CN100369665C - High-capacity hydrogen-storage material with NaAlH4 and preparation method thereof - Google Patents
High-capacity hydrogen-storage material with NaAlH4 and preparation method thereof Download PDFInfo
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- CN100369665C CN100369665C CNB2005100462054A CN200510046205A CN100369665C CN 100369665 C CN100369665 C CN 100369665C CN B2005100462054 A CNB2005100462054 A CN B2005100462054A CN 200510046205 A CN200510046205 A CN 200510046205A CN 100369665 C CN100369665 C CN 100369665C
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Abstract
The present invention relates to improvement technique on the hydrogen-storage materials, which more specifically provides a high-capacity hydrogen-storage material with NaAlH4 and the impurity of transition metal and a preparation method thereof. A hydrogen-storage system provided by the present invention is composed of a basic material, a catalyst, and an auxiliary structure. In the doping process, the present invention directly uses transition metal powder as the catalyst. Meanwhile, alkali metal/alkali metal hydride or alkaline earth metal/alkaline earth metal hydride is added to be as auxiliary structure phase. Besides, ball grinding operation is performed under an inertia protective atmosphere or a reactive hydrogen atmosphere. The invention has the advantages that the provided preparation method has simple technology, easy operation and low price; the present invention can fundamentally solve the problems of inertia by-product generation, foreign gas pollution, etc. existing in the traditional doping method; the provided material system has the advantages of high capacity of hydrogen storage, high cycle stability, proper operating temperature and no foreign gas pollution. The actual hydrogen capacity can achieve 4.7 wt% in some systems, which is increased by 40% than the present level of congener systems.
Description
Technical field
The present invention relates to the improvement technology of hydrogen storage material, be specially a kind of transient metal doped high-capacity hydrogen-storage material with NaAlH 4 and preparation method thereof.
Background technology
Development high-performance hydrogen-storage system is a Hydrogen Energy key in application link for the application terminal provides hydrogen source.In various potential storage hydrogen modes, material storage hydrogen is stored significantly being better than high pressure gas storage and low temperature liquid aspect security, the practicality, is generally believed tool development prospect.Though traditional metal/alloy hydride system and nanostructured carbon material generally have dynamic performance excellence, advantage that operating temperature is low, its storage hydrogen capacity is lower, can't satisfy multiple application terminal, fuel cell car for example, the commercialization demand.
The researcher finds recently: through a small amount of transition-metal catalyst of overdoping (especially Ti catalyst), NaAlH
4The suction hydrogen desorption kinetics can be improved at all and can realized reversible storage hydrogen below 200 ℃.Because NaAlH
4The theoretical hydrogen capacity up to 5.6wt.%, its operating temperature approaches to satisfy the job requirement of on-vehicle fuel in addition, this discovery has promoted the development of vehicle-mounted hydrogen storage material system rapidly.But further investigation shows: Ti-NaAlH
4The actual storage hydrogen capacity of system only reaches 3～4wt.% far below its theoretical value, has seriously restricted its practical application.Its reason is: adopting the Ti compounds in the doping techniques at present more.When obtaining catalysis efficiency, a considerable amount of anion are introduced in the system and react with the hydride matrix material and generate the inertia accessory substance.So not only consume the hydrogen storage material of a great deal of, also significantly reduced effective storage hydrogen composition of material.As for organic catalyst, except that causing capacitance loss, also there is application terminal--the drawback of Proton Exchange Membrane Fuel Cells of hydrocarbon gas pollutant harm storage hydrogen system.Thereby develop novel doping method and material system is to improve NaAlH with effective removal inertia accessory substance at all
4The key of system hydrogen storage performance.
Summary of the invention
The object of the present invention is to provide transient metal doped high-capacity hydrogen-storage material with NaAlH 4 and preparation method thereof.
