CN104401941A - Reversible hydrogen storage material and preparation method thereof - Google Patents
Reversible hydrogen storage material and preparation method thereof Download PDFInfo
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- CN104401941A CN104401941A CN201410624206.1A CN201410624206A CN104401941A CN 104401941 A CN104401941 A CN 104401941A CN 201410624206 A CN201410624206 A CN 201410624206A CN 104401941 A CN104401941 A CN 104401941A
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- hydrogen storage
- storage material
- hydrogen
- reversible hydrogen
- reversible
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
The reversible hydrogen storage material is prepared by depositing a layer of metal on the surface of metal borohydride and has a chemical formula Mg<x>Zn<1-x>(BH4)2-M, wherein x=0.05-0.95 and M is one of Pd, Pt, and Co. The preparation method comprises the following steps: co-depositing magnesium, zinc, and boron onto a silicon sheet in a hydrogen atmosphere through a physical vapor deposition method so as to obtain a metal borohydride Mg<x>Zn<1-x>(BH4)2; and then depositing palladium, platinum, or cobalt onto the surface of the obtained metal borohydride in a vacuum hydrogen-free environment through a vacuum sputtering method so as to obtain the reversible hydrogen storage material. The prepared reversible hydrogen storage material has good thermal stability and reversibility, the hydrogenation condition of the material is mild, moreover the primary dehydrogenation temperature is greatly reduced, thus the material can be applied to hydrogen storage and transportation, and the storage and transportation may become high efficient and more safe. The material can also be used to manufacture hydrogen fuel cell.
Description
Technical field
The invention belongs to hydrogen storage material preparing technical field, particularly a kind of with palladium, platinum or cobalt metal borohydride that is top layer and preparation method thereof.
Background technology
Modern social development's heavy dependence fossil energy, it consumes the problem of environmental pollution of the global range brought in a large number and energy dilemma is increasingly sharpened, and develops new forms of energy " Hydrogen Energy " extremely urgent.The development that Hydrogen Energy depends primarily on hydrogen storage technology can be realized in the near future.Existing technology comprises gaseous state storage hydrogen, liquid storage hydrogen and solid hydrogen storage material.Gaseous state storage hydrogen needs high pressure and heavy storage tank, and poor stability, weight density are low; Liquid storage hydrogen needs high energy consumption to maintain low temperature and loss ratio is in use larger.Solid hydrogen storage material can reversibly absorb and release hydrogen, is the emerging hydrogen storage material of a class, its good security, high volume hydrogen storage capability and make it obtain studying more and more widely in countries in the world without the need to the feature such as high pressure and heat-insulated container.
Solid hydrogen storage material is the highest with the hydrogen storage capability of complex hydrides, and existing research method is that the mixture adopting mechanical attrition method or wet method to process metal and some doping agents under hydrogen environment prepares complex hydrides mostly.But there is reversibility difference, add/the problem such as desorption temperature and hypertonia, dynamic performance difference and poor heat stability in the complex hydrides that these methods obtain, especially high adding/desorption temperature under complex hydrides there is the problem of thermolysis.The exploitation with the high-performance hydrogen storage material of reversibility, good dynamics and thermostability depends on the solution of the problems referred to above.
Summary of the invention
The object of the invention is to, for the defect that existing coordinate hydride hydrogen-storing material exists, provide a kind of reversible hydrogen storage material, it is formed by metal borohydride surface deposition layer of metal, meets chemical general formula Mg
xzn
1-x(BH
4)
2-M, wherein x=0.05 ~ 0.95, M is the one in Pd, Pt, Co.
Reversible hydrogen storage material of the present invention, has good thermostability and reversibility, and its hydroconversion condition is gentle, and reduces initial desorption temperature to a great extent.
Further, the circulation hydrogenation temperature of described reversible hydrogen storage material is normal temperature, and hydrogen pressure is 1MPa.
Further, the initial desorption temperature of described reversible hydrogen storage material is 450K, and the highest desorption temperature is 982K, and lifting/lowering temperature speed is 23K/s.
