CN101565168B - Preparation method of multi-light metal coordination aluminum hydride hydrogen storage material - Google Patents

Preparation method of multi-light metal coordination aluminum hydride hydrogen storage material Download PDF

Info

Publication number
CN101565168B
CN101565168B CN2009100961845A CN200910096184A CN101565168B CN 101565168 B CN101565168 B CN 101565168B CN 2009100961845 A CN2009100961845 A CN 2009100961845A CN 200910096184 A CN200910096184 A CN 200910096184A CN 101565168 B CN101565168 B CN 101565168B
Authority
CN
China
Prior art keywords
hydrogen
powder
ball
lih
nah
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN2009100961845A
Other languages
Chinese (zh)
Other versions
CN101565168A (en
Inventor
陈立新
范修林
肖学章
陈长聘
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang University ZJU
Original Assignee
Zhejiang University ZJU
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang University ZJU filed Critical Zhejiang University ZJU
Priority to CN2009100961845A priority Critical patent/CN101565168B/en
Publication of CN101565168A publication Critical patent/CN101565168A/en
Application granted granted Critical
Publication of CN101565168B publication Critical patent/CN101565168B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Abstract

The invention discloses a preparation method of multi-light metal coordination aluminum hydride hydrogen storage material, NaxLi(3-x)AlH6 (0<=x<=3). The method comprises the following steps of: mixing NaH, LiH and simple substance Al powder, adding a small amount of Ti, Zr, V, Sc or rear earth-based catalysts, and mechanically milling for 60 to140h at the atmosphere of hydrogen so as to synthetize the NaxLi(3-x)AlH6 (0<=x<=3) multi-light metal coordination aluminum hydride. The method has the advantages that: the provided synthetic method is capable of directly synthesizing the final product of NaxLi(3-x)AlH6 (0<=x<=3) at room temperature by ball milling, the operation is simple, the energy consumption is low, the method is safe and reliable; in addition, the synthesized material has high yield, and high reversible hydriding and dehydriding capacity at medium and low temperature, thus being a novel hydrogen storage material with infinite commercial value.

