CN1259584A - Hydrogen storage alloy/carbon nanometer tube composite hydrogen storage material - Google Patents

Hydrogen storage alloy/carbon nanometer tube composite hydrogen storage material Download PDF

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CN1259584A
CN1259584A CN00100505A CN00100505A CN1259584A CN 1259584 A CN1259584 A CN 1259584A CN 00100505 A CN00100505 A CN 00100505A CN 00100505 A CN00100505 A CN 00100505A CN 1259584 A CN1259584 A CN 1259584A
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hydrogen storage
alloy
type
storage alloy
carbon nanotube
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CN1100154C (en
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高学平
秦学
吴锋
叶世海
刘宏
袁华堂
宋德瑛
申泮文
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Nankai University
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Priority to PCT/CN2000/000484 priority patent/WO2001053550A1/en
Priority to AU2001215126A priority patent/AU2001215126A1/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
    • C01B3/0021—Carbon, e.g. active carbon, carbon nanotubes, fullerenes; Treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
    • C01B3/0031—Intermetallic compounds; Metal alloys; Treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
    • C01B3/0031—Intermetallic compounds; Metal alloys; Treatment thereof
    • C01B3/0047—Intermetallic compounds; Metal alloys; Treatment thereof containing a rare earth metal; Treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
    • C01B3/0078—Composite solid storage mediums, i.e. coherent or loose mixtures of different solid constituents, chemically or structurally heterogeneous solid masses, coated solids or solids having a chemically modified surface region
    • 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 present invention relates to composite hydrogen storage material especially the mfg. of hydrogen storage alloy/carbon nanometer pipe composite hydrogen storage material, it includes hydrogen storage alloy and carbon nanometer pipe, in which the content of hydrogen storage alloy is 1-90 wt.%, it is mfg. by using catalytic cracking or mechanical recombination method; said hydrogen storage alloy is rare earth nickel series AB2 type, zirconium base or titanium base or rare earth nickel base laves phase series AB2 type, titanium nickel series or titanium iron series AB type, Magnesium base alloy A2B type or amorphous alloy of any one or more than two binary or multielement hydrogen storage alloy. The invented composite hydrogen storage material is stable in performance.

Description

Hydrogen storage alloy/carbon nanometer tube composite hydrogen storage material
The present invention relates to composite hydrogen storage material, particularly the manufacturing of hydrogen storage alloy/carbon nanometer tube composite hydrogen storage material.
The hydrogen storage alloy of reversible hydrogen adsorption and desorption is since twentieth century discovery at the end of the sixties under mild conditions, and people have carried out continuous research and development, and the hydrogen-adsorped alloy electrode material that is used in particular for nickel metal hydride battery has been realized industrialization.Hydrogen storage alloy generally is divided into four classes: (the AB of rare earth nickel system 5Type), titanium nickel and ferrotianium system (AB type), Magnuminium (A 2Type B) be (AB with the zirconium base mutually with titanium base Laves 2Type).Under certain condition (as temperature and pressure), hydrogen contacts hydrogen molecule (H with the hydrogen storage alloy surface 2) be adsorbed to alloy surface and catalysis and be dissociated into hydrogen atom (H) and enter into the alloy lattice gap and store, when changing ambient conditions (as temperature or/and pressure), hydrogen atom is diffused into alloy surface and is combined into hydrogen molecule and discharges from the alloy lattice gap.The theoretical hydrogen storage capability of all kinds of hydrogen storage alloys is respectively: AB 5Alloy is (with LaNi 5H 6Be example) be about 1.4wt%, AB alloy (with TiFeH 1.9Be example) be 1.8wt%, A 2The B alloy is (with Mg 2Ni is an example) be 3.6wt%, AB 2Alloy is (with ZrV 2H 4.5Be example) be 2.0wt%.The hydrogen storage alloy preparation method can be by Metal Melting method, powder metallurgic method, mechanize alloyage, chemical reduction diffusion process and codeposition chemical reduction diffusion process etc.
