CN102935997A - Metal borohydride-metal hydride reaction composite hydrogen storage material and preparation method thereof - Google Patents
Metal borohydride-metal hydride reaction composite hydrogen storage material and preparation method thereof Download PDFInfo
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- CN102935997A CN102935997A CN2012104251885A CN201210425188A CN102935997A CN 102935997 A CN102935997 A CN 102935997A CN 2012104251885 A CN2012104251885 A CN 2012104251885A CN 201210425188 A CN201210425188 A CN 201210425188A CN 102935997 A CN102935997 A CN 102935997A
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Abstract
The invention relates to a modification technology of a hydrogen storage material and particularly relates to a metal borohydride-metal hydride reaction composite hydrogen storage material system and a preparation method thereof. The problems that in the prior art, transition metal boride nucleating agents are generated partly and the dispersed degree of transition metal boride nucleating agents is low caused by the fact that the reactivity of additives and the reactivity of base materials are different are solved. Under the protection of inert atmosphere, transition metal halide and borohydride base materials are subjected to simple ball milling, a ball milling sample is subjected to heat processing at certain hydrogen pressure and temperature, and the ball milling sample and metal hydride base materials are subjected to mall milling. The mol rate of metal borohydride and additives are 1:0.01-1:0.2, and the mol rate of the metal borohydride and the metal hydride is 2:1-6:1. By the aid of the preparation method, the transition metal boride nucleating agents are promoted to be generated greatly, the transition metal boride nucleating agents can be distributed in base materials highly, and the hydrogen desorption capability, the hydrogen desorption dynamics and the cyclical stability of the hydrogen storage material are improved greatly.
Description
Affiliated technical field
The present invention relates to the improvement technology of hydrogen storage material, be specially a kind of metal borohydride-metal hydride reaction composite hydrogen storage material system and preparation method thereof.
Background technology
Development high-performance hydrogen-storage system is the applicable key link of hydrogen for the application terminal provides hydrogen source.The light metal hydroborate contains the hydrogen storage capability of superelevation, is acknowledged as hydrogen storage material the most with potential applications.But hydroborate contains the ion/covalent linkage of high directivity, causes that thermodynamics is too stable and suctions/hydrogen desorption kinetics is slow, centers on to improve the metal borohydride hydrogen storage property and carried out a large amount of research work, has developed multiple improvement means.Wherein, to improve effect particularly remarkable by forming the reaction compound system with metal hydride, and use this strategy development and go out multiple hydride reaction compound system, wherein 2LiBH
4-MgH
2(mol ratio is 2:1) reaction compound system is Typical Representative.2LiBH
4-MgH
2Compound system is put hydrogen (2LiBH through two-step reaction under certain hydrogen pressure
4+ MgH
2→ 2LiBH
4+ Mg+H
2→ 2LiH+MgB
2+ 4H
2), with pure LiBH
4Compare reversibility [reference 1:Vajo, J.J. that this system has lower hydrogen discharge reaction enthalpy change and significantly improves; Skeith, S.L.; Mertens, F.Reversible Storage of Hydrogen in Destabilized LiBH
4.Journal of Physical Chemistry B2005,109,3719-3722.].Mechanism Study shows, second step is put hydrogen and generated MgB
2The key that its hydrogen storage property is significantly improved, but on kinetics, MgB
2Form the incubation period that needs for a long time.Recently research is found by adding a small amount of transistion metal compound, especially transition metal halide can significantly shorten even eliminate incubation period, its improvement mechanism is that transition metal can change the generation transition metal boride in the halogenide, and it can be used as heterogeneous nucleating agent and significantly promotes MgB
2Generation [reference 2:Bosenberg, U.; Kim, J.W.; Gosslar, D.; Eigen, N.; Jensen, T.R.; Von Colbe, J.M.B.; Zhou, Y.; Dahms, M.; Kim, D.H.; Gunther, R.; Cho, Y.W.; Oh, K.H.; Klassen, T.; Bormann, R.; Dornheim, M.Role of additives in LiBH
4-MgH
2Reactive hydride composites for sorption kinetics.Acta Mater2010,58,3381-3389.].Usually adopt at present a step ball milled preparation feedback compound system hydrogen storage material, research is found because transition metal halide not only can react with the metal borohydride body material, and can react with the metal hydride body material, even stronger with latter reaction's property, and generate transition metal hydride with the metal hydride reaction, it further generates transition metal boride with the metal borohydride reactive moieties, obviously, generate and stablize the middle formation efficiency that has reduced mutually transition metal boride of transition metal hydride with dispersed, thereby reduced the improved performance effect of additive.Thereby the preparation method that development is efficient, disperse generates transition metal boride improves the key of system hydrogen storage property at all.
