spin coating 45s, the complete film-forming of standing 24h, makes base material;
2) take Ti as the raw material of Catalytic Layer 1, take pure Fe as the raw material of diffusion layer 2, take Mg-Al alloy as the raw material of Mg-base hydrogen-bearing layer 3, wherein the weight part ratio of Mg-Al is 2 ︰ 1, and three kinds of raw materials are made respectively to corresponding target;
3) by vacuum ionic electroplating technology (PVD), above-mentioned three kinds of targets are deposited successively and obtain thin-film material, thin-film material is followed successively by Catalytic Layer 1, diffusion layer 2, Mg-base hydrogen-bearing layer 3, diffusion layer 2 and Catalytic Layer 1; Wherein, the thickness of Catalytic Layer 1 is 5nm, and diffusion layer 2 thickness are 2nm, and the thickness of Mg-base hydrogen-bearing layer 3 is 10nm;
4) after thin-film material is taken off together with base material, rub after tinfoil paper, put into acetone soln and soak 75s, after PMMA dissolves completely, take tinfoil paper away;
5) thin-film material and organic solution are put into 50ml centrifuge tube, centrifugal 30min under 15000rpm rotating speed, after layering, elimination upper solution, then add residual PAMM on acetone soln washing thin-film material, continue centrifugal, and then elimination upper solution, this process that circulates repeatedly 2～5 times, after finally gained solid film material being dried under vacuum room temperature environment, the solid film material obtaining is put into and is vacuumized silica tube;
6) to being placed with in the vitreosil pipe of solid film material, pass into hydrogen, air pressure remains 2.5kPa, and under 300 ℃ of conditions, microwave power is that the microwave thermal of 150W is processed 3min, closes microwave source, and continues to pass into hydrogen, be cooled to room temperature, obtain Mg-base hydrogen-bearing thin-film material.
It inhales hydrogen curve as shown in Figure 2, and its Hydrogen desorption isotherms as shown in Figure 3.As seen from the figure, the storage of the nano Mg base after microwave thermal is processed hydrogen thin-film material has more significantly advantage in storage hydrogen efficiency.In Fig. 3, nano Mg base powder hydrogen storag powder end is a kind of MgH2(30nm preparing by ball milled) powder is at the same Hydrogen desorption isotherms figure under hydrogen condition of putting, as seen from the figure, on ultrathin nanometer magnesium-base hydrogen storage material prepared by the magnesium-base hydrogen storage material of preparing by ball milled and the physical deposition sputtering method hydrogen releasing efficient when for process microwave treatment, have obvious difference, physical deposition method is prepared with better hydrogen storage property.
Embodiment 3
A preparation method for Mg-base hydrogen-bearing film, comprises the following steps:
1) tinfoil paper is wrapped on substrate, PET is rotated and is coated on tinfoil paper under the rotating speed of 4500rpm, after spin coating 30s, the complete film-forming of standing 20h, makes base material;
2) take Ti and Ni as the raw material of Catalytic Layer 1, take the alloy of Fe and Li as the raw material of diffusion layer 2, take pure Mg alloy as the raw material of Mg-base hydrogen-bearing layer 3, wherein the weight part ratio of Ti and Ni is 3 ︰ 1, in the alloy of Fe and Li, weight part ratio 1 ︰ 2 of Fe and Li, makes respectively corresponding target by three kinds of raw materials;
3) by magnetron sputtering method, above-mentioned three kinds of targets are deposited successively and obtain thin-film material, thin-film material is followed successively by Catalytic Layer 1, diffusion layer 2, Mg-base hydrogen-bearing layer 3, diffusion layer 2 and Catalytic Layer 1; Wherein, the thickness of Catalytic Layer 1 is 3nm, and diffusion layer 2 thickness are 3nm, and the thickness of Mg-base hydrogen-bearing layer 3 is 30nm
4) after thin-film material is taken off together with base material, rub after tinfoil paper, put into acetone soln and soak 120s, after PET dissolves completely, take tinfoil paper away;
5) thin-film material and organic solution are put into 50ml centrifuge tube, centrifugal 60min under 10000rpm rotating speed, after layering, elimination upper solution, then add residual PET on acetone soln washing thin-film material, continue centrifugal, and then elimination upper solution, this process that circulates repeatedly 2～5 times, after finally gained solid film material being dried under vacuum room temperature environment, the solid film material obtaining is put into and is vacuumized silica tube;
6) to being placed with in the vitreosil pipe of solid film material, pass into hydrogen, air pressure remains 2.0kPa, and under 350 ℃ of conditions, microwave power is that the microwave thermal of 250W is processed 2min, closes microwave source, and continues to pass into hydrogen, be cooled to room temperature, obtain Mg-base hydrogen-bearing thin-film material.
