CN100590065C - Hydrogen generating material, preparing method for the same and method of preparing hydrogen - Google Patents
Hydrogen generating material, preparing method for the same and method of preparing hydrogen Download PDFInfo
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- CN100590065C CN100590065C CN200680001060A CN200680001060A CN100590065C CN 100590065 C CN100590065 C CN 100590065C CN 200680001060 A CN200680001060 A CN 200680001060A CN 200680001060 A CN200680001060 A CN 200680001060A CN 100590065 C CN100590065 C CN 100590065C
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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
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- 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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- 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
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Abstract
A hydrogen generating material reacts with water to produce hydrogen and includes at least one metal material selected from the group consisting of aluminum, magnesium, and their alloys. The metal material includes particles with a particle size of 60 mum or less in a proportion of 80 wt % or more. The hydrogen generating material can produce hydrogen easily and efficiently at low temperatures. Ahydrogen generator can be made portable by using the hydrogen generating material. Moreover, the use of the hydrogen generating material as a hydrogen fuel source can reduce the size of a fuel cell and improve the electrical efficiency.
Description
Technical field
The present invention relates to by generating the hydrogen generating material of hydrogen and manufacture method thereof with water reaction and with the method for preparing hydrogen of this hydrogen generating material as hydrogen source.
Background technology
In recent years, along with popularizing of Wireless electrical appliances such as PC, mobile telephone, wish secondary cell miniaturization day by day, high capacity as its power supply.At present, as the secondary cell that can realize energy density height, miniaturization and, lithium-ion secondary cell is practicability, increases as the needs of portable power supplies.But according to the kind of the Wireless electrical appliance that uses, this lithium secondary battery does not reach the degree that guarantees competent continuous duration of service as yet.
In this case, an example that can satisfy the battery of above-mentioned hope is a polymer electrolyte fuel cell.Ionogen adopts solid macromolecule electrolyte, positive active material to adopt polymer electrolyte fuel cell that airborne oxygen, negative electrode active material adopt fuel (hydrogen, methyl alcohol etc.) to receive publicity than the lithium ion battery battery of high-energy-densityization more also as being expected.As long as fueling and oxygen, fuel cell just can use continuously.Though can enumerate several candidate things about the employed fuel of fuel cell, there is variety of issue respectively, still can not make final decision.
About the fuel cell that acts as a fuel with hydrogen, for example, supply with the method be stored in high pressure vessel or be stored in the hydrogen in hydrogen storage alloy container part practicability.But, adopt the fuel cell of this hydrogen storage container because its volume and weight is big, energy density is low, thereby be not suitable for portable power supplies.
In addition, the fuel of the battery that acts as a fuel also has the method that adopts hydrocarbon based fuel, its modification is extracted hydrogen.But, adopt the fuel cell of hydrocarbon based fuel because need reforming apparatus, exist to reforming apparatus heat supply and problem such as heat insulation, therefore still be not suitable for portable power supplies.
In addition, also to have with methyl alcohol be fuel, by the direct methanol fuel cell that direct electrode reacts the methyl alcohol that acts as a fuel, and this battery is easy to miniaturization, is expected to as portable power supplies in the future.But, directly in the methanol fuel cell,, the methyl alcohol penetrate solid electrolyte of negative pole one side gets over (crossover) phenomenon because reaching anodal, there is the problem that voltage is low and energy density descends.
On the other hand, the also known method of in the fuel of fuel cell, using by the hydrogen that generates in the biochemical reaction of the occurs at low temperatures below 100 ℃ (patent documentation 1～5).These methods are for example aluminium, magnesium, silicon, zinc etc. and water reaction to be generated the metal of hydrogen as hydrogen source.
Patent documentation 1: No. 6506360 communique of United States Patent (USP)
Patent documentation 2: specially permit communique No. 2566248
Patent documentation 3: the spy opens the 2004-231466 communique
Patent documentation 4: the spy opens the 2001-31401 communique
Patent documentation 5: No. 6582676 communique of United States Patent (USP)
The technology that makes aluminium and alkali or acid-respons is disclosed in the above-mentioned patent documentation 1～3, but use these technology,, must add and normal alkali of balance aluminum or acid though generate hydrogen easily with chemical process, because the ratio of the material beyond the hydrogen source increases, so the problem that reduces of generate energy density.In addition, resultant of reaction oxide compound or oxyhydroxide form surface film on the surface of aluminium, and the aluminium of film inboard can't contact with water, is easy to generate the problem that oxidizing reaction only is stuck in the aluminium surface.
On the other hand, disclosedly in the patent documentation 4 remove surface film and avoid in the technology of this problem with mechanical system, existence need be used to remove the mechanical means of surface film thereby the problem that device maximizes.
In the disclosed technology, conducts such as interpolation aluminum oxide are in order to be difficult to form the catalyzer of above-mentioned hydroxide film, so that hydrogen generates at low temperature in the patent documentation 5.But, exist only can not to generate hydrogen with metals such as aluminium owing to add catalyzer, as the content of the metals such as aluminium of hydrogen source reduce, the low problem of growing amount of hydrogen.
Summary of the invention
Hydrogen generating material of the present invention, it is characterized in that, be to contain the hydrogen generating material that is selected from least a kind of metallic substance in aluminium and the aluminium alloy, above-mentioned metallic substance has surface film, and this surface film comprises the mutually nonactive of the metallographic phase of the aluminium that contains metallic state and oxide compound that contains aluminium or oxyhydroxide.
The manufacture method of hydrogen generating material of the present invention, it is characterized in that, it is the manufacture method that contains the hydrogen generating material of metallic substance with surface film, described metallic substance forms by being selected from aluminium and the aluminium alloy a kind at least, and described surface film comprises the mutually nonactive of the metallographic phase of the aluminium that contains metallic state and oxide compound that contains aluminium or oxyhydroxide, and this method is included in the operation of pulverizing aluminum or aluminum alloy in the liquid that contains water and organic solvent.
Method for preparing hydrogen of the present invention is characterized in that, thereby the hydrogen generating material and the water that comprise by making the invention described above react the operation that generates hydrogen.
According to the present invention, can provide can simple and effective the hydrogen generating material of ground generation hydrogen and manufacture method thereof and with the method for preparing hydrogen of above-mentioned hydrogen generating material as hydrogen source.As hydrogen source, can realize the miniaturization of apparatus for forming hydrogen and fuel cell etc. with hydrogen generating material of the present invention.
Description of drawings
Fig. 1 is the observations synoptic diagram by the cross section of the conventional aluminium powder form that adopts among the electron microscope observation embodiment 1.