Summary of the invention
The object of the present invention is to provide a kind of heavy body metal borohydride that adds transition metal halide-metal hydride reaction composite hydrogen storage material system and preparation method thereof, solve transition metal boride formation efficiency and the low problem of disperse degree of distribution among the existing preparation method.
Technical scheme of the present invention is:
A kind of metal borohydride-metal hydride reaction composite hydrogen storage material, this hydrogen storage material is comprised of metal borohydride and metal hydride body material and transition metal halide additive, and body material metal borohydride and metal hydride mol ratio are 2:1 ~ 6:1; Metal borohydride and transition metal halide additive mol ratio are 1:0.01 ~ 1:0.2.
The preparation method of described metal borohydride-metal hydride reaction composite hydrogen storage material may further comprise the steps:
(1) under inert atmosphere protection, only place ball grinder reaction vessel ball milling even with the metal borohydride body material Powdered transition metal halide additive in proportion, wherein the mol ratio of metal borohydride and transition metal halide is 1:0.01 ~ 1:0.2;
(2) powdered sample behind the ball milling is heat-treated, thermal treatment temp is room temperature to 450 ℃, and hydrogen pressure is 1 ~ 10MPa, 0.5 ~ 10 hour time;
(3) add in proportion another metal hydride body material in heat treated sample, and carry out together ball milling under inert atmosphere, wherein metal borohydride and metal hydride mol ratio are 2:1 ~ 6:1.
In described step (1) and (3), during ball milling, ball material mass ratio is greater than 5:1 under inert atmosphere, and Ball-milling Time was greater than 10 minutes.Ball material mass ratio is preferably (20～100): 1, and Ball-milling Time is preferably 1～5 hour.
In the described step (2), thermal treatment temp is preferably 300 to 400 ℃, and hydrogen pressure is preferably 2 ~ 6MPa, 1 ~ 5 hour time.
Among the present invention, metal borohydride is one or more the combination in alkali metal borohydride, the alkaline-earth metal boron hydride; Metal hydride is one or more the combination in alkaline earth metal hydride, transition metal hydride, the rare earth metal hydride; Transition metal halide is one or more the combination in transition metal chloride and the transition metal fluorides.
Among the present invention, basic metal is Li, Na or K; Alkaline-earth metal is Mg or Ca; Magnesium-yttrium-transition metal is Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb or Mo; Alkaline earth metal hydride is MgH
2, CaH
2Or SrH
2Transition metal hydride is ScH
2, YH
3, TiH
2Or ZrH
2Rare earth metal hydride is LaH
2Or CeH
2Transition metal halide is MCln or MFn, n=2 ~ 4, one of M=Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo or two or more combinations.
The invention has the advantages that:
1, the present invention optionally adds transition metal halide, and directly, all generates transition metal boride without the centre phase, has significantly improved formation efficient.
2, the present invention first forms transition metal boride in a kind of body material, then with another body material mixing and ball milling, improved transition metal boride at body material, especially at the interface dispersity, thereby significantly improved the hydrogen storage property of system.
3, metal borohydride provided by the invention-metal hydride reaction compound system preparation method one is multistep processes, at first with transition metal additive and the independent ball milling of metal borohydride body material, then under certain temperature and hydrogen pressure, milled sample is heat-treated, add at last metal hydride therewith ball milling make.