Technical scheme of the present invention is:
The invention provides high-capacity hydrogen-storage material with NaAlH 4, the formation of hydrogen storing material system comprises: matrix material, catalyst and supplementary structure are mutually.With the mixture of NaH and Al powder, or coordination sodium alanate NaAlH
4Be matrix material; As catalyst, catalyst comprises a kind of among Sc, Ti, Fe, V, Cr, Co, Ni, V, Zr, Mn, Nb, the Zn or several combination with the transition metal powder; Supplementary structure comprises mutually: alkali metal M or alkali metal hydride MH (M=Li, K, Rb), alkaline-earth metal N or alkaline earth metal hydride NH
2A kind of in (N=Mg, Ca, Sr) or several combination.Each mutually shared molar content is: matrix material 60～100%; Catalyst 0～10%; Supplementary structure phase 0～30%.According to different proportionings are selected in the requirement of hydrogen storage capability and hydrogenation speed.
Among the present invention, by the mole percentage composition, matrix material is preferably 90～96%; Catalyst is preferably 2～5%; Supplementary structure is preferably 2～5% mutually.
Among the present invention, count in molar ratio,
Al=1: 1.
The invention provides a kind of method for preparing high-capacity hydrogen-storage material with NaAlH 4, in matrix material, add catalyst simultaneously and carry out composite mixed mutually with supplementary structure.Matrix material, catalyst and supplementary structure are mixed mutually by a certain percentage ball milling under inert protective atmosphere or reactive hydrogen atmosphere; Ratio of grinding media to material was greater than 5: 1; The ball milling time was greater than 0.5 hour.
Among the present invention, during ball milling, initial pressure is 1～20 atmospheric pressure under reactive hydrogen atmosphere.
Among the present invention, ratio of grinding media to material is generally (5～100): 1; The ball milling time was generally 0.5～100 hour.
Material system provided by the invention and preparation method select at catalyst, adopted a series of advanced persons' method and technology aspect doped structure design and the doping process control:
1, is different from employing chemical combination attitude catalyst in traditional doping method, directly adopts the transition metal powder to implement to mix in the method provided by the invention as catalyst.
2, be different from the simple catalyst that adopts in traditional doping method, adopt complex phase to mix in the method provided by the invention, in doped catalyst, add supplementary structure and adjust matrix hydride structure mutually.
3, be different from and only adopt inert protective atmosphere in traditional doping method, for some material system, under reactive hydrogen atmosphere, implement to mix in the method provided by the invention.
With respect to the chemical combination attitude catalyst that is adopted in traditional doping method, the direct use of element state transition metal greatly reduces material cost.The more important thing is: constitute by optimizing the system composition, fundamentally solved in traditional doping method and to generate because of the inertia accessory substance that uses chemical combination attitude catalyst to cause and problem such as foreign gas pollution; Can in matrix hydride, form the lattice structure that part substitutes mutually by adding supplementary structure simultaneously, for the activated centre catalysis efficiency fully, stable performance provides more favourable structure/chemical environment; The use of reactive hydrogen atmosphere can cause material that the part in-situ hydrogenization takes place in the doping process in the mechanical milling process, has improved doping efficiency.
The invention has the advantages that:
1, the present invention directly adopts the transition metal powder as catalyst in the doping process, adds alkali metal/alkali metal hydride or alkaline-earth metal/alkaline earth metal hydride simultaneously as the supplementary structure phase, and implement ball milling under inert protective atmosphere or reactive hydrogen atmosphere.This preparation method's technology is simple, easy operating, cheap;
2, preparation method provided by the present invention has fundamentally solved problem such as generation of inertia accessory substance and foreign gas pollution in traditional doping method;
3, material system provided by the present invention has high storage hydrogen capacity, high cyclical stability, operating temperature is moderate and the free from admixture gaseous contamination.Can reach 4.7wt.% at the actual storage of some material system hydrogen capacity, more present similar system increase rate reaches 40%.
With relevant comparative example in detail the present invention is described in detail by the following examples.
Description of drawings
Fig. 1: with 0.96NaH+Al+0.04Ti+0.04KH is the hydrogen desorption kinetics curve that material circulated in the 4th after initiation material mixed.Putting hydrogen (DH) temperature is 150 ℃.