Embodiment 4
A preparation method for Mg-base hydrogen-bearing film, comprises the following steps:
1) tinfoil paper is wrapped on substrate, PI and photoresist material are rotated and are coated on tinfoil paper under the rotating speed of 4000rpm, after spin coating 60s, the complete film-forming of standing 30h, makes base material; Wherein the weight ratio of PI and photoresist material is 1 ︰ 1;
2) take Ti, LaNi 5with the raw material of ZnO as Catalytic Layer 1, take the alloy of Fe and Li as the raw material of diffusion layer 2, take pure Mg as the raw material of Mg-base hydrogen-bearing layer 3, wherein Ti, LaNi 5with the weight part ratio of ZnO be 1 ︰ 1 ︰ 1, in the alloy of Fe and Li, weight part ratio 1 ︰ 4 of Fe and Li, makes respectively corresponding target by three kinds of raw materials;
3) by magnetron sputtering method, above-mentioned three kinds of targets are deposited successively and obtain thin-film material, thin-film material is followed successively by Catalytic Layer 1, diffusion layer 2, Mg-base hydrogen-bearing layer 3, diffusion layer 2 and Catalytic Layer 1; Wherein, the thickness of Catalytic Layer 1 is 2nm, and diffusion layer 2 thickness are 2nm, and the thickness of Mg-base hydrogen-bearing layer 3 is 40nm
4) after thin-film material is taken off together with base material, rub after tinfoil paper, put into acetone soln and soak 20s, after PI dissolves completely, take tinfoil paper away;
5) thin-film material and organic solution are put into 50ml centrifuge tube, centrifugal 60min under 10000rpm rotating speed, after layering, elimination upper solution, then add residual PI on acetone soln washing thin-film material, continue centrifugal, and then elimination upper solution, this process that circulates repeatedly 2～5 times, after finally gained solid film material being dried under vacuum room temperature environment, the solid film material obtaining is put into and is vacuumized silica tube;
6) to being placed with in the vitreosil pipe of solid film material, pass into hydrogen, air pressure remains 3.0kPa, and under 250 ℃ of conditions, microwave power is that the microwave thermal of 350W is processed 10min, closes microwave source, and continues to pass into hydrogen, be cooled to room temperature, obtain Mg-base hydrogen-bearing thin-film material.
Embodiment 5
This preparation method is identical with aforesaid method, and difference is:
2) take LaNi 5and ZrV 2as the raw material of Catalytic Layer 1, take the alloy of Fe and Li as the raw material of diffusion layer 2, take Mg, MgAlH 4and Mg 2ni is as the raw material of Mg-base hydrogen-bearing layer 3, wherein LaNi 5and ZrV 2weight part ratio be 1 ︰ 1, weight part ratio 1 ︰ 1 of Fe and Li in the alloy of Fe and Li, Mg, MgAlH 4and Mg 2the weight ratio of Ni is 2 ︰ 1 ︰ 1, and three kinds of raw materials are made respectively to corresponding target;
3) by magnetron sputtering method, above-mentioned three kinds of targets are deposited successively and obtain thin-film material, thin-film material is followed successively by Catalytic Layer 1, diffusion layer 2, Mg-base hydrogen-bearing layer 3, diffusion layer 2 and Catalytic Layer 1; Wherein, the thickness of Catalytic Layer 1 is 10nm, and diffusion layer 2 thickness are 10nm, and the thickness of Mg-base hydrogen-bearing layer 3 is 50nm.
Embodiment 6
This preparation method is identical with aforesaid method, and difference is:
2) take ZnO, CuO and TiO 2as the raw material of Catalytic Layer 1, take the alloy of Fe and Li as the raw material of diffusion layer 2, take MgLi alloy as the raw material of Mg-base hydrogen-bearing layer 3, wherein, ZnO, CuO and TiO 2weight part ratio be 1 ︰ 1 ︰ 1, weight part ratio 1 ︰ 2 of Fe and Li in the alloy of Fe and Li, the weight ratio of Mg and Li is 3 ︰ 1, and three kinds of raw materials are made respectively to corresponding target;
3) by magnetron sputtering method, above-mentioned three kinds of targets are deposited successively and obtain thin-film material, thin-film material is followed successively by Catalytic Layer 1, diffusion layer 2, Mg-base hydrogen-bearing layer 3, diffusion layer 2 and Catalytic Layer 1; Wherein, the thickness of Catalytic Layer 1 is 1nm, and diffusion layer 2 thickness are 1nm, and the thickness of Mg-base hydrogen-bearing layer 3 is 30nm.
