CN104445069A - Ferrite catalyst modified NaAlH4 (sodium aluminium hydride) hydrogen storage material - Google Patents

Ferrite catalyst modified NaAlH4 (sodium aluminium hydride) hydrogen storage material Download PDF

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Publication number
CN104445069A
CN104445069A CN201410697133.9A CN201410697133A CN104445069A CN 104445069 A CN104445069 A CN 104445069A CN 201410697133 A CN201410697133 A CN 201410697133A CN 104445069 A CN104445069 A CN 104445069A
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China
Prior art keywords
naalh
storage material
hydrogen storage
ferrite
hydrogen
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CN201410697133.9A
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Chinese (zh)
Inventor
徐丽
陈新
马光
李平
盛鹏
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State Grid Corp of China SGCC
University of Science and Technology Beijing USTB
Smart Grid Research Institute of SGCC
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State Grid Corp of China SGCC
University of Science and Technology Beijing USTB
Smart Grid Research Institute of SGCC
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Priority to CN201410697133.9A priority Critical patent/CN104445069A/en
Publication of CN104445069A publication Critical patent/CN104445069A/en
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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
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

The invention provides a ferrite catalyst modified NaAlH4 (sodium aluminium hydride) hydrogen storage material. Light-weight hydride NaAlH4 of which the purity is not less than 90% is selected as the hydrogen storage material, one or more of nanometer nickel ferrite, nanometer manganese ferrite, nanometer cobalt ferrite, nanometer manganese-zinc ferrite and nanometer nickel-cobalt ferrite are selected as a catalyst, and the proportion of the catalyst is 1-10mol%. The modified hydrogen storage material is obtained through high-energy ball milling treatment of the mixture of the catalyst and NaAlH4, a ball milling pot with a PV (polyvinyl) inner lining is used for ball milling zirconium oxide, the ratio of balls to materials is 15:1, and argon gas of which the purity is not less than 99.5% is used as a protective gas in the ball milling process; each time the ball milling is performed for 10 minutes, the ball milling is suspended for 5 minutes, and after the ball milling is performed for 30-300 minutes, the required high-performance hydrogen storage material can be obtained. The thermodynamics performance, the dynamics performance and the reversibility of the ferrite catalyst modified NaAlH4 hydrogen storage material provided by the invention are totally and obviously improved.