Hydrogen Storage in Carbon Nanotubes is studied nearest 2 years just report (Dillon A.C., et al., Nature, 386 (1997) 377; ChenP., et al., Science, 285 (1999) 91; Liu C., et al., Science, 286 (1999) 1127).Hydrogen molecule (H 2) enter into carbon nanotube under certain condition and store, because of the condition difference, the hydrogen storage capability of report is difference to some extent, from 4wt% to 20wt%.But there is following shortcoming in hydrogen Storage in Carbon Nanotubes, promptly inhales hydrogen pressure height (greater than 12MPa), dehydrogenation difficulty and lacks the platform features etc. of Chu Qing.Best result inhales hydrogen down for the 12MPa hydrogen pressure and reaches 4.3wt%, can only discharge 2/3 of hydrogen under mild conditions, i.e. 3wt%.The preparation of carbon nanotube mainly contains three kinds of methods: arc discharge method, chemical Vapor deposition process and pulse laser method of evaporation, catalyzer are metals such as Co, Ni, Fe and Y and composition thereof.
Purpose of the present invention aims to provide a kind of composite hydrogen storage material and preparation method; it is the hydrogen storage alloy/carbon nanometer tube composite hydrogen storage material in conjunction with two class hydrogen storage material advantages (the high hydrogen storage capability of hydrogen storage alloy high catalytic activity and carbon nanotube); can overcome the deficiencies in the prior art, the composite hydrogen storage material of this hydrogen storage alloy/carbon nanotube can be applicable to the purification of hydrogen source, nickel metal hydride battery, hydrogen of mass-producing accumulating, the fuel cell of hydrogen and organic hydrogenation catalyst etc.
Hydrogen storage alloy/carbon nanometer tube composite hydrogen storage material of the present invention comprises hydrogen storage alloy and carbon nanotube, and wherein the weight content scope of hydrogen storage alloy is 1～90%.
Hydrogen storage alloy of the present invention is that rare earth nickel is AB 5Type, zirconium base or titanium base or rare-earth Ni-base Laves are AB mutually 2Type, nickel titante series or ferrotianium are AB type, Magnuminium A 2Any one or two kinds of above binary or the polynary hydrogen storage alloys of Type B or non-crystaline amorphous metal; Hydrogen storage alloy middle-weight rare earths nickel is AB 5The type alloy composition is LNi N-x-y-zCo xN yM z, L is norium, La, Ce, Nd, Pr, Y, N and M are respectively Mn, V, Cr, Al, Fe, Cu, Zn, Sn, 4≤n≤6,0≤x≤2,0≤y≤2,0≤z≤2; Zirconium base or titanium base or rare-earth Ni-base Laves are AB mutually 2The type alloy composition is KNi A-b-c-dV bG cJ d, K is Zr, Ti, Hf, norium, La, Ce, Nd, Pr, Y, G and J are respectively Co, Mn, Cr, Al, Fe, Cu, Zn, Sn, 1.2≤a≤2.8,0≤b≤2,0≤c≤2,0≤d≤2; Nickel titante series or ferrotianium are that AB type alloy composition is HNi M-k-jFe kP j, H is Zr, Hf, P is Co, Mn, V, Cr, Al, Cu, Zn, Sn, 0.6≤m≤1.5,0≤k≤1.5,0≤j≤1: Magnuminium A 2The Type B alloy composition is Mg G-fE fNi L-p-qCo pT q, E is Ca, Zr, Ti, Hf, norium, La, Ce, Nd, Pr, Y, T is Mn, V, Cr, Al, Fe, Cu, Zn, Sn, 0.8≤g≤2.5,0≤f≤1,0≤p≤0.6,0≤q≤0.6;
Carbon nanotube of the present invention is single-walled nanotube or many walls nanotube, and the carbon nanotube external diameter is 0.5-150nm.
The preparation method of hydrogen storage alloy/carbon nanometer tube composite hydrogen storage material provided by the invention has following several:
1) hydrogen storage alloy is a catalyzer, and hydrocarbon polymer (or CO) cracking prepares the composite hydrogen storage material of hydrogen storage alloy/carbon nanotube.
As the optional rare earth nickel (AB of system of the hydrogen storage alloy of catalyzer 5Type), zirconium base or titanium base Laves are (AB mutually 2Type), nickel titante series and ferrotianium system (AB type), Magnuminium (A 2Type B) and any (or two or more) binary or the polynary hydrogen storage alloy of non-crystaline amorphous metal.Hydrogen storage alloy granularity＜70 μ m.Hydrogen storage alloy through surface treatment (as alkaline solution or fluoridize solution) can obtain nano level catalytic site, and reactant gases is CH 4, C 2H 2, C 2H 4, C 6H 6Or CO.
