CN107585743A - A kind of method for improving sodium alanate hydrogen storage property - Google Patents
A kind of method for improving sodium alanate hydrogen storage property Download PDFInfo
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- CN107585743A CN107585743A CN201710853202.4A CN201710853202A CN107585743A CN 107585743 A CN107585743 A CN 107585743A CN 201710853202 A CN201710853202 A CN 201710853202A CN 107585743 A CN107585743 A CN 107585743A
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- sodium alanate
- hydrogen storage
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- alanate
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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 method for improving sodium alanate hydrogen storage property, belong to hydrogen storage material technical field.This method comprises the steps：Nickel sheet and aluminium flake are smelted into by alloy using vacuum induction melting method first, and its mechanical crushing is less than 300 mesh powders into granularity；Then, alloy powder is added in sodium hydroxide solution and stirred, washed after 1h using deionized water and absolute ethyl alcohol, then be dried in vacuo, obtain alkali process product；Finally, mass ratio is weighed as 1:1~4 sodium alanate and alkali process product, pours into anhydrous tetrahydrofuran solution and stirs, then under vacuo that solution extraction is clean, you can obtains modified sodium alanate.The advantage of the invention is that：Modified sodium alanate hydrogen discharging temperature is low, speed is fast, good reversibility；The method of the improvement sodium alanate hydrogen storage property provided, its raw material sources is wide, cheap, and technique is simple, securely and reliably.
Description
Technical field
The invention belongs to hydrogen storage material technical field, and in particular to a kind of method for improving sodium alanate hydrogen storage property.
Background technology
In numerous novel renewable energies, Hydrogen Energy has calorific value high, abundance and the remarkable advantage such as pollution-free, is
The ideal substitute of the traditional fossil energies such as oil, natural gas and coal, it can be hydrogen to carry out solid-state storage to hydrogen using hydrogen storage material
Can the safe and efficient hydrogen storage technology of scale application offer.Metal coordinate hydride, because having high hydrogen storage capability, turn into hydrogen storage
Investigation of materials and the emphasis of exploitation, wherein, sodium alanate (NaAlH4) there is 7.4wt.% theoretical hydrogen content, and be to be at present
One of few complex hydrides of commercially viable production of number, development and application value is higher.However, sodium alanate puts hydrogen temperature
Degree higher (more than 220 and 250 DEG C start the first step and second step puts hydrogen respectively, and the 3rd step, which puts hydrogen, then needs more than 425 DEG C), put
The hydrogen uptake condition again harsher (200~400 DEG C, 10~40MPa) of hydrogen product, put that hydrogen/inhale again hydrogen speed is relatively slow and stable circulation
Property is poor, and these greatly limit NaAlH4Practical application.
Sodium alanate puts hydrogen/inhale destruction and reconstruction that hydrogen process is related to crystal structure and chemical bond again, in order to improve it
Hydrogen storage property, people have developed such as catalyst doping and the methods of nanosizings.Conventional sodium alanate catalyst has transition golden
Belong to halide, rare earth halide, carbon material and alloy containing Al etc., for example, Fan etc. passes through 100h high energy with NaH and Al raw materials
Ball milling is prepared for CeCl3And CeAl4The sodium alanate of doping, it is found that the addition of both catalyst can improve the suction of material and put
Hydrogen performance, and it is doped with CeAl4Sodium alanate reversible hydrogen storage capacity than adulterate CeCl3Height, hydrogen storage content 4.77~
Between 4.92wt.% [Fan X, Xiao X, Chen L, et al, Chem Commun, 2009,44:6857-6859].To aluminium hydrogen
Changing sodium progress nanosizing processing mainly has two kinds of means, first, the particle of nanoscale is obtained by high-energy ball milling, second, by
Specific nanoporous matrix carries out nanometer constraint to sodium alanate.The matrix of conventional sodium alanate nanometer constraint has mesoporous
SiO2, mesoporous carbon and metal organic framework compound etc., for example, Li etc. carries out complete nanometer using mesoporous carbon to sodium alanate
Constraint, had both improved the dynamic performance for putting hydrogen, and had substantially improved suction again and put hydrogen cyclical stability [Li Y, Zhou G, Fang
F,et al,Acta Mater,2011,59:1829-1838].Although existing research-and-development activity achieves many fronts
As a result, the synthesis hydrogen storage property of sodium alanate still needs to further improve, and the simplicity and price of preparation technology also have to be reduced.
The content of the invention
The present invention is directed to the deficiency of existing sodium alanate hydrogen storage technology, there is provided a kind of improvement sodium alanate hydrogen storage property
Method.
This method specifically includes following steps：
(1) nickel sheet and aluminium flake are smelted into by alloy using vacuum induction melting method；
(2) alloy mechanical obtained by step (1) is ground into granularity and is less than 300 mesh powders；
(3) alloy powder obtained by step (2) is added in sodium hydroxide solution and stirred, deionized water is used after 1h
Washed, then be dried in vacuo with absolute ethyl alcohol, obtain alkali process product；
(4) sodium alanate and the alkali process product obtained by step (3) are weighed, pours into anhydrous tetrahydrofuran solution and stirs
Mix, then it is under vacuo that solution extraction is clean, you can obtain modified sodium alanate.