Fig. 2 is the observations synoptic diagram by the cross section of the used metallic substance of hydrogen generating material of the present invention of preparation among the electron microscope observation embodiment 1.
Fig. 3 is the size-grade distribution synoptic diagram of the metallic substance of embodiment 1,2 and 5.
Fig. 4 be pattern the sectional view of the surface film structure of embodiment 2～6 described metallic substance is shown.
Fig. 5 be pattern the sectional view of the structure of apparatus for forming hydrogen is shown.
Embodiment
Fluor of the present invention is that the briliancy reduction that contains is few, is the nitride phosphor that is applicable to VFD, FED, PDP, CRT, White LED etc. therefore.Be expected in the design of the material of various display unit flexible Application greatly from now on, for industrial development is made contributions.
Hydrogen generating material of the present invention is to contain the material that is selected from least a kind of metallic substance in aluminium and the aluminium alloy.Above-mentioned metallic substance is made of particle inside that mainly is made of aluminum metal or aluminium alloy and the surface film that is covered this particle inside.This surface film comprises the metallographic phase of the aluminium that contains metallic state and contains the oxide compound of aluminium or the nonactive phase of the oxyhydroxide of aluminium.Contain aluminum metal or aluminium alloy in the aluminium of the metallic state of the invention described above.Because hydrogen generating material contains the metallic substance of above-mentioned form, thereby can generate hydrogen fast and efficiently.
Above-mentioned metallic substance is made of aluminium (fine aluminium) or aluminium alloy.As aluminium alloy, so long as with aluminium for the main composition element gets final product, be not particularly limited for the composition of alloy.As alloying element, for example be silicon, iron, copper, manganese, magnesium, zinc, nickel, titanium, lead, tin or chromium.Aluminium from improve metallic substance contain ratio to increase the viewpoint of hydrogen growing amount, the content of aluminium is preferably more than the 80 quality % in the aluminium alloy.
In general, aluminium forms the densification that the oxyhydroxide by the oxide compound of aluminium or aluminium constitutes and is insoluble in the nonactive surface film that constitutes mutually (oxide film) of water on the surface as the particle inside of aluminum metal.When aluminium and water reaction, the above-mentioned surface film of water saturates just generates hydrogen in case water arrives the aluminum metal of particle inside.Therefore, as hydrogen the conventional hydrogen generating material in source takes place with aluminium, beginning to generate hydrogen to it needs the regular hour.
The result that the inventor studies intensively repeatedly shows, when adopting aluminium to make hydrogen, according to the condition of surface of aluminum particulate, reaching time of beginning to generate hydrogen and reaching the maximum time up to the hydrogen formation speed has very big-difference.Particularly, find: when at least a portion of the surface film that aluminum particulate had, having the metallographic phase of the aluminium that contains metallic state, compare when only having the dense film that the oxyhydroxide by the oxide compound of aluminium or aluminium constitutes, can shorten up to time that hydrogen begins to generate with up to the hydrogen formation speed and reach the maximum time with the surface of aluminum particulate.
Its reason it is believed that and is: owing to there is the metallographic phase of the aluminium that contains metallic state in the surface film of at least a portion, the water saturates surface film, arrive at water before the aluminum metal of particle inside, the above-mentioned metallographic phase that is present on the surface film just reacts with water, become the starting point of reaction, promoted the inner reaction with water of particle, therefore shortened up to time that hydrogen begins to generate with up to the hydrogen formation speed and reach the maximum time.
Be not particularly limited with nonactive form mutually for the metallographic phase in the above-mentioned surface film, but at least a portion of above-mentioned metallographic phase forms stratiform respectively with above-mentioned nonactive at least a portion mutually, if surface film constitutes with the mutual stacked laminate part of the above-mentioned nonactive layer that constitutes mutually by containing the layer that is made of above-mentioned metallographic phase, then the reaction of metallographic phase and water is carried out continuously, and it is higher that reactivity becomes.In addition, the metallographic phase of nominal particle size also can be the dispersive form in nonactive inside mutually.
Do like this, contained metallic substance in the hydrogen generating material of the present invention, because the structure of its surface film, thereby the metallic substance that constitutes with in the past aluminum or aluminum alloy promptly the surface metallic substance that only forms fine and close oxide film compare, shortened up to time that hydrogen begins to generate with up to the hydrogen formation speed and reached the maximum time, can make hydrogen simply, efficiently.
The surface film of above-mentioned metallic substance preferably has hole.Utilize hole water to be easy to be impregnated into the aluminum metallic matrix of surface film and the aluminum metal of particle inside.For example, under the situation that has hole at the interface of the inside of the laminate part of above-mentioned surface film or above-mentioned laminate part and above-mentioned particle inside, the water capacity easily is impregnated into above-mentioned laminate part and above-mentioned particle inside, the contained metallographic phase or the metal of above-mentioned particle inside and the reaction of water become easily in the above-mentioned laminate part, thereby preferred.
The observations in the cross section that utilizes the following embodiment 1 used conventional aluminium powder form of electron microscope observation has been shown among Figure 1A～C.Fig. 2 A～C shows and utilizes electron microscope observation to be all the observations in the cross section of the used metallic substance of hydrogen generating material of the present invention that embodiment 1 makes.Figure 1A and Fig. 2 A show the image that utilizes the observed above-mentioned cross section of scanning electronic microscope (SEM), Figure 1B and Fig. 2 B show the image that utilizes the observed above-mentioned cross section of scanning transmission electron microscope (STEM), Fig. 1 C and Fig. 2 C show in Figure 1B and Fig. 2 B visual field separately, the distribution diagram of element that utilizes X ray energy dispersive analyser (EDX) to obtain.
Show that by Figure 1A for conventional aluminium powder form, there is the surface film of the densification of the about 5nm of thickness in the outside surface of particle inside.Distribute from the element of Fig. 1 C,, therefore think that surface film is the oxide compound or the oxyhydroxide of aluminium because oxygen mostly only is distributed in the surface of aluminium powder form.And, mostly only be aluminium owing to be distributed in the element of particle inside, therefore think that inside is to be made of aluminum metal.
What is called " protective membrane " shown in Figure 1A, B and Fig. 2 A, the B be when electron microscope observation for the protection particle is added in analysis film on the particle surface, the part that is present in the aluminium powder form outmost surface is the part shown in " surface film ".