Embodiment 7
This preparation method is identical with aforesaid method, and difference is:
2) take Ni as the raw material of Catalytic Layer 1, take the alloy of Fe and Li as the raw material of diffusion layer 2, take MgLi alloy as the raw material of Mg-base hydrogen-bearing layer 3, wherein, weight part ratio 1 ︰ 2 of Fe and Li in the alloy of Fe and Li, the weight ratio of Mg and Li is 3 ︰ 1
Three kinds of raw materials are made respectively to corresponding target;
3) by magnetron sputtering method, above-mentioned three kinds of targets are deposited successively and obtain thin-film material, thin-film material is followed successively by Catalytic Layer 1, diffusion layer 2, Mg-base hydrogen-bearing layer 3, diffusion layer 2 and Catalytic Layer 1; Wherein, the thickness of Catalytic Layer 1 is 1nm, and diffusion layer 2 thickness are 1nm, and the thickness of Mg-base hydrogen-bearing layer 3 is 50nm.
Embodiment 8
This preparation method is identical with aforesaid method, and difference is:
2) take CuO as the raw material of Catalytic Layer 1, take pure Fe as the raw material of diffusion layer 2, take pure Mg as the raw material of Mg-base hydrogen-bearing layer 3, three kinds of raw materials are made respectively to corresponding target;
3) by magnetron sputtering method, above-mentioned three kinds of targets are deposited successively and obtain thin-film material, thin-film material is followed successively by Catalytic Layer 1, diffusion layer 2, Mg-base hydrogen-bearing layer 3, diffusion layer 2 and Catalytic Layer 1; Wherein, the thickness of Catalytic Layer 1 is 5nm, and diffusion layer 2 thickness are 5nm, and the thickness of Mg-base hydrogen-bearing layer 3 is 40nm.
Embodiment 9
This preparation method is identical with aforesaid method, and difference is:
2) take ZnO as the raw material of Catalytic Layer 1, take FeLi alloy as the raw material of diffusion layer 2, take Mg and MgAl as the raw material of Mg-base hydrogen-bearing layer 3, wherein, weight part ratio 1 ︰ 3 of Fe and Li in the alloy of Fe and Li, the weight ratio of Mg and MgAl is 6 ︰ 1
Three kinds of raw materials are made respectively to corresponding target;
3) by magnetron sputtering method, above-mentioned three kinds of targets are deposited successively and obtain thin-film material, thin-film material is followed successively by Catalytic Layer 1, diffusion layer 2, Mg-base hydrogen-bearing layer 3, diffusion layer 2 and Catalytic Layer 1; Wherein, the thickness of Catalytic Layer 1 is 2nm, and diffusion layer 2 thickness are 2nm, and the thickness of Mg-base hydrogen-bearing layer 3 is 45nm.
Table 1 is that comparing embodiment one, two, three, four, five, six, seven, eight, nine is at 100 ℃, suction hydrogen massfraction (wt%) when 150s, 300s, 600s respectively, as seen from table, variation in thickness along with deposition sputtered film, and the difference of the ratio of thickness between Catalytic Layer 1, diffusion layer 2 and Chu Qing layer, also have choosing of main selected target composition, these all have certain impact to storage hydrogen efficiency.
Table 1
Sample 150s hydrogen－sucking amount (wt%) 300s hydrogen－sucking amount (wt%) 600s hydrogen－sucking amount (wt%)
Embodiment mono- 4.0 4.9 6.0
Embodiment bis- 4.7 5.8 6.4
Embodiment tri- 4.0 4.9 5.5
Embodiment tetra- 3.6 4.4 5.2
Embodiment five 3.0 4.2 5
Embodiment six 3.0 3.7 4.2
Embodiment seven 2.1 2.8 4.0
Embodiment eight 3.5 4.1 5.2
Embodiment nine 3.0 4.0 4.8
[0104]other unspecified part is prior art.Although above-described embodiment has been made detailed description to the present invention; but it is only a part of embodiment of the present invention; rather than whole embodiment, people can also obtain other embodiment according to above-described embodiment under without creative prerequisite, and these embodiment belong to protection scope of the present invention.

