CN101151208A - Hydrogen storage structure - Google Patents
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- CN101151208A CN101151208A CNA2006800104841A CN200680010484A CN101151208A CN 101151208 A CN101151208 A CN 101151208A CN A2006800104841 A CNA2006800104841 A CN A2006800104841A CN 200680010484 A CN200680010484 A CN 200680010484A CN 101151208 A CN101151208 A CN 101151208A
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 390
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 390
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 260
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 131
- 238000009792 diffusion process Methods 0.000 claims abstract description 85
- 239000000463 material Substances 0.000 claims abstract description 45
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 28
- 239000000956 alloy Substances 0.000 claims abstract description 28
- 239000011777 magnesium Substances 0.000 claims description 91
- 229910052749 magnesium Inorganic materials 0.000 claims description 36
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 21
- 229910010389 TiMn Inorganic materials 0.000 claims description 8
- 229910010340 TiFe Inorganic materials 0.000 claims description 5
- 229910010169 TiCr Inorganic materials 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 19
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 42
- 238000000034 method Methods 0.000 description 12
- 239000011358 absorbing material Substances 0.000 description 8
- 238000005070 sampling Methods 0.000 description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 239000000446 fuel Substances 0.000 description 3
- 150000004678 hydrides Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910017961 MgNi Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 229910020068 MgAl Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910001234 light alloy Inorganic materials 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
- C01B3/0084—Solid storage mediums characterised by their shape, e.g. pellets, sintered shaped bodies, sheets, porous compacts, spongy metals, hollow particles, solids with cavities, layered solids
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- 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
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- 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
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- 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
- C01B3/0031—Intermetallic compounds; Metal alloys; Treatment thereof
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- 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
- C01B3/0031—Intermetallic compounds; Metal alloys; Treatment thereof
- C01B3/0042—Intermetallic compounds; Metal alloys; Treatment thereof only containing magnesium and nickel; Treatment thereof
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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
- Y02E60/32—Hydrogen storage
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Abstract
ABSTRACT A hydrogen storage structure, of which a hydrogen absorption amount is large and a hydrogen absorption rate in the vicinity of room temperature is fast, is provided. The hydrogen storage structure comprises a hydrogen absorption layer, which includes Mg or a Mg-based hydrogen absorption alloy, and hydrogen diffusion layers, which are disposed so as to sandwich the hydrogen absorption layer and include a hydrogen diffusion material.
Description
Technical field
The present invention relates to a kind of hydrogen storage structure with stratified structure.
Background technology
Because the appearance of environment in recent years problem, energy problem etc., fuel cell motor vehicle have obtained development rapidly.The storage of hydrogen is a subject matter of development fuel cell motor vehicle, and needs exploitation to be used for the high-density hydrogen-absorbing material of fuel cell motor vehicle.
As the example of hydrogen-absorbing material, can enumerate with TiCrV base hydrogen adsorbing alloy is the room temperature hydrogen-absorbing material of representative.But for the hydrogen adsorbing alloy of TiCrV base, hydrogen is stuck in and is slightly larger than 2 quality %.In contrast, because hydrogen-storage amount is bigger, so carried out using with the experiment as the light element of representative such as magnesium (Mg).But magnesium base hydrogen adsorbing alloy has unpractical problem, although because hydrogen-storage amount is very big, needs 350 ℃ and above high temperature to absorb and discharge hydrogen, and the absorption of hydrogen and rate of release are very slow.Therefore, carried out hydrogen absorption and the release characteristics that various experiments improve magnesium base hydrogen adsorbing alloy.For example, in Japanese Patent Application Publication (JP-A) No.2002-105576, a kind of layered structure that stores up hydrogen is disclosed, it is provided with inhales hydrogen layer and a pair of hydrogen transference layer, be formed film inhaling hydrogen layer Mg of place or Mg base alloy, described a pair of hydrogen transference layer is stacked in the mode that will inhale the hydrogen layer and be clipped between them.In addition, in the disclosing of the open and JP-A No.2004-346418 of JP-A No.2004-66653, the technology relevant with the multilayered structure of hydrogen-absorbing material disclosed.
Disclosed suction hydrogen layered structure has following structure in JP-A No.2002-105576 open: the hydrogen transference layer is disposed in the both sides of inhaling the hydrogen layer as the catalyst layer that makes hydrogen be dissociated into atomic form, inhales the hydrogen layer and is made of magnesium etc.In addition, as example, exemplified the suction hydrogen layered structure with three layers of form, wherein a pair of palladium layer is disposed in the both sides of magnesium layer.But near normal temperature, the hydrogen uptake rate of this suction hydrogen layered structure can not be satisfactory.