The composite hydrogen storage material preparation of hydrogen storage alloy/carbon nanotube is carried out on fixed bed gas continuous flowing type reaction unit.A certain amount of catalyzer is warming up to 523K～1073K under hydrogen stream, keeps after 10～70 minutes temperature adjustment, change reactant gases into, flow velocity 2～40ml/cm to 673K～1273K 2Min reacts and stops heating and cooling after 10～70 minutes, collects product.Through SEM (scanning electron microscope) or XRD (X-diffraction) and TEM (transmission electron microscope, sample is through ultrasonication) analytical test, product is the composite hydrogen storage material of hydrogen storage alloy/carbon nanotube.
2) any or metal mixture of metals such as Ni, Co, Fe, Cu is catalyzer, hydrocarbon polymer (or CO) cracking prepares carbon nanotube, becomes hydrogen storage alloy to obtain the composite hydrogen storage material of hydrogen storage alloy/carbon nanotube with prepared in reaction such as magnesium, titanium, zirconium rare earth metal or noriums catalyst metal again.
(A) with any metal oxide among a certain amount of catalyst precursor NiO, CoO, FeO, the CuO etc. or the mixture of several metal oxides, be placed in the fixed bed gas continuous flowing type reaction unit, under hydrogen stream, be warming up to 523K～1073K, keep after 0.5～5 hour temperature adjustment to 673K～1273K, change reactant gases into, flow velocity 2～40ml/cm 2Min, react stop after 10～70 minutes the heating and the cooling, reactant gases is CH 4, C 2H 2, C 2H 4, C 6H 6Deng or CO.With making the mixture of carbon nanotube and catalyst metal and the Mg powder or the Ti powder thorough mixing of metering, put into voltage-resistant reactor, under the Ar of 0.2～0.8MPa atmosphere, 723K～1273K constant temperature spread 1～6 hour, made catalyst metal form Mg 2Ni or Mg 2Cu or TiNi, Ti 2Hydrogen storage alloy such as Ni or TiFe or hydrogen storage alloy mixture, thereby the composite hydrogen occluding alloy material of acquisition hydrogen storage alloy/carbon nanotube.Through SEM, XRD and TEM (transmission electron microscope, sample is through ultrasonication) analytical test turns out to be hydrogen storage alloy/carbon nanotube composite hydrogen occluding alloy material.
(B) be equipped with the presoma La of hydrogen storage alloy with the co-precipitation reduction legal system 2O 310NiO, Mm 2O 310NiO, TiO 2NiO, TiO 20.5NiO and TiO 2Fe 2O 3Be preparation carbon nano-tube catalyst presoma Deng complex metal oxides.Carry out with (A) described step, obtain carbon nanotube and catalyst metal Ni, Co or Fe and La 2O 3Or Mm 2O 3Or TiO 2Mixture.CaH with this mixture and metering 2Or the Ca thorough mixing, in argon gas stream, be warming up to 973K～1273K, be incubated 1～5 hour, be cooled to room temperature, neutrality is washed-be washed to products therefrom through washing-1% acetic acid, and vacuum-drying obtains hydrogen storage alloy/carbon nano tube compound material.Through SEM, XRD and TEM (transmission electron microscope, sample is through ultrasonication) analytical test turns out to be hydrogen storage alloy/carbon nano tube compound material.
3) composite hydrogen storage material of hydrogen storage alloy and the compound preparation hydrogen storage alloy/carbon nanotube of carbon nanotube direct mechanical.
The optional rare earth nickel (AB of system of hydrogen storage alloy 5Type), zirconium base or titanium base Laves are (AB mutually 2Type), nickel titante series and ferrotianium system (AB type), Magnuminium (A 2Type B) and any (or two or more) binary or the polynary hydrogen storage alloy of non-crystaline amorphous metal.Hydrogen storage alloy granularity＜70 μ m.Mechanical ball milling is compound down under vacuum or argon gas atmosphere or in treatment soln (comprise alkaline solution and fluoridize solution etc.) with carbon nanotube behind the hydrogen storage alloy of surface treatment (as alkaline solution or fluoridize solution).Concentrated alkali solution comprises the aqueous solution of KOH or NaOH, and strength of solution is 0.5-8mol.L -1, containing hydroborate (K or Na) in the solution, the concentration of hydroborate (K or Na) is 0.0-2mol.L -1Fluoridize solution and comprise and contain fluorine anion and other negatively charged ion, other negatively charged ion is chlorion, sulfate ion, nitrate ion, and positively charged ion is H +, K +, Na +, NH 4 +, Ni 2+, Co 2+, Fe 2+Ion.Fluorine anion concentration is 0.01-2mol.L -1, other anion concentration is 0.0-1mol.L -1, cation concn is 0.01-2mol.L -1The mechanical ball milling time is controlled between 10 minutes to 3 hours.It is catalyzer that made of carbon nanotubes adopts Ni, Co, metals such as Fe, Cu any or metal mixture, the hydrocarbon polymer cracking, and reactant gases is CH 4, C 2H 2, C 2H 4, C 6H 6Deng.Through SEM or XRD and TEM (transmission electron microscope, sample is through ultrasonication) analytical test, product is the composite hydrogen storage material of hydrogen storage alloy/carbon nanotube.