Fig. 2: with 0.96NaH+Al+0.04Ti+0.04KH is the circulation storage hydrogen capacity of material after initiation material mixes, and comprises the NaAlH that adopts the single-phase doping of metal Ti powder
4The circulation storage hydrogen capacity of material is to contrast.
Fig. 3: with 0.95NaH+Al+0.05Ni+0.05KH is the hydrogen desorption kinetics curve of initiation material doping back material the 2nd circulation.Putting hydrogen (DH) temperature is 150 ℃.
Fig. 4: with 0.96NaH+Al+0.04Ti+0.02MgH
2Be the hydrogen desorption kinetics curve of initiation material doping back material the 3rd circulation.Putting hydrogen (DH) temperature is 150 ℃.
Fig. 5: with 0.96NaH+Al+0.04Fe+0.04LiH is the hydrogen desorption kinetics curve of initiation material doping back material the 2nd circulation.Putting hydrogen (DH) temperature is 150 ℃.
Fig. 6: adopt conventional method TiCl
3The NaAlH that mixes
4Hydrogen desorption kinetics contrast with material provided by the invention (embodiment 1).Putting hydrogen (DH) temperature is 150 ℃.
Fig. 7: the NaAlH that adopts the single-phase doping preparation of metal Ti powder
4The hydrogen desorption kinetics contrast of material and material provided by the invention (embodiment 1).Putting hydrogen (DH) temperature is 150 ℃.
The specific embodiment
With the NaH/Al powder mixture is that composite mixed KH of matrix and Ti powder prepare the NaAlH that Ti mixes
4Hydrogen storage material.
The employing raw material is: NaH (purity 95% ,～200 orders), KH (be scattered in the Dormant oils, weight percentage is 30%), Al powder (purity 99.95+% ,～200 orders) and Ti powder (purity 99.98% ,～325 orders).Except that KH, all unprocessed direct employing of other raw material.Adopt pentane to extract KH in the argon atmospher glove box from Dormant oils, after repeatedly pentane washs and filters, the vacuum removal pentane obtains pure KH.0.96NaH+Al+0.04Ti+0.04KH proportion raw material mixture is inserted in the stainless steel jar mill in molar ratio, grinds 10 hours on the Fritsch7 planetary ball mill.Milling atmosphere is high-purity hydrogen (purity 99.999%), and initial pressure is about 8 atmospheric pressure.Ratio of grinding media to material is 40: 1.
Adopt the hydrogen storage property of volumetric method test material.Cycling condition is: put hydrogen for 150 ℃; Inhale hydrogen for 120 ℃, the initial hydrogen pressure that fills is about 120 atmospheric pressure.
Fig. 1 has provided typical hydrogen desorption kinetics curve.Material need be put hydrogen 4.7wt.% in about 10 hours down at 150 ℃; Need 12 hours approximately at 120 ℃ of saturated suction hydrogen.
Fig. 2 has provided material and has inhaled the hydrogen capacity of putting in the hydrogen circulation at 10 times.Material is put hydrogen circulation back capacity in the 1st suction of experience and is stabilized in about 4.7wt.%.
With the NaH/Al powder mixture is the NaAlH of composite mixed KH of matrix and the preparation of Ni powder
4Hydrogen storage material.
Adopt Ni powder (purity 99.99% ,～100 orders) in the raw material, NaH, Al powder and KH are with embodiment 1.The initiation material of 0.95NaH+Al+0.05Ni+0.05KH proportioning is in molar ratio inserted in the stainless steel jar mill, on Fritsch 7 planetary ball mills, ground 20 hours.Milling atmosphere is high-purity argon gas (purity 99.999%), and initial pressure is 1 atmospheric pressure.Ratio of grinding media to material is 60: 1.
As shown in Figure 3: material was transferred hydrogen 14 hours at 150 ℃ in the 2nd circulation, hydrogen desorption capacity can reach 3.8wt.%; Need 15 hours approximately at 120 ℃ of saturated suction hydrogen.Material is put in the hydrogen circulation in suction, and hydrogen capacity and dynamic performance are stable.
