CN101108331A - Coordination hydride catalyzed reversible hydrogen storage materials and method of preparing the same - Google Patents
Coordination hydride catalyzed reversible hydrogen storage materials and method of preparing the same Download PDFInfo
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- CN101108331A CN101108331A CNA2006100897864A CN200610089786A CN101108331A CN 101108331 A CN101108331 A CN 101108331A CN A2006100897864 A CNA2006100897864 A CN A2006100897864A CN 200610089786 A CN200610089786 A CN 200610089786A CN 101108331 A CN101108331 A CN 101108331A
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Abstract
The invention relates to a novel high capacity hydrogen storage material, namely coordination hydride, the chemical formula is A(MH4)n. The invention adds titanium catalyst Ti(OC4H9)4 or TiC13 .1/3 AlCl3 in the classic coordination hydride lithium aluminium hydride and sodium aluminum hydride by the high energy ball mill method under the protection of hydrogen pressure, therefore reaching reversible storage hydrogen. The preparation method of the coordination hydride catalyzing reversible storage hydrogen seals the coordination hydride (LiA1H4 or NaA1H4), titanium catalyst Ti(OC4H9)4 or TiC13 .1/3 AlCl3 and steel ball in a stainless ball mill Pot, and mill ball with high energy under the protection of hydrogen pressure. The material can be used as a high capacity hydrogen storage material, the reversible hydrogen adsorption volume can reach above 4.0wt per cent at 150 DEG C., the reversible hydrogen adsorption volume to 0.1MPa hydrogen pressure also can reach above 3.0 wt per cent.
Description
Technical field
The present invention relates to a kind of coordination hydride catalyzed reversible hydrogen storage materials and preparation method thereof.By high-energy ball milling method at complex hydrides A (MH
4)
n(LiAlH
4Or NaAlH
4) the middle Ti-base catalyst (Ti (OC that adds
4H
9)
4Or TiCl
31/3AlCl
3), thereby obtain the novel hydrogen storage material of high power capacity.
Background technology
The energy is the source of mankind's activity, and clean energy resource is the basis of human society realization sustainable development especially, and fossil fuel such as oil, coal is exhausted day by day because of undue exploitation in recent years, thereby has caused the deep energy crisis of human society.Therefore, the new energy development of alternative fossil fuel all is a urgent important topic to the whole mankind.In all novel energies, Hydrogen Energy becomes the human following energy with most probable.In recent years, hydrogen abundant as a kind of reserves, can store and eco-friendly secondary energy sources more and more are subjected to people's attention.In the whole hydrogen energy system, storage hydrogen is the link of most critical.Storage method commonly used at present has Compressed Gas storing method, liquid hydrogen storing method and hydride hydrogen-storing.Through the exploitation of 30 years of researches, hydrogen-storage alloy has been widely used in the storage and the fields such as transportation, hydrogen isotope separation, temperature and pressure sensor, hydrogenating organic compounds catalyst for reaction and Ni-MH battery of hydrogen.Yet, traditional hydrogen-storage alloy AB
5, AB
2All be no more than 2wt% with the hydrogen storage amount percentage by weight of AB type hydrogen-storage alloy.This some field (as fuel cell) of using for hydrogen-storage alloy is far from being enough.According to the estimation of USDOE (DOE), for Proton Exchange Membrane Fuel Cells (PEMFC) automobile of a standard, stroke 480km needs the about 3.58kg of hydrogen.This requires the hydrogen storage amount of hydrogen-storage alloy to surpass 6wt%, and volume ratio density surpasses 60kgm
-3(H
2).It is 5wt% that international energy association (IEA) also requires hydrogen storage amount, and hydrogen discharging temperature is lower than 423K, and cycle life is above 1000 times.World energy sources Network Dept. (WENET) is though requiring to 3wt% of reduction hydrogen storage amount requires hydrogen discharging temperature to be no more than 373K (this also is the requirement of hydrogen-storage alloy practicability) simultaneously, and cycle life is above 5000 times.Though the requirement to the hydrogen-storage alloy hydrogen storage amount still has arguement, traditional hydrogen-storage alloy has faced great challenge.Therefore, nearest 5 years, the research and development of hydrogen storage material turned to the research of high capacity hydrogen storage material, and complex hydrides (catalyzed complex hydrides) is exactly one of them.
