CN106517089B - A kind of lithium borohydride/composite alkali aluminum hydride/calcium carbide composite hydrogen storage material and preparation method thereof - Google Patents
A kind of lithium borohydride/composite alkali aluminum hydride/calcium carbide composite hydrogen storage material and preparation method thereof Download PDFInfo
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- CN106517089B CN106517089B CN201611025480.2A CN201611025480A CN106517089B CN 106517089 B CN106517089 B CN 106517089B CN 201611025480 A CN201611025480 A CN 201611025480A CN 106517089 B CN106517089 B CN 106517089B
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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
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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
- Y02E60/32—Hydrogen storage
Abstract
The invention discloses a kind of lithium borohydride/composite alkali aluminum hydride/calcium carbide composite hydrogen storage materials and preparation method thereof, belong to hydrogen storage material technical field.The composite hydrogen storage material is made of lithium borohydride, composite alkali aluminum hydride and calcium carbide, and wherein the molar ratio of lithium borohydride and composite alkali aluminum hydride is 2:1, and the additive amount of calcium carbide is 12~25mol%；The composite alkali aluminum hydride is lithium aluminium hydride reduction or sodium alanate.When preparation, first the powder at granularity less than 500 μm is mechanically pulverized in the calcium carbide by purity not less than 97%, it weighs lithium borohydride, composite alkali aluminum hydride and carbonization calcium powder according to the ratio again and mixes, ball-milling treatment is finally carried out to mixed-powder using planetary ball mill.The present invention has the advantages that provided composite hydrogen storage material preparation process is simple, safe and reliable, there is low hydrogen discharging temperature, high hydrogen desorption capacity and good reversible hydrogen sucking function again；Improve the hydrogen storage property of material using calcium carbide, raw material sources are wide, low in cost.
Description
Technical field
The invention belongs to hydrogen storage material technical fields, and in particular to a kind of lithium borohydride/composite alkali aluminum hydride/calcium carbide
Composite hydrogen storage material and preparation method thereof.
Background technique
The development and utilization of novel renewable energy is the only way for solving energy crisis and environmental pollution.Hydrogen Energy has
The advantages that calorific value is high, combustion product is clean and rich reserves, is the best substitution of the traditional fossil energies such as coal, oil and natural gas
Object, it is considered to be the ideal secondary energy sources of human future.The development and utilization of Hydrogen Energy are a great system engineerings, how to be realized
The safe and efficient and economic storage of hydrogen is the key that Hydrogen Energy scale utilizes.Compared with gaseous state and liquid hydrogen storage mode, storage is utilized
It is hydrogen storage technology most with prospects that hydrogen material, which carries out solid-state storage to hydrogen,.In developed hydrogen storage material system, gold
Belonging to boron hydride has high hydrogen storage capability, is the emphasis of current solid-state hydrogen storage material research and development.For example, lithium borohydride resolves into
LiH and simple substance B can discharge the up to hydrogen of 13.8wt.%, however, there are hydrogen discharging temperatures for lithium borohydride towards practical application
High (for example, 600 DEG C of whens can only discharge about 50% hydrogen), again hydrogen uptake condition harsh (15MPa, 600 DEG C) and hydrogen release/inhale again
The disadvantages of hydrogen dynamics is poor [P.Mauron, F.Buchter, O.Friedrichs, et al., J.Phys.Chem.B, 2008,
112:906]。
The hydrogen release of lithium borohydride/inhale hydrogen process again is related to the destruction and reconstruct of its lattice, can in order to improve lithium borohydride
Inverse hydrogen storage property, people have developed the sides such as reaction unstability system construction, zwitterion substitution, catalyst addition and nanometer confinement
Method [C.Li, P.Peng, D.W.Zhou, et al., Int.J.Hydrogen Energy, 2011,36:14512].Wherein, by boron
Lithium hydride is compound with other materials and constructs and reacts unstability system, can regulate and control hydroboration by the variation in hydrogen discharge reaction path
The hydrogen release enthalpy change of lithium, to reduce thermodynamic stability and hydrogen discharging temperature, but the operating temperature of existing reaction unstability system is still
It is higher；Meanwhile the variation in hydrogen discharge reaction path may bring the by-product of Irreversible hydrogen-absorbing.To the Li in lithium borohydride+From
Son or [BH4 -] group progress element substitution, hydrogen discharging temperature can be effectively reduced, but reversible hydrogen sucking function again is often poor.To boron
Catalyst (such as carbon material, metal oxide or halide) is added in lithium hydride can reduce the activation energy of hydrogen release, but be catalyzed
Often preparation process is complicated, price is higher for the catalyst of the good nanoscale of effect.Using the method for nanometer confinement by hydroboration
The particle size or crystallite dimension of lithium are down to nanoscale, can substantially improve the hydrogen release of lithium borohydride/inhale hydrogen dynamics again
Performance, but its effective hydrogen storage capability has biggish loss.