4, multistep preparation method provided by the present invention is that from the essential distinction of one step of tradition ball milling method the generative process of interpolation opportunity of transition metal halide and transition metal boride is different.
In a word; the present invention is under inert atmosphere protection; additive (transition metal halide) and hydroborate (basic metal or alkaline-earth metal boron hydride) body material are carried out simple ball milling; then under certain hydrogen pressure and temperature, milled sample is being heat-treated, adding another metal hydride (alkaline-earth metal or rare earth metal hydride) body material and ball milling together by proportioning more at last.This preparation method is when promoting that significantly the transition metal boride nucleating agent generates, guarantee that its high diffusive in body material distributes, thereby what significantly improved hydrogen storage material puts hydrogen capacity, hydrogen desorption kinetics and cyclical stability, solves in the existing technology of preparing to cause part generation transition metal boride nucleating agent and the low problem of dispersity because additive and body material are reactive different.
Description of drawings
Fig. 1: adopt respectively one step of tradition ball milled and the invention provides the made sample of multistep processes at the X-of different steps ray diagram.(a) 2LiBH
4+ MgH
2+ 0.08TiF
3Sample adopted the direct ball milling of single stage method 2 hours; (b) LiBH
4+ 0.04TiF
3Sample ball milling 30 minutes; (c) ball milling b sample thermal treatment 1 hour under 320 ℃, 3MPa condition; (d) add MgH
2In sample c and further ball milling 2 hours.
Fig. 2: adopt respectively a step ball milled and the invention provides the made sample of multistep processes at the x-ray photoelectron spectroscopy figure of different steps.(a) 2LiBH
4+ MgH
2+ 0.08TiF
3Sample adopted the direct ball milling of single stage method 2 hours; (b) sample a is put hydrogen through the first step; (c) LiBH
4+ 0.04TiF
3Milled sample thermal treatment 1 hour under 320 ℃, 3MPa condition; (d) add MgH
2In sample c and further ball milling 2 hours.For the ease of comparing TiB
2And TiH
2Ti 2p photoelectron spectral line also comprises wherein in the reference sample.
Fig. 3: the transmission electron microscopy of putting hydrogen aspect product reaches distribution diagram of element mutually.(a) adopt the made sample of multistep processes provided by the invention and Li, B, Mg, Ti distribution diagram of element; (b) adopt one step of the tradition made sample of ball milled and Li, B, Mg, Ti distribution diagram of element.
Fig. 4: pure 2LiBH
4+ MgH
2Sample and the prepared 2LiBH of employing different methods
4+ MgH
2+ 0.08TiF
3The hydrogen desorption kinetics curve of sample.Putting hydrogen condition is 400 ℃, 3 bar (bar) hydrogen pressure.
Fig. 5: adopt the prepared 2LiBH of different methods
4+ MgH
2+ 0.08TiF
3First three of sample time circulation Hydrogen desorption isotherms.Putting hydrogen condition is 400 ℃, 3bar hydrogen pressure; Hydrogen uptake condition is 350 ℃, 10MPa hydrogen pressure.
Fig. 6: with 2LiBH
4+ MgH
2+ 0.08TiCl
3Be starting raw material, adopt respectively one step of tradition ball milled and the hydrogen desorption kinetics correlation curve that the invention provides the made sample of multistep processes.Putting hydrogen condition is 400 ℃, 3bar hydrogen pressure.
Fig. 7: with 2NaBH
4+ MgH
2+ 0.08TiF
3Be starting raw material, adopt respectively one step of tradition ball milled and the hydrogen desorption kinetics correlation curve that the invention provides the made sample of multistep processes.Putting hydrogen condition is 480 ℃, 0.1bar hydrogen pressure.
Embodiment
The present invention is mainly with 2LiBH
4+ MgH
2+ 0.08TiF
3Be example, comparative illustration multistep preparation method provided by the present invention tradition one goes on foot ball milling method by promoting metal boride to form to improve the superiority of system hydrogen storage property aspect.