On the other hand, about metallic substance shown in Fig. 2 A～C, by Fig. 2 A as can be known, at the surface film that exists on the outside surface of the particle inside that is considered to constitute below the about 1 μ m of thickness by aluminum metal.Distribute by the element of Fig. 2 C and to analyze this surface film; as can be known; from outmost surface side (inboard of protective membrane); mainly distributing oxygen layer (promptly; the nonactive layer that constitutes mutually by the oxyhydroxide of oxide compound that contains aluminium or aluminium), with the layer of the aluminium that mainly distributing (promptly; the layer that is made of the metallographic phase of the aluminium that contains metallic state) stratification laminate part mutually, all there be (referring to Fig. 2 B) more than 2 layers in every kind of layer in this laminate part.By Fig. 2 A also as can be known, form hole in the above-mentioned surface film.
Can be at least a portion of the above-mentioned surface film on the hydrogen generating material or have above-mentioned laminate part on the whole, for example, on the part of above-mentioned surface film, form above-mentioned laminate part, other parts only by nonactive constitute mutually also harmless.Particularly, for example for above-mentioned surface film, the ratio of above-mentioned laminate part can account for 25～100 long-pending area % of all surfaces of hydrogen generating material.
Above-mentioned laminate part on the above-mentioned surface film, also can be by metallographic phase constitute the layer and nonactive constitute mutually the layer by successively stacked separately structure, for example also can be, shown in Fig. 2 B, have layer that metallographic phase constitutes and nonactive layer separately 2 layers of mutual stacked structure that constitute mutually.The number of plies upper limit of laminate part does not have special stipulation, for example can be that each layer is respectively 4～5 layers.
The thickness of the above-mentioned laminate part on the above-mentioned surface film for example is preferably below the 2 μ m.If laminate part is blocked up, then, there is the low situation of hydrogen formation efficiency with the increasing proportion of the oxyhydroxide of the oxide compound of the irrelevant aluminium of the reaction that generates hydrogen or aluminium.The lower thickness limit of above-mentioned laminate part for example can be 10nm.
Above-mentioned metallic substance preferably contains the aluminium of the above metallic state of 60 quality %, more preferably contains more than the 70 quality %.If the content of the metallic aluminum in the metallic substance is low, then the hydrogen generating capacity is low.
Though aluminium is in warm-up mode, the part on surface and water reaction generate hydrogen, but because in surface formation stable oxide film, become under piece (bulk) state in tabular, bulk or the what is called such as particle more than the 1mm not react with water, the hydrogen growing amount of at room temperature every 1g metallic substance is below the 5mL.
Therefore, the ratio of the particle that the metallic substance preferable particle size 60 μ m that hydrogen generating material of the present invention adopts are following is more than the 80 volume %, more preferably more than the 90 volume %.As the median size of metallic substance, below the preferred 30 μ m, more preferably below the 20 μ m.But the form of metallic substance is not limited to particle state, and the shape of tinsel one class is also harmless.
Think that aluminium generates the reaction of hydrogen and oxidation resultant according to any carries out in following formula (1)～(3).
2Al+6H
2O→Al
2O
3·3H
2O+3H
2(1)
2Al+4H
2O→Al
2O
3·H
2O+3H
2(2)
2Al+3H
2O→Al
2O
3+3H
2(3)
As mentioned above, aluminium carries out above-mentioned reaction with block state, because of form the oxide film stabilization on the surface.But by reducing particle diameter, the aluminium of particle inside and the reaction of water are not easy to be subjected to the obstruction of oxide film, and the reaction that therefore generates hydrogen is carried out continuously.That is, have at metallic substance under the situation of above-mentioned size-grade distribution and median size, can reduce hydrogen is generated because of the formation of oxide film restraining effect to the reaction of aluminium and water.
On the other hand, under the too small situation of the particle diameter of metallic substance, improve though generate the speed of hydrogen, inflammableness improves, and carries out the operation difficulty that becomes in air.And because volume density reduces, the tamped density of hydrogen generating material reduces easily in the apparatus for forming hydrogen, and energy density reduces easily.Therefore, the median size of metallic substance is preferably more than the 0.1 μ m in the hydrogen generating material.
The median size of the metallic substance described in this specification sheets is meant the value of accumulative total ratio (accumulative total volume fraction) 50% particle diameter according to volume reference.The size-grade distribution of the metallic substance described in this specification sheets and median size are meant the value of utilizing laser diffraction-scattering method.Particularly this method is to have utilized the determination object material irradiating laser in making liquid phases such as being scattered in water and the measuring method that detects the size distribution of scattering strength.Utilize the particle size distribution analyzer of laser diffraction-scattering method for example can adopt " MICROTRAC HRA " that Nikkiso Company Limited makes etc.
Metallic substance with the surface film that contains above-mentioned laminate part can obtain by following method: in the liquid that contains water and organic solvent, pulverize aluminum or aluminum alloy, carry out the surface modification of above-mentioned metallic substance after, remove aforesaid liquid.
Aluminium that uses as hydrogen generation source and aluminium alloy are by being pulverized, and its surface-area increases, and the formation speed of hydrogen improves., stampping general mechanical crushing method pulverizing aluminium such as method, ball milled, vibro-grinding method if adopt herein, is that the metal that is imbued with ductility extends into the paper tinsel shape owing to aluminium then, becomes the flakey powder with metalluster.
Relative therewith, if in the liquid that contains water and organic solvent mechanical disintegration aluminium and aluminium alloy, then can access the granular micro mist of black, mince with the aluminium powder that adopts above-mentioned general mechanical disintegration manufactured and compare, become the metallic substance that can generate hydrogen fast.Its reason it is believed that and is: as mentioned above, by adopting above-mentioned preparation method, form surface film on the surface of above-mentioned metallic substance, this surface film comprises oxyhydroxide mutually nonactive of the metallographic phase of the aluminium that contains metallic state and oxide compound that contains aluminium or aluminium.In addition, by adopting above-mentioned preparation method, at least a portion of metallographic phase and at least a portion of non-active layer form stratiform respectively, and above-mentioned surface film becomes layer and the mutual stacked laminate part of the above-mentioned nonactive layer that constitutes mutually with above-mentioned metallographic phase formation.And, in the above-mentioned surface film that particle surface forms, form hole by adopting above-mentioned preparation method.
As mentioned above, hydrogen generating material of the present invention utilizes the metallic substance of pulverizing aluminum or aluminum alloy formation in the liquid that contains water and organic solvent to obtain.Only do not constitute if the liquid that uses when pulverizing is moisture by organic solvent, then part or all of pulverizing back metallic substance becomes the flakey particle with metalluster, the formation efficiency of hydrogen is low, and, adhere to crushed material easily on the inner-wall surface of the pulverizing of shredding unit with vessel etc., so can not make required metallic substance efficiently.
