CN107585743B - A method of improving sodium alanate hydrogen storage property - Google Patents
A method of improving sodium alanate hydrogen storage property Download PDFInfo
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- CN107585743B CN107585743B CN201710853202.4A CN201710853202A CN107585743B CN 107585743 B CN107585743 B CN 107585743B CN 201710853202 A CN201710853202 A CN 201710853202A CN 107585743 B CN107585743 B CN 107585743B
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- sodium alanate
- hydrogen storage
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- hydrogen
- 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
Abstract
The invention discloses a kind of methods for improving sodium alanate hydrogen storage property, belong to hydrogen storage material technical field.This method includes the following steps: that nickel sheet and aluminium flake are smelted into alloy using vacuum induction melting method first, and granularity is mechanically pulverized into less than 300 mesh powders；Then, alloy powder is added in sodium hydroxide solution and is stirred, washed after 1h using deionized water and dehydrated alcohol, then be dried in vacuo, obtain alkali process product；Finally, weighing the sodium alanate and alkali process product that mass ratio is 1:1~4, pours into anhydrous tetrahydrofuran solution and stir, then is under vacuum that solution extraction is clean, can be obtained modified sodium alanate.The present invention has the advantages that modified sodium alanate hydrogen discharging temperature is low, speed is fast, good reversibility；The provided method for improving sodium alanate hydrogen storage property, raw material sources are wide, cheap, simple process, securely and reliably.
Description
Technical field
The invention belongs to hydrogen storage material technical fields, and in particular to a method of improve sodium alanate hydrogen storage property.
Background technique
In numerous novel renewable energies, Hydrogen Energy has calorific value high, abundance and the remarkable advantages such as pollution-free, is
The ideal substitute of the traditional fossil energies such as petroleum, natural gas and coal, carrying out solid-state storage to hydrogen using hydrogen storage material can be hydrogen
It can the safe and efficient hydrogen storage technology of scale application offer.Metal coordinate hydride becomes hydrogen storage because having high hydrogen storage capability
The emphasis of investigation of materials and exploitation, wherein sodium alanate (NaAlH4) the theoretical hydrogen content with 7.4wt.%, and be to be at present
One of the complex hydrides of the few commercially viable production of number, development and application value are higher.However, the hydrogen release temperature of sodium alanate
It spends higher (220 and 250 DEG C or more start the first step and second step hydrogen release respectively, and third step hydrogen release then needs 425 DEG C or more), put
The hydrogen uptake condition again of hydrogen product harsher (200~400 DEG C, 10~40MPa), hydrogen release/inhale again hydrogen speed is relatively slow and stable circulation
Property is poor, these greatly limit NaAlH4Practical application.
The hydrogen release of sodium alanate/inhale hydrogen process again is related to the destruction and reconstruction of crystal structure and chemical bond, in order to improve it
Hydrogen storage property, people have developed such as the methods of catalyst doping and nanosizing.Common 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 the high energy of 100h with NaH and Al raw material
Ball milling is prepared for CeCl3And CeAl4The sodium alanate of doping finds 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
Change sodium and carries out means there are mainly two types of nanosizing processing, first is that the particle of nanoscale is obtained by high-energy ball milling, second is that by
Specific nanoporous matrix carries out nanometer constraint to sodium alanate.The matrix of common sodium alanate nanometer constraint has mesoporous
SiO2, mesoporous carbon and metal organic framework compound etc., for example, Li et al. carries out complete nanometer to sodium alanate using mesoporous carbon
Constraint, had not only improved the dynamic performance of hydrogen release, but also substantially improved and inhale hydrogen release 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 increase, the simplicity and price of preparation process also has to be reduced.
Summary of the invention
The present invention is directed to the deficiency of existing sodium alanate hydrogen storage technology, and providing a kind of improves sodium alanate hydrogen storage property
Method.