Summary of the invention
The present invention be directed to existing lithium borohydride hydrogen storage technology deficiency, provide a kind of hydrogen storage property it is excellent, it is at low cost, system
The composite hydrogen storage material and preparation method thereof of standby simple process.
To achieve the above object, the technical solution adopted by the present invention are as follows:
Composite hydrogen storage material provided by the present invention is made of lithium borohydride, composite alkali aluminum hydride and calcium carbide, wherein
The molar ratio of lithium borohydride and composite alkali aluminum hydride is 2:1, the additive amount of calcium carbide be hydrogen storage material integral molar quantity 12~
25%.The composite alkali aluminum hydride is lithium aluminium hydride reduction or sodium alanate.
The preparation method of composite hydrogen storage material provided by the present invention includes the following steps:
(1) powder at granularity less than 500 μm is mechanically pulverized in the small blocky calcium carbide by purity not less than 97%；
(2) lithium borohydride, composite alkali aluminum hydride and carbonization calcium powder are weighed by said ratio and mixed；
(3) ball-milling treatment is carried out to mixed-powder using planetary ball mill.
The ball-milling treatment carries out under the protection of 1~5atm argon gas, and ratio of grinding media to material is 20~30:1, revolving speed 400rpm, ball
Time consuming is 8~10h.
The principles of science of the invention is as follows:
Calcium carbide and lithium borohydride, composite alkali aluminum hydride are compounded to form multiple groups elementary reaction unstability system by the present invention.?
Calcium carbide and lithium borohydride, composite alkali aluminum hydride generation under heating condition, promote the fracture of B-H key in lithium borohydride,
Reduce thermodynamic stability and hydrogen discharging temperature.In addition, carrying out high-energy ball milling to calcium carbide, lithium borohydride and composite alkali aluminum hydride
Can with refinement of particle size and increase surface defect, so as to shorten hydrogen diffusion length and improve material put hydrogen abstraction reaction activity.
Compared with prior art, the invention has the benefit that
(1) lithium borohydride provided by/composite alkali aluminum hydride/calcium carbide composite hydrogen storage material has low hydrogen release temperature
Degree, high hydrogen desorption capacity and good reversibility.
(2) improve the hydrogen storage property of lithium borohydride sill using calcium carbide, it is low in cost.
(3) preparation process of composite hydrogen storage material provided by is simple, securely and reliably.
Detailed description of the invention
Fig. 1 is 2LiBH in the embodiment of the present invention 14+LiAlH4+0.5CaC2And pure LiBH4Heating Hydrogen desorption isotherms.
Fig. 2 is 2LiBH in the embodiment of the present invention 14+LiAlH4+0.5CaC2Secondary temperature elevation Hydrogen desorption isotherms.
Fig. 3 is 2LiBH in the embodiment of the present invention 24+NaAlH4+0.7CaC2Heating Hydrogen desorption isotherms.
Fig. 4 is 2LiBH in the embodiment of the present invention 34+LiAlH4+CaC2Heating Hydrogen desorption isotherms.
Specific embodiment
The present invention is described in detail below in conjunction with the drawings and specific embodiments, but the present invention is not limited to following embodiments.
Embodiment 1
By commercially available irregular small blocky calcium carbide (CaC2, purity is not less than 97%) mechanical crushing at granularity less than 500 μ
The powder of m；Lithium borohydride (LiBH is weighed respectively according to 2:1:0.5 molar ratio4), lithium aluminium hydride reduction (LiAlH4) and carbonization calcium powder
And it mixes；By LiBH4、LiAlH4And CaC2Mixed-powder pours into the ball grinder for the stainless steel material that volume is 250mL, and to
5atm argon gas is filled in ball grinder；Carrying out 10h ball-milling treatment to mixed-powder using planetary ball mill, (ratio of grinding media to material 20:1 turns
Fast 400rpm), it can be obtained the 2LiBH4+LiAlH4+0.5CaC2Composite hydrogen storage material.As seen from Figure 1, gained 2LiBH4
+LiAlH4+0.5CaC2Composite hydrogen storage material hydrogen release since 110 DEG C, 440 DEG C of hydrogen releases terminate substantially, and hydrogen desorption capacity reaches 6.3wt.%.