The present invention also aims to, a kind of preparation method of above-mentioned reversible hydrogen storage material is provided, comprises the following steps:
(1) under hydrogen environment, codeposition is on silicon chip by MAGNESIUM METAL, zinc, boron to adopt physical vapor deposition, and vacuum tightness is 5.2x10
-4pa, sedimentation rate is 2.5nm/min, obtains metal borohydride, Mg
xzn
1-x(BH
4)
2, wherein x=0.05 ~ 0.95;
(2) adopt vacuum sputtering that palladium metal (Pd), platinum (Pt) or cobalt (Co) are deposited on above-mentioned metal borohydride surface under without hydrogen vacuum environment, vacuum tightness is 1x10
-8pa, sedimentation rate is 1.5nm/min, and deposit thickness is 2 ~ 20nm, obtains reversible hydrogen storage material.
Reversible hydrogen storage material prepared by the present invention has the following advantages: hydroconversion condition is gentle, and hydrogenation temperature is normal temperature, and hydrogenation pressure is low, is only 1MPa; Initial desorption temperature low (450K), dehydrogenation rate is fast; High temperature circulation add/certain embodiments in Heat stability is good, there is good reversibility; Can be used for the efficient accumulating of hydrogen and transport safely, also can be used for hydrogen fuel cell.
Accompanying drawing explanation
Fig. 1 is that embodiment 1 puts pure palladium and Mg in hydrogen process
0.1zn
0.9(BH
4)
2the hydrogen dividing potential drop of-Pd.
Fig. 2 is Mg prepared by embodiment 1
0.1zn
0.9(BH
4)
2sEM photo after 982K puts hydrogen.
Fig. 3 is Mg prepared by embodiment 1
0.1zn
0.9(BH
4)
2the SEM photo of-Pd after 982K puts hydrogen.
Embodiment
Be specifically described the present invention below in conjunction with embodiment, what be necessary to herein means out is that following examples are only used to further illustrate the present invention, and can not be interpreted as limiting the scope of the invention.Some nonessential improvement and adjustment that the person skilled in the art in this field does the present invention according to the invention described above content, all can not depart from protection category of the present invention.
A preparation method for reversible hydrogen storage material, specifically comprises the following steps:
(1) under hydrogen environment, codeposition is on silicon chip by MAGNESIUM METAL, zinc, boron to adopt physical vapor deposition, and vacuum tightness is 5.2x10
-4pa, sedimentation rate is 2.5nm/min, obtains metal borohydride, Mg
xzn
1-x(BH
4)
2, wherein x=0.05 ~ 0.95;
(2) adopt vacuum sputtering that palladium metal (Pd), platinum (Pt) or cobalt (Co) are deposited on above-mentioned metal borohydride surface under without hydrogen vacuum environment, vacuum tightness is 1x10
-8pa, sedimentation rate is 1.5nm/min, and deposit thickness is 2 ~ 20nm, obtains reversible hydrogen storage material, Mg
xzn
1-x(BH
4)
2-M, wherein x=0.05 ~ 0.95, M is the one in Pd, Pt, Co.
Embodiment 1
With Mg prepared by aforesaid method
0.1zn
0.9(BH
4)
2and Mg
0.1zn
0.9(BH
4)
2-Pd (palladium layers thickness is 10nm) puts hydrogen round-robin test do suction.The top temperature of putting hydrogen is 982K, and temperature rise rate is 23K/s; Following cycle hydrogenation temperature is normal temperature, pressure 1MPa, 7.5 hours time.Result shows, without the Mg of palladium layers
0.1zn
0.9(BH
4)
2do not show the reversibility of hydrogen storage property, putting in hydrogen process after following cycle hydrogenation does not detect hydrogen, and Mg
0.1zn
0.9(BH
4)
2-Pd then shows good hydrogenation reversibility.Also put hydrogen dividing potential drop in hydrogen process from Fig. 1, this hydrogen storage material is reversible, releases the starting temperature of hydrogen for three times almost without any change.SEM photo shows, without the Mg of palladium layers
0.1zn
0.9(BH
4)
2material most of material after putting hydrogen through 982K hydrogenation peels off (Fig. 2) from substrate, and Mg
0.1zn
0.9(BH
4)
2-Pd still shows as complete, continuous print form (Fig. 3).Show that the existence of palladium layers both improve Mg
0.1zn
0.9(BH
4)
2thermostability, impart again its reversibility.