Further, nickel sheet and the mol ratio of aluminium flake are 1 in the step (1):3, purity is not less than 99.5%.
Further, the mass ratio of sodium alanate and alkali process product is 1 in the step (4):1~4.
Further, the concentration of sodium hydroxide solution is 4~6mol/L in the step (3), and whipping temp is 70~85
℃。
The principles of science of the present invention is as follows：
The invention provides a kind of method for improving sodium alanate hydrogen storage property, its principles of science is mainly reflected in three sides
Face：(1) main chemical compositions of the nickel alumin(i)um alloy after naoh treatment are nickel, and nickel has very strong electronegativity, can promoted
Sodium ion and [AlH4] charge migration between ion cluster, the combination energy of Al-H keys is reduced, so as to which reduce sodium alanate puts hydrogen
Temperature.(2) the nickel alumin(i)um alloy particle after naoh treatment is tiny, loose porous, has larger specific surface area, can increase
Contact area between sodium alanate, so as to play stronger catalytic function.(3) nickel alumin(i)um alloy after naoh treatment
Nano pore can form the nanometer effect of restraint to sodium alanate, inhale hydrogen desorption kineticses and improvement invertibity so as to improve.
Compared with prior art, beneficial effects of the present invention are：
(1) through the modified sodium alanate hydrogen discharging temperature of technology provided by the present invention it is low (can put hydrogen from 85 DEG C, 260 DEG C
Hydrogen-based is put originally to terminate), speed it is fast (e.g., 180 DEG C when 12min in be basically completed hydrogen process of putting, hydrogen desorption capacity reaches 3.6wt.%), it is reversible
Property is good.
(2) method of the improvement sodium alanate hydrogen storage property provided, using metallic nickel and aluminium as initial feed, source is wide,
It is cheap.
(3) method of the improvement sodium alanate hydrogen storage property provided, its technique is simple, securely and reliably.
Brief description of the drawings
Fig. 1 is the heating Hydrogen desorption isotherms of modified sodium alanate and fine aluminium sodium hydride in the embodiment of the present invention 1.
Fig. 2 is the hydrogen desorption kineticses curve of modified sodium alanate in the embodiment of the present invention 1.
Fig. 3 is the secondary temperature elevation Hydrogen desorption isotherms of modified sodium alanate in the embodiment of the present invention 1.
Fig. 4 is the heating Hydrogen desorption isotherms of modified sodium alanate in the embodiment of the present invention 2.
Fig. 5 is the heating Hydrogen desorption isotherms of modified sodium alanate in the embodiment of the present invention 3.
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
According to 1:3 mol ratio weighs metal nickel sheet and aluminium flake of the purity not less than 99.5%；Using high frequency magnetic suspension sense
Answer smelting furnace that nickel sheet and aluminium flake are smelted into alloy；Bulk alloy mechanical crushing obtained by melting is less than to the conjunction of 300 mesh into granularity
Bronze end；The 5mol/L of measured amounts sodium hydroxide solution is placed in 80 DEG C of water-bath in beaker, and by beaker, will
Alloy powder is added in sodium hydroxide solution and stirred, and is washed successively using deionized water and absolute ethyl alcohol after 1h, then
It is dried in vacuo, obtains alkali process product；According to 1:4 mass ratio weighs sodium alanate and alkali process product, pours into anhydrous
In tetrahydrofuran solution and stir, then it is under vacuo that solution extraction is clean, obtain modified sodium alanate.As seen from Figure 1, pass through
Modified sodium alanate puts hydrogen since 85 DEG C, puts hydrogen-based for 260 DEG C and originally terminates, and hydrogen desorption capacity (produces up to 5.2wt.% without alkali process
Thing weight, similarly hereinafter), compare, unmodified sodium alanate since 195 DEG C just put hydrogen, terminate to put hydrogen at about 315 DEG C.By Fig. 2
It can be seen that modified sodium alanate has fast hydrogen discharging speed at 180,200 and 250 DEG C, 12min, which is basically completed, puts hydrogen process,
Hydrogen desorption capacity up to 3.6,4.0 and 4.3wt.%, compares respectively, and unmodified sodium alanate 90min when putting hydrogen for 180 DEG C puts hydrogen
Amount only have 0.5wt.% [Li Y, Zhou G, Fang F, et al, Acta Mater, 2011,59:1829-1838].Can by Fig. 3
See, after modified sodium alanate inhales hydrogen 12h again under 150 DEG C and 7MPa temperate conditions, can be begun paying out from 95 DEG C
3.0wt.% hydrogen, show good invertibity.