Description

The NaAlH of ferrite catalyst modification 4hydrogen storage material
Technical field
The present invention relates to a kind of hydrogen storage material and preparation method thereof, specifically relate to a kind of hydrogen storage material of ferrite catalyst modification.
Background technology
Hydrogen storage material, as a kind of energy functional materials, plays very important effect in hydrogen utilization.High power capacity storage hydrogen material is one of critical material of hydrogen cell automobile application.The hydrogen storage material system of heavy body has three major types: magnesium-base hydrogen storage material, carbon nanotube and coordinate hydride hydrogen-storing material, and wherein complex hydrides is owing to having higher hydrogen-storage amount, and receives the concern of numerous investigators.In numerous coordinate hydride hydrogen-storing material, NaAlH 4one of the material closest to practical application, first NaAlH 4scale operation feasible, secondly NaAlH 4application in hydrogen container has obtained comparatively systematic research.But due to NaAlH 4decompose and in repeated hydrogenation process along with the destruction of lattice and chemical bond and reconstruct, cause the energy that its de-hydrogenation process needs are larger, pure NaAlH 4just slow desorption is started 220 DEG C time, and NaAlH 4there is dynamic behavior comparatively slow, the shortcoming that reversible hydrogenation reaction is poor.For the problems referred to above, investigator successively have employed the multiple methods such as catalysis doping, hydride reaction unstability, nanometer respectively, improves, and serve certain effect to its hydrogen storage property.
Doped catalyst makes NaAlH 4kinetics and thermomechanical property significantly improve, mainly being interacted by complex hydrides and catalyst surface forms active intermediate, thus changes the activation energy of reaction process, and then improves its hydrogen storage property.Katalysis is widely studied, and mainly comprises the kind of catalyzer, quantity, granularity, pattern, contact dispersion situation and doping process, and the interaction etc. when two kinds of different catalyzer adulterate simultaneously.Research shows that containing Ti catalyzer and halide catalyst be current comparatively effective two kinds of catalyzer, and they not only can improve NaAlH 4reversible hydrogen adsorption and desorption performance, but also can accelerate inhale hydrogen desorption kinetics speed and reduce temperature of reaction, but it is large to there is weight in this two classes catalyzer, easy and body material generation untoward reaction in mechanical milling process, thus reduction is put hydrogen capacity and is caused working cycle decay to increase.Therefore, need to provide a kind of new catalyst to improve the performance of hydrogen storage material.
Summary of the invention
The object of this invention is to provide a kind of NaAlH of catalyst modification 4hydrogen storage material, realizes hydrogen storage material thermodynamics, dynamic performance and reversible obvious improvement.
For achieving the above object, the present invention takes following technical scheme:
Hydrogen storage material provided by the invention be with by high-energy ball milling process by ferrite catalyst and lightweight hydride NaAlH 4obtain, wherein catalyst ratio is 0.5-15mol%.
Described modification NaAlH provided by the invention 4in first optimal technical scheme of hydrogen storage material, ferrite catalyst is one or more in nano level Ni ferrite, Mn ferrite, vectolite, Mn-Zn ferrite and Ni-Co ferrite.
Described modification NaAlH provided by the invention 4in second optimal technical scheme of hydrogen storage material, NaAlH used 4purity be more than or equal to 90%.
Described modification NaAlH provided by the invention 4in 3rd optimal technical scheme of hydrogen storage material, catalyst ratio is 1-10mol%.
Described modification NaAlH provided by the invention 4the ball-milling processing of hydrogen storage material, carries out under the argon atmospher of purity>=99.5%.
Described modification NaAlH provided by the invention 4the ball-milling processing of hydrogen storage material, ball milling adopts the ball grinder of PV liner and the abrading-ball of zirconium white material.
Described modification NaAlH provided by the invention 4the ball-milling processing of hydrogen storage material, ratio of grinding media to material is 15:1.
Described modification NaAlH provided by the invention 4the ball-milling processing of hydrogen storage material, every ball milling 10min, suspend 5min, Ball-milling Time is 30-300min.
Compared with prior art, beneficial effect of the present invention:
The NaAlH of ferrite catalyst modification provided by the invention 4hydrogen storage material, its temperature of initial decomposition can reduce by more than 50%, and dynamic performance is significantly improved, and has good reversibility.
Constant temperature Hydrogen desorption isotherms shows to add NiFe 2o 4significantly can improve NaAlH 4hydrogen desorption kinetics performance.
Accompanying drawing illustrates:
Fig. 1 is (a) original NaAlH in embodiment 1 4, the NaAlH after (b) ball milling 4, and add (c) 1mol%, (d) 2mol%, (e) 3mol% and (f) 5mol%NiFe 2o 4nanometer particle-modified NaAlH 4heat decomposition curve.
Fig. 2 is (a) original NaAlH in embodiment 1 4, the NaAlH after (b) ball milling 4, and add (d) 3mol%NiFe 2o 4nanometer particle-modified NaAlH 4(hereinafter abbreviated as NaAlH 4+ 3mol%NiFe 2o 4) 150 DEG C of constant temperature Hydrogen desorption isotherms, and (c) is NaAlH 4+ 3mol%NiFe 2o 4120 DEG C of constant temperature Hydrogen desorption isotherms.
Fig. 3 is NaAlH in embodiment 1 4+ 3mol%NiFe 2o 4the suction hydrogen curve of first three time, is labeled as (a) for the first time respectively, and (b) second time and (c) are for the third time.
Fig. 4 is NaAlH in embodiment 1 4+ 3mol%NiFe 2o 4the Hydrogen desorption isotherms of first three time, is labeled as (a) for the first time respectively, and (b) second time and (c) are for the third time.