The present invention provides a kind of novel high-capacity composite hydrogen storage material in conjunction with two class hydrogen storage material advantages (the high hydrogen storage capability of hydrogen storage alloy high catalytic activity and carbon nanotube), and its stable performance is widely used.
The invention will be further described below by example:
Embodiment 1
LaNi with the high frequency furnace smelting 4.5Fe 0.5Be crushed to 10 μ m-20 μ m, at 6mol.l -1Handle after 30 minutes under the room temperature in the KOH solution, vacuum-drying promptly gets prepared alloy catalyst sample.The preparation of hydrogen storage alloy/carbon nanometer tube composite hydrogen storage material is to carry out on fixed bed gas continuous flow reaction formula device.The 1g alloy catalyst is warming up to 873K under hydrogen atmosphere, stablize 20 minutes after, feed flow velocity 10ml/cm 2.min methane reacts and stops after 60 minutes, at H 2Be cooled to room temperature under the atmosphere, collect product, carbon nanotube output is 0.2g.Measure its gas-solid hydrogen storage property in standard Sievert ' s reaction unit, its hydrogen storage capability is 2.5wt%
Embodiment 2
With 2mol.l -1NiCl 2And 2mol.l -1LaCl 3The aqueous solution mixed in 5: 1 by volume, slowly added 1.5mol.l under constantly stirring -1Na 2CO 3Solution generates precipitation.Adopt second distillation water washing to water layer not have chlorion repeatedly, after the filtration, in baking oven, under 373K, dry, promptly get prepared catalyst precursor sample.The preparation of carbon nanotube is carried out on fixed bed gas continuous flow reaction formula device.The 5g catalyzer is warming up to 923K under hydrogen atmosphere, stablize 30 minutes after, feed flow velocity 20ml/cm 2The methane of min reacts and stops after 30 minutes, collects product, with this product and CaH 2By mass ratio is to mix at 1: 1.1 to put into fixed bed gas continuous flow reaction formula device and react, and is warming up to 1223K under hydrogen atmosphere, constant temperature 4 hours.Cooled product is collected product to room temperature rapidly.This product is washed with distilled water to neutrality, and vacuum-drying obtains product, and hydrogen storage alloy and carbon nanotube weight ratio are 2/1.Measure its gas-solid hydrogen storage property in standard Sievert ' s reaction unit, its hydrogen storage capability is 4.5wt%
Embodiment 3
ZrV with electric arc furnace smelting 0.2Mn 0.6Co 0.1Ni 1.2Be crushed to 10 μ m-20 μ m, 0.5mol.l under 343K then -1NiF 2/ NH 4Handle in the F solution and promptly got prepared alloy catalyst sample in 0.5 hour.The preparation of hydrogen storage alloy/carbon nanometer tube composite hydrogen storage material is carried out on fixed bed gas continuous flow reaction formula device.The 1g catalyzer is warming up to 873K under hydrogen atmosphere, stablize 10 minutes after, feed flow velocity 15ml/cm 2.min methane reacts and stops after 60 minutes, at H 2Be cooled to room temperature under the atmosphere, collect product, carbon nanotube output is 0.4g.Measure its gas-solid hydrogen storage property in standard Sievert ' s reaction unit, its hydrogen storage capability is 3.8wt%
Real in example 4