This method specifically includes the following steps:
(1) nickel sheet and aluminium flake are smelted by alloy using vacuum induction melting method；
(2) step (1) resulting alloy mechanical is ground into granularity less than 300 mesh powders；
(3) step (2) resulting alloy powder is added in sodium hydroxide solution and is stirred, deionized water is used after 1h
It is washed, then is dried in vacuo with dehydrated alcohol, obtain alkali process product；
(4) sodium alanate and the resulting alkali process product of step (3) are weighed, pours into anhydrous tetrahydrofuran solution and stirs
It mixes, then under vacuum that solution extraction is clean, can be obtained modified sodium alanate.
Further, nickel sheet and the molar ratio of aluminium flake are 1:3 in the step (1), and purity is not less than 99.5%.
Further, the mass ratio of sodium alanate and alkali process product is 1:1~4 in the step (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 invention is as follows:
The present invention provides a kind of method for improving sodium alanate hydrogen storage property, the 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 promote
Sodium ion and [AlH4] charge migration between ion cluster, the combination energy of Al-H key is reduced, to reduce the hydrogen release of sodium alanate
Temperature.(2) the nickel alumin(i)um alloy particle after naoh treatment is tiny, loose porous, has biggish specific surface area, can increase
Contact area between sodium alanate, 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 kinetics and improvement invertibity to improve.
Compared with prior art, the invention has the benefit that
(1) through the modified sodium alanate hydrogen discharging temperature of technology provided by the present invention it is low (from 85 DEG C can hydrogen release, 260 DEG C
Hydrogen release terminates substantially), speed it is fast (e.g., 180 DEG C when 12min in be basically completed hydrogen release process, hydrogen desorption capacity reaches 3.6wt.%), it is reversible
Property is good.
(2) improve the method for sodium alanate hydrogen storage property provided by, using metallic nickel and aluminium as initial feed, source is wide,
It is cheap.
(3) method of improvement sodium alanate hydrogen storage property provided by, simple process, securely and reliably.
Detailed description of the invention
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 kinetics 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.
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
Metal nickel sheet and aluminium flake of the purity not less than 99.5% are weighed according to the molar ratio of 1:3；Using high frequency magnetic suspension sense
Answer smelting furnace that nickel sheet and aluminium flake are smelted into alloy；The conjunction at granularity less than 300 mesh is mechanically pulverized in bulk alloy obtained by melting
Bronze end；The sodium hydroxide solution of a certain amount of 5mol/L is measured in beaker, and is placed the beaker in 80 DEG C of water-bath, it will
Alloy powder is added in sodium hydroxide solution and stirs, and is successively washed using deionized water and dehydrated alcohol after 1h, then
It is dried in vacuo, obtains alkali process product；Sodium alanate and alkali process product are weighed according to the mass ratio of 1:4, is poured into anhydrous
It in tetrahydrofuran solution and stirs, then under vacuum that solution extraction is clean, obtains modified sodium alanate.As seen from Figure 1, it passes through
Modified sodium alanate hydrogen release since 85 DEG C, 260 DEG C of hydrogen releases terminate substantially, and hydrogen desorption capacity (is produced up to 5.2wt.% without alkali process
Object weight, similarly hereinafter), compare, unmodified sodium alanate since 195 DEG C just hydrogen release, about 315 DEG C of whens terminate hydrogen release.By Fig. 2
As it can be seen that modified sodium alanate has fast hydrogen discharging speed at 180,200 and 250 DEG C, 12min is basically completed hydrogen release process,
Hydrogen desorption capacity up to 3.6,4.0 and 4.3wt.%, compares respectively, the hydrogen release of unmodified sodium alanate 90min in 180 DEG C of hydrogen releases
Amount only has 0.5wt.% [Li Y, Zhou G, Fang F, et al, Acta Mater, 2011,59:1829-1838].It can by Fig. 3
See, after modified sodium alanate inhales hydrogen 12h under 150 DEG C and 7MPa temperate condition again, can be begun releasing from 95 DEG C
The hydrogen of 3.0wt.% shows good invertibity.