Complex hydrides is a class has important use in industrial and many different chemical field a compound.The main feature of complex hydrides be hydrogen storage amount up to 5.5wt%～18.5wt%, considerably beyond traditional hydrogen-storage alloy, and it is lower to form enthalpy.Of the present invention is typical complex hydrides lithium aluminium hydride reduction and sodium aluminum hydride.The both is white crystalline solid, stable in dry air under the room temperature, to moisture with to contain proton solvent very responsive, wherein lithium aluminium hydride reduction has higher solubility in ether solvent, and sodium aluminum hydride is insoluble to ether, but is soluble in oxolane and the glycol dimethyl ether.
The key reaction mechanism of putting hydrogen is (with NaAlH
4Be example) be following two-step reaction:
NaAlH
41/3Na
3AlH
6+2/3Al+H
2(1)
1/3Na
3AlH
6+2/3Al+H
2NaH+Al+3/2H
2(2)
Because bond energy is very high, the NaH decomposition condition is relatively harsher, therefore should not decomposition reaction take place as reversible sources of hydrogen.Calculate from stoichiometric number, the first step in the above-mentioned reaction has the hydrogen of 3.7wt% to emit, and then there was 1.9wt% in second step, and the reversible hydrogen reserves more than the 5.6wt% are arranged on this reaction theory.
The complex hydrides thermodynamic property is quite outstanding, and the problem dynamic performance that to be this material put hydrogen in the suction below 150 ℃ is slower.1997, the Bogdanovic ' of Germany reported that containing the dynamics that makes sodium aluminum hydride react (1) (2) behind the catalyst of Ti by adding greatly takes on a new look, thereby has excited the research interest of people to complex hydrides storage hydrogen.
Coordination hydride catalyzed reversible storage hydrogen is a kind of brand-new storage hydrogen methods.As a kind of hydrogen storage material of high power capacity, the thermodynamics after coordination hydride catalyzed is outstanding, and can under lower temperature, inhale and put hydrogen, and the sucking/placing hydrogen amount height.
High-energy ball milling method (high-energy ball milling has another name called mechanical alloying mechanicalalloying) just becomes a kind of important channel of preparation super-fine material once appearance.High-energy ball-milling process is that the powder that needs ball milling is put into high energy ball mill spherical tank ball milling.By the strong interaction between abrading-ball, powder and the spherical tank, external energy is delivered in element powders or the compound powder particle, powder particle deforms, fracture and cold welding, and by constantly refinement, constantly come out in unreacted surface, the obvious like this contact area that increases reaction, shortened the diffusion length of atom, impel diffusion and solid-state reaction take place between the heterogeneity, mixed-powder is realized alloying on atom magnitude level, form superfines.Mechanical energy is participated in directly or caused chemical reaction is a kind of new approaches.The basic principle of high-energy ball milling method is to utilize mechanical energy to come induced chemical reaction or induced material tissue, structure and changes of properties, prepares new material with this.As a kind of new technology, it has obvious reduction reaction activity, crystal grain thinning, greatly improves powder activity and improve even particle distribution and strengthen combining of interface between body and the matrix, promote the solid ionic diffusion, bring out the cryochemistry reaction, thereby having improved the performance such as packing, electricity, calorifics of material, is a kind of energy-conservation, material preparation technology efficiently.Use high-energy ball milling method among the present invention and be exactly in order to prepare the material of superfine nano-crystalline, thereby and make catalyst be distributed in the material suction hydrogen desorption kinetics that catalysis better improves material equably.The high-energy ball milling method vibration frequency that adopts among the present invention is 800～1500 times/minute, and amplitude reaches 40～44mm.
Summary of the invention
Purpose of the present invention aims to provide a kind of coordination hydride catalyzed reversible hydrogen storage materials, and this material can be inhaled under relatively mild condition and put hydrogen (150 ℃, 7MPa inhales hydrogen, 150 ℃, 0.1MPa is put hydrogen), and reversible hydrogen storage amount reaches more than the 3wt%.