TiFe with the electric arc furnace smelting preparation 0.9Ni 0.1Alloy powder is broken to 50 μ m-70 μ m, then at 0.5mol.l -1NiF 2/ NH 4Ball milling in the F solution (planetary ball mill) promptly got prepared superfine alloy catalyst samples in 70 hours.The preparation of hydrogen storage alloy/carbon nanometer tube composite hydrogen storage material is carried out on fixed bed gas continuous flow reaction motion device.The 1g catalyzer is warming up to 973K under hydrogen atmosphere, stablize 10 minutes after, feed flow velocity 25ml/cm 2.min methane reacts and stops after 60 minutes, at H 2Be cooled to room temperature under the atmosphere, collect product, carbon nanotube output is 0.3g.Measure its gas-solid hydrogen storage property in standard Sievert ' s reaction unit, its hydrogen storage capability is 3.1wt%
Embodiment 5
With Mg 2The Ni alloy powder is broken to 50 μ m-70 μ m, and ball milling promptly got prepared amorphous alloy catalyst sample in 70 hours under the argon gas atmosphere condition then.The preparation of the composite hydrogen storage material of hydrogen storage alloy/carbon nanotube is carried out on fixed bed gas continuous flow reaction formula device.The 1g catalyzer is warming up to 823K under hydrogen atmosphere, feeds flow velocity 30ml/cm 2.min acetylene reacts and stops after 60 minutes, at H 2Be cooled to room temperature under the atmosphere, collect product, carbon nanotube output is 0.6g.Measure its gas-solid hydrogen storage property in standard Sievert ' s reaction unit, its hydrogen storage capability is 5.2wt%.
Embodiment 6
With ZrV 0.2Mn 0.6Ni 1.2Alloy powder is broken to 50 μ m-70 μ m, then at 0.5mol.l -1NiF 2/ NH 4Ball milling promptly got prepared superfine alloy sample in 40 hours in the F solution, added the carbon nanotube that caliber is 5-20nm again, and the weight ratio of hydrogen storage alloy and carbon nanotube is 1/2, and the ball milling time is 30 minutes, product washing final vacuum drying.Product is measured its gas-solid hydrogen storage property in standard Sievert ' s reaction unit, its hydrogen storage capability is 3.4wt%.

Claims (7)

1, a kind of composite hydrogen storage material is characterized in that it comprises hydrogen storage alloy and carbon nanotube composition, and wherein the weight content scope of hydrogen storage alloy is 1～90%.
2, by the described composite hydrogen storage material of claim 1, it is characterized in that described hydrogen storage alloy is that rare earth nickel is AB 5Type, zirconium base or titanium base or rare-earth Ni-base Laves are AB mutually 2Type, nickel titante series or ferrotianium are AB type, Magnuminium A 2Any one or two kinds of above binary or the polynary hydrogen storage alloys of Type B or non-crystaline amorphous metal;
Hydrogen storage alloy middle-weight rare earths nickel is AB 5The type alloy composition is: LNi N-x-y-zCo xN yM z, L is norium, La, Ce, Nd, Pr, Y, N and M are respectively Mn, V, Cr, Al, Fe, Cu, Zn, Sn, 4≤n≤6,0≤x≤2,0≤y≤2,0≤z≤2; Zirconium base or titanium base or rare-earth Ni-base Laves are AB mutually 2The type alloy composition is: KNi A-b-c-dV bG cJ d, K is Zr, Ti, Hf, norium, La, Ce, Nd, Pr, Y, G and J are respectively Co, Mn, Cr, Al, Fe, Cu, Zn, Sn, 1.2≤a≤2.8,0≤b≤2,0≤c≤2,0≤d≤2; Nickel titante series or ferrotianium are that AB type alloy composition is: HNi M-k-jFe kP j, H is Zr, Hf, P is Co, Mn, V, Cr, Al, Cu, Zn, Sn, 0.6≤m≤1.5,0≤k≤1.5,0≤j≤1; Magnuminium A 2The Type B alloy composition is: Mg G-fE fNi L-p-qCo pT q, E is Ca, Zr, Ti, Hf, norium, La, Ce, Nd, Pr, Y, T is Mn, V, Cr, Al, Fe, Cu, Zn, Sn, 0.8≤g≤2.5,0≤f≤1,0≤p≤0.6,0≤q≤0.6;
Non-crystaline amorphous metal is for comprising that above rare earth nickel is AB 5Type, zirconium base or titanium base Laves are AB mutually 2Type, nickel titante series and ferrotianium are AB type, Magnuminium A 2Any one or two kinds of above binary or the polynary non-crystaline amorphous metals of Type B.