The employing raw material is: LiBH
4(purity 95wt.%), MgH
2(purity 98wt.%), TiF
3(purity 99.9%).In the argon atmospher glove box, with the LiBH of 1:0.04 mol ratio
4/ TiF
3Mixture and Stainless Steel Ball are packed in the stainless steel jar mill, seal; Then ball grinder is placed on Fritsch 7 planetary ball mills, 25 ℃ of lower grindings 0.5 hour of room temperature, ball material mass ratio is 100:1; Then with milled sample thermal treatment 1 hour under 320 ℃, 3MPa hydrogen pressure, add at last MgH
2(with LiBH
4Mol ratio is 1:2) and ball milling 2 hours together.For relatively, with the LiBH of 2:1:0.08 mol ratio
4/ MgH
2/ TiF
3The direct ball milling of mixture 2 hours, other ball milling condition is identical.
X-ray testing apparatus and condition: Rigaku D/max 2500, Cu Ka ray.Fig. 1 has provided a step milled sample and multistep prepares sample at the X-of different steps ray diagram.After adopting a step ball milling, mainly see LiBH in the sample
4And MgH
2The body material phase is not seen any Ti of containing phase.Adopt the multistep preparation method, LiBH
4/ 0.04TiF
3Kept thinking stability behind the ball milling, do not reacted; Through seeing remaining LiBH after the Isothermal Hot processing
4Mutually with LiF mutually, show TiF
3Reaction has occured in complete and body material, but does not see equally any Ti of containing phase; Add at last MgH
2And together behind the ball milling, except LiF mutually other and a step milled sample identical.XRD does not see that any Ti of containing shows that mutually it is amorphous state or disperse nanophase, need to further confirm to contain by XPS the chemical state of Ti phase.
X-ray photoelectron spectroscopy testing apparatus and condition: VG ESCALAB 250, Al Ka X-ray source.The combination of element can be corrected according to C1s peak position (284.6eV).Fig. 2 has provided single stage method and the made sample of multistep processes in the XPS spectrum of different steps.Show TiF behind the employing single stage method ball milling in conjunction with XRD result
3With MgH
2Reaction has generated TiH
2, TiH
2Generating TiB through the first step hydrogen discharge reaction rear section
2And employing multistep preparation method, TiF after the thermal treatment
3With LiBH
4Complete reaction has generated TiB
2, and add MgH
2TiB behind the ball milling
2Do not change.These phases/chemical state presentation of results, in the step ball milled, TiF
3With MgH
2The body material preferential reaction has generated TiH
2Phase, put in the hydrogen process and LiBH in the first step heating this centre
4The matrix phase reactive moieties changes TB into
2Fully different therewith, in the multistep preparation method, TiF
3Directly and LiBH
4Complete reaction generates TB
2Thereby, significantly improved the efficient that transition metal halide changes transition metal boride into.
Transmission electron microscope testing apparatus and condition: FEI Tecnai G2 F30, operating voltage 300kV is furnished with HAADF detector and EELS spectrum.Fig. 3 has contrasted TEM figure and the EELS spectrum that adopts after traditional single stage method and the made sample of multistep processes provided by the present invention are put hydrogen under the same conditions.As seen from the figure, Li, Mg, B matrix phase element distribute all more even, do not have significant difference, illustrate and put hydrogen product LiH and MgB
2Mix.But carefully contrast finds that there is notable difference in the distribution of Ti element.Multistep processes prepares in the sample, the TB from several nanometers to tens nanometers
2Uniform particles is distributed in the matrix phase, and adopts in the made sample of single stage method, only has the TB of minority
2Grain is distributed in the matrix phase unevenly.TiB
2High diffusive distribute should be owing to promoting TiB
2Form and the step by step effect of ball milling two aspects, and expection causes the remarkable improvement of hydrogen storage property.