On the other hand, pulverize in the aluminum or aluminum alloy that employed liquid does not contain organic solvent and when only being made of water, the oxidation of metal material surface or hydroxide can be carried out excessively because of pulverizing.If therefore oxide compound or oxyhydroxide can form in a large number, the growing amount of the then content of the metallic aluminium in metallic substance reduction, hydrogen reduces.That is, contain organic solvent in the aforesaid liquid by making, oxidizing reaction or hydroxide reaction when aluminum or aluminum alloy is pulverized in control, can the adjustment sheet facial mask in the thickness of above-mentioned laminate part.Can also adjust the thickness of above-mentioned laminate part by the control pulverizing time.
With regard to pulverizing the employed aforesaid liquid of aluminum or aluminum alloy, for forming above-mentioned surface film structure, for aluminum or aluminum alloy 1 mass parts of pulverizing, the content of water is preferably more than 0.02 mass parts, more preferably more than 0.1 mass parts.On the other hand, in order to suppress the oxidation of aluminum or aluminum alloy in pulverizing, the content of water is preferably below 2 mass parts, more preferably below 1 mass parts, most preferably below 0.4 mass parts.If the hypovolia in the aforesaid liquid, then the surface modification of metallic substance is insufficient, obtains having the flakey powder of metalluster easily, and the hydrogen formation efficiency of metallic substance descends.If the hypervolia in the aforesaid liquid, then the metallic aluminium content in the metallic substance reduces, and causes the hydrogen growing amount low.
Being used to constitute the organic solvent of aforesaid liquid, if difficult solvent with aluminium and aluminium alloy reaction then is not particularly limited, and is also harmless with the immiscible solvent of water.Particularly, aliphatic hydrocarbons such as aromatic hydrocarbons, hexane, hexanaphthene such as toluene for example, ketones such as acetone, ethers, N, dinethylformamide etc.In the above-mentioned organic solvent, the solvent that becomes azeotropic mixture with water for example toluene, hexanaphthene etc. owing to from crushed material, remove aforesaid liquid easily, therefore more suitable.Above-mentioned organic solvent only adopt a kind also can, adopt also harmless more than 2 kinds.In addition, also can adopt alcohols, the alcohol of lower molecular weight (for example carbon number is below 10) is compared with the above-mentioned organic solvent of enumerating as methyl alcohol and ethanol, it is reactive high solvent with aluminium, though also with good grounds condition and reactive aluminum generate the possibility of metal alkoxides alkoxide, but with water than being the quite low solvent of this reactivity, therefore can replace the above-mentioned organic solvent of enumerating or together use with the above-mentioned organic solvent of enumerating.
The aforesaid liquid that adopts for the pulverizing of aluminum or aluminum alloy, the usage rate of water and organic solvent not necessarily will limit, but for example for water 1 mass parts, the carrying out that suppresses the oxidation of metallic substance for appropriateness, the amount of organic solvent is preferably more than 5 mass parts, on the other hand, in order to improve the effect of surface modification, the amount of organic solvent is preferably below 300 mass parts.
There is no particular restriction for the method for pulverizing aluminum or aluminum alloy in the liquid that contains water and organic solvent, for example can adopt the mechanical crushing method that uses ball mill, sand mill, vibrating mill or injector-type mill etc.During the metallic substance that in making hydrogen generating material of the present invention, adopted,, the mechanism that discharges this hydrogen is set preferably in shredding unit as described above owing in pulverizing, generate hydrogen.
Can utilize the metallic substance that obtains by such operation to make hydrogen generating material of the present invention, but as mentioned above, above-mentioned metallic substance preferably contain more than the aluminium 60 quality % of metallic state, more preferably contains more than the 70 quality %.If the content of the aluminium of metallic state is low in the metallic substance, then the growing amount of hydrogen is low.Among the present invention,, therefore be difficult to make the aluminium element that contains in the metallic substance all to become metallic state owing in liquid, aqueous, pulverize.But as mentioned above, contain organic solvent by making in the used liquid of pulverizing, control the water-content in this liquid, can control the amount of oxidation of aluminum or aluminum alloy in the pulverizing, thus the present invention can adopt the aluminium that contains a large amount of metallic states, and the metallic substance that can efficiently generate hydrogen make hydrogen generating material.
In this specification sheets, the content of the aluminium of metallic state in the metallic substance (aluminum metal or aluminium alloy) is measured by following manner.If with X-ray diffraction device analysis metallic substance, may observe aluminum metal and aluminium hydroxide.Therefore, utilize x-ray fluorescence analysis (XRF) to measure the aluminium element in the metallic substance and the content of oxygen element, obtain the content of aluminium hydroxide again by the content of oxygen element, the content of remainder as the aluminium of metallic state.
If in aforesaid liquid, pulverize aluminum or aluminum alloy, can access approximate spherical or irregular granulous metallic substance.Such metallic substance is thicker than the flakey particle that adopts general mechanical efflorescence method to make.
Hydrogen generating material of the present invention can be made by above-mentioned metallic substance is mixed with following exothermic material and additive etc.But, because above-mentioned metallic substance and water is reactive good, even therefore reduce the content of exothermic material and additive etc. or do not add, also can be easy and hydrogen is generated, can make the energy density raising.
In addition, the form of above-mentioned hydrogen generating material is not particularly limited,, more preferably is configured as bead (pellet) shape or particulate state even for example the powder shaped of above-mentioned metallic substance (particle shape) form is also passable.If with the hydrogen generating material compression molding of powder shaped is coccoid, then because tamped density improves, volume reduces, energy density improves.When being configured as particulate state,, can improve the formation speed of hydrogen by granulation makes it to become for example particulate state of millimeter level size to hydrogen generating material.
Hereinafter will describe in detail, to hydrogen generating material of the present invention, preferably heating when itself and water are reacted, except that from indirect heating, can also coexist when hydrogen generating material and the water reaction by making the exothermic material that generate heat with water reaction, thereby utilize the reaction of this exothermic material and water and the heat that produces.Therefore, above-mentioned hydrogen generating material also preferably contains the exothermic material of heating with the water reaction.Can exemplify out the reaction of calcium oxide, magnesium oxide, calcium chloride, magnesium chloride, calcium sulfate etc. and water and generate heat or as such exothermic material by the basic metal of hydration heating or the exothermic materials such as oxide compound of alkaline-earth metal.Also can adopt the metal powder that as iron powder, generates heat as exothermic material with the oxygen reaction.
When in making hydrogen generating material of the present invention, containing above-mentioned exothermic material, from improving the viewpoint of hydrogen formation speed, the content of above-mentioned exothermic material for example is preferably more than the 1 quality % with respect to the hydrogen generating material total mass, more preferably more than the 3 quality %, and from the viewpoint of the growing amount of hydrogen, below for example preferred 15 quality %, more preferably below the 10 quality %.