The storage hydrogen layered structure of describing in the disclosed example according to JP-A No.2002-105576 (wherein Mg or Mg base hydrogenous alloy are clipped in the middle by Pd layer etc.), perhaps, be difficult under the situation that is lower than 350 ℃ to carry out hydrogen absorption and/or release at a high speed according to the openly middle multilayered structure suction hydrogen body of describing of JP-A No.2004-66653 and the openly multilayered structure of middle description of JP-A No.2004-346418.
The situation that has many use predetermined particle size hydrogen-absorbing materials.But because the bulk density of granular solid is about 60% of a real density, under the situation of the light alloy that uses Mg etc., density will significantly reduce.As a result, be difficult to improve hydrogen significantly with respect to volume.
Summary of the invention
Consider above-mentioned prior art problems and designed the present invention, and near the hydrogen storage structure faster of the hydrogen-absorption speed the big and room temperature of a kind of hydrogen is provided.
A first aspect of the present invention is a kind of hydrogen storage structure, and it comprises: the suction hydrogen layer that comprises magnesium or magnesium base hydrogen adsorbing alloy; With a pair of hydrogen diffusion layer that comprises the hydrogen diffusion material, it is arranged to described suction hydrogen layer is clipped in the middle.
A second aspect of the present invention is a kind of hydrogen storage structure, and it comprises a plurality of suction hydrogen layer and a plurality of hydrogen diffusion layers that comprise the hydrogen diffusion material that comprise magnesium or magnesium base hydrogen adsorbing alloy that are arranged alternately.
In above-mentioned all respects, the hydrogen balance pressure of hydrogen diffusion material under 25 ℃ can be 0.1MPa at least, and is higher than magnesium or the hydrogen balance pressure of magnesium base hydrogen adsorbing alloy under 25 ℃.
In above-mentioned all respects, the hydrogen diffusion material can be to be selected from least a among TiMn, TiCr, TiFe, Ti and the V.
In above-mentioned all respects, described hydrogen diffusion material can be stable with respect to hydrogen, and the hydrogen diffusion material is higher than magnesium or the hydrogen diffusion coefficient of magnesium base hydrogen adsorbing alloy under 25 ℃ at the hydrogen diffusion coefficient under 25 ℃.
In above-mentioned all respects, described hydrogen diffusion material can be Ni.
In above-mentioned all respects, the hydrogen disassociation layer outermost layer as hydrogen storage structure that comprises hydrogen disassociation material can be set further.
According to the present invention, can provide near the hydrogen storage structure faster of the hydrogen-absorption speed the big and room temperature of a kind of hydrogen-storage amount.
Description of drawings
Fig. 1 illustrates the skeleton view that relates to the hydrogen storage structure of first embodiment of the present invention.
Fig. 2 illustrates the skeleton view that relates to the hydrogen storage structure of second embodiment of the present invention.
Fig. 3 illustrates the skeleton view that relates to the hydrogen storage structure of the 3rd embodiment of the present invention.
Fig. 4 is the schematic structure view of PCT equipment.
Fig. 5 is the transmission electron microscope image of the cross section of hydrogen storage structure #35.
Fig. 6 is the figure line that the hydrogen release temperature dependent properties high-volume of hydrogen storage structure #33 to #35 is shown.
Embodiment
Hydrogen storage structure of the present invention will be described in detail.
Fig. 1 illustrates the skeleton view that relates to the hydrogen storage structure of first embodiment of the present invention.The hydrogen storage structure of present embodiment comprises: the suction hydrogen layer 1 that comprises Mg or Mg base hydrogen adsorbing alloy; With a pair of hydrogen diffusion layer 2 that comprises the hydrogen diffusion material, hydrogen diffusion layer 2 is arranged to suction hydrogen layer 1 is clipped between them.
Be included in Mg or the Mg base hydrogen adsorbing alloy of inhaling hydrogen layer 1 place and have high hydrogen-storage amount, and have 350-400 ℃ hydrogen absorption/release temperature, and hydrogen absorption/release at room temperature is relatively poor.Be included in the high speed diffusion motion that hydrogen diffusion material in the hydrogen diffusion layer 2 shows hydrogen atom.Hydrogen atom enters hydrogen diffusion layer 2 by the front surface and the rear surface of hydrogen diffusion layer 2, by being diffused in quick travel in the hydrogen diffusion layer 2, thereby and be included in the Mg that inhales hydrogen layer 1 place or Mg base hydrogen adsorbing alloy and combine form storage with metal hydride.As a result, hydrogen storage structure of the present invention can at room temperature be inhaled hydrogen at a high speed.Note, be used for room temperature of the present invention and refer to common free air temperature, represent about 0-40 ℃.
In addition, Mg or Mg base hydrogen adsorbing alloy are easy to oxidation, and can react to produce heat etc. with oxygen or water.But, be clipped between a pair of hydrogen diffusion layer 2 because inhale hydrogen layer 1, so Mg or Mg base hydrogen adsorbing alloy can directly not contact atmosphere, thereby make hydrogen storage structure of the present invention more safely to be disposed.