With the NaH/Al powder mixture is the composite mixed CaH of matrix
2Prepare the NaAlH that Ti mixes with the Ti powder
4Hydrogen storage material.
Adopt MgH in the raw material
2(purity 95% ,～40 orders), NaH, Al powder and Ti powder are with embodiment 1.To 0.96NaH+Al+0.04Ti+0.02MgH in molar ratio
2The initiation material of proportioning is inserted in the stainless steel jar mill, grinds 10 hours on Fritsch 7 planetary ball mills.Milling atmosphere is high-purity hydrogen (purity 99.999%), and initial pressure is 10 atmospheric pressure.Ratio of grinding media to material is 50: 1.
As shown in Figure 4: material was transferred hydrogen 15 hours at 150 ℃ in the 3rd circulation, hydrogen desorption capacity can reach 4.0wt.%; Need 20 hours approximately at 120 ℃ of saturated suction hydrogen.Material is put in the hydrogen circulation in suction, and hydrogen capacity and dynamic performance are stable.
With the NaH/Al powder mixture is the NaAlH of composite mixed LiH of matrix and the preparation of Fe powder
4Hydrogen storage material.
Adopt LiH (purity 95% ,～30 orders), Fe powder (purity 98% ,～100 orders) in the raw material, NaH and Al powder are with embodiment 1.The initiation material of 0.96NaH+Al+0.04Fe+0.04LiH proportioning is in molar ratio inserted in the stainless steel jar mill, on Fritsch 7 planetary ball mills, ground 20 hours.Milling atmosphere is high-purity hydrogen (purity 99.999%), and initial pressure is 10 atmospheric pressure.Ratio of grinding media to material is 50: 1.
As shown in Figure 5: material was transferred hydrogen 23 hours at 150 ℃ in the 2nd circulation, hydrogen desorption capacity can reach 4.1wt.%; Need 20 hours approximately at 120 ℃ of saturated suction hydrogen.
Relevant comparative example 1
The catalyst TiCl that uses traditional doping method and adopt usually at present
3The Ti-NaAlH of preparation
4Hydrogen storage material.
NaAlH
4After purifying, use TiCl
3Pressed powder directly uses.To NaAlH in molar ratio
4+ 0.04TiCl
3The proportion raw material mixture is inserted in the stainless steel jar mill, grinds 0.5 hour on Fritsch 7 planetary ball mills.Milling atmosphere is high-purity argon gas (purity 99.999%), and initial pressure is about 1 atmospheric pressure.Ratio of grinding media to material is 40: 1.
Fig. 6 has provided the typical hydrogen desorption kinetics curve contrast of adopting prepared material of conventional method and storeroom provided by the invention.Though a little less than conventional method institute prepared material, material provided by the invention has significant advantage on hydrogen capacity aspect hydrogen discharging rate, the amplitude of raising reaches 40%.
Relevant comparative example 2
Adopting the NaH/Al powder mixture is that the simple doping metals Ti of matrix powder prepares NaAlH
4Hydrogen storage material.
NaH, Al powder and Ti powder are with embodiment 1 in the employing raw material.NaH+Al+0.04Ti proportion raw material mixture is inserted in the stainless steel jar mill in molar ratio, grinds 10 hours on Fritsch 7 planetary ball mills.Milling atmosphere is high-purity hydrogen (purity 99.999%), and initial pressure is 8 atmospheric pressure.Ratio of grinding media to material is 40: 1.
Fig. 7 has provided the KH+Ti complex phase dopant material of the present invention's proposition and the typical hydrogen desorption kinetics curve contrast between the single-phase dopant material of Ti.Fig. 2 has provided the recycle hydrogen capacity comparison of two kinds of materials.Aspect hydrogen discharging rate and hydrogen capacity, KH+Ti complex phase dopant material all significantly is better than the single-phase dopant material of Ti, and the amplitude that hydrogen capacity improves is near 40%.