When in making above-mentioned hydrogen generating material, containing above-mentioned exothermic material, preferably be configured as the hydrogen generating material that also contains this exothermic material coccoid or particulate state.
Can make hydrogen generating material of the present invention contain multiple additives according to various purposes.
For example make and contain hydrophilic oxide (aluminum oxide, silicon-dioxide, magnesium oxide, zinc oxide etc.), carbon, absorbent polymer (carboxymethyl cellulose, polyvinyl alcohol, polyoxyethylene glycol etc.) etc. in the hydrogen generating material, can make hydrogen is generated as above-mentioned additive.These additives can only use a kind, more than 2 kinds and with also harmless.Can think like this: owing to contain above-mentioned additive, above-mentioned metallic substance becomes good with contacting of water, can prevent that the resultant of reaction and the unreacted metal material that are generated by the reaction of metallic substance and water from condensing, and, making under the situation of following bead, because the effect of water saturates to bead inside etc. can make hydrogen generate efficiently.
When adopting above-mentioned various additive, viewpoint from the formation efficiency of hydrogen, above-mentioned content of additive for example is preferably more than the 1 quality % with respect to the hydrogen generating material total mass, more preferably more than the 10 quality %, and from the viewpoint of hydrogen growing amount, for example the total mass with respect to hydrogen generating material is preferably below the 30 quality %, more preferably below the 20 quality %.
Hydrogen generating material of the present invention and manufacture method thereof are illustrated method for preparing hydrogen and the hydrogen production device that adopts hydrogen generating material of the present invention as mentioned above below.
Hydrogen generating material of the present invention is to generate hydrogen by it is contacted with water, but in order to make the reactive hydrogen formation speed more than the certain value that improves, obtains, should obtain promoting by make reaction from indirect heating.Heating temperature is preferred more than 40 ℃, for anti-sealing evaporates preferred below 95 ℃.As heating means, if hydrogen generating material and water can be remained on the method for said temperature scope, then there is no particular restriction to this method, for example can adopt by to the electrically heated of resistance energising, utilize the chemical heat of chemical exothermic reaction etc., can adopt the method that the container that hydrogen generating material and water are housed is heated from the outside.
As the employed pyrotoxin of above-mentioned chemical heat, for example, can adopt the reaction of above-mentioned conduct that exemplifies out and water and all cpds of exothermic material of heating.About exothermic material, make the reaction of itself and water and generate heat, the reaction vessel of hydrogen generating material is equipped with in available this heat heating, but also can together be contained in exothermic material and hydrogen generating material in the reaction vessel, makes it at reaction vessel internal heat generation, direct heating hydrogen generating material.In this case, preferably the above-mentioned suitable content when making hydrogen generating material contain exothermic material in advance is identical for the usage quantity of exothermic material.That is, the usage quantity of above-mentioned exothermic material is preferably more than the 1 quality % with respect to the total mass of hydrogen generating material and exothermic material, and below the preferred 30 quality %.
Therefore the reaction of aluminum or aluminum alloy and water is thermopositive reaction, rises if prevent the heat release of this reaction heat, the temperature that reaction heat is used for hydrogen generating material and water, then even without above-mentioned pyrotoxin hydrogen is generated continuously.
And,, can control the growing amount of hydrogen by controlling the supply of the water that reacts with hydrogen generating material.
Hydrogen generating material of the present invention can use as hydrogen generation source in apparatus for forming hydrogen, and described apparatus for forming hydrogen has the container that holds this hydrogen generating material and water, makes the portion's reaction within it of this hydrogen generating material and water, has the mechanism that extracts the hydrogen that generates.Said vesse in the above-mentioned apparatus for forming hydrogen can adopt the above-mentioned heating means from indirect heating hydrogen generating material and water, also can adopt the method that promotes that hydrogen generates as required.At this moment, can control the growing amount of hydrogen by the control Heating temperature.
Form and shape to the said vesse in the above-mentioned apparatus for forming hydrogen are not particularly limited, but preferably have the supplying opening of water and hydrogen relief outlet and can sealed inside, water and hydrogen can be to the structures of external leakage.Even, then be not particularly limited if the material that said vesse adopted is that be difficult to permeate water and hydrogen and be heated to 100 ℃ can damaged material yet.For example can adopt metal and resins such as polyethylene, polypropylene such as thermal glass, titanium, nickel.Fig. 5 be pattern the sectional view of an example of above-mentioned apparatus for forming hydrogen is shown.Among Fig. 5, apparatus for forming hydrogen 1 is made of container body 2 and lid 3, and lid 3 has the relief outlet 5 that is used to supply with the supplying opening 4 of water and is used to make hydrogen to discharge.Supplying opening 4 is connected by supply-pipe 7 with tubular pump 6.Vent pipe 8 is connected on the relief outlet 5.The inside housing hydrogen generating material 9 of container body 2.Utilize tubular pump 6 to supply with water 10 to apparatus for forming hydrogen 1 continuously, make hydrogen generating material 9 and the water 10 generation hydrogen that reacts, this hydrogen (H
2) can take out from the vent pipe 8 that is connected on the relief outlet 5.Tubular pump 6 can adopt the encloses container of resin layer system to constitute.
The hydrogen relief outlet 5 of above-mentioned apparatus for forming hydrogen preferably strainer is set so that the content in the container body 2 not to external leakage.If this strainer is can be by gas but be difficult to then be not particularly limited by liquid and solid structure, also can adopt the gas-liquid separation membrane of used porousness tetrafluoroethylene system such as fuel cell.Also can adopt the membranous polypropylene system porous film that is used as battery.
In the above-mentioned apparatus for forming hydrogen 1, preferably can dominant discharge to the supply of the water of the inside of container body 2, by as the supply of above-mentioned control water, can control the amount that generates hydrogen.
The hydrogen that utilizes hydrogen generating material of the present invention to generate is not contained in the CO and the CO that become problem in the hydrogen that utilizes the hydrocarbon based fuel modification to obtain
2Therefore, the above-mentioned problem that causes poisoning of catalyst because of gas does not take place at the polymer electrolyte fuel cell of working below 100 ℃, and, owing to relate to water in the reaction, so contain amount of water in the gas for being very useful for the fuel cell of fuel with hydrogen.
The present invention is described in detail according to embodiment below.