Mg base hydrogen adsorbing alloy used in this invention for example is MgNi, MgAl, MgB etc.Inhale hydrogen layer 1 and preferably include a kind of hydrogen-absorbing material that is selected from MgNi and Mg, and be more preferably and comprise Mg.
The hydrogen diffusion material is not particularly limited, as long as this material has hydrogen atom to carry out the characteristic of diffusion motion at a high speed.But for example, such material preferably has the hydrogen balance pressure of 0.1MPa at least under 25 ℃, and this is higher than Mg or the hydrogen balance pressure of Mg base alloy under 25 ℃.By using such material, the hydrogen diffusion property under the room temperature becomes favourable, and can improve significantly and inhale hydrogen temperature and hydrogen-absorption speed.
At least a being used as that is selected among for example TiMn, TiCr, TiFe, Ti and the V shows the material of the hydrogen balance pressure of 0.1MPa at least under 25 ℃, this is higher than Mg or the hydrogen balance pressure of Mg base hydrogen adsorbing alloy under 25 ℃.
The hydrogen balance pressure of material can be from passing through PCT (pressure-component-temperature; Below identical) obtain (Sieverts method) in the PCT curve of device measuring.
Be higher than the material of Mg or the hydrogen diffusion coefficient of Mg base hydrogen adsorbing alloy under 25 ℃ preferably as hydrogen diffusion material used in this invention with respect to stabilized hydrogen and at the hydrogen diffusion coefficient under 25 ℃.For the present invention, comprise following material with respect to the hydrogen diffusion material of stabilized hydrogen, it can not produce hydride in the atmosphere that hydrogen storage structure of the present invention uses therein.
Make and inhale hydrogen layer 1 contraction or expansion owing to Mg or Mg base hydrogen adsorbing alloy absorbs or discharge hydrogen.The hydrogen diffusion layer 2 that comprises the hydrogen diffusion material that stop to produce hydride also expands or shrinks (volume change), but its volume change is different with the volume change of suction hydrogen layer 1.As a result, tension strain is applied on the suction hydrogen layer 1 that has absorbed hydrogen and shunk, and makes that inhaling hydrogen layer 1 can not change or 2 contractions of expansible hydrogen diffusion layer hardly from volume, inhales hydrogen and carries out reposefully.As a result, can realize inhaling hydrogen at low temperatures.
Ni etc. are used as the example that is higher than the material of Mg or the hydrogen diffusion coefficient of Mg base hydrogen adsorbing alloy under 25 ℃ with respect to the hydrogen diffusion coefficient under stabilized hydrogen and 25 ℃.
The hydrogen diffusion coefficient of material can be measured by electrochemistry launching technique or THE METHOD OF THERMAL DESORPTION.
The thickness of inhaling hydrogen layer 1 is preferably 10-1000nm, more preferably 10-100nm.If inhaling the thickness of hydrogen layer 1 is 10-1000nm, can realize that then hydrogen absorbs and discharges fast.
The thickness of hydrogen diffusion layer 2 is preferably 1-150nm, more preferably 10-100nm.If the thickness of hydrogen diffusion layer 2 is 1-150nm, can realize that then hydrogen absorbs and discharges fast.
Ratio A/the B that inhales between the thickness B (total thickness of a pair of hydrogen diffusion layer 2) of the thickness A of hydrogen layer 1 and hydrogen diffusion layer 2 is preferably 1.5 or bigger, and more preferably 2 or bigger.If A/B is 1.5 or bigger, can realize that then hydrogen absorbs and discharges fast.In addition, in order to prevent owing to A/B is excessive to be enlarged markedly the suction hydrogen time length, A/B preferably is not more than 10.
The shape of the hydrogen storage structure relevant with first embodiment, size etc. are not particularly limited.But the bond length of hydrogen storage structure preferably is not more than 20cm.Be set at 20cm or littler by bond length, can realize that hydrogen absorbs and discharges fast hydrogen storage structure.
Fig. 2 is the skeleton view that the hydrogen storage structure relevant with second embodiment of the present invention is shown.This hydrogen storage structure further is provided with hydrogen disassociation layer 3, its comprise the hydrogen storage structure that is in first embodiment the outermost layer place hydrogen disassociation material arranged.The hydrogen storage structure of second embodiment all is provided with hydrogen disassociation layer 3 in two surface, but also can only be provided with hydrogen disassociation layer 3 at the one surface place.
Hydrogen disassociation material serves as the catalyzer that makes hydrogen molecule be dissociated into hydrogen atom.V and Pd are used as the example of hydrogen disassociation material.In these materials, preferred Pd, it shows strong katalysis.By hydrogen disassociation layer 3 is set at the outermost layer place, can realize that hydrogen absorbs fast.
