CN102935997B - 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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- CN102935997B CN102935997B CN201210425188.5A CN201210425188A CN102935997B CN 102935997 B CN102935997 B CN 102935997B CN 201210425188 A CN201210425188 A CN 201210425188A CN 102935997 B CN102935997 B CN 102935997B
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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 application terminal provides hydrogen source.The hydrogen storage capability that light metal hydroborate contains superelevation, is acknowledged as hydrogen storage material the most with potential applications.But ion/covalent linkage that hydroborate contains high directivity, causes that thermodynamics is too stable and suction/hydrogen desorption kinetics is slow, has carried out a large amount of research work around improving metal borohydride hydrogen storage property, has developed multiple improvement means.Wherein, by forming and react compound system to improve effect particularly remarkable with metal hydride, and apply 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
2that its hydrogen storage property is able to the key of significantly improving, but in kinetics, MgB
2form the incubation period needing 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 and eliminate incubation period, its improvement mechanism is that in halogenide, transition metal can change generation transition metal boride, 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.].Conventionally 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 metal borohydride body material, and can react with metal hydride body material, even stronger with latter reaction's property, generate transition metal hydride and react with metal hydride, it further generates transition metal boride with metal borohydride reactive moieties, obviously, generate and stablize the formation efficiency that has reduced mutually transition metal boride in the middle of transition metal hydride with dispersed, thereby reduce 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-metal hydride reaction composite hydrogen storage material system of adding transition metal halide and preparation method thereof, solve transition metal boride formation efficiency and the low problem of disperse degree of distribution in 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 made up 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, comprises the following steps:
(1) under inert atmosphere protection, by Powdered transition metal halide additive, to be only placed in ball grinder reaction vessel ball milling even with metal borohydride body material in proportion, and wherein the mol ratio of metal borohydride and transition metal halide is 1:0.01 ~ 1:0.2;
(2) powdered sample after ball milling is heat-treated, thermal treatment temp is room temperature to 450 DEG C, 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 under inert atmosphere, carry out together ball milling, wherein metal borohydride and metal hydride mol ratio are 2:1 ~ 6:1.
In described step (1) and (3), under inert atmosphere, when ball milling, ball material mass ratio is greater than 5:1, and Ball-milling Time is greater than 10 minutes.Ball material mass ratio is preferably (20～100): 1, and Ball-milling Time is preferably 1～5 hour.
In described step (2), thermal treatment temp is preferably 300 to 400 DEG C, and hydrogen pressure is preferably 2 ~ 6MPa, 1 ~ 5 hour time.
In the present invention, metal borohydride is one or more the combination in alkali metal borohydride, alkaline-earth metal boron hydride; Metal hydride is one or more the combination in alkaline earth metal hydride, transition metal hydride, rare earth metal hydride; Transition metal halide is one or more the combination in transition metal chloride and transition metal fluorides.
In 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
2; Transition metal hydride is ScH
2, YH
3, TiH
2or ZrH
2; Rare earth metal hydride is LaH
2or CeH
2; Transition 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 centre phase, has significantly improved formation efficiency.
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 dispersity of interface, 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, first by 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, finally add metal hydride therewith ball milling make.
4, multistep preparation method provided by the present invention is that from the essential distinction of a traditional step ball milling method interpolation opportunity of transition metal halide is different with the generative process of transition metal boride.
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 to simple ball milling; then at certain hydrogen pressure and temperature, milled sample is being heat-treated, finally adding another metal hydride (alkaline-earth metal or rare earth metal hydride) body material ball milling together by proportioning again.This preparation method is in significantly promoting that transition metal boride nucleating agent generates, ensure that its high diffusive in body material distributes, thereby what significantly improved hydrogen storage material puts hydrogen capacity, hydrogen desorption kinetics and cyclical stability, solve in existing technology of preparing and cause part to generate transition metal boride nucleating agent and the low problem of dispersity because additive and body material are reactive different.
Brief description of the drawings
Fig. 1: adopt respectively a traditional step 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 adopts 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 DEG C, 3MPa condition; (d) add MgH
2in sample c further ball milling 2 hours.
Fig. 2: adopt respectively a step ball milled and the invention provides the x-ray photoelectron spectroscopy figure of the made sample of multistep processes in different steps.(a) 2LiBH
4+ MgH
2+ 0.08TiF
3sample adopts 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 DEG C, 3MPa condition; (d) add MgH
2in sample c further ball milling 2 hours.For the ease of comparing, TiB
2and TiH
2in reference sample, Ti 2p photoelectron spectral line also comprises wherein.
