CN106698334B - A kind of composite hydrogen storage material and preparation method thereof containing calcium carbide - Google Patents
A kind of composite hydrogen storage material and preparation method thereof containing calcium carbide Download PDFInfo
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- CN106698334B CN106698334B CN201611025519.0A CN201611025519A CN106698334B CN 106698334 B CN106698334 B CN 106698334B CN 201611025519 A CN201611025519 A CN 201611025519A CN 106698334 B CN106698334 B CN 106698334B
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- hydrogen storage
- calcium carbide
- storage material
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- lithium borohydride
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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
- C01B3/0078—Composite solid storage mediums, i.e. coherent or loose mixtures of different solid constituents, chemically or structurally heterogeneous solid masses, coated solids or solids having a chemically modified surface region
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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
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Abstract
The invention discloses a kind of composite hydrogen storage material and preparation method thereof containing calcium carbide, belongs to hydrogen storage material technical field.The composite hydrogen storage material is made of lithium borohydride, magnesium hydride (or magnesium fluoride) and calcium carbide；Wherein: the molar ratio of lithium borohydride and magnesium hydride (or magnesium fluoride) is 2:1, and the additive amount of calcium carbide is 12~25mol%.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, magnesium hydride (or magnesium fluoride) 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 improving the hydrogen storage property of material using calcium carbide, raw material sources are wide, low in cost；Provided composite hydrogen storage material preparation process is simple, safe and reliable, has low hydrogen discharging temperature, high hydrogen desorption capacity and good invertibity.
Description
Technical field
The invention belongs to hydrogen storage material technical fields, and in particular to a kind of composite hydrogen storage material and its preparation containing calcium carbide
Method.
Background technique
In face of the dual test of energy crisis and environmental pollution, the mankind are badly in need of developing and utilizing novel renewable energy.Its
In, it is the ideal substitution of traditional fossil energy that Hydrogen Energy, which has many advantages, such as that calorific value is high, the complete pollution-free and rich reserves of combustion product,
Product, it is considered to be the secondary energy sources of ideals of human being.The development of hydrogen storage technology to the scale of Hydrogen Energy using most important, with gaseous state
It is compared with liquid hydrogen storage mode, carrying out solid-state storage to hydrogen using hydrogen storage material, to have that hydrogen-storage density is high and safety is good etc. excellent
Point.Alkali or alkaline earth metal complex hydrides has high hydrogen storage capability, is the weight of solid-state hydrogen storage material research and development
Point.For example, the theoretical hydrogen storage content of lithium borohydride is up to 13.8wt.% (LiBH4 LiH+B+3/2H2), however, high hydrogen release temperature
The disadvantages of hydrogen release of degree, harsh hydrogen uptake condition again and difference/inhale hydrogen dynamics again, seriously hinders its practical application
[P.Mauron,F.Buchter,O.Friedrichs,et al.,J.Phys.Chem.B,2008,112:906]。
In order to improve the hydrogen storage property of lithium borohydride, people have developed nanostructure modulation, zwitterion replaces, multicomponent
The methods of reaction system building and catalyst addition [C.Li, P.Peng, D.W.Zhou, et al., Int.J.Hydrogen
Energy,2011,36:14512].Wherein, it is modulated using nanostructure and drops the particle size of lithium borohydride or crystallite dimension
To nanoscale, can be effectively improved lithium borohydride puts/inhales hydrogen dynamics, but its hydrogen storage capability often has biggish damage
It loses.To in lithium borohydride lithium ion or borine radical group replace, hydrogen discharging temperature can be effectively reduced, but reversible inhale hydrogen again
It can be undesirable.By lithium borohydride and other materials (such as metal alanates, metal hydride or metal fluoride) it is compound and
Multicomponent reaction system is constructed, lithium borohydride can be made to react unstability, so that thermodynamic stability and hydrogen discharging temperature are reduced,
But the hydrogen discharging temperature of existing reaction system is still higher and reaction is slower, meanwhile, it may be produced while changing response path
The by-product of raw Irreversible hydrogen-absorbing.Catalyst (such as carbonaceous material, transition metal oxide or fluoride are added into lithium borohydride
Deng) activation energy of hydrogen release can be reduced, but invertibity is poor, and the nanocatalyst preparation process of excellent catalytic effect it is more complex,
Price is higher.
Summary of the invention
The present invention is directed to the deficiency of existing lithium borohydride hydrogen storage technology, provides a kind of function admirable, at low cost, preparation work
Simple composite hydrogen storage material of skill and preparation method thereof.
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 magnesium hydride or magnesium fluoride with lithium borohydride, calcium carbide, in which:
The molar ratio of magnesium hydride or magnesium fluoride and lithium borohydride is 1:2, the additive amount of calcium carbide be hydrogen storage material integral molar quantity 12~
25%.
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 commercially available small blocky calcium carbide (purity is not less than 97%)；
(2) magnesium hydride or magnesium fluoride, lithium borohydride and carbonization calcium powder are weighed according to the ratio and are mixed；
(3) ball-milling treatment is carried out to mixed-powder using planetary ball mill.
The ball-milling treatment carries out under 1~2atm argon gas or nitrogen protection, and ratio of grinding media to material is 20~30:1, and revolving speed is
400rpm, Ball-milling Time are 8~10h.