For the hydrogen storage structure relevant with second embodiment, the hydrogen dissociating power material more excellent than hydrogen diffusion material can be used in the hydrogen disassociation layer 3.The contrast advantage of the hydrogen dissociating power of various materials is known, and for example, the hydrogen dissociating power of Pd is better than V.Therefore, constructing with V under the situation of hydrogen diffusion layer 2, constructing hydrogen disassociation layer 3 with Pd.
The thickness of hydrogen disassociation layer 3 is preferably maximum 5nm.If the thickness of hydrogen disassociation layer 3 is 5nm or littler, can realize that hydrogen absorbs fast.
The preferable range of the preferable range of the suction hydrogen layer 1 relevant with second embodiment and the thickness of hydrogen diffusion layer 2 and the bond length of preferred material and hydrogen storage structure and the situation of first embodiment are similar.
Fig. 3 is the skeleton view that the hydrogen storage structure relevant with the 3rd embodiment of the present invention is shown.The hydrogen storage structure of the 3rd embodiment alternately is provided with a plurality of suction hydrogen layers 1 and a plurality of hydrogen diffusion layer 2, described a plurality of suction hydrogen layer 1 comprises Mg or Mg base hydrogen adsorbing alloy, described a plurality of hydrogen diffusion layer 2 comprises the hydrogen diffusion material, and this hydrogen storage structure also is provided with the hydrogen disassociation layer 3 that comprises hydrogen disassociation material at the outermost layer place.
The hydrogen storage structure that is provided with the 3rd embodiment of a plurality of suction hydrogen layers is inhaled the hydrogen storage structure of first embodiment of hydrogen layer being better than being provided with individual layer aspect hydrogen-absorption speed and the hydrogen, even the total thickness of their suction hydrogen layer is identical.This is considered to because by replacing individual layer with a plurality of suction hydrogen layers, makes that hydrogen diffusion layer 2 and the contact area of inhaling between the hydrogen layer 1 are bigger, and diffusion length is shorter simultaneously.The hydrogen-absorbing material of Mg etc. is different from the hydrogen-absorbing material of so-called room temperature type, and is not dissolved hydrogen, but forms such as MgH
2And so on hydride (ionic bonding) and store hydrogen.Formed MgH
2Itself hinder the hydrogen diffusion, and it is believed that when material surface is hydrogenated, hydrogen diffusion subsequently slows down slow.But, inhale hydrogen layer 1 and hydrogen diffusion layer 2 by alternately being provided with each other, can be so that the contact area of hydrogen diffusion layer 2 and suction hydrogen layer 1 be bigger.As a result, hydrogenation owing to material surface taking place, to reduce the possibility of situation of hydrogen diffusibility less.
Be not provided with at hydrogen storage structure under the situation of hydrogen disassociation layer 3, preferably, hydrogen diffusion layer 2 is arranged on the outermost layer place.Because be positioned at the hydrogen diffusion layer 2 at outermost layer place, hydrogen storage structure can be disposed safely, can directly not contact atmosphere because comprise the suction hydrogen layer 1 of Mg or Mg base hydrogen adsorbing alloy.
In the hydrogen storage structure relevant with the 3rd embodiment, the number of plies of inhaling hydrogen layer 1 and hydrogen diffusion layer 2 preferably is not less than 10 layers altogether, and especially preferably is not less than 100 layers.
Each thickness of inhaling hydrogen layer 1 is preferably 10-100nm, more preferably 10-50nm.If inhaling the thickness of hydrogen layer 1 is 10-100nm, can realize that then hydrogen absorbs and discharges fast.
The thickness of each hydrogen diffusion layer 2 is preferably 1-10nm, more preferably 1-5nm.If the thickness of hydrogen diffusion layer 2 is 1-10nm, can realize that then hydrogen absorbs and discharges fast.
If be provided with hydrogen disassociation layer 3, then the thickness of each hydrogen disassociation layer 3 is preferably maximum 5nm.If the thickness of hydrogen disassociation layer 3 is 5nm or littler, can realize that then hydrogen absorbs and discharges fast.
Ratio A/B between the thickness A (all inhale the total thickness of hydrogen layers 1) of suction hydrogen layer 1 and the thickness B (total thickness of all hydrogen diffusion layers 2) of hydrogen diffusion layer 2 preferably is at least 1, and more preferably is at least 5, most preferably is at least 10.If A/B is 1 or bigger, can realize that then hydrogen absorbs and discharges fast.Notice that when being provided with hydrogen disassociation layer, thickness B comprises the total thickness of all hydrogen diffusion layers 2 and all hydrogen disassociation layer 3.
In addition, in order to prevent that inhaling the hydrogen time length becomes several hrs or longer, A/B preferably is not more than 50.
The preferable range of the bond length of the hydrogen storage structure relevant with the 3rd embodiment etc. are similar with the situation of first embodiment.