Description

A kind of preparation method of multi-light metal coordination aluminum hydride hydrogen storage material
Technical field
The invention belongs to the hydrogen storage material technical field, specifically is a kind of preparation method who directly synthesizes multi-light metal coordination aluminum hydride hydrogen storage material with mechanical ball milling.
Background technology
Face the dual-pressure of the day by day deficient and deterioration of the ecological environment of petroleum resources, utilize this clean energy of Hydrogen Energy to replace the common recognition that has become the whole world based on the existing energy of fossil oil.With hydrogen is that the Proton Exchange Membrane Fuel Cells of fuel and the technical progress and the marketization of electromobile have further promoted hydrogen energy system Study on Technology and development, and in hydrogen energy system technology chain, hydrogen storage technology is considered to the key link.So far, all successful operations on hydrogen-burning automobile or electromobile of the liquid hydrogen in the hydrogen storage technology, lightweight high pressure vessel and metal hydride system.The security of metal hydride is best in above-mentioned three kinds of hydrogen storage systems, the volume hydrogen-storage density is the highest, but the unit weight hydrogen-storage density is very low.For example, only the hydrogen-storage amount with hydrogen storage material itself is an example, and titanium is AB type and AB 2The hydrogen storage capability of type hydrogen storage alloy all is lower than 2.0wt.%, and rare earth is AB 5The type alloy only is 1.4wt.%.
1997, the investigator found, by a small amount of transition-metal catalyst that mixes (especially Ti catalyzer), NaAlH 4Hydrogen discharging temperature drop to 160 ℃ from traditional 250 ℃, and realized reversible hydrogen adsorption and desorption.This technology makes the metal-complexing alanate be expected to develop into a kind of hydrogen storage material of new heavy body, so caused widely and pay close attention to.For the multi-element metal coordination aluminum hydride, early stage, document P. Claudy, B.Bonnetot, J.-P.Bastide, J.-M.Letoffe, Mater.Res.Bull.17 (1982) 1499 reports utilize LiAlH 4In toluene, carry out high pressure, pyroreaction with preparation Na with NaH 2LiAlH 6Technology, but this method needs to filter, cleans, oven dry, just can obtain comparatively purified Na 2LiAlH 6, whole process must be finished under inert gas atmosphere, and is very loaded down with trivial details.Recently, document J.Huot, S.Boily, V.G ü ther, R.Schulz, J.Alloys Compd.383 (1999) 304 utilizes the method for high-energy ball milling, with NaH, LiH and NaAlH 4For raw material has synthesized Na 2LiAlH 6Document A.Fossdal, H.W.Brinks, J.E.
Figure G2009100961845D00011
B.C.Hauback, J.Alloys Compd.397 (2005) 135 utilizes the method for high-energy ball milling, with LiH and NaAlH 4For raw material has synthesized Na 2LiAlH 6Though these two kinds of preparation methods have avoided steps such as filtration, cleaning, oven dry, be raw material but still need alanate, and the preparation of alanate itself is just very complicated, cost is also high especially, and therefore, these two kinds of methods also are difficult to large-scale application.
Chinese patent 200810060367.6 discloses the directly synthetic coordination aluminum hydride MNH of employing mechanical ball milling method 4The method of hydrogen storage material has the advantages that raw material is simple, energy consumption is low, cost is low.But the synthetic material is inhaled and to be put the hydrogen process and will could inhale that to put hydrogen complete through two-step reaction.
Summary of the invention
Of the present invention on Chinese patent 200810060367.6 bases, adopt different proportioning raw materials, synthesized the new complex hydrides Na of a class xLi 3-xAlH 6(0≤x＜3) hydrogen storage material, hydrogen is put in the suction of synthetic material only needs single step reaction to finish.
A kind of multi-light metal coordination aluminum hydride hydrogen storage material Na of the present invention xLi 3-xAlH 6The preparation method, 0≤x in the formula＜3 is characterized in that: with NaH, LiH and simple substance Al powder is raw material, it is synthetic at next step ball milling of hydrogen atmosphere to be catalyzer with titanium, zirconium, vanadium, scandium, rare earth, preparation process is as follows:
(1) under the protective atmosphere of room temperature and rare gas element, with the mol ratio of NaH, LiH and simple substance Al powder is NaH: LiH: Al=x: 3-x: 1 mixes, add metal-powder or one or more catalyzer uniform mixing of its halogenide of titaniferous, zirconium, vanadium, scandium, rare earth, the mol ratio of described raw material and catalyzer is 1: 0.01～0.08;
(2) raw material that (1) is obtained and the catalyst mix powder ball grinder that places ball mill, the degassing of sealing final vacuum is to 10 -3Bar;
(3) ball grinder after will outgasing charges into the hydrogen of 1～9MPa, places ball milling 60～140h on the ball mill, just can obtain Na xLi 3-xAlH 6
Put into ball grinder after mixture of the present invention mixes and put into Wimet abrading-ball about diameter 10mm simultaneously, the weight ratio of abrading-ball and mix powder is 10-100: 1.
When ball milling synthesized, catalyzer can be metal-powder or one or more mixing of its halogenide of titanium, zirconium, vanadium, scandium, rare earth.As the chemosynthesis reaction material that participates in reaction, the height of hydrogen pressure is extremely important.As the hydrogen concentration deficiency that participates in reacting, reacting driving force is little, Na in hydrogenation process xLi 3-xAlH 6The forming core motivating force of product a little less than, can't directly synthesize Na xLi 3-xAlH 6, perhaps synthetic Na xLi 3-xAlH 6Productive rate very low.Be higher than 9MPa when reacting hydrogen pressure, building-up process will under high pressure be carried out, and production cost improves, and processing safety reduces.The present invention is controlled at hydrogen pressure P: 1MPa＜P＜9MPa.Take all factors into consideration the productive rate and the energy consumption of multi-light metal alanate, the present invention is set in t with ball milling time t and is: 60h＜t＜140h.