Embodiment 2
According to 1:3 mol ratio weighs metal nickel sheet and aluminium flake of the purity not less than 99.5%；Using high frequency magnetic suspension sense
Answer smelting furnace that nickel sheet and aluminium flake are smelted into alloy；Bulk alloy mechanical crushing obtained by melting is less than to the conjunction of 300 mesh into granularity
Bronze end；The 6mol/L of measured amounts sodium hydroxide solution is placed in 75 DEG C of water-bath in beaker, and by beaker, will
Alloy powder is added in sodium hydroxide solution and stirred, and is washed successively using deionized water and absolute ethyl alcohol after 1h, then
It is dried in vacuo, obtains alkali process product；According to 1:2 mass ratio weighs sodium alanate and alkali process product, pours into anhydrous
In tetrahydrofuran solution and stir, then it is under vacuo that solution extraction is clean, obtain modified sodium alanate.From fig. 4, it can be seen that through
Modified sodium alanate puts hydrogen since 95 DEG C, puts hydrogen-based for 290 DEG C and originally terminates, and hydrogen desorption capacity reaches 5.0wt.%.
Embodiment 3
According to 1:3 mol ratio weighs metal nickel sheet and aluminium flake of the purity not less than 99.5%；Using high frequency magnetic suspension sense
Answer smelting furnace that nickel sheet and aluminium flake are smelted into alloy；Bulk alloy mechanical crushing obtained by melting is less than to the conjunction of 300 mesh into granularity
Bronze end；The 4mol/L of measured amounts sodium hydroxide solution is placed in 85 DEG C of water-bath in beaker, and by beaker, will
Alloy powder is added in sodium hydroxide solution and stirred, and is washed successively using deionized water and absolute ethyl alcohol after 1h, then
It is dried in vacuo, obtains alkali process product；According to 1:1 mass ratio weighs sodium alanate and alkali process product, pours into anhydrous
In tetrahydrofuran solution and stir, then it is under vacuo that solution extraction is clean, obtain modified sodium alanate.As seen from Figure 5, pass through
Modified sodium alanate puts hydrogen since 115 DEG C, puts hydrogen-based for 305 DEG C and originally terminates, and hydrogen desorption capacity reaches 4.9wt.%.
Claims (4)
- A kind of 1. method for improving sodium alanate hydrogen storage property, it is characterised in that comprise the following steps：(1) nickel sheet and aluminium flake are smelted into by alloy using vacuum induction melting method；(2) alloy mechanical obtained by step (1) is ground into granularity and is less than 300 mesh powders；(3) alloy powder obtained by step (2) is added in sodium hydroxide solution and stirred, deionized water and nothing are used after 1h Water-ethanol is washed, then is dried in vacuo, and obtains alkali process product；(4) sodium alanate and the alkali process product obtained by step (3) are weighed, pours into anhydrous tetrahydrofuran solution and stirs, then It is under vacuo that solution extraction is clean, you can to obtain modified sodium alanate.
- A kind of 2. method for improving sodium alanate hydrogen storage property as claimed in claim 1, it is characterised in that the step (1) Middle nickel sheet and the mol ratio of aluminium flake are 1:3, purity is not less than 99.5%.
- A kind of 3. method for improving sodium alanate hydrogen storage property as claimed in claim 1, it is characterised in that the step (3) The concentration of middle sodium hydroxide solution is 4~6mol/L, and whipping temp is 70~85 DEG C.
- A kind of 4. method for improving sodium alanate hydrogen storage property as claimed in claim 1, it is characterised in that the step (4) The mass ratio of middle sodium alanate and alkali process product is 1:1~4.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1565731A (en) * | 2003-06-13 | 2005-01-19 | 上海师范大学 | Method for preparing novel Raney Ni catalyzer and its application |
| CN102502488A (en) * | 2011-10-26 | 2012-06-20 | 安徽工业大学 | Method for improving hydrogen storage property of lithium borohydride |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1565731A (en) * | 2003-06-13 | 2005-01-19 | 上海师范大学 | Method for preparing novel Raney Ni catalyzer and its application |
| CN102502488A (en) * | 2011-10-26 | 2012-06-20 | 安徽工业大学 | Method for improving hydrogen storage property of lithium borohydride |
Non-Patent Citations (7)
| Title |
|---|
| H.-J. QIU ET AL.: ""Fabrication of large-scale nanoporous nickel with a tunable pore size for energy storage"", 《JOURNAL OF POWER SOURCES》 * |
| ZHENHUA DAN ET AL.: ""Bimodal nanoporous nickel prepared by dealloying Ni38Mn62 alloys"", 《INTERMETALLICS》 * |
| 周琦 等: ""不同去合金化法对制备纳米多孔合金微观结构的影响"", 《兰州理工大学学报》 * |
| 周琦 等: ""不同成分Ni-Al合金去合金化过程中的结构演化与机理"", 《兰州理工大学学报》 * |
| 蔡荣 等: ""膨胀石墨/LiBH4 复合储氢材料脱氢性能研究"", 《研究与设计 电源技术》 * |
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| 陈益林 等: ""掺杂Co、Ni 对LiBH4解氢性能影响的第一原理研究"", 《热加工工艺》 * |
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