3, by the described composite hydrogen storage material of claim 1, it is characterized in that described carbon nanotube is single-walled nanotube or many walls nanotube, the carbon nanotube external diameter is 0.5-150nm.
4, the preparation method of the described composite hydrogen storage material of claim 1 is characterized in that it is that hydrogen storage alloy with alloy granularity＜70 μ m is a catalyzer, makes the hydrogen storage alloy surface can obtain nano level catalytic site through surface treatment in treatment soln; Catalyzer is warming up to 523K～1073K under hydrogen stream, keeps after 10～70 minutes temperature adjustment, change reactant gases into, flow velocity 2～40ml/cm to 673K～1273K 2Min, react stop after 10～70 minutes the heating and reduce to room temperature, reactant gases is CH 4, C 2H 2, C 2H 4, C 6H 6Or CO.
5, the preparation method of the described composite hydrogen storage material of claim 1, it is characterized in that it is is catalyzer with Ni, Co, Fe, Cu metal any or metal mixture, hydrocarbon polymer or CO cracking prepare carbon nanotube, become hydrogen storage alloy to obtain the composite hydrogen storage material of hydrogen storage alloy/carbon nanotube with magnesium, titanium, zirconium or rare earth metal or norium prepared in reaction catalyst metal again; (A) prepare the carbon nanotube that contains Ni, Co, Fe, Cu metal catalyst, make catalyst metal and magnesium, titanium, zirconium, rare earth metal or norium metal-powder more directly under the Ar of 0.2～0.8MPa atmosphere, 723K～1273K constant temperature spread 1～6 hour, reduce to room temperature, prepare the composite hydrogen storage material of hydrogen storage alloy/carbon nanotube; (B) prepare and contain carbon nanotube and catalyst metal Ni, Co or Fe and La 2O 3Or Mm 2O 3Or TiO 2The mixture of metal oxide is with this mixture and metering CaH 2Or the Ca thorough mixing, in argon gas stream, be warming up to 973K～1273K, be incubated 1～5 hour, reduce to room temperature, neutrality is washed-be washed to products therefrom through washing-1% acetic acid, and vacuum-drying prepares the composite hydrogen storage material of hydrogen storage alloy/carbon nanotube.
6, the preparation method of the described composite hydrogen storage material of claim 1 is characterized in that hydrogen storage alloy and carbon nanotube mechanical ball milling under vacuum or argon gas atmosphere or in treatment soln compoundly, and the mechanical ball milling time is controlled between 10 minutes to 3 hours.
7, by the preparation method of claim 4,6 described composite hydrogen storage materials, it is characterized in that alkaline solution is the aqueous solution of KOH or NaOH in the described treatment soln, strength of solution is 0.5-8mol.L -1, contain hydroborate in the solution, i.e. POTASSIUM BOROHYDRIDE or sodium borohydride, the concentration of hydroborate is 0.0-2mol.L -1The described solution of fluoridizing comprises and contains fluorine anion and other negatively charged ion, and other negatively charged ion is chlorion, sulfate ion or nitrate ion, and positively charged ion is H +, K +, Na +, NH 4 +, Ni 2+, Co 2+Or Fe 2+Ion; Fluorine anion concentration is 0.01-2mol.L -1, other anion concentration is 0.0-1mol.L -1, cation concn is 0.01-2mol.L -1
CN00100505A 2000-01-20 2000-01-20 Hydrogen storage alloy/carbon nanometer tube composite hydrogen storage material Expired - Fee Related CN1100154C (en)

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PCT/CN2000/000484 WO2001053550A1 (en) 2000-01-20 2000-11-23 Composite hydrogen storage material of hydrogen storage alloy/carbon nanotube and producing method thereof
AU2001215126A AU2001215126A1 (en) 2000-01-20 2000-11-23 Composite hydrogen storage material of hydrogen storage alloy/carbon nanotube and producing method thereof

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Cited By (23)

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WO2002094712A1 (en) * 2001-05-21 2002-11-28 Forschungszentrum Karlsruhe Gmbh Material for storing hydrogen
CN1302139C (en) * 2005-03-02 2007-02-28 山东大学 Ferro-trialunminum intermetallic compound and carbon nanotube composites and method for preparing same
CN100357019C (en) * 2005-11-10 2007-12-26 上海大学 Method for preparing magnesium composite carbon nanometer tube hydrogen-storage material
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