Embodiment 2
With Mg prepared by aforesaid method
0.2zn
0.8(BH
4)
2and Mg
0.2zn
0.8(BH
4)
2-Pd (palladium layers thickness is 20nm) puts hydrogen round-robin test do suction.The top temperature of putting hydrogen is 982K, and temperature rise rate is 23K/s; Following cycle hydrogenation temperature is normal temperature, pressure 1MPa, 6 hours time.Result shows, without the Mg of palladium layers
0.2zn
0.8(BH
4)
2do not show the reversibility of hydrogen storage property, putting in hydrogen process after following cycle hydrogenation does not detect hydrogen, and Mg
0.2zn
0.8(BH
4)
2-Pd then shows good hydrogenation reversibility.Without the Mg of palladium layers
0.2zn
0.8(BH
4)
2material most of material after putting hydrogen through 982K hydrogenation peels off from substrate, and Mg
0.2zn
0.8(BH
4)
2-Pd still shows as complete, continuous print form.Show that the existence of palladium layers both improve Mg
0.2zn
0.8(BH
4)
2thermostability, impart again its reversibility.
Embodiment 3
With Mg prepared by aforesaid method
0.1zn
0.9(BH
4)
2and Mg
0.1zn
0.9(BH
4)
2-Pt (platinum layer thickness is 8nm) puts hydrogen round-robin test do suction.The top temperature of putting hydrogen is 982K, and temperature rise rate is 23K/s; Following cycle hydrogenation temperature is normal temperature, pressure 1MPa, 4 hours time.Result shows, without the Mg of platinum layer
0.1zn
0.9(BH
4)
2do not show the reversibility of hydrogen storage property, putting in hydrogen process after following cycle hydrogenation does not detect hydrogen, and Mg
0.1zn
0.9(BH
4)
2-Pt then shows good hydrogenation reversibility.Without the Mg of platinum layer
0.1zn
0.9(BH
4)
2material most of material after putting hydrogen through 982K hydrogenation peels off from substrate, and Mg
0.1zn
0.9(BH
4)
2-Pt still shows as complete, continuous print form.Show that the existence of platinum layer both improve Mg
0.1zn
0.9(BH
4)
2thermostability, impart again its reversibility.
Embodiment 4
With Mg prepared by aforesaid method
0.6zn
0.4(BH
4)
2and Mg
0.6zn
0.4(BH
4)
2-Pt (platinum layer thickness is 12nm) puts hydrogen round-robin test do suction.The top temperature of putting hydrogen is 982K, and temperature rise rate is 23K/s; Following cycle hydrogenation temperature is normal temperature, pressure 1MPa, 7 hours time.Result shows, without the Mg of platinum layer
0.6zn
0.4(BH
4)
2do not show the reversibility of hydrogen storage property, putting in hydrogen process after following cycle hydrogenation does not detect hydrogen, and Mg
0.6zn
0.4(BH
4)
2-Pt then shows good hydrogenation reversibility.Without the Mg of platinum layer
0.6zn
0.4(BH
4)
2material most of material after putting hydrogen through 982K hydrogenation peels off from substrate, and Mg
0.6zn
0.4(BH
4)
2-Pt still shows as complete, continuous print form.Show that the existence of platinum layer both improve Mg
0.6zn
0.4(BH
4)
2thermostability, impart again its reversibility.