The principles of science of the invention is as follows:
Calcium carbide and lithium borohydride, magnesium hydride or magnesium fluoride are compounded to form multicomponent reaction system by the present invention.It is heating
Under the conditions of calcium carbide react with lithium borohydride, magnesium hydride or magnesium fluoride, promote lithium borohydride in B-H key fracture, reduce
Thermodynamic stability and hydrogen discharging temperature.It can be in addition, carrying out high-energy ball milling to calcium carbide, lithium borohydride and magnesium hydride or magnesium fluoride
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) composite hydrogen storage material containing calcium carbide provided by has low hydrogen discharging temperature, high hydrogen desorption capacity and good
Reversible hydrogen sucking function again.
(2) improve the hydrogen storage property of lithium borohydride sill using calcium carbide, it is low in cost, and expanded coal chemical industry production
Product calcium carbide utilizes field.
(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+MgH2+0.5CaC2And pure LiBH4Heating Hydrogen desorption isotherms.
Fig. 2 is 2LiBH in the embodiment of the present invention 14+MgH2+0.5CaC2Secondary temperature elevation Hydrogen desorption isotherms.
Fig. 3 is 2LiBH in the embodiment of the present invention 24+MgF2+0.7CaC2Heating Hydrogen desorption isotherms.
Fig. 4 is 2LiBH in the embodiment of the present invention 34+MgH2+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), magnesium hydride (MgH2) and carbonization calcium powder and mix
It closes；By LiBH4、MgH2And CaC2Mixed-powder pours into the ball grinder for the stainless steel material that volume is 250mL, and to ball grinder
In be filled with 1atm argon gas；10h ball-milling treatment (ratio of grinding media to material 20:1, revolving speed are carried out to mixed-powder using planetary ball mill
400rpm), it can be obtained the 2LiBH4+MgH2+0.5CaC2Composite hydrogen storage material.As seen from Figure 1, gained 2LiBH4+MgH2
+0.5CaC2Composite hydrogen storage material hydrogen release since 330 DEG C, 430 DEG C of hydrogen releases terminate substantially, and hydrogen desorption capacity reaches 6.8wt.%.It compares
Compared with pure LiBH4Hydrogen discharging temperature is high, and hydrogen release is slow, and hydrogen desorption capacity at 500 DEG C only has 3.7wt.%.Meanwhile from Figure 2 it can be seen that
2LiBH4+MgH2+0.5CaC2After composite hydrogen storage material inhales hydrogen again under the conditions of 450 DEG C and 9MPa, it can be basically completed and put at 440 DEG C
Hydrogen process, total hydrogen desorption capacity are 5.9wt.%, and reversible hydrogen adsorption and desorption is functional.
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, magnesium fluoride (MgF2) and CaC2Powder simultaneously mixes；By LiBH4、
MgF2And CaC2Mixed-powder pours into the ball grinder for the stainless steel material that volume is 250mL, and 1atm argon is filled with into ball grinder
Gas；10h ball-milling treatment (ratio of grinding media to material 20:1, revolving speed 400rpm) is carried out to mixed-powder using planetary ball mill, can be obtained
The 2LiBH4+MgF2+0.7CaC2Composite hydrogen storage material.As seen from Figure 3, gained 2LiBH4+MgF2+0.7CaC2Composite hydrogen occluding
Material hydrogen release since 300 DEG C, 430 DEG C of hydrogen releases terminate substantially, and hydrogen desorption capacity reaches 4.5wt.%.
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、MgH2And CaC2Powder simultaneously mixes；By LiBH4、MgH2And CaC2It is mixed
It closes powder to pour into the ball grinder for the stainless steel material that volume is 250mL, and is filled with 2atm nitrogen into ball grinder；Using planet
Formula ball mill carries out 8h ball-milling treatment (ratio of grinding media to material 30:1, revolving speed 400rpm) to mixed-powder, can be obtained the 2LiBH4+
MgH2+CaC2Composite hydrogen storage material.From fig. 4, it can be seen that gained 2LiBH4+MgH2+CaC2Composite hydrogen storage material is put since 325 DEG C
Hydrogen, 420 DEG C of hydrogen releases terminate substantially, and hydrogen desorption capacity reaches 4.7wt.%.
Claims (1)
1. a kind of composite hydrogen storage material containing calcium carbide, which is characterized in that the composite hydrogen storage material by magnesium hydride or magnesium fluoride with
Lithium borohydride, calcium carbide composition, in which: the molar ratio of magnesium hydride or magnesium fluoride and lithium borohydride is 1:2, the additive amount of calcium carbide
It is the 12~25% of hydrogen storage material integral molar quantity；
The preparation of the composite hydrogen storage material includes 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) magnesium hydride or magnesium fluoride, lithium borohydride, carbonization calcium powder are weighed according to the ratio and are mixed；
(3) ball-milling treatment is carried out to mixed-powder using planetary ball mill；
The ball-milling treatment carries out under 1~2atm argon gas or nitrogen protection, ratio of grinding media to material be 20~30:1, revolving speed 400rpm,
Ball-milling Time is 8~10h.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583241A (en) * | 2012-03-16 | 2012-07-18 | 四川大学 | Sodium borohydride matrix composite used for generating hydrogen by hydrolysis |
| CN104607222A (en) * | 2015-01-20 | 2015-05-13 | 浙江大学 | Preparation method of MPC (macroporous carbon) supported Li2C2 and application of Li2C2 in hydrogen storage material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583241A (en) * | 2012-03-16 | 2012-07-18 | 四川大学 | Sodium borohydride matrix composite used for generating hydrogen by hydrolysis |
| CN104607222A (en) * | 2015-01-20 | 2015-05-13 | 浙江大学 | Preparation method of MPC (macroporous carbon) supported Li2C2 and application of Li2C2 in hydrogen storage material |
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