Another object of the present invention provides a kind of method for preparing coordination hydride catalyzed reversible hydrogen storage materials.
For achieving the above object, the present invention takes following technical scheme:
A kind of coordination hydride catalyzed reversible hydrogen storage materials, this material are in lithium aluminium hydride reduction or sodium aluminum hydride, add 0.5mol%～6mol% Ti-base catalyst Ti (OC
4H
9)
4Or TiCl
31/3AlCl
3, under the hydrogen pressure protection, make through high-energy ball milling.
A kind of method for preparing coordination hydride catalyzed reversible hydrogen storage materials, this method comprises the steps:
(1) in lithium aluminium hydride reduction or sodium aluminum hydride, adds 0.5mol%～6mol% Ti-base catalyst Ti (OC
4H
9)
4Or TiCl
31/3AlCl
3
(2) raw material of getting ready in the step (1) is packed in the glove box of argon shield ball grinder; ball material weight ratio is 4/1～20/1; in ball grinder, charge into 0.1MPa～5MPa hydrogen pressure protection again; carry out high-energy ball milling; wherein, the high-energy ball milling method vibration frequency is 800～1500 times/minute, and amplitude reaches 40～44mm; the time of ball milling is 0.1h～6h, promptly makes coordination hydride catalyzed reversible hydrogen storage materials.
In the step (1) of the inventive method, add the Ti-base catalyst Ti (OC of lithium aluminium hydride reduction or sodium aluminum hydride
4H
9) 4 or TiCl
31/3AlCl
3Be preferably 2mol%.
In the step (2) of the inventive method, in described step (2), described ball material weight ratio is preferably 10/1, and hydrogen pressure is preferably 3Mpa, and the time of ball milling is preferably 4h.
In the present invention, the high-energy ball milling method that is adopted does not have special requirement to the material of ball, the material of ball can be stainless steel, also can adopt general plain ball or other Metal Ball, can also adopt carbide or other Ceramic Balls, only otherwise all can with the hard ball of ball milling material generation chemical reaction.In the present invention because the material of ball grinder is a stainless steel, so preferred stainless steel ball.
In the present invention, the diameter of ball is preferably 4-15mm, can adopt the ball of single diameter to carry out ball milling, can also adopt the combination at the various balls of above-mentioned diameter range.The present invention more preferably adopts the ball of the single diameter in above-mentioned diameter range to carry out ball milling; Most preferably adopting single diameter is that the stainless steel ball of 8mm carries out ball milling.
In the present invention, the consumption of ball is provided by ratio of grinding media to material, and the ball material weight ratio that adopts among the present invention is 4/1～20/1.
In a word, the material of ball, parameters such as the size of ball are the general known technology of high-energy ball milling, and changing these conditions within the specific limits generally influences not quite the result, can both reach purpose of the present invention.
The complex hydrides that the present invention adopts is lithium aluminium hydride reduction and sodium aluminum hydride, and chemical formula is respectively LiAlH
4And NaAlH
4, catalyst is Ti (OC
4H
9)
4And TiCl
31/3AlCl
3, adding molar percentage in complex hydrides is n (being expressed as n mol%) Ti-base catalyst Ti (OC
4H
9)
4Or TiCl
31/3AlCl
3The value of n satisfies following relationship formula: 0.5≤n≤6, and the most preferably value of n value is 2; The ball milling time, t satisfied following relational expression: 0.1h≤t≤6h, and the most preferably value of t is 4h; Ball material weight ratio X satisfies following relational expression: 4/1≤X≤20/1, and the most preferably value of X value is 10/1; Hydrogen pressure Y satisfies following relational expression: 0.1Mpa≤Y≤5Mpa, and the most preferably value of Y value is 3Mpa.
Advantage of the present invention is:
This material is as a kind of new chemical hydrogen storage material, can inhale to put hydrogen (150 ℃, 7MPa inhales hydrogen, 150 ℃, 0.1MPa is put hydrogen) under relatively mild condition, and reversible hydrogen storage amount reaches more than the 3wt%.