Experiment 1: the preparation of metallic substance and hydrogen generating material and the test that generates hydrogen
To be that (particle diameter: 2 μ m) 85g puts into the pulverizing of planetary ball mill with vessel, with the speed of rotation pulverizing aluminium powder form of 200rpm for the bead of aluminium powder form 5g, toluene 15g, water 1g (is 0.2 mass parts with respect to 1 mass parts aluminium powder form) and the zirconium white system of 55 μ m by the median size of atomization preparation.Owing in crushing process, generated hydrogen, stop even therefore rotate rotate after 10 minutes, after being given off, rotates once more the hydrogen that generates in the vessel.Carry out this operation repeatedly, make vessel add up to rotation 1 hour.Subsequently, remove toluene and water, obtain being used to constitute the metallic substance of hydrogen generating material of the present invention by drying under reduced pressure.The metallic substance that obtains has lost surperficial metalluster and has presented black dark brownly, and becoming median size is the irregular granulous particle of 12 μ m.The median size of metallic substance utilizes Nikkiso Company Limited's system " MICROTRACHRA " to measure.When measuring the content of metallic aluminium in this metallic substance with aforesaid method, this content is 80 quality %.When measuring as raw material, content by the metallic aluminium in the aluminium powder form of atomization preparation with same way as, this content is more than the 99 quality %.
Illustrated among Figure 1A～C by electron microscope observation arrive when the preparation embodiment 1 described metallic substance, as starting material, the cross-section result of aluminium powder form by the atomization preparation.Illustrated among Fig. 2 A～C by electron microscope observation to embodiment 1 in the cross-section result of metallic substance of preparation.As previously mentioned, Figure 1A and Fig. 2 A show the image that utilizes the observed above-mentioned cross section of scanning electronic microscope (SEM), Figure 1B and Fig. 2 B show the image that utilizes the observed above-mentioned cross section of scanning transmission electron microscope (STEM), and Fig. 1 C and Fig. 2 C show the element reflection that utilizes X ray energy dispersive spectrum (EDX) to obtain respectively in Figure 1B and Fig. 2 B visual field separately.
As mentioned above, there is the compact surfaces film of about 5nm of the oxygen that mainly distributing in the starting material aluminium powder form shown in Figure 1A～C on the outside surface of the particle inside of the aluminium that mainly distributing.That is, the starting material aluminium powder form is being considered to exist the surface film that is considered to oxide film on the particle surface that is made of aluminum metal.
Relative therewith, embodiment 1 described metallic substance shown in Fig. 2 A～C, in the particle inside of the aluminium that mainly distributing (promptly, the particle inside that constitutes by aluminum metal) on the outside surface, exist by the main oxygen that distributing the layer (promptly, nonactive mutually that contains the oxyhydroxide of the oxide compound of aluminium or aluminium) and the layer (that is the metallographic phase that, contains the aluminium of metallic state) of the aluminium that mainly distributing is successively alternately laminated, to contain laminate part, thickness with each layer of plural layer be the following surface film of about 1 μ m.
Use above-mentioned metallic substance to make hydrogen generating material separately, carried out generating the test of hydrogen.Above-mentioned metallic substance 1g and water 10g are put into sample plasma bottle, at the arranged outside resistance of sample plasma bottle.By resistance sample plasma bottle is heated to 50 ℃, hydrogen is generated, utilize substitution method waterborne to collect the hydrogen that generates, measure the growing amount of hydrogen.
Comparative example 1
Keep intact as hydrogen generating material being used as raw-material aluminium powder form among the embodiment 1, carry out the test of the generation hydrogen identical, measured the growing amount of hydrogen with embodiment 1.
For the hydrogen generating material of embodiment 1 and comparative example 1, measured the amount of the hydrogen that both sides collect separately respectively every two minutes, obtain from on-test of generating hydrogen to the time that begins to generate hydrogen.Simultaneously, change according to time of the collecting amount of hydrogen and to obtain the formation speed of hydrogen, and the formation speed of obtaining up to hydrogen reaches the peaked time.These results are as shown in table 1.
[table 1]
According to table 1, by in the liquid that contains water and organic solvent, aluminium powder form being pulverized the embodiment 1 described metallic substance for preparing, compare with the raw material powder as metallic substance in the comparative example 1, it is up to the time that generates hydrogen and reach the maximum time up to the formation speed of hydrogen and all significantly shorten.Consider from particle cross-sectional image shown in Fig. 2 A～C, this is because the part of surface film is made of with nonactive laminate part mutually metallographic phase, the water saturates surface film, before water arrives the aluminum metal of particle inside, metallographic phase just reacts the starting point that becomes reaction with water in the above-mentioned laminate part of surface film, the inner reaction with water of particle is promoted, thereby up to the time that generates hydrogen with reach the maximum time up to the formation speed of hydrogen and significantly shorten.In addition, the inner hole that exists of observed above-mentioned laminate part also is significantly to shorten up to the time that generates hydrogen and reach the one of the main reasons of maximum time up to the formation speed of hydrogen in embodiment 1 described metallic substance.
Change to the 0.5g (is 0.1 mass parts with respect to 1 mass parts aluminium powder form) except pulverizing the water yield that aluminium powder form adopts, adopt the mode identical to prepare metallic substance, generate the test of hydrogen, the growing amount of mensuration hydrogen with embodiment 1.
Except the more quantitative change of 3g, water more the 3g (is 1 mass parts with respect to 1 mass parts aluminium powder form) of the quantitative change of the aluminium powder form that uses in pulverizing, adopt the mode identical to prepare metallic substance with embodiment 1, generate the test of hydrogen, the growing amount of mensuration hydrogen.
Except the more quantitative change of 1g, water more the 3g (is 3 mass parts with respect to 1 mass parts aluminium powder form) of the quantitative change of the aluminium powder form that uses in pulverizing, adopt the mode identical to prepare metallic substance with embodiment 1, generate the test of hydrogen, the growing amount of mensuration hydrogen.
Except the TRH of pulverizing with vessel changed to 10 minutes, adopt the mode identical to prepare metallic substance with embodiment 1, generate the test of hydrogen, the growing amount of mensuration hydrogen.
Change to the 0.05g (is 0.01 mass parts with respect to 1 mass parts aluminium powder form) except pulverizing the water yield that aluminium powder form adopts, adopt the mode identical to prepare metallic substance, generate the test of hydrogen, the growing amount of mensuration hydrogen with embodiment 1.
The metallic substance 0.9g and the median size aluminum oxide 0.1g that is 1 μ m of preparation among the embodiment 1 are mixed the preparation hydrogen generating material in mortar.Adopt this hydrogen generating material, utilize the mode identical to generate the test of hydrogen, the growing amount of mensuration hydrogen with embodiment 1.