Embodiment 2
Metal nickel sheet and aluminium flake of the purity not less than 99.5% are weighed according to the molar ratio of 1:3；Using high frequency magnetic suspension sense
Answer smelting furnace that nickel sheet and aluminium flake are smelted into alloy；The conjunction at granularity less than 300 mesh is mechanically pulverized in bulk alloy obtained by melting
Bronze end；The sodium hydroxide solution of a certain amount of 6mol/L is measured in beaker, and is placed the beaker in 75 DEG C of water-bath, it will
Alloy powder is added in sodium hydroxide solution and stirs, and is successively washed using deionized water and dehydrated alcohol after 1h, then
It is dried in vacuo, obtains alkali process product；Sodium alanate and alkali process product are weighed according to the mass ratio of 1:2, is poured into anhydrous
It in tetrahydrofuran solution and stirs, then under vacuum that solution extraction is clean, obtains modified sodium alanate.From fig. 4, it can be seen that through
Modified sodium alanate hydrogen release since 95 DEG C, 290 DEG C of hydrogen releases terminate substantially, and hydrogen desorption capacity reaches 5.0wt.%.
Embodiment 3
Metal nickel sheet and aluminium flake of the purity not less than 99.5% are weighed according to the molar ratio of 1:3；Using high frequency magnetic suspension sense
Answer smelting furnace that nickel sheet and aluminium flake are smelted into alloy；The conjunction at granularity less than 300 mesh is mechanically pulverized in bulk alloy obtained by melting
Bronze end；The sodium hydroxide solution of a certain amount of 4mol/L is measured in beaker, and is placed the beaker in 85 DEG C of water-bath, it will
Alloy powder is added in sodium hydroxide solution and stirs, and is successively washed using deionized water and dehydrated alcohol after 1h, then
It is dried in vacuo, obtains alkali process product；Sodium alanate and alkali process product are weighed according to the mass ratio of 1:1, is poured into anhydrous
It in tetrahydrofuran solution and stirs, then under vacuum that solution extraction is clean, obtains modified sodium alanate.As seen from Figure 5, it passes through
Modified sodium alanate hydrogen release since 115 DEG C, 305 DEG C of hydrogen releases terminate substantially, and hydrogen desorption capacity reaches 4.9wt.%.
Claims (3)
1. a kind of method for improving sodium alanate hydrogen storage property, it is characterised in that include the following steps:
(1) nickel sheet and aluminium flake are smelted by alloy using vacuum induction melting method；The nickel sheet and the molar ratio of aluminium flake are 1:3,
Purity is not less than 99.5%；
(2) step (1) resulting alloy mechanical is ground into granularity less than 300 mesh powders；
(3) step (2) resulting alloy powder is added in sodium hydroxide solution and is stirred, deionized water and nothing are used after 1h
Water-ethanol is washed, then is dried in vacuo, and alkali process product is obtained；
(4) sodium alanate and the resulting alkali process product of step (3) are weighed, pours into anhydrous tetrahydrofuran solution and stirs, then
It is under vacuum that solution extraction is clean, it can be obtained modified sodium alanate.
2. a kind of method for improving sodium alanate hydrogen storage property as described in claim 1, which is characterized in that the step (3)
The concentration of middle sodium hydroxide solution is 4~6mol/L, and whipping temp is 70~85 DEG C.
3. a kind of method for improving sodium alanate hydrogen storage property as described in claim 1, which is characterized in that the step (4)
The mass ratio of middle sodium alanate and alkali process product is 1:1~4.
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|---|---|---|---|---|
| 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 (5)
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| "不同去合金化法对制备纳米多孔合金微观结构的影响";周琦 等;《兰州理工大学学报》;20131031;第39卷(第５期);第1-4页 * |
| "不同成分Ni-Al合金去合金化过程中的结构演化与机理";周琦 等;《兰州理工大学学报》;20170630;第43卷(第3期);第1-5页 * |
| "原始合金制备方法对Raney Ni催化剂结构及加氢活性的影响";陆致龙 等;《催化学报》;19970331;第18卷(第2期);第110-114页 * |
| "掺杂Co、Ni 对LiBH4解氢性能影响的第一原理研究";陈益林 等;《热加工工艺》;20130630;第42卷(第12期);第58-62页 * |
| "膨胀石墨/LiBH4 复合储氢材料脱氢性能研究";蔡荣 等;《研究与设计 电源技术》;20160831;第40卷(第8期);第1615-1617、1632页 * |
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