Compared with prior art, beneficial effect of the present invention is:
1) with solvent in the high-temperature high-pressure chemical reaction synthesis process relatively, synthetic method of the present invention can at room temperature be carried out, need not high temperature and a large amount of organic solvents participate in, also needn't carry out such as subsequent disposal such as filtration, cleaning and oven dry, simple to operate, production efficiency is high, energy consumption is low;
2) with utilize NaH, LiH, NaAlH 4Deng being the synthetic Na of raw material xLi 3-xAlH 6Compare, raw materials used simple, have the advantage that energy consumption is low, cost is low.
3) with the doped catalyst ball milling after carry out hydrogenation again the synthetic complex hydrides of two step method relatively, the present invention is as long as the mechanical ball milling operation can synthesize Na once the step xLi 3-xAlH 6Productive rate is at the multi-light metal coordination aluminum hydride final product more than 90%.As seen, Production Flow Chart of the present invention is simpler, and production efficiency is higher, and cost is lower, and energy consumption still less is particularly useful for specialized scale operation.
Description of drawings
Fig. 1 mixes Ti catalyst spheres mill synthetic Na 1.8Li 1.2AlH 6The curve of hydrogen desorption kinetics first of complex hydrides;
Fig. 2 mixes TiF 3The catalyst spheres break-in becomes Na 2LiAlH 6XRD figure spectrum before and after the complex hydrides;
Fig. 3 mixes V catalyst spheres mill synthetic Na 2.4Li 0.6AlH 4The curve of hydrogen desorption kinetics first of complex hydrides and preceding 10 round-robin thereof are put the hydrogen capacity contrast.
Embodiment
Embodiment 1
According to chemical formula is Na xLi 3-xAlH 6Coordinate hydride hydrogen-storing material, x=1.8 promptly constitute Na 1.8Li 1.2AlH 6Complex hydrides.With NaH, LiH and Al powder is raw material, and simple substance Ti powder is a catalyzer, presses NaH: LiH: Al=1.8: 1.2: 1 (mol ratio) calculates the weight proportion of LiH, NaH and Al powder, calculates the doping of Ti powder again by the 4mol.% of (NaH+LiH+Al) integral molar quantity.Above-mentioned NaH purity 〉=95%, particle diameter are 74 μ m; LiH purity 〉=97%, particle diameter are 74 μ m; Al powder purity 〉=99%, particle diameter are 74～154 μ m; Ti powder purity 〉=99%, particle diameter＜74 μ m.Raw material packed in the ball grinder with catalyzer and add abrading-ball by 40: 1 ratio of grinding media to material.Earlier ball grinder is found time to be vented to vacuum tightness 10 before the ball milling -3Bar charges into 3.5MPa purity again greater than 99.9% hydrogen, then ball milling 120h at room temperature.Prepared Na 1.8Li 1.2AlH 6It is 3.10wt.% that hydrogen capacity is put in actual measurement when putting hydrogen first.
The main chemical reactions that reaction process comprises is:
Prepared complex hydrides all adopts " constant volume-pressure differential method " to measure its hydrogen storage property.Suction subsequently, put the hydrogen cycling condition and be: under 100 ℃ and 5MPa, inhale hydrogen, transfer hydrogen (down with) at 170～220 ℃ and 0.1MPa.
Fig. 1 is for mixing the synthetic Na of Ti catalyzer institute 1.8Li 1.2AlH 6The curve of hydrogen desorption kinetics first of complex hydrides.Prepared material is transferred hydrogen can reach 3.10wt.% in the time of 4.5 hours the hydrogen capacity of putting at 200 ℃.
Embodiment 2
According to chemical formula is Na xLi 3-xAlH 6Coordinate hydride hydrogen-storing material, x=2 promptly constitutes Na 2LiAlH 6Complex hydrides.With NaH, LiH and Al powder is raw material, TiF 3Be catalyzer, press NaH: LiH: Al=2: 1: 1 (mol ratio) calculates the weight proportion of NaH, LiH and Al powder, and the 2mol.% by (NaH+LiH+Al) integral molar quantity calculates TiF again 3Doping.Above-mentioned NaH purity 〉=95%, particle diameter are 74 μ m; LiH purity 〉=97%, particle diameter are 74 μ m; Al powder purity 〉=99%, particle diameter are 74～154 μ m; TiF 3Powder purity 〉=99%, particle diameter≤154 μ m.Raw material packed in the ball grinder with catalyzer and add abrading-ball by 30: 1 ratio of grinding media to material.Earlier ball grinder is found time to be vented to vacuum tightness 10 before the ball milling -3Bar charges into purity 〉=99.9%, 2.5MPa hydrogen again, then ball milling 100h at room temperature, the so Na of preparation 2LiAlH 6The hydrogen storage capability actual measurement is 3.14wt.%.
The main chemical reactions that reaction process comprises is:
Figure G2009100961845D00032
Fig. 2 is for mixing TiF 3The catalyst spheres break-in becomes Na 2LiAlH 6XRD figure spectrum before and after the complex hydrides.Na in the ball milling synthetic materials 2LiAlH 6Complex hydrides content is up to more than 90%.
Embodiment 3
According to chemical formula is Na xLi 3-xAlH 6Coordinate hydride hydrogen-storing material, x=2.4 promptly constitutes Na 2.4Li 0.6AlH 6Complex hydrides.With NaH, LiH and Al powder is raw material.Selecting simple substance V powder is catalyzer.Press earlier NaH: LiH: Al=2.4: 0.6: 1 (mol ratio) calculates the weight proportion of NaH, LiH and Al powder, calculates the doping of V catalyzer again by the 4mol.% of (NaH+LiH+Al) integral molar quantity, and V powder median size is about 50 μ m, purity＞99%.Raw material parameters such as the purity of NaH, LiH and Al, particle diameter are with embodiment 1.Earlier ball grinder is found time to be vented to vacuum tightness 10 before the ball milling -3Bar charges into 3.8MPa purity again greater than 99.99% hydrogen, ball milling 130h at room temperature then, the Na for preparing 2.4Li 0.6AlH 6The actual measurement hydrogen storage capability of complex hydrides is 3.03wt.%.
The main chemical reactions that reaction process comprises is:
Figure G2009100961845D00041
Fig. 3 is for mixing V catalyst spheres mill synthetic Na 2.4Li 0.6AlH 6The curve of hydrogen desorption kinetics first of complex hydrides and preceding 10 round-robin thereof are put the hydrogen capacity contrast.Prepared Na 2.4Li 0.6AlH 6Can reach the hydrogen capacity of putting of 3.03wt.% when material is put hydrogen first under 190 ℃ in 4 hours, its hydrogen capacity of putting in the hydrogen circulation in 10 suctions subsequently of putting all remains on more than the 2.68wt.%.