The manufacture method of hydrogen storage structure of the present invention is not particularly limited, but can use known film formation method to make, for example sputtering method, flash method etc.
Example
Below with reference to example the present invention is described more specifically.But, the invention is not restricted to following example.
The manufacturing of hydrogen storage structure
Use the multi-source sputtering equipment, to the described structure of table 5, dissociate and make hydrogen storage structure # 1 to #35 on the aluminium film that is stacked in the A4 size layer by layer by inhaling hydrogen layer, hydrogen diffusion layer and hydrogen as required based on table 1.
The measurement of hydrogen
Measure hydrogen by PCT equipment.
Fig. 4 is the view that the schematic structure of PCT equipment is shown.In equipment 10, hydrogen cylinder 11, buffer container 12, sampling receptacle 13, vacuum pump 14, pressure warning unit 15 and wet flow indicator 18 are connected via pipeline 16.Valve V0 to V6 is arranged on pipeline 16 places.Sampling receptacle 13 is covered by well heater 19, makes that the hydrogen storage structure (for example measure sample 17) in the sampling receptacle 13 is heated.
At first, close and under the state that valve V1-V4 opens, the pressure of operated vacuum pumps 14 in buffer container 12, sampling receptacle 13 and pipeline 16 is predetermined pressure or is lower than predetermined pressure at valve V0, V5 and V6.
When the pressure in buffer container 12, sampling receptacle 13 and the pipeline 16 is predetermined pressure or when being lower than predetermined pressure, shut-off valve V3 also stops vacuum pump 14.
Shut-off valve V2 opens valve V0, and hydrogen is charged in the buffer container 12.Afterwards, shut-off valve V0 and V1.The pressure that measure by pressure warning unit 15 this moment is defined as P0.Then, open valve V2, and make the constant pressure of buffer container 12 and sampling receptacle 13.The pressure that measure by pressure warning unit 15 this moment is defined as P1.Obtain hydrogen (quality %) by the pressure reduction between pressure P 0 and the P1.Along band ground, this system is known as Sieverts method (stereometry) usually.
The measurement of the hydrogen amount that discharges
In equipment shown in Figure 4 10, be placed in the sampling receptacle 13 that is heated to preset temperature in the measure sample 17 that has for example absorbed hydrogen by well heater 19, and valve V0 to V2, V4 and V5 close and under the state that valve V3 and V6 open, guide in the wet flow indicator 18 and measure the hydrogen amount that hydrogen volume obtains discharging by the hydrogen that will discharge under each temperature.
In addition, the hydrogen amount based on the release that obtains can obtain the volume storage density.Here, the hydrogen volume of the hydrogen storage structure of volume storage density representation unit volume storage.
For the hydrogen storage structure # 1 to #4 that makes by aforesaid method, under preset temperature, obtained the hydrogen release time length (release duration) of 90% suction hydrogen time length (absorbing the time length) and 90%.The result who obtains is as shown in table 1.Note, 90% suction hydrogen time length represents that the hydrogen that makes of each hydrogen storage structure # 1 to #4 reaches 90% required time length of maximum hydrogen, and 90% hydrogen release time length represents that the hydrogen release that makes of each hydrogen storage structure # 1 to #4 high-volume reaches 90% required time length of maximum hydrogen.
Table 1
| Example | Structure | Absorb | Discharge | |||||||
| Inhale the hydrogen layer | The hydrogen diffusion layer | Hydrogen disassociation layer | Temperature (℃) | Absorb the time length (min.) | Temperature (℃) | Release duration (min.) | ||||
| nm | | nm | ||||||||
| # | ||||||||||
| 1 | Mg | 800 | TiMn | 40 | Pd | 20 | 150 | 20 | 300 | 8 |
| 90 | (2hrs) | 250 | - | |||||||
| #2 | Mg | 800 | TiFe | 40 | Pd | 20 | 150 | 35 | 300 | 12 |
| 90 | (3hrs) | 250 | - | |||||||
| #3 | Mg | 800 | Ni | 40 | Pd | 20 | 150 | 15 | 300 | 14 |
| 90 | (2hrs) | 250 | - | |||||||
| #4 | Mg film (70 μ m are thick) | 300 | 30 | 400＜ | Can not carry out 90% release | |||||
As shown in table 1, should be appreciated that hydrogen storage structure # 1 to #3 related to the present invention can inhale hydrogen down at 150 ℃, and discharge hydrogen down at 300 ℃.Should be appreciated that with hydrogen storage structure # 4 and compare, improved hydrogen absorption characteristic and hydrogen release characteristic as the Mg film.
To #7, suction hydrogen time length (absorbing the time length) of 90% and hydrogen release time length (release duration) of 90% have been obtained under the preset temperature for the hydrogen storage structure #5 (identical) that makes by aforesaid method with #1.The result who obtains is as shown in table 2.