Adopt the hydrogen discharging performance of volumetric method test material.Hydrogen condition is put in suction: put hydrogen under 400 ℃, 3bar, inhale hydrogen under 300 ℃, 10MPa.Fig. 4 provides the hydrogen desorption kinetics curve that adopts respectively single stage method and the made sample of multistep processes, has also comprised the hydrogen discharging performance of pure reaction compound system simultaneously.Pure reaction compound system second step is put hydrogen and is generated MgB
2The front need experienced 14 hours incubation period.Add TiF
3The post inoculation phase significantly reduces even has eliminated, and especially the made sample of multistep processes has been finished two step hydrogen discharge reactions in 1 hour, and average hydrogen discharging rate has improved twice than the made sample of single stage method.In addition, this because preparation method changes the improved performance effect that causes to put the hydrogen circulation particularly evident through inhaling.Fig. 5 has provided first three time of two kinds of made samples of preparation method circulation Hydrogen desorption isotherms.Contrast is found, adopt the made sample of multistep processes to have better cyclical stability with regard to hydrogen desorption kinetics and hydrogen storage capability aspect, adopt the made sample of single stage method to show obvious performance degradation, reach 1.1wt% through three cycle capacity loss, surpass 3 times of the former loss amount.But adopt the made sample inverse put of multistep method hydrogen capacity to surpass 10wt%, this value is better than the bibliographical information value.
Difference from Example 1 is, with 2LiBH
4+ MgH
2+ 0.08TiCl
3For adopting respectively one step of tradition ball milling method and multistep preparation method provided by the invention, starting raw material prepares sample.
The employing raw material is: LiBH
4(purity 95wt.%), MgH
2(purity 98wt.%), TiCl
3(purity 99.99%).All the other sample preparation conditions are with embodiment 1.Put hydrogen condition: 400 ℃, 3bar.To change the process that generates metal boride identical with example 1 described process for transition metal fluorides among two kinds of preparation methods, and improved performance mechanism is also therefore similar, therefore only carry out the hydrogen storage property comparative illustration.As can be seen from Figure 6, adopt the hydrogen desorption kinetics of the made sample of multistep preparation method and put hydrogen capacity significantly to be better than adopting the made sample of tradition one step ball milling method, further illustrate the superiority that the invention provides multistep method.
Difference from Example 1 is, with 2NaBH
4+ MgH
2+ 0.08TiF
3For adopting respectively one step of tradition ball milling method and multistep preparation method provided by the invention, starting raw material prepares sample.
The employing raw material is: NaBH
4(purity 95wt.%), MgH
2(purity 98wt.%), TiF
3(purity 99.9%).All the other sample preparation conditions are with embodiment 1.Put hydrogen condition: 480 ℃, 0.1bar.As can be seen from Figure 7, adopt the hydrogen desorption kinetics of the made sample of multistep preparation method significantly to be better than adopting the made sample of tradition one step ball milling method, illustrate that the method has universality.
Sample result shows, the multistep preparation method of preparation metal borohydride provided by the invention-metal hydride reaction compound system can significantly promote the formation of transition metal boride and promote it in the disperse degree of matrix phase/at the interface, therefore compare with one step of tradition ball milling method, significantly improve the hydrogen storage property of system, promoted the practical application potentiality of this system.
Claims (9)
1. metal borohydride-metal hydride reacts composite hydrogen storage material, it is characterized in that: this hydrogen storage material is comprised of metal borohydride and metal hydride body material and transition metal halide additive, and body material metal borohydride and metal hydride mol ratio are 2:1 ~ 6:1; Metal borohydride and transition metal halide additive mol ratio are 1:0.01 ~ 1:0.2.
2. according to metal borohydride claimed in claim 1-metal hydride reaction composite hydrogen storage material, it is characterized in that: metal borohydride is one or more the combination in alkali metal borohydride, the alkaline-earth metal boron hydride; Metal hydride is one or more the combination in alkaline earth metal hydride, transition metal hydride, the rare earth metal hydride; Transition metal halide is one or more the combination in transition metal chloride and the transition metal fluorides.