Description of drawings
Fig. 1 is the suction hydrogen desorption kinetics curve map under 150 ℃ of embodiment 1 materials
Fig. 2 is the suction hydrogen desorption kinetics curve map under 150 ℃ of embodiment 2 materials
Fig. 3 is the suction hydrogen desorption kinetics curve map under 150 ℃ of embodiment 3 materials
Fig. 4 is the suction hydrogen desorption kinetics curve map under 150 ℃ of embodiment 4 materials
Fig. 5 is the suction hydrogen desorption kinetics curve map under 150 ℃ of embodiment 5 materials
Fig. 6 is the suction hydrogen desorption kinetics curve map under 150 ℃ of embodiment 6 materials
Fig. 7 is the suction hydrogen desorption kinetics curve map under 80 ℃ of embodiment 7 materials
The specific embodiment
Coordination hydride catalyzed reversible hydrogen storage materials production method of the present invention is: in following embodiment 1-8, get the raw materials ready according to the pairing raw material of stoicheiometry of the material of each embodiment.The ball grinder of in the glove box of argon shield, packing into, ball material weight ratio 4/1～20/1 charges into 0.1MPa～5MPa hydrogen pressure protection again in ball grinder, carry out high-energy ball milling, and the high-energy ball milling method vibration frequency is 1000 times/minute, and amplitude reaches 44mm.Used ball all is that single diameter is the stainless steel ball of 8mm among all embodiment of the present invention.
Adopt high-energy ball milling ball-milling method (ball material weight ratio 4/1, hydrogen pressure 3MPa) to prepare NaAlH
4Middle 1mol%Ti (the OC that adds
4H
9)
4The material of ball milling 4h, the suction hydrogen desorption kinetics curve under its 150 ℃ as shown in Figure 1, this material hydrogen in 6h reaches 2.9wt%, hydrogen desorption capacity has only 1.2wt%.
Adopt high-energy ball milling ball-milling method (ball material weight ratio 10/1, hydrogen pressure 3MPa) to prepare NaAlH
4Middle 2mol%Ti (the OC that adds
4H
9)
4The material of ball milling 4h, the suction hydrogen desorption kinetics curve under its 150 ℃ as shown in Figure 2, this material hydrogen in 6h reaches 4.3wt%, hydrogen desorption capacity can reach 3.4wt%.
Adopt high-energy ball milling ball-milling method (ball material weight ratio 20/1, hydrogen pressure 3MPa) to prepare NaAlH
4Middle 6mol%Ti (the OC that adds
4H
9)
4The material of ball milling 4h, the suction hydrogen desorption kinetics curve under its 150 ℃ as shown in Figure 3, this material hydrogen in 6h reaches 3.8wt%, hydrogen desorption capacity reaches 2.7wt%.
Adopt high-energy ball milling ball-milling method (ball material weight ratio 10/1, hydrogen pressure 0.1MPa) to prepare NaAlH
4Middle 2mol%Ti (the OC that adds
4H
9)
4The material of ball milling 0.5h, the suction hydrogen desorption kinetics curve under its 150 ℃ as shown in Figure 4, this material hydrogen in 6h reaches 3.5wt%, hydrogen desorption capacity has only 2.0wt%.
Adopt high-energy ball milling ball-milling method (ball material weight ratio 10/1, hydrogen pressure 5MPa) to prepare NaAlH
4Middle 2mol%Ti (the OC that adds
4H
9)
4The material of ball milling 6h, the suction hydrogen desorption kinetics curve under its 150 ℃ as shown in Figure 5, this material hydrogen in 6h reaches 3.7wt%, hydrogen desorption capacity has only 2.1wt%.
Adopt high-energy ball milling ball-milling method (ball material weight ratio 10/1, hydrogen pressure 3MPa) to prepare NaAlH
4The middle 2mol%TiCl that adds
31/3AlCl
3The material of ball milling 4h, the suction hydrogen desorption kinetics curve under its 150 ℃ as shown in Figure 6, this material hydrogen in 6h reaches 4.3wt%, hydrogen desorption capacity reaches 3.1wt%.