It compares, pure LiBH4The just slow hydrogen release since 320 DEG C, hydrogen desorption capacity at 500 DEG C only have 3.7wt.%.Meanwhile it can by Fig. 2
See, 2LiBH4+LiAlH4+0.5CaC2It, can be basic at 425 DEG C after composite hydrogen storage material inhales hydrogen again under the conditions of 450 DEG C and 9MPa
Hydrogen release process is completed, total hydrogen desorption capacity is 3.8wt.%, shows good reversible hydrogen adsorption and desorption performance.
Embodiment 2
By commercially available irregular small blocky calcium carbide (CaC2, purity is not less than 97%) mechanical crushing at granularity less than 500 μ
The powder of m；LiBH is weighed respectively according to 2:1:0.7 molar ratio4, sodium alanate (NaAlH4) and CaC2Powder simultaneously mixes；It will
LiBH4、NaAlH4And CaC2Mixed-powder pours into the ball grinder for the stainless steel material that volume is 250mL, and fills into ball grinder
Enter 1atm argon gas；8h ball-milling treatment (ratio of grinding media to material 30:1, revolving speed 400rpm) is carried out to mixed-powder using planetary ball mill, i.e.,
It can get the 2LiBH4+NaAlH4+0.7CaC2Composite hydrogen storage material.As seen from Figure 3, gained 2LiBH4+NaAlH4+
0.7CaC2Composite hydrogen storage material has apparent hydrogen release phenomenon at 200 DEG C, and 570 DEG C of hydrogen releases terminate substantially, and hydrogen desorption capacity reaches
6.1wt.%.
Embodiment 3
By commercially available irregular small blocky calcium carbide (CaC2, purity is not less than 97%) mechanical crushing at granularity less than 500 μ
The powder of m；LiBH is weighed respectively according to 2:1:1 molar ratio4、LiAlH4And CaC2Powder simultaneously mixes；By LiBH4、LiAlH4With
CaC2Mixed-powder pours into the ball grinder for the stainless steel material that volume is 250mL, and 1atm argon gas is filled with into ball grinder；It adopts
8h ball-milling treatment (ratio of grinding media to material 30:1, revolving speed 400rpm) is carried out to mixed-powder with planetary ball mill, can be obtained described
2LiBH4+LiAlH4+CaC2Composite hydrogen storage material.From fig. 4, it can be seen that gained 2LiBH4+LiAlH4+CaC2Composite hydrogen storage material from
100 DEG C of beginning hydrogen releases, 425 DEG C of hydrogen releases terminate substantially, and hydrogen desorption capacity reaches 5.3wt.%.
Claims (4)
1. a kind of lithium borohydride/composite alkali aluminum hydride/calcium carbide composite hydrogen storage material, which is characterized in that the composite hydrogen-storage material
Material is made of lithium borohydride, composite alkali aluminum hydride and calcium carbide；Wherein: the molar ratio of lithium borohydride and composite alkali aluminum hydride
For 2:1, the additive amount of calcium carbide is the 12~25% of hydrogen storage material integral molar quantity.
2. a kind of lithium borohydride/composite alkali aluminum hydride/calcium carbide composite hydrogen storage material as described in claim 1, feature
It is, the composite alkali aluminum hydride is lithium aluminium hydride reduction or sodium alanate.
3. a kind of lithium borohydride/composite alkali aluminum hydride/calcium carbide composite hydrogen storage material preparation side as described in claim 1
Method, it is characterised in that include the following steps:
(1) powder at granularity less than 500 μm is mechanically pulverized in the calcium carbide by purity not less than 97%；
(2) proportion according to claim 1 weighs lithium borohydride, composite alkali aluminum hydride and carbonization calcium powder and mixes；
(3) ball-milling treatment is carried out to mixed-powder using planetary ball mill.
4. a kind of lithium borohydride/composite alkali aluminum hydride/calcium carbide composite hydrogen storage material preparation side as claimed in claim 3
Method, which is characterized in that the ball-milling treatment of the step (3): carrying out under the protection of 1~5atm argon gas, and ratio of grinding media to material is 20~30:1,
Revolving speed is 400rpm, and Ball-milling Time is 8~10h.
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