Fig. 5 is (a) original NaAlH in embodiment 2 4, the NaAlH after (b) ball milling 4, and add (c) 3mol%, (d) 5mol%, (e) 7mol% and (f) 9mol%MnFe 2o 4nanometer particle-modified NaAlH 4heat decomposition curve.
Fig. 6 is (a) original NaAlH in embodiment 2 4, the NaAlH after (b) ball milling 4, and add (d) 7mol%MnFe 2o 4nanometer particle-modified NaAlH 4(hereinafter abbreviated as NaAlH 4+ 7mol%NiFe 2o 4) 150 DEG C of constant temperature Hydrogen desorption isotherms, and (c) is NaAlH 4+ 7mol%MnFe 2o 4120 DEG C of constant temperature Hydrogen desorption isotherms.
Fig. 7 is NaAlH in embodiment 2 4+ 7mol%MnFe 2o 4the suction hydrogen curve of first three time, is labeled as (a) for the first time respectively, and (b) second time and (c) are for the third time.
Fig. 8 is NaAlH in embodiment 2 4+ 7mol%MnFe 2o 4the Hydrogen desorption isotherms of first three time, is labeled as (a) for the first time respectively, and (b) second time and (c) are for the third time.
Embodiment
Embodiment 1
Select the lightweight hydride NaAlH that purity is greater than 93% 4, nano level Ni ferrite selected by catalyzer, and purity is more than or equal to 99.99%, about average particle 20nm.Catalyst ratio is 1,2,3,5mol%.Adopt the ball grinder of PV liner, abrading-ball is zirconium white material, and ratio of grinding media to material is 15:1.Argon gas is filled with as shielding gas in mechanical milling process.In order to prevent the too high hydride that causes of heat produced in mechanical milling process from decomposing in mechanical milling process, every ball milling 10min, suspends 5min.Required high-performance hydrogen storage material can be obtained by high-energy ball milling 30min.
Heat decomposition curve shows (as shown in Figure 1): add NiFe 2o 4after nanocatalyst, NaAlH 4hydrogen discharging performance obtain obvious improvement, the initial hydrogen discharging temperature of sample has had and has very significantly declined, and not only the initial hydrogen discharging temperature in the first and second stages significantly declines, and the initial hydrogen discharging temperature of phase III there has also been remarkable reduction.As NaAlH 4+ 3mol%NiFe 2o 4the initial hydrogen discharging temperature of sample is 93 DEG C; Pure NaAlH 4the initial hydrogen discharging temperature of sample is 179 DEG C.
Constant temperature Hydrogen desorption isotherms shows (as shown in Figure 2): NaAlH 4+ 3mol%NiFe 2o 4sample is 150 DEG C time, and in 180min, its hydrogen desorption capacity is 4.79wt%; But, under the same conditions, pure NaAlH 4hydrogen desorption capacity only has 0.05wt%.Add NiFe 2o 4significantly can improve NaAlH 4hydrogen desorption kinetics performance.
Inhale Hydrogen desorption isotherms to show (as shown in Figure 3, Figure 4): NaAlH 4+ 3mol%NiFe 2o 4at 150 DEG C, under 5MPa hydrogen pressure, the hydrogen－sucking amount of first three time in 180min and hydrogen desorption capacity, hydrogen－sucking amount drops to 4.20wt% from 4.29wt%, and hydrogen desorption capacity drops to 3.76wt% from 3.90wt%; But, pure NaAlH 4again can not inhale hydrogen under the same conditions.
Embodiment 2
NaAlH 4purity is greater than or equal to 93%, and nano level MnFe selected by catalyzer 2o 4, purity is greater than or equal to 99.9%, and mean particle size is about 15nm.NaAlH 4with the MnFe of different mol ratio (3mol%, 5mol%, 7mol%, 9mol%) 2o 4nanoparticle mixes, then ball milling 30min on high energy ball mill.All samples all load in the glove box being filled with high-purity argon gas, adopt the ball grinder of PV liner, ZrO 2abrading-ball, ratio of grinding media to material is 15:1.
Heat decomposition curve shows (as shown in Figure 5): add MnFe 2o 4after nanocatalyst, NaAlH 4hydrogen discharging performance obtain obvious improvement, the initial hydrogen discharging temperature of the three phases of sample has had remarkable reduction.MnFe 2o 4the NaAlH of catalyst modification 4initial hydrogen discharging temperature all lower than 130 DEG C.With pure NaAlH 4contrast, adds 3mol% and 5mol%MnFe 2o 4naAlH 4the initial hydrogen discharging temperature of sample first stage have dropped 54 DEG C and 64 DEG C respectively, and the initial hydrogen discharging temperature of subordinate phase reduces 60 DEG C and 75 DEG C respectively, and the initial hydrogen discharging temperature of phase III reduces 44 DEG C and 56 DEG C respectively.
Constant temperature Hydrogen desorption isotherms shows (as shown in Figure 6): NaAlH 4+ 7mol%MnFe 2o 4sample, at 120 DEG C, releases 4.43wt% hydrogen in 180min.When hydrogen discharging temperature is elevated to 150 DEG C, in same time, the hydrogen desorption capacity of sample reaches 4.67wt%.At 150 DEG C, add MnFe 2o 4sample in 10min, just can release 3.11wt% hydrogen, this illustrates MnFe 2o 4nanoparticle significantly can improve NaAlH 4hydrogen desorption kinetics performance, but, under the same conditions, pure NaAlH 4hydrogen desorption capacity is only 0.05wt%.
Inhale hydrogen graphic representation 7 to show, at 150 DEG C, under 5MPa hydrogen pressure, in 180min, hydrogen curve is inhaled in first three time, along with the increase of cycle index, and NaAlH 4+ 7mol%MnFe 2o 4sample hydrogen－sucking amount only drops to 3.81wt% from 3.90wt%.Hydrogen desorption isotherms Fig. 8 shows, NaAlH 4+ 7mol%MnFe 2o 4it is fine that sample hydrogen desorption capacity also keeps, and after three circulations, hydrogen desorption capacity only drops to 3.64wt% from 3.76wt%.Therefore, MnFe is added 2o 4nanoparticle is to NaAlH 4in, can NaAlH be made 4keep good hydrogen storage property.But, pure NaAlH 4again can not inhale hydrogen under the same conditions.
Above embodiment is only in order to illustrate that technical scheme of the present invention is not intended to limit; those of ordinary skill in the field are to be understood that; can modify to the specific embodiment of the present invention with reference to above-described embodiment or equivalent to replace, these do not depart from any amendment of spirit and scope of the invention or equivalently to replace within the claims that all awaits the reply in application.