Claims (7)
1. high-capacity hydrogen-storage material with NaAlH 4, it is characterized in that: hydrogen storage material is made of mutually matrix material, catalyst and supplementary structure; With the mixture of NaH and Al powder, or NaAlH
4Be matrix material; With Ti, Fe or Ni transition metal powder as catalyst; Supplementary structure is alkali metal hydride MH, alkaline earth metal hydride NH mutually
2In a kind of; Each mutually shared molar content is: 60≤matrix material＜100%; 0＜catalyst≤10%; 0＜supplementary structure phase≤30%.
2. according to the described high-capacity hydrogen-storage material with NaAlH 4 of claim 1, it is characterized in that: M=Li, K or Rb; N=Mg, Ca or Sr.
3. according to the described high-capacity hydrogen-storage material with NaAlH 4 of claim 1, it is characterized in that: count in molar ratio,
4. according to the described high-capacity hydrogen-storage material with NaAlH 4 of claim 1, it is characterized in that: by the mole percentage composition, matrix material is 90～96%; Catalyst is 2～5%; Supplementary structure is 2～5% mutually.
5. according to the preparation method of one of claim 1-4 described high-capacity hydrogen-storage material with NaAlH 4, it is characterized in that: in matrix material, add catalyst simultaneously and carry out composite mixed mutually with supplementary structure; Matrix material, catalyst and supplementary structure are mixed mutually ball milling under inert protective atmosphere or reactive hydrogen atmosphere in described ratio; Ratio of grinding media to material was greater than 5: 1; The ball milling time was greater than 0.5 hour.
6. according to the preparation method of the described high-capacity hydrogen-storage material with NaAlH 4 of claim 5, it is characterized in that: during ball milling, initial pressure is 1～20 atmospheric pressure under reactive hydrogen atmosphere.
7. according to the preparation method of the described high-capacity hydrogen-storage material with NaAlH 4 of claim 5, it is characterized in that: described ratio of grinding media to material is (greater than 5 to smaller or equal to 100): 1; The described ball milling time is to smaller or equal to 100 hours greater than 0.5.
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| CN102127670B (en) * | 2011-02-15 | 2013-06-12 | 白朴存 | Na-Al composite material and preparation method thereof |
| CN102992263A (en) * | 2011-09-15 | 2013-03-27 | 中国科学院大连化学物理研究所 | Al-Bi-NaCl-alkali metal or hydride hydrolysis hydrogen production composite materials and preparation thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1318033A (en) * | 1998-08-06 | 2001-10-17 | 夏威夷大学 | Novel hydrogen storage materials and method of making by dry homogenation |
| WO2004000726A1 (en) * | 2002-06-19 | 2003-12-31 | Sony Corporation | Hydrogen occluding material and method for use thereof |
| US6680042B1 (en) * | 2000-11-07 | 2004-01-20 | Hydro-Quebec | Method of rapidly carrying out a hydrogenation of a hydrogen storage material |
| CN1546366A (en) * | 2003-12-04 | 2004-11-17 | 复旦大学 | Aluminum-containing nano complex hydrogen storage material and its preparation method |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1318033A (en) * | 1998-08-06 | 2001-10-17 | 夏威夷大学 | Novel hydrogen storage materials and method of making by dry homogenation |
| US6680042B1 (en) * | 2000-11-07 | 2004-01-20 | Hydro-Quebec | Method of rapidly carrying out a hydrogenation of a hydrogen storage material |
| WO2004000726A1 (en) * | 2002-06-19 | 2003-12-31 | Sony Corporation | Hydrogen occluding material and method for use thereof |
| CN1546366A (en) * | 2003-12-04 | 2004-11-17 | 复旦大学 | Aluminum-containing nano complex hydrogen storage material and its preparation method |
Non-Patent Citations (1)
| Title |
|---|
| 一种氢燃料电池汽车用新型储氢材料--NaAlH4的研究进展. 罗艳，周康根等.材料与冶金学报，第4卷第1期. 2005 * |
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