3. according to metal borohydride claimed in claim 2-metal hydride reaction composite hydrogen storage material, it is characterized in that: basic metal is Li, Na or K; Alkaline-earth metal is Mg or Ca; Magnesium-yttrium-transition metal is Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb or Mo; Alkaline earth metal hydride is MgH
2, CaH
2Or SrH
2Transition metal hydride is ScH
2, YH
3, TiH
2Or ZrH
2Rare earth metal hydride is LaH
2Or CeH
2Transition metal halide is MCln or MFn, n=2 ~ 4, one of M=Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo or two or more combinations.
4. the preparation method of metal borohydride claimed in claim 1-metal hydride reaction composite hydrogen storage material is characterized in that, may further comprise the steps:
(1) under inert atmosphere protection, only place ball grinder reaction vessel ball milling even with the metal borohydride body material Powdered transition metal halide additive in proportion, wherein the mol ratio of metal borohydride and transition metal halide is 1:0.01 ~ 1:0.2;
(2) powdered sample behind the ball milling is heat-treated, thermal treatment temp is room temperature to 450 ℃, and hydrogen pressure is 1 ~ 10MPa, 0.5 ~ 10 hour time;
(3) add in proportion another metal hydride body material in heat treated sample, and carry out together ball milling under inert atmosphere, wherein metal borohydride and metal hydride mol ratio are 2:1 ~ 6:1.
5. react the preparation method of composite hydrogen storage material according to metal borohydride claimed in claim 4-metal hydride, it is characterized in that, in the described step (1), metal borohydride is one or more the combination in alkali metal borohydride, the alkaline-earth metal boron hydride; Metal hydride is one or more the combination in alkaline earth metal hydride, transition metal hydride, the rare earth metal hydride; Transition metal halide is one or more the combination in transition metal chloride and the transition metal fluorides.
6. according to metal borohydride claimed in claim 5-metal hydride reaction composite hydrogen storage material, it is characterized in that: basic metal is Li, Na or K; Alkaline-earth metal is Mg or Ca; Magnesium-yttrium-transition metal is Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb or Mo; Alkaline earth metal hydride is MgH
2, CaH
2Or SrH
2Transition metal hydride is ScH
2, YH
3, TiH
2Or ZrH
2Rare earth metal hydride is LaH
2Or CeH
2Transition metal halide is MCln or MFn, n=2 ~ 4, one of M=Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo or two or more combinations.
7. react the preparation method of composite hydrogen storage material according to metal borohydride claimed in claim 4-metal hydride, it is characterized in that: in described step (1) and (3), during ball milling, ball material mass ratio is greater than 5:1 under inert atmosphere, and Ball-milling Time was greater than 10 minutes.
8. according to the preparation method of metal borohydride claimed in claim 7-metal hydride reaction composite hydrogen storage material, it is characterized in that: ball material mass ratio is preferably (20～100): 1, and Ball-milling Time is preferably 1～5 hour.
9. react the preparation method of composite hydrogen storage material according to metal borohydride claimed in claim 4-metal hydride, it is characterized in that: in the described step (2), thermal treatment temp is preferably 300 to 400 ℃, and hydrogen pressure is preferably 2 ~ 6MPa, 1 ~ 5 hour time.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106430097A (en) * | 2016-08-31 | 2017-02-22 | 北京理工大学 | Composite hydrogen storage material and preparation method thereof |
| CN107004843A (en) * | 2014-12-10 | 2017-08-01 | 巴斯夫公司 | metal hydride compositions and lithium ion battery |
| CN107915203A (en) * | 2016-10-11 | 2018-04-17 | 中国科学院大连化学物理研究所 | The preparation method and complex hydride hydrogen storage material of complex hydride hydrogen storage material |