The metallic substance 0.93g and carbon (" バ Le カ Application XC-72R " that the キ ヤ ボ Star ト company makes) 0.07g of preparation among the embodiment 1 are mixed the preparation hydrogen generating material.Adopt this hydrogen generating material, utilize the mode identical to generate the test of hydrogen, the growing amount of mensuration hydrogen with embodiment 1.
The metallic substance 0.96g and carboxymethyl cellulose (manufacturing of the ダ イ セ Le company) 0.04g of preparation among the embodiment 1 are mixed the preparation hydrogen generating material.Adopt this hydrogen generating material, utilize the mode identical to generate the test of hydrogen, the growing amount of mensuration hydrogen with embodiment 1.
Comparative example 2
Except pulverizing the used liquid of aluminium powder form only be the water 16g, adopts the mode identical with embodiment 1 to prepare metallic substance, generates the test of hydrogen, the growing amount of mensuration hydrogen.
Comparative example 3
Except pulverizing the used liquid of aluminium powder form only be the toluene 15g, adopts the mode identical with embodiment 1 to prepare metallic substance, generates the test of hydrogen, the growing amount of mensuration hydrogen.
Adopt the mode identical to measure the median size of metallic substance in embodiment 2～9 and the comparative example 2,3 and the content of the metallic aluminium in the metallic substance with embodiment 1.Its result is also as shown in table 2.
In Fig. 3, be transverse axis, be the size distribution curve that the longitudinal axis shows metallic substance in embodiment 1,2 and 5 with frequency (volume %) with the particle diameter (μ m) of metallic substance.As seen from Figure 3, particle diameter is that the ratio of the following particle of 60 μ m is more than the 80 quality % in embodiment 1,2 and each metallic substance of 5.
[table 2]
[table 3]
By in the liquid that contains water and organic solvent, pulverizing embodiment 1～9 described hydrogen generating material that aluminium powder form prepares, wherein any material up to the time that begins to generate hydrogen and to reach maximum time up to the formation speed of hydrogen all short than comparative example 1 described hydrogen generating material, can obtain and can react and the hydrogen generating material of generation hydrogen with water easily.But, because the forms of size-grade distribution and surface film etc. are because of the treatment condition of metallic substance are different, so the maximum value of the formation speed of the growing amount of hydrogen and hydrogen there are differences.
Embodiment 2 compares with embodiment 1 described hydrogen generating material with embodiment 5 described hydrogen generating materials, and the value of the growing amount of hydrogen and the formation speed of hydrogen is less.This is that the particle diameter of the particle diameter ratio embodiment 1 described metallic substance of embodiment 2 and embodiment 5 described metallic substance is big because as shown in Figure 3, and surface-area is lower.Embodiment 3 described hydrogen generating materials, though the formation speed of hydrogen improves, the growing amount of hydrogen reduces.Its reason is, because the particle diameter of metallic substance diminishes, thereby reaction area increases, and the formation speed of hydrogen is improved, but because the water that adds during pulverization process is many, aluminium generation oxidation, thereby the aluminium of metallic state reduces.Because the ratio of the water that when pulverization process, adds of embodiment 4 described hydrogen generating materials many than among the embodiment 3, and aluminium generation oxidation, so the formation speed of the growing amount of hydrogen and hydrogen low than among the embodiment 1.Therefore think that the ratio of aluminium and water when changing pulverization process can be controlled the content of metallic aluminium, can control the growing amount of hydrogen and the formation speed of hydrogen.Clear and definite in addition, the ratio of aluminium and water can be controlled the particle diameter of metallic substance during by the change pulverization process.By embodiment 5 as can be known, also can control particle diameter by changing the pulverizing time.Think and to control particle diameter, thereby can control the growing amount of hydrogen and the formation speed of hydrogen by controlling these pulverization conditions.
The metallic substance that embodiment 6 adopts reduces the ratio of pulverizing the water in the used liquid of aluminium powder form and prepares, but the metallic substance major part after pulverizing is attached to the surface of pulverizing with vessel.In addition, can obtain the lepidiod particle that a part has metalluster.When generating the test of hydrogen as hydrogen generating material,, be difficult to and the water reaction, so the growing amount of hydrogen is lower than embodiment 1 because metallic substance floats on the water with this metallic substance.On the contrary, the metallic substance that embodiment 1～5 and embodiment 7～9 adopt sinks in the water, and is good with the affinity of water.
Among the embodiment 7, owing to be to add the hydrogen generating material that aluminum oxide is made as additive, therefore compare with embodiment 1 described hydrogen generating material, though the content of metallic substance is reduced to 90 quality %, but because aluminum oxide promotes reaction, the reactivity of aluminium improves in the metallic substance, therefore can obtain hydrogen growing amount and the hydrogen formation speed equal with embodiment 1.Reason it is believed that and be, by adding aluminum oxide, prevented the condensing of resultant of reaction of unreacted metal material and metallic substance.Make the embodiment 8 and the adding absorbent polymer carboxymethyl cellulose of hydrogen generating material makes as additive among the embodiment 9 of hydrogen generating material as additive at adding carbon, similarly to Example 7, though compare the content of metallic substance reduces with the hydrogen generating material of embodiment 1, but also can guarantee 1 equal above hydrogen growing amount and hydrogen formation speed with embodiment, about carbon in the hydrogen generating material and absorbent polymer, clear and definite they also have and the same effect of embodiment 7 used aluminum oxide.
On the other hand, pulverize in the comparative example 2 of aluminium powder form, because most of aluminium oxidation in the pulverization process, so generate in the test of hydrogen and can only obtain very a spot of hydrogen with the water reaction at water only.
In comparative example 3, only carried out the pulverizing of aluminium powder form with water-free organic solvent, but attached to pulverizing with the amount of the crushed material of vessel surface and to have a ratio of flakey particle of metalluster bigger than embodiment 6.And, promptly use this crushed material to generate the test of hydrogen, crushed material also floats on the water, and the growing amount of hydrogen is extremely low.Its reason it is believed that and is: have irregular granulous form with respect to embodiment 1～5 described metallic substance, comparative example 3 described crushed materials are the flakey form, and surface texture is also different, and the generation of hydrogen is had detrimentally affect.
About embodiment 2～6 described metallic substance, by with its cross section of electron microscope observation the time or corrode its surface with Ar and adopt x-ray photoelectron spectroscopy (XPS) simultaneously, when carrying out the analysis of depth direction based on the peak of the metallic state of aluminium with based on the peak of the 2p of oxide compound (or oxyhydroxide), there is surface film in the surface that can confirm each metallic substance, and this surface film has the laminate part of structure shown in the mode chart of Fig. 4.
The temperature of sample plasma bottle changes to 45 ℃ in the test that generates hydrogen, adopts the mode identical with embodiment 1 to measure the growing amount of hydrogen.