Table 2
| Example | Structure | Absorb | Discharge | |||||||
| Inhale the hydrogen layer | The hydrogen diffusion layer | Hydrogen disassociation layer | Temperature (℃) | Absorb the time length (min.) | Temperature (℃) | Release duration (min.) | ||||
| nm | nm | nm | ||||||||
| #5 | Mg | 800 | TiMn | 40 | Pd | 20 | 150 | 20 | 300 | 8 |
| #6 | Mg | 250 | TiMn | 40 | Pd | 20 | 150 | 2 | 300 | 4 |
| #7 | Mg | 160 | TiMn | 40 | Pd | 20 | 150 | 1 | 250 | 2 |
According to Fig. 2, should be appreciated that by making the thickness of inhaling the hydrogen layer thinner, can reduce the hydrogen release temperature.
For the hydrogen storage structure # 8 to #18 that makes by aforesaid method, the hydrogen under having obtained 25 ℃, volume storage density and suction hydrogen time length of 90%.The result who obtains is as shown in table 3.
Table 3
| Example | Structure | A/B | Absorption characteristic | ||||||||||
| Inhale the hydrogen layer | The hydrogen diffusion layer | Hydrogen disassociation layer | Hydrogen | The volume storage density | Absorb the time length (min.) | ||||||||
| Nm * number of plies | Nm * number of plies | Nm * number of | |||||||||||
| # | |||||||||||||
| 8 | Mg | 600 | 1 | Ni | 40 | 2 | Pd | 0 | 0 | 7.5 | 5.7 | 2250 | 1500 |
| #9 | Mg | 160 | 1 | Ni | 40 | 2 | Pd | 0 | 0 | 2 | 3.2 | 2000 | 120 |
| #10 | |
100 | 1 | Ni | 40 | 2 | Pd | 0 | 0 | 1.25 | 2.5 | 1800 | 70 |
| #11 | Mg | 5 | 1 | Ni | 1.25 | 2 | Pd | 0 | 0 | 2 | 3.3 | 2100 | 5 days |
| #12 | |
100 | 1 | Ni | 20 | 2 | Pd | 0 | 0 | 2.5 | 4 | 2200 | 50 |
| #13 | |
200 | 1 | Ni | 20 | 2 | Pd | 0 | 0 | 5 | 5 | 2300 | 180 |
| #14 | |
10 | 1 | Ni | 0.5 | 2 | |
1 | 2 | 3.3 | 6 | 2100 | 5 days |
| #15 | |
10 | 1 | |
2 | 2 | |
1 | 2 | 1.7 | 3.8 | 2200 | 1200 |
| #16 | Mg | 800 | 1 | Ni | 150 | 2 | |
1 | 2 | 2.6 | 3.9 | 2200 | 2600 |
| #17 | Mg | 800 | 1 | |
200 | 2 | |
1 | 2 | 2 | 3.3 | 2100 | 2100 |
| #18 | Mg | 800 | 1 | |
200 | 2 | Pd | 0 | 0 | 2 | 3.4 | 2100 | 2700 |
According to table 3, should be appreciated that inhaling hydrogen at 25 ℃ is fine.In addition, can also further understand following content.
(1) according to the result of hydrogen storage structure # 8 to #10, should be appreciated that when hydrogen disassociation layer is not set, form thinlyyer by making suction hydrogen layer, can obtain 90% and inhale the hydrogen storage structure of hydrogen time length excellence.
(2) according to the result of hydrogen storage structure # 11 to #13, should be appreciated that hydrogen when disassociation layer be not set that the hydrogen under 25 ℃ is bigger, and by the thickness setting that will inhale the hydrogen layer is 100nm or bigger (and A/B is 2 or bigger), can shorten 90% and inhale the hydrogen time length.
(3), should be appreciated that under the situation that is provided with hydrogen disassociation layer by A/B being set at 1.7 to 2.6, hydrogen, the volume storage density and 90% that can obtain under 25 ℃ are inhaled the hydrogen storage structure of hydrogen time length excellence according to the result of hydrogen storage structure # 14 to #17.
(4), should be appreciated that according to whether existing hydrogen to dissociate layer (Pd) the hydrogen-absorption speed difference according to the result of hydrogen storage structure # 17 and #18.
For the hydrogen storage structure # 19 to #32 that makes by aforesaid method, hydrogen, the volume storage density and 90% that can obtain under 25 ℃ are inhaled the hydrogen time length.The result who obtains is as shown in table 4.