Claims (2)

1. multi-light metal coordination aluminum hydride hydrogen storage material Na xLi 3-xAlH 6The preparation method, 0≤x in the formula＜3 is characterized in that: with NaH, LiH and simple substance Al powder is raw material, it is synthetic at next step ball milling of hydrogen atmosphere to be catalyzer with titanium, zirconium, vanadium, scandium, rare earth, preparation process is as follows:
(1) under the protective atmosphere of room temperature and rare gas element, with the mol ratio of NaH, LiH and simple substance Al powder is NaH: LiH: Al=x: 3-x: 1 mixes, add metal-powder or one or more catalyzer uniform mixing of its halogenide of titaniferous, zirconium, vanadium, scandium, rare earth, the mol ratio of described raw material and catalyzer is 1: 0.01～0.08;
(2) raw material that (1) is obtained and the catalyst mix powder ball grinder that places ball mill, the degassing of sealing final vacuum is to 10 -3Bar;
(3) ball grinder after will outgasing charges into the hydrogen of 1～9MPa, places ball milling 60～140h on the ball mill, just can obtain Na xLi 3-xAlH 6
2. the described multi-light metal coordination aluminum hydride hydrogen storage material Na of root a tree name claim 1 xLi 3-xAlH 6The preparation method, it is characterized in that putting into after mixture mixes ball grinder and put into Wimet abrading-ball about diameter 10mm simultaneously, the weight ratio of abrading-ball and mix powder is 10-100: 1.
CN2009100961845A 2009-02-19 2009-02-19 Preparation method of multi-light metal coordination aluminum hydride hydrogen storage material Expired - Fee Related CN101565168B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2009100961845A CN101565168B (en) 2009-02-19 2009-02-19 Preparation method of multi-light metal coordination aluminum hydride hydrogen storage material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2009100961845A CN101565168B (en) 2009-02-19 2009-02-19 Preparation method of multi-light metal coordination aluminum hydride hydrogen storage material