Fig. 3: transmission electron microscopy phase and the distribution diagram of element of putting hydrogen aspect product.(a) adopt the made sample of multistep processes provided by the invention and Li, B, Mg, Ti distribution diagram of element; (b) adopt the made sample of a traditional step 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 DEG C, 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 DEG C, 3bar hydrogen pressure; Hydrogen uptake condition is 350 DEG C, 10MPa hydrogen pressure.
Fig. 6: with 2LiBH
4+ MgH
2+ 0.08TiCl
3for starting raw material, adopt respectively a traditional step ball milled and the hydrogen desorption kinetics correlation curve that the invention provides the made sample of multistep processes.Putting hydrogen condition is 400 DEG C, 3bar hydrogen pressure.
Fig. 7: with 2NaBH
4+ MgH
2+ 0.08TiF
3for starting raw material, adopt respectively a traditional step ball milled and the hydrogen desorption kinetics correlation curve that the invention provides the made sample of multistep processes.Putting hydrogen condition is 480 DEG C, 0.1bar hydrogen pressure.
Embodiment
Embodiment 1
The present invention is mainly with 2LiBH
4+ MgH
2+ 0.08TiF
3for example, the more traditional step ball milling method of comparative illustration multistep preparation method provided by the present invention is by promoting metal boride to form to improve the superiority of system hydrogen storage property aspect.
Employing raw material is: LiBH
4(purity 95wt.%), MgH
2(purity 98wt.%), TiF
3(purity 99.9%).In argon atmospher glove box, by the LiBH of 1:0.04 mol ratio
4/ TiF
3mixture and Stainless Steel Ball pack in stainless steel jar mill, seal; Then ball grinder is placed on Fritsch 7 planetary ball mills, at 25 DEG C of room temperatures, grinds 0.5 hour, ball material mass ratio is 100:1; Then by milled sample thermal treatment 1 hour under 320 DEG C, 3MPa hydrogen pressure, finally add MgH
2(with LiBH
4mol ratio is 1:2) and ball milling 2 hours together.For relatively, by 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 is prepared sample at the X-of different steps ray diagram.Adopt after a step ball milling, in sample, mainly see LiBH
4and MgH
2body material phase, does not see any containing Ti phase.Adopt multistep preparation method, LiBH
4/ 0.04TiF
3after ball milling, keep thinking stability, do not reacted; After processing, Isothermal Hot sees remaining LiBH
4phase and LiF phase, show TiF
3completely occur to react with body material, but do not seen equally any containing Ti phase; Finally add MgH
2and together after ball milling, except LiF, other is identical with a step milled sample mutually.XRD does not see that any Ti of containing shows that it is amorphous state or disperse nanophase mutually, need to further confirm the chemical state containing Ti phase by XPS.
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 the multistep processes XPS spectrum in different steps.Show TiF after 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
2; And employing multistep preparation method, TiF after thermal treatment
3with LiBH
4complete reaction has generated TiB
2, and add MgH
2tiB after ball milling
2do not change.These thing phase/chemical state presentation of results, in a step ball milled, TiF
3with MgH
2body material preferential reaction has generated TiH
2phase, this centre in hydrogen process is put in the first step heating with LiBH
4matrix phase reactive moieties changes TB into
2.Completely different therewith, in multistep preparation method, TiF
3directly and LiBH
4complete reaction generates TB
2thereby, significantly improved transition metal halide and changed into the efficiency of transition metal boride.