Claims (8)

1. a modification NaAlH 4hydrogen storage material, is characterized in that, this hydrogen storage material is by ferrite catalyst and lightweight hydride NaAlH by ball-milling processing 4obtain, the ratio wherein shared by catalyzer is 0.5-15mol%.
2. modification NaAlH according to claim 1 4hydrogen storage material, is characterized in that, described ferrite catalyst is one or more materials selected from one group of material of nano level Ni ferrite, Mn ferrite, vectolite, Mn-Zn ferrite and Ni-Co ferrite composition.
3. modification NaAlH according to claim 1 4hydrogen storage material, is characterized in that, NaAlH used 4purity be more than or equal to 90%.
4. modification NaAlH according to claim 1 4hydrogen storage material, is characterized in that, the ratio shared by described catalyzer is 1-10mol%.
5. modification NaAlH according to claim 1 4hydrogen storage material, is characterized in that, described ball-milling processing is carried out under the argon atmospher of purity>=99.5%.
6. modification NaAlH according to claim 1 4hydrogen storage material, is characterized in that, described ball milling adopts the ball grinder of PV liner and the abrading-ball of zirconium white material.
7. modification NaAlH according to claim 1 4hydrogen storage material, is characterized in that, ball heavy burder during ball milling is than being 15:1.
8. modification NaAlH according to claim 1 4hydrogen storage material, is characterized in that, ball-milling processing is pressed 10min/ time, suspends 5min, and Ball-milling Time is 30-300min altogether.
CN201410697133.9A 2014-11-26 2014-11-26 Ferrite catalyst modified NaAlH4 (sodium aluminium hydride) hydrogen storage material Pending CN104445069A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105329852A (en) * 2015-11-27 2016-02-17 国网智能电网研究院 Nano doping agent modified LiBH4 hydrogen storage material and preparation method thereof
CN108439331A (en) * 2018-05-28 2018-08-24 桂林电子科技大学 A kind of preparation method and application of the sodium aluminum hydride hydrogen storage material of metatitanic acid additive Mn

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US20030165423A1 (en) * 2002-01-29 2003-09-04 Gross Karl J. Direct synthesis of hydride compounds using a titanium aluminate dopant
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CN101602485A (en) * 2008-06-10 2009-12-16 北京有色金属研究总院 The NaAlH of Ce hydride catalytic 4Composite hydrogen storage material and preparation method

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US20030165423A1 (en) * 2002-01-29 2003-09-04 Gross Karl J. Direct synthesis of hydride compounds using a titanium aluminate dopant
CN101052587A (en) * 2004-09-27 2007-10-10 Utc电力公司 Metal alanates doped with oxygen
CN101602485A (en) * 2008-06-10 2009-12-16 北京有色金属研究总院 The NaAlH of Ce hydride catalytic 4Composite hydrogen storage material and preparation method

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105329852A (en) * 2015-11-27 2016-02-17 国网智能电网研究院 Nano doping agent modified LiBH4 hydrogen storage material and preparation method thereof
CN108439331A (en) * 2018-05-28 2018-08-24 桂林电子科技大学 A kind of preparation method and application of the sodium aluminum hydride hydrogen storage material of metatitanic acid additive Mn
CN108439331B (en) * 2018-05-28 2021-09-24 桂林电子科技大学 Preparation method and application of manganese titanate doped sodium aluminum hydride hydrogen storage material

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Application publication date: 20150325