Publications (2)

Publication Number Publication Date
CN101565168A CN101565168A (en) 2009-10-28
CN101565168B true CN101565168B (en) 2011-05-04

Family

ID=41281571

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2009100961845A Expired - Fee Related CN101565168B (en) 2009-02-19 2009-02-19 Preparation method of multi-light metal coordination aluminum hydride hydrogen storage material

Country Status (1)

Country Link
CN (1) CN101565168B (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102502488B (en) * 2011-10-26 2013-09-04 安徽工业大学 Method for improving hydrogen storage property of lithium borohydride
CN103407964B (en) * 2013-08-02 2015-04-15 浙江大学 Method for preparing metal coordination hydride nanorods
AU2016239913B2 (en) * 2015-04-02 2020-08-27 Albemarle Germany Gmbh Highly reactive metal hydrides, process for their preparation and use
CN105645351A (en) * 2015-12-24 2016-06-08 浙江大学 Aluminum hydride hydrogen storage material and preparation method thereof
CN111498799A (en) * 2020-06-09 2020-08-07 世能氢电科技有限公司 Metal alanate composite hydrogen storage material and preparation method thereof
CN111704156B (en) * 2020-07-06 2022-07-15 宁夏大学 Transition metal alanate and preparation method thereof

Also Published As

Publication number Publication date
CN101565168A (en) 2009-10-28

Similar Documents

Publication Publication Date Title
CN101264863B (en) Method for synthesizing metal coordinate hydride hydrogen-storing material directly by reaction ball milling
CN101565168B (en) Preparation method of multi-light metal coordination aluminum hydride hydrogen storage material
CN101476070B (en) Magnesium-based hydrogen occluding alloy and manufacturing method thereof
Li et al. Sodium alanate system for efficient hydrogen storage
CN101733155B (en) Li-Mg-B-N-H catalytic and reversible hydrogen storage material and preparation method thereof
CN102030313B (en) Organic matter and ammonia borane compounded hydrogen storage material and preparation method thereof
CN101920936A (en) Metallic lithium base composite hydrogen storage material, preparation method and application thereof
CN101613083A (en) Metal ammonia borane compound hydrogen storage material and preparation method thereof
CN102556963A (en) Light-metal and high-capacity composite hydrogen storage material and preparation method thereof
JP2009190966A (en) Hydrogen storage material and related method
CN113908818A (en) Transition metal monoatomic catalyst and preparation method and application thereof
CN101811667A (en) Magnesium base hydride composite system for hydrolysis hydrogen production and preparation method and application thereof
US7608233B1 (en) Direct synthesis of calcium borohydride
CN102173385B (en) Method for synthesizing high-capacity solid hydrogen storage material ammonia borane by using amino complex
CN109052403B (en) Two-dimensional titanium carbide-doped lithium aluminum hydride hydrogen storage material and preparation method thereof
Congwen et al. Mechanochemical synthesis of the α-AlH3/LiCl nano-composites by reaction of LiH and AlCl3: Kinetics modeling and reaction mechanism
CN102807191A (en) Method for synthesizing Li-Mg-B-H hydrogen storage material
CN113148956A (en) Preparation method of graphene-loaded nano flaky transition metal hydride and hydrogen storage material
JP2004196634A (en) Hydride powder used for hydrogen storing/discharging system
CN101734622A (en) Preparation method of hydrogen storage material of Li-Al-H complex hydride
Züttel et al. Hydrogen storage
CN102765723A (en) Method for synthesizing KSi hydrogen storage alloy
CN109467048A (en) Composite hydrogen storage material and its preparation method and application
CN102530871A (en) Modified borane ammoniate hydrogen storage material and preparation method thereof
CN101406843B (en) Nano-catalyst of sodium aluminum hydride complex hydride as well as preparation method and application thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20110504

Termination date: 20150219

EXPY Termination of patent right or utility model