The temperature of sample plasma bottle changes to 40 ℃ in the test that generates hydrogen, adopts the mode identical with embodiment 1 to measure the growing amount of hydrogen.
With regard to the foregoing description 10 and 11, the maximum value of the growing amount of hydrogen and the formation speed of hydrogen is as shown in table 4.
[table 4]
The embodiment 10 and 11 that the Heating temperature of sample plasma bottle is changed can confirm that also it all generates hydrogen, can confirm if hydrogen generating material is heated to more than 40 ℃ the growing amount of hydrogen and the formation speed of hydrogen are significantly improved.Sample plasma bottle is heated to 50 ℃ embodiment 1, and it is in the heating beginning after 14 minutes that the formation speed of hydrogen reaches maximum, and the formation speed of hydrogen sharply descends subsequently.In contrast, with the embodiment 10 and the embodiment 11 of 45 ℃ and 40 ℃ heating sample bottles,, can generate hydrogen long-term and stably though the formation speed of hydrogen is lower than embodiment 1.Therefore think,, also can control the formation speed of hydrogen by the control Heating temperature.
Experiment 2: utilize apparatus for forming hydrogen to generate the test of hydrogen
To adopt metallic substance 1g to put into the glass container body that internal volume shown in Figure 5 is 50mL with the preparation of embodiment 1 same way as.With the lid of the relief outlet of supplying opening with water and hydrogen with this container body sealing.At the arranged outside of container body resistance as the heating measure.Confirmed to resistance energising container body is being heated under 50 ℃ the state, when the speed of dividing with 0.02mL/ from the supplying opening of water with tubular pump supplies water, with the embodiment 1 the same hydrogen that generates.And stop to generate hydrogen after having confirmed to stop to supply water several minutes.
Embodiment 13
Confirm to replace stopping among the embodiment 12 to supply water, when stopping heating and make the container naturally cooling, stopped generating hydrogen after several minutes.
Experiment 3: the manufacturing of polymer electrolyte fuel cell
Adopt the mode identical that hydrogen is generated, the hydrogen supply polymer electrolyte fuel cell that generates is carried out discharge test with embodiment 1.Consequently can at room temperature obtain 200mW/cm
2High-output power, visible hydrogen generating material of the present invention is effective as the fuel source of small-sized movable-type fuel cell.
Among the present invention, in the scope that does not break away from its purport, also has the embodiment of form except that above-mentioned.Disclosed example is some examples wherein among the application, and is not limited to this.Compare with the content of above-mentioned specification sheets record, scope of the present invention is preferentially put down in writing with the scope of additional claims and is explained that the whole changes in the scope identical with the scope of claim all comprise within the scope of the claims.
Industrial applicibility
As mentioned above, if utilize the present invention, just can provide easy and generate efficiently the hydrogen generation material of hydrogen Material and manufacture method thereof and the method for preparing hydrogen take above-mentioned hydrogen generating material as hydrogen source. With institute of the present invention State hydrogen generating material as hydrogen source, can realize the miniaturization of apparatus for forming hydrogen and fuel cell.
Claims (19)
1. hydrogen generating material, it is to contain the hydrogen generating material that is selected from least a kind of metallic substance in aluminium and the aluminium alloy, it is characterized in that described metallic substance has surface film, this surface film comprises the mutually nonactive of the metallographic phase of the aluminium that contains metallic state and oxide compound that contains aluminium or oxyhydroxide.
2. hydrogen generating material as claimed in claim 1 is characterized in that, described surface film contains the laminate part of the layer that is made of described metallographic phase and the described nonactive mutual stratification of layer that constitutes mutually.
3. hydrogen generating material as claimed in claim 2 is characterized in that, described laminate part is the layer and the described nonactive layer separately stratification more than 2 layers that constitutes mutually that is made of described metallographic phase.
4. hydrogen generating material as claimed in claim 2 is characterized in that, the thickness of described laminate part is below the 2 μ m.
5. hydrogen generating material as claimed in claim 1 is characterized in that described surface film has hole.
6. hydrogen generating material as claimed in claim 1 is characterized in that, contained particle diameter is that the ratio of the following particle of 60 μ m is more than the 80 volume % in the described metallic substance.
7. hydrogen generating material as claimed in claim 1 is characterized in that, the median size of described metallic substance is below the 30 μ m.
8. hydrogen generating material as claimed in claim 1 is characterized in that, described metallic substance contains more than the aluminium 60 quality % of metallic state.
9. hydrogen generating material as claimed in claim 1 is characterized in that, also contains the exothermic material of heating with the water reaction.
10. hydrogen generating material as claimed in claim 1 is characterized in that, also contains to be selected from hydrophilic oxide, carbon and the absorbent polymer at least a kind additive.
11. the manufacture method of hydrogen generating material, the manufacture method that it is served as reasons and is selected from least a kind of formation in aluminium and the aluminium alloy and contains the hydrogen generating material of the metallic substance with surface film, and this surface film comprises the mutually nonactive of the metallographic phase of the aluminium that contains metallic state and oxide compound that contains aluminium or oxyhydroxide, it is characterized in that this method is included in the operation of pulverizing aluminum or aluminum alloy in the liquid that contains water and organic solvent.
12. the manufacture method of hydrogen generating material as claimed in claim 11 is characterized in that, the content of water is more than 0.02 mass parts below 2 mass parts with respect to 1 mass parts aluminum or aluminum alloy in the described liquid.
13. the manufacture method of hydrogen generating material as claimed in claim 11 is characterized in that, the content of water is more than 0.1 mass parts below 1 mass parts with respect to 1 mass parts aluminum or aluminum alloy in the described liquid.
14. the manufacture method of hydrogen generating material as claimed in claim 11 is characterized in that, described organic solvent contains toluene.
15. the manufacture method of hydrogen generating material as claimed in claim 11 is characterized in that, also is included in the operation of adding the exothermic material of heating with the water reaction in the aluminum or aluminum alloy through pulverizing.
16. the manufacture method of hydrogen generating material as claimed in claim 11 is characterized in that, described surface film contains the laminate part of the layer that is made of described metallographic phase and the described nonactive mutual stratification of layer that constitutes mutually.
17. the manufacture method of hydrogen generating material as claimed in claim 11 is characterized in that, described surface film has hole.
18. method for preparing hydrogen is characterized in that, comprises by making the reaction of described hydrogen generating material of claim 1 and water generate the operation of hydrogen.
19. method for preparing hydrogen as claimed in claim 18 is characterized in that, also comprises the operation of described hydrogen generating material of heating and water.
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