Embodiment 5
With Mg prepared by aforesaid method
0.3zn
0.7(BH
4)
2and Mg
0.3zn
0.7(BH
4)
2-Co (cobalt layers thickness is 15nm) puts hydrogen round-robin test do suction.The top temperature of putting hydrogen is 982K, and temperature rise rate is 23K/s; Following cycle hydrogenation temperature is normal temperature, pressure 1MPa, 6 hours time.Result shows, without the Mg of cobalt layers
0.3zn
0.7(BH
4)
2do not show the reversibility of hydrogen storage property, putting in hydrogen process after following cycle hydrogenation does not detect hydrogen, and Mg
0.3zn
0.7(BH
4)
2-Co then shows good hydrogenation reversibility.Without the Mg of cobalt layers
0.3zn
0.7(BH
4)
2material most of material after putting hydrogen through 982K hydrogenation peels off from substrate, and Mg
0.3zn
0.7(BH
4)
2-Co still shows as complete, continuous print form.Show that the existence of cobalt layers both improve Mg
0.3zn
0.7(BH
4)
2thermostability, impart again its reversibility.
Embodiment 6
With condition Direct precipitation Pd on silicon chip that embodiment 1 second step is identical, palladium layers thickness is 10nm.Under normal temperature, hydrogen pressure 1MPa, hydrogenation 8 hours, is then warmed up to 982K with the temperature rise rate of 23K/s and puts hydrogen.Result shows, this palladium layers does not have the hydrogen release that can detect, illustrates that palladium layers just imparts Mg
xzn
1-x(BH
4)
2lower floor Mg in-Pd material
xzn
1-x(BH
4) storage reversible hydrogen and improve its thermostability, itself do not have under this experiment condition storage reversible hydrogen.
Claims (7)
1. a reversible hydrogen storage material, is characterized in that, meets chemical general formula Mg
xzn
1-x(BH
4)
2-M, wherein x=0.05 ~ 0.95, M is the one in Pd, Pt, Co.
2. a kind of reversible hydrogen storage material according to claim 1, is characterized in that, is formed by metal borohydride surface deposition layer of metal.
3. a kind of reversible hydrogen storage material according to claim 1-2, is characterized in that, the circulation hydrogenation temperature of described reversible hydrogen storage material is normal temperature, and hydrogen pressure is 1MPa.
4. a kind of reversible hydrogen storage material according to claim 1-2, is characterized in that, the initial desorption temperature of described reversible hydrogen storage material is 450K, and the highest desorption temperature is 982K, and lifting/lowering temperature speed is 23K/s.
5. a preparation method for reversible hydrogen storage material, is characterized in that, comprises the following steps:
(1) MAGNESIUM METAL, zinc, boron codeposition under hydrogen environment on silicon chip, is obtained metal borohydride, Mg
xzn
1-x(BH
4)
2, wherein x=0.05 ~ 0.95;
(2) palladium metal, platinum or cobalt are deposited on above-mentioned metal borohydride surface under without hydrogen vacuum environment, deposit thickness is 2 ~ 20nm, obtains reversible hydrogen storage material.
6. the preparation method of a kind of reversible hydrogen storage material according to claim 5, is characterized in that, the deposition method that step (1) adopts is physical vapor deposition, and vacuum tightness is 5.2x10
-4pa, sedimentation rate is 2.5nm/min.
7. the preparation method of a kind of reversible hydrogen storage material according to claim 5, is characterized in that, the deposition method that step (2) adopts is vacuum sputtering, and vacuum tightness is 1x10
-8pa, sedimentation rate is 1.5nm/min.
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|---|---|---|---|
| CN201410624206.1A CN104401941A (en) | 2014-11-07 | 2014-11-07 | Reversible hydrogen storage material and preparation method thereof |
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|---|---|---|---|
| CN201410624206.1A CN104401941A (en) | 2014-11-07 | 2014-11-07 | Reversible hydrogen storage material and preparation method thereof |
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-
2014
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Patent Citations (7)
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| WO2006009927A1 (en) * | 2004-06-18 | 2006-01-26 | H2Volt, Inc. | Combination metal-based and hydride-based hydrogen sources and processes for producing hydrogen |
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| CN101279272A (en) * | 2008-05-13 | 2008-10-08 | 北京理工大学 | Double-activity composite catalyst and preparation method and application thereof |
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Effective date of abandoning: 20170517 |
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