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 and has adopted traditional single stage method and the made sample of multistep processes provided by the present invention to put under the same conditions TEM figure and the EELS spectrum after hydrogen.As seen from the figure, Li, Mg, B matrix phase element distribute all more even, there is no significant difference, illustrate and put hydrogen product LiH and MgB
2mix.But carefully contrast finds that the distribution of Ti element exists notable difference.Multistep processes is prepared in sample, the TB from several nanometers to tens nanometers
2uniform particles is distributed in matrix phase, and adopts in the made sample of single stage method, only has the TB of minority
2grain is distributed in matrix phase unevenly.TiB
2high diffusive distribute should owing to promote TiB
2form and the effect of ball milling two aspects step by step, 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 DEG C, 3bar, inhale hydrogen under 300 DEG C, 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
2front need experienced the incubation period of 14 hours.Add TiF
3the post inoculation phase significantly reduces even and has eliminated, and especially the made sample of multistep processes has completed two step hydrogen discharge reactions in 1 hour, and average hydrogen discharging rate has improved twice compared with the made sample of single stage method.It is in addition, this that because preparation method changes the improved performance effect that causes, through inhaling, to put hydrogen circulation particularly evident.Fig. 5 has provided first three circulation Hydrogen desorption isotherms of two kinds of made samples of preparation method.Contrast is found, adopt the made sample of multistep processes to there is better cyclical stability with regard to hydrogen desorption kinetics and hydrogen storage capability aspect, adopt single stage method made sample to show obvious performance degradation, reach 1.1wt% through three cycle capacity loss, exceed 3 times of the former loss amount.Adopt the made sample of multistep method to exceed 10wt% by inverse put hydrogen capacity, this value is better than bibliographical information value.
Embodiment 2
Difference from Example 1 is, with 2LiBH
4+ MgH
2+ 0.08TiCl
3for adopting respectively a traditional step ball milling method and multistep preparation method provided by the invention, starting raw material prepares sample.
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 DEG C, 3bar.In two kinds of preparation methods, the process of transition metal fluorides transformation generation metal boride is identical with process described in example 1, and improved performance mechanism is also therefore similar, therefore only carry out 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 to be significantly better than adopting the made sample of a traditional step ball milling method, further illustrate the superiority that the invention provides multistep method.
Embodiment 3
Difference from Example 1 is, with 2NaBH
4+ MgH
2+ 0.08TiF
3for adopting respectively a traditional step ball milling method and multistep preparation method provided by the invention, starting raw material prepares sample.
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 DEG C, 0.1bar.As can be seen from Figure 7, adopt the hydrogen desorption kinetics of the made sample of multistep preparation method to be significantly better than adopting the made sample of a traditional step ball milling method, illustrate that the method has universality.
Sample result shows, the multistep preparation method who prepares metal borohydride-metal hydride reaction compound system provided by the invention can significantly promote the formation of transition metal boride and promote its disperse degree in matrix phase/interface, therefore compared with a traditional step ball milling method, significantly improve the hydrogen storage property of system, promoted the practical application potentiality of this system.
Claims (5)
1. the preparation method of metal borohydride-metal hydride reaction composite hydrogen storage material, it is characterized in that: this hydrogen storage material is made up 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 of this metal borohydride-metal hydride reaction composite hydrogen storage material comprises the following steps:
(1) under inert atmosphere protection, by Powdered transition metal halide additive, to be only placed in ball grinder reaction vessel ball milling even with metal borohydride body material in proportion, and wherein the mol ratio of metal borohydride and transition metal halide is 1:0.01～1:0.2;
(2) powdered sample after ball milling is heat-treated, thermal treatment temp is 300 to 400 DEG C, and hydrogen pressure is 2～6MPa, 1～5 hour time;
(3) add in proportion another metal hydride body material in heat treated sample, and under inert atmosphere, carry out together ball milling, wherein metal borohydride and metal hydride mol ratio are 2:1～6:1.
2. according to the preparation method of 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, alkaline-earth metal boron hydride; Metal hydride is one or more the combination in alkaline earth metal hydride, transition metal hydride, rare earth metal hydride; Transition metal halide is one or more the combination in transition metal chloride and transition metal fluorides.
3. according to the preparation method of 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
2; Transition metal hydride is ScH
2, YH
3, TiH
2or ZrH
2; Rare earth metal hydride is LaH
2or CeH
2; Transition 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. according to the preparation method of metal borohydride claimed in claim 1-metal hydride reaction composite hydrogen storage material, it is characterized in that: in described step (1) and (3), under inert atmosphere, when ball milling, ball material mass ratio is greater than 5:1, and Ball-milling Time is greater than 10 minutes.
5. according to the preparation method of metal borohydride claimed in claim 4-metal hydride reaction composite hydrogen storage material, it is characterized in that: ball material mass ratio is preferably (20～100): 1, Ball-milling Time is preferably 1～5 hour.
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| 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 |
| CN114436209B (en) * | 2022-03-08 | 2023-07-14 | 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 |
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