| CN114436209A (en) * | 2022-03-08 | 2022-05-06 | 广东省科学院资源利用与稀土开发研究所 | Magnesium hydride-in-situ generated metal borohydride hydrolysis hydrogen production material and preparation method thereof |
| CN115367701A (en) * | 2022-09-29 | 2022-11-22 | 重庆大学 | MgH 2 -AlH 3 -TiF 3 Composite hydrogen storage material and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060013766A1 (en) * | 2004-03-26 | 2006-01-19 | Vajo John J | Methods for reversibly storing hydrogen |
| US20060194695A1 (en) * | 2004-08-27 | 2006-08-31 | Westinghouse Savannah River Co., Llc | Destabilized and catalyzed borohydrided for reversible hydrogen storage |
| US20070264182A1 (en) * | 2005-03-22 | 2007-11-15 | Gm Global Technology Operations, Inc. | Reversible hydrogen storage systems |
| CN101549854A (en) * | 2009-05-13 | 2009-10-07 | 安徽工业大学 | Mg-based composite hydrogen storage material containing alkaline earth metals-aluminum hydride and preparation method thereof |
| CN102219181A (en) * | 2011-05-10 | 2011-10-19 | 浙江大学 | Niobium-based coordination hydroboron composite hydrogen storage material and preparation method and applications |
-
2012
- 2012-10-30 CN CN201210425188.5A patent/CN102935997B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060013766A1 (en) * | 2004-03-26 | 2006-01-19 | Vajo John J | Methods for reversibly storing hydrogen |
| US20060194695A1 (en) * | 2004-08-27 | 2006-08-31 | Westinghouse Savannah River Co., Llc | Destabilized and catalyzed borohydrided for reversible hydrogen storage |
| US20070264182A1 (en) * | 2005-03-22 | 2007-11-15 | Gm Global Technology Operations, Inc. | Reversible hydrogen storage systems |
| CN101549854A (en) * | 2009-05-13 | 2009-10-07 | 安徽工业大学 | Mg-based composite hydrogen storage material containing alkaline earth metals-aluminum hydride and preparation method thereof |
| CN102219181A (en) * | 2011-05-10 | 2011-10-19 | 浙江大学 | Niobium-based coordination hydroboron composite hydrogen storage material and preparation method and applications |
Non-Patent Citations (6)
| Title |
|---|
| 《Acta Materialia》 20100310 U. Bosenberg et al. Role of additives in LiBH4-MgH2 reactive hydride composites for sorption kinetics 3381-3389 1-9 第58卷, * |
| DONGAN LIU ET AL.: "Studies of the effects of TiCl3 in LiBH4/CaH2/TiCl3 reversible hydrogen storage system", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
| JAE-HAG LIM ET AL.: "Rehydrogenation and cycle studies of LiBH4-CaH2 composite", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》 * |
| JUSTIN PUREWAL ET AL.: "Hydrogen Sorption Behavior of the ScH2-LiBH4 System: Experimental Assesment of Chemical Destabilization Effects", 《J. PHYS. CHEM. C》 * |
| PATTARAPORN SRIDECHPRASAT ET AL.: "Catalyzed LiBH4 and MgH2 mixture for hydrogen storage", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》 * |
| U. BOSENBERG ET AL.: "Role of additives in LiBH4–MgH2 reactive hydride composites for sorption kinetics", 《ACTA MATERIALIA》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107004843A (en) * | 2014-12-10 | 2017-08-01 | 巴斯夫公司 | metal hydride compositions and lithium ion battery |
| CN106430097A (en) * | 2016-08-31 | 2017-02-22 | 北京理工大学 | Composite hydrogen storage material and preparation method thereof |
| CN106430097B (en) * | 2016-08-31 | 2019-09-10 | 北京理工大学 | Composite hydrogen storage material and preparation method thereof |
| CN107915203A (en) * | 2016-10-11 | 2018-04-17 | 中国科学院大连化学物理研究所 | The preparation method and complex hydride hydrogen storage material of complex hydride hydrogen storage material |
| CN114436209A (en) * | 2022-03-08 | 2022-05-06 | 广东省科学院资源利用与稀土开发研究所 | Magnesium hydride-in-situ generated metal borohydride hydrolysis hydrogen production material and preparation method thereof |
| CN115367701A (en) * | 2022-09-29 | 2022-11-22 | 重庆大学 | MgH 2 -AlH 3 -TiF 3 Composite hydrogen storage material and preparation method thereof |
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