Embodiment 7
Adopt high-energy ball milling ball-milling method (ball material weight ratio 10/1, hydrogen pressure 3MPa) to prepare LiAlH
4Middle 2mol%Ti (the OC that adds
4H
9)
4The material of ball milling 4h, the suction hydrogen desorption kinetics curve under its 80 ℃ as shown in Figure 7, this material hydrogen in 6h reaches 3.3wt%, hydrogen desorption capacity reaches 3.0wt%.
Embodiment 8
Adopt high-energy ball milling ball-milling method (ball material weight ratio 10/1, hydrogen pressure 3MPa) to prepare LiAlH
4The middle 2mol%TiCl that adds
31/3AlCl
3The material of ball milling 4h, the suction hydrogen desorption kinetics under its 80 ℃, this material hydrogen in 6h reaches 3.5wt%, and hydrogen desorption capacity can reach 3.2wt%.
Claims (4)
1. coordination hydride catalyzed reversible hydrogen storage materials, it is characterized in that: this material is in lithium aluminium hydride reduction or sodium aluminum hydride, adds 0.5mol%～6mol% Ti-base catalyst Ti (OC
4H
9)
4Or TiCl
31/3AlCl
3, under the hydrogen pressure protection, make through ball milling.
2. method for preparing coordination hydride catalyzed reversible hydrogen storage materials, it is characterized in that: this method comprises the steps:
(1) in lithium aluminium hydride reduction or sodium aluminum hydride, adds 0.5mol%～6mol% Ti-base catalyst Ti (OC
4H
9)
4Or TiCl
31/3AlCl
3
(2) raw material of getting ready in the step (1) is packed in the glove box of argon shield ball grinder; ball material weight ratio is 4/1～20/1; in ball grinder, charge into 0.1MPa～5MPa hydrogen pressure protection again; carry out high-energy ball milling; wherein, the high-energy ball milling method vibration frequency is 800～1500 times/minute, and amplitude reaches 40～44mm; the time of ball milling for O.1h～6h, promptly make coordination hydride catalyzed reversible hydrogen storage materials.
3. the method for preparing coordination hydride catalyzed reversible hydrogen storage materials according to claim 2 is characterized in that: in described step (1), add the Ti-base catalyst Ti (OC of lithium aluminium hydride reduction or sodium aluminum hydride
4H
9)
4Or TiCl
31/3AlCl
3Be 2mol%.
4. according to claim 2 or the 3 described methods that prepare coordination hydride catalyzed reversible hydrogen storage materials, it is characterized in that: in described step (2), described ball material weight ratio is 10/1, and hydrogen pressure is 3Mpa, and the time of ball milling is 4h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101746719B (en) * | 2008-11-28 | 2012-06-13 | 北京有色金属研究总院 | NaAlH4-titanium-vanadium base solid solution hydrogen storage composite material and preparation method thereof |
| CN104030246A (en) * | 2014-04-30 | 2014-09-10 | 燕山大学 | Aluminum and lithium hydrogen storage material and preparation method thereof |
| CN113735057A (en) * | 2021-08-31 | 2021-12-03 | 苏州睿分电子科技有限公司 | Activation-free hydrogen storage material and preparation method and device thereof |
| CN115571854A (en) * | 2016-04-19 | 2023-01-06 | 智能能源有限公司 | Hydrogen-generating composition for fuel cell |
-
2006
- 2006-07-17 CN CNA2006100897864A patent/CN101108331A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101746719B (en) * | 2008-11-28 | 2012-06-13 | 北京有色金属研究总院 | NaAlH4-titanium-vanadium base solid solution hydrogen storage composite material and preparation method thereof |
| CN104030246A (en) * | 2014-04-30 | 2014-09-10 | 燕山大学 | Aluminum and lithium hydrogen storage material and preparation method thereof |
| CN104030246B (en) * | 2014-04-30 | 2016-01-06 | 燕山大学 | A kind of aluminium lithium hydrogen storage material and preparation method thereof |
| CN115571854A (en) * | 2016-04-19 | 2023-01-06 | 智能能源有限公司 | Hydrogen-generating composition for fuel cell |
| CN113735057A (en) * | 2021-08-31 | 2021-12-03 | 苏州睿分电子科技有限公司 | Activation-free hydrogen storage material and preparation method and device thereof |
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