Table 4
| Example | Structure | A/B | Absorption characteristic | ||||||||||
| Inhale the hydrogen layer | The hydrogen diffusion layer | Hydrogen disassociation layer | Hydrogen | The volume storage density | Absorb the time length (min.) | ||||||||
| Nm * number of plies | Nm * number of plies | Nm * number of plies | |||||||||||
| #19 | |
10 | 2 | |
2 | 3 | |
2 | 2 | 2 | 1.9 | 1700 | 5 days |
| #20 | |
10 | 11 | |
2 | 2 | |
2 | 2 | 3.9 | 3.4 | 2200 | 300 |
| #21 | Mg | 22 | 5 | |
2 | 6 | |
2 | 2 | 6.9 | 4.5 | 2400 | 1300 |
| #22 | Mg | 22 | 11 | |
2 | 12 | |
2 | 2 | 8.6 | 4.9 | 2400 | 330 |
| #23 | Mg | 22 | 100 | |
2 | 101 | |
2 | 2 | 11 | 5.1 | 2300 | 7 |
| #24 | Mg | 6 | 150 | |
2 | 151 | |
2 | 2 | 2.9 | 2.8 | 1900 | 2 |
| #25 | |
10 | 150 | |
2 | 151 | |
2 | 2 | 5 | 3.7 | 2200 | 3 |
| #26 | Mg | 30 | 150 | |
2 | 151 | |
2 | 2 | 15 | 5.6 | 2300 | 6 |
| #27 | |
100 | 150 | |
2 | 151 | |
2 | 2 | 49 | 6.9 | 1900 | 43 |
| #28 | |
200 | 150 | |
2 | 151 | |
2 | 2 | 99 | 7.2 | 1700 | 170 |
| #29 | Mg | 22 | 150 | Ni | 0.5 | 151 | |
2 | 2 | 41.5 | 7.4 | 1600 | 80 |
| #30 | Mg | 22 | 150 | |
2 | 151 | |
2 | 2 | 10.8 | 6.9 | 1800 | 43 |
| #31 | Mg | 22 | 150 | |
10 | 151 | |
2 | 2 | 2.2 | 5 | 2300 | 40 |
| #32 | Mg | 22 | 150 | Ni | 20 | 151 | |
2 | 2 | 1.1 | 3.5 | 2200 | 40 |
According to table 4, should be appreciated that inhaling hydrogen at 25 ℃ is fine.In addition, can also further understand following content.
(1) according to the result of hydrogen storage structure # 19 and #20, should be appreciated that by making the number of plies of inhaling the hydrogen layer more, can shorten 90% of hydrogen storage structure and inhale the hydrogen time length.
(2), should be appreciated that along with the number of plies of inhaling hydrogen layer and hydrogen diffusion layer becomes big, hydrogen and 90% is inhaled the hydrogen time length and improved according to the result of hydrogen storage structure #21 to #23.
(3) according to the result of hydrogen storage structure #24 to #28, should be appreciated that under the bigger situation of the number of plies of inhaling hydrogen layer and hydrogen diffusion layer, be set to thinlyyer by each thickness of inhaling the hydrogen layer, can obtain 90% and inhale the hydrogen storage structure of hydrogen time length excellence.
(4), should be appreciated that under the bigger situation of the number of plies of inhaling hydrogen layer and hydrogen diffusion layer be provided with thicklyer by the thickness with each hydrogen diffusion layer, raised path between farm fields is inhaled the hydrogen storage structure of hydrogen time length excellence to obtain 90% according to the result of hydrogen storage structure #29 to #32.
(5) in addition,, it is also understood that under the bigger situation of the number of plies of inhaling hydrogen layer and hydrogen diffusion layer, be set to 1 to 15, can obtain 90% and inhale the hydrogen storage structure of hydrogen time length excellence by A/B according to the result of hydrogen storage structure #24 to #32.
Hydrogen storage structure #33 to #35 by the aforesaid method manufacturing makes the hydrogen diffusion layer and the hydrogen disassociation layer adjacency of 60nm thickness.The transmission electron microscope image of the cross section of hydrogen storage structure #35 as shown in Figure 5.
Table 5
| Example | Structure | |||||
| Inhale the hydrogen layer | The hydrogen diffusion layer | Hydrogen disassociation layer | ||||
| Nm * number of plies | Nm * number of plies | Nm * number of plies | ||||
| #33 | Mg | 44×15 | TiFe | 5×14 60×2 | Pd | 20 |
| #34 | Mg | 33×15 | TiMn | 14×14 60×2 | Pd | 20 |
| #35 | Mg | 40×15 | |
14×14 | Pd | 20 |
Use hydrogen storage structure #33 to #35, studied hydrogen release temperature dependent properties high-volume.What obtain the results are shown among Fig. 6.Be appreciated that by using Ni from Fig. 6, can realize hydrogen release being lower than under 100 ℃ the situation as the hydrogen diffusion material.
Industrial applicibility
According to the present invention, the hydrogen-absorption speed that the large and near room temperature of a kind of hydrogen storage content can be provided is hydrogen storage structure faster.