Claims (10)

1. a Mg-base hydrogen-bearing film, it is characterized in that: this film has five-layer structure, in the middle of it, be Mg-base hydrogen-bearing layer (3), described Mg-base hydrogen-bearing layer (3) two sides is compounded with respectively diffusion layer (2), and described diffusion layer (2) outside is compounded with respectively Catalytic Layer (1); Wherein,
Described Catalytic Layer (1) is for having any one or a few in transition metal, metal oxide and the intermetallic compound of catalytic activity;
The chemical composition of described diffusion layer (2) is the alloy of Fe or Fe and Li, and all the other are inevitable impurity;
The chemical composition of described Mg-base hydrogen-bearing layer (3) is any one or a few in Mg, Mg alloy and Mg coordination compound.
2. Mg-base hydrogen-bearing film according to claim 1, is characterized in that: described transition metal is any one or a few in Pd, La, Zr, Ce, Pt, V, Ti, Ni, Cr and Y, and described metal oxide is ZnO, CuO and TiO 2in any one or a few, described intermetallic compound is ZrV 2, LaNi 5, FeTi, Ti xv yand Zr xpd yin any one or a few.
3. Mg-base hydrogen-bearing film according to claim 1 and 2, is characterized in that: the parts by weight proportioning in described Fe and Li alloy is: Fe ︰ Li=1 ︰ 1～4.
4. Mg-base hydrogen-bearing film according to claim 1 and 2, is characterized in that: described Mg alloy is any one or a few in the alloy of Mg and Al, Li, Ni, Ce, La; Described Mg coordination compound is Mg xni y, Mg xla y, Mg xpa y, Mg xal yni, Mg xv yti z, Mg xli yti z, Mg xli yni zand Mg xal yni zin any one or a few.
5. Mg-base hydrogen-bearing film according to claim 1 and 2, is characterized in that: in described Mg-base hydrogen-bearing layer (3), Mg content is more than or equal to 60%.
6. Mg-base hydrogen-bearing film according to claim 1 and 2, is characterized in that: the thickness of described Catalytic Layer (1) is that the thickness of 1～10nm, diffusion layer (2) is that the thickness of 1～10nm, Mg-base hydrogen-bearing layer (3) is 10～50nm.
7. Mg-base hydrogen-bearing film according to claim 6, is characterized in that: described Catalytic Layer (1) is 1 ︰ 10～20 with the Thickness Ratio of Mg-base hydrogen-bearing layer (3); Described diffusion layer (2) is 1 ︰ 10～20 with the Thickness Ratio of Mg-base hydrogen-bearing layer (3).
8. a preparation method for Mg-base hydrogen-bearing film described in claim 1, is characterized in that: comprise the following steps:
1) tinfoil paper is wrapped on substrate, processable organism is rotated and is coated on tinfoil paper under the rotating speed of 2500～4500rpm, standing its complete film-forming for the treatment of, makes base material;
2) by described proportioning, take Catalytic Layer (1), diffusion layer (2) and the required raw material of Mg-base hydrogen-bearing layer (3), and be prepared into target;
3) by physical deposition method, above-mentioned three kinds of targets are deposited on the prepared base material of step 1) by described level, obtain thin-film material, this thin-film material is followed successively by Catalytic Layer (1), diffusion layer (2), Mg-base hydrogen-bearing layer (3), diffusion layer (2) and Catalytic Layer (1);
4) after this thin-film material is taken off together with base material, rub after tinfoil paper, put into corresponding organic solvent and soak 20～120s, after processable organism dissolves completely, take tinfoil paper away;
5) centrifugal 20～60min under 10000～25000rpm rotating speed by this thin-film material and organic solution, elimination upper solution after layering, add again processable organism residual on corresponding organic solvent washing thin-film material, continue centrifugal, and then elimination upper solution, this process that circulates repeatedly 2～5 times;
6) this thin-film material is placed under vacuum room temperature environment and is dried, remove the debris on it; Pass into again hydrogen, and microwave thermal is processed 2～10min under 250～350 ℃ of conditions, finally in hydrogen environment, is cooled to room temperature, obtains Mg-base hydrogen-bearing thin-film material.
9. the preparation method of Mg-base hydrogen-bearing film according to claim 8, is characterized in that: in described step 1), processable organism is any one or a few in polyimide, polyethylene terephthalate, polymethyl acrylic acid and photoresist material.
10. the preparation method of Mg-base hydrogen-bearing film according to claim 8 or claim 9, is characterized in that: in described step 5), pass into after hydrogen, air pressure remains 2.0～3.0kPa, and microwave power is 150～250W.
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