Claims (7)
1. hydrogen storage structure comprises:
The suction hydrogen layer that comprises magnesium or magnesium base hydrogen adsorbing alloy; With
The a pair of hydrogen diffusion layer that comprises the hydrogen diffusion material, it is arranged to described suction hydrogen layer is clipped in the middle.
2. hydrogen storage structure comprises:
A plurality of suction hydrogen layers that comprise magnesium or magnesium base hydrogen adsorbing alloy; With
A plurality of hydrogen diffusion layers that comprise the hydrogen diffusion material, wherein, described a plurality of suction hydrogen layers and described a plurality of hydrogen diffusion layer are arranged alternately.
3. hydrogen storage structure according to claim 1 and 2, wherein, the hydrogen balance pressure of described hydrogen diffusion material under 25 ℃ is 0.1MPa at least, and is higher than described magnesium or the hydrogen balance pressure of magnesium base hydrogen adsorbing alloy under 25 ℃.
4. according to each described hydrogen storage structure in the claim 1 to 3, wherein, described hydrogen diffusion material is to be selected from least a among TiMn, TiCr, TiFe, Ti and the V.
5. hydrogen storage structure according to claim 1 and 2, wherein, described hydrogen diffusion material is stable with respect to hydrogen, and described hydrogen diffusion material is higher than described magnesium or the hydrogen diffusion coefficient of magnesium base hydrogen adsorbing alloy under 25 ℃ at the hydrogen diffusion coefficient under 25 ℃.
6. according to each described hydrogen storage structure in the claim 1,2 and 5, wherein, described hydrogen diffusion material is Ni.
7. according to each described hydrogen storage structure in the claim 1 to 6, wherein, the hydrogen disassociation layer outermost layer as described hydrogen storage structure that comprises hydrogen disassociation material is set also.
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| JP105085/2005 | 2005-03-31 | ||
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| JP (1) | JP2008531445A (en) |
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| CN103668070A (en) * | 2013-12-05 | 2014-03-26 | 中盈长江国际新能源投资有限公司 | Magnesium-base hydrogen storage film and preparation method thereof |
| CN113739067A (en) * | 2021-09-02 | 2021-12-03 | 西北工业大学太仓长三角研究院 | Dual-cavity-based hydrogen charging control device, hydrogen charging control method and equipment |
| CN114182205A (en) * | 2021-12-10 | 2022-03-15 | 中国工程物理研究院材料研究所 | Nano multilayer structure metal hydrogen absorption film and preparation method and application thereof |
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| US9045335B2 (en) | 2010-08-18 | 2015-06-02 | The Governors Of The University Of Alberta | Kinetic stabilization of magnesium hydride |
| WO2012021996A1 (en) * | 2010-08-18 | 2012-02-23 | The Governors Of The University Of Alberta | Kinetic stabilization of magnesium hydride |
| KR101524350B1 (en) * | 2013-05-06 | 2015-06-05 | 전북대학교산학협력단 | Hydrogen permeation barrier layer comprising active/passive hybrid blocking layers |
| JP6348330B2 (en) * | 2014-04-22 | 2018-06-27 | 株式会社テックコーポレーション | Hydrogen discharger, hydrogen gas supply method, and hydrogen release system |
| RU168280U1 (en) * | 2015-12-16 | 2017-01-26 | Акционерное общество "ТЕХНОАТОМ" | HETTER DEVICE FOR MOLECULAR HYDROGEN SELECTIVE PUMPING |
| WO2018230447A1 (en) * | 2017-06-15 | 2018-12-20 | 株式会社クリーンプラネット | Heat generating device and method for generating heat |
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| EP1116797A1 (en) * | 1999-07-16 | 2001-07-18 | Sumitomo Electric Industries, Ltd. | Hydrogen-occluding material and process for producing the same |
| US6627148B1 (en) * | 1999-11-06 | 2003-09-30 | Energy Conversion Devices, Inc. | Safe, ecomomical transport of hydrogen in pelletized form |
| JP2002105576A (en) * | 2000-09-29 | 2002-04-10 | Univ Hiroshima | Hydrogen occluding laminated structure |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103668070A (en) * | 2013-12-05 | 2014-03-26 | 中盈长江国际新能源投资有限公司 | Magnesium-base hydrogen storage film and preparation method thereof |
| WO2015081781A1 (en) * | 2013-12-05 | 2015-06-11 | 中盈长江国际新能源投资有限公司 | Magnesium-based hydrogen occluding thin film and preparation method thereof |
| CN113739067A (en) * | 2021-09-02 | 2021-12-03 | 西北工业大学太仓长三角研究院 | Dual-cavity-based hydrogen charging control device, hydrogen charging control method and equipment |
| CN114182205A (en) * | 2021-12-10 | 2022-03-15 | 中国工程物理研究院材料研究所 | Nano multilayer structure metal hydrogen absorption film and preparation method and application thereof |
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| WO2006104274A1 (en) | 2006-10-05 |
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