CN1132675C - Hydrogen storing metal or alloy modified one-dimensional hydrogen storing carbon nano-material - Google Patents
Hydrogen storing metal or alloy modified one-dimensional hydrogen storing carbon nano-material Download PDFInfo
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- CN1132675C CN1132675C CN02138977A CN02138977A CN1132675C CN 1132675 C CN1132675 C CN 1132675C CN 02138977 A CN02138977 A CN 02138977A CN 02138977 A CN02138977 A CN 02138977A CN 1132675 C CN1132675 C CN 1132675C
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/30—Hydrogen technology
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Abstract
The present invention relates to a hydrogen storing metal or hydrogen storing alloy modified one-dimensional nanometer carbon hydrogen storing material. The hydrogen storing material is a high performance hydrogen storing material made by the method that the surface of one-dimensional nanometer carbon etched by microwave plasma is doped or deposited with hydrogen storing metal or hydrogen storing alloy, wherein the one-dimensional nanometer carbon is composed of carbon nanotubes or carbon nanofibers or a mixture of the carbon nanotubes and the carbon nanofibers of a compounding ratio of any ratio. Each carbon nanotube has a single wall or more walls, and the diameter of the carbon nanotube is greater than 0.4 nm. The hydrogen storing metal comprises heat release dissolving type metal in groups Ia to IVb in the periodic table and heat absorption dissolving type metal except for the heat release dissolving type metal Pd in groups Vb to VIII. The hydrogen storing alloy is AB5 type alloy of a crystalline state RE nickel series, AB2 type alloy of a zirconium group or titanium group Laves series, AB type alloy of a titanium nickel series and a ferrotitanium series, magnesium group A2B type alloy or binary or polybasic amorphous hydrogen storing alloy of any one or more than two kinds of the previous hydrogen storing alloy. The hydrogen storing capacity of the hydrogen storage material is from 3.5 to 5.5 wt%.
Description
Technical field
The present invention relates to the one-dimensional nano carbon high-performance hydrogen storage material that a kind of hydrogen storage metal or hydrogen storage alloy are modified, particularly on the unidimensional nanocarbon surface of microwave plasma-etching, mix or deposition hydrogen storage metal or the prepared high-performance hydrogen storage material of hydrogen storage alloy.
Background technology
Current hydrogen storage technology commonly used mainly contains compression storage hydrogen, liquefaction storage hydrogen, metal storage hydrogen and cryogenic absorption Chu Qing etc.Usually, the weight storage hydrogen of compression storage hydrogen is lower; Though liquefaction storage hydrogen increases aspect hydrogen storage capability, keep the liquid hydrogen state, system need not be higher than-252.6 ℃ temperature, and energy consumption is bigger, and also there is similar problem in activated carbon storage hydrogen.The volume capacity of metal storage hydrogen is bigger, and the hydrogen adsorption volume is hydrogen storage metal or more than 100 times of hydrogen storage alloy volume often, but its weight hydrogen storage capability is lower, waits problem slowly but also exist suction, hydrogen discharging speed.
1-dimention nano such as carbon nano fiber, carbon nanotube carbon material, because of its working temperature is low, operating pressure is moderate, and weight storage hydrogen generally causes various countries scholar's concern than advantage such as big, that shape selective is good.1997, big many of the hydrogen adsorptive capacity specific activity charcoal of U.S. Dillon etc. report Single Walled Carbon Nanotube (SWNTs), and infer that the SWNTs hydrogen storage capability is 5～10wt%.1998, U.S. Chambers etc. report carbon nano fiber under 12Mpa hydrogen storage capability up to 22.3 liters of hydrogen/gram carbon nano fiber.1999, the hydrogen storage capability of the multi-walled carbon nano-tubes (MWNTs) of report Li doped such as Singapore Chen, K reached 20wt% and 14wt% respectively.But in fact, experimental results such as Chambers and Chen are not repeatable, and their experimental result has been considered to be subjected to the influence of water.In recent years, (JP10-072201) reported the technology of preparing of a kind of hydrogen storage alloy/carbon nanotube (carbon nano fiber) matrix material in the patent of invention of Japanese Toyota Company, and at ambient temperature, its hydrogen storage capability is up to more than the 10wt%.In addition, Toshiba also prepares alkali doped ionic hydrogen storage alloy/carbon nanotube (carbon nano fiber) matrix material, and its hydrogen storage capability is 1～8wt% (JP 2001-146408).In recent years, China is obtaining certain progress aspect the Chu Qing of one-dimensional nano carbon.1999, reported in the patent of invention of Shenyang metal institute of the Chinese Academy of Sciences that the hydrogen storage capability of the Single Walled Carbon Nanotube of preparation is 4.2wt% (ZL991122902.4), carbon nano fiber has the hydrogen storage capability (CN12779953A) up to 10～12wt%.Nankai University adopts with Toyota Company's diverse ways and prepares hydrogen storage alloy/carbon nanometer tube composite hydrogen storage material, its hydrogen storage capability be 2.5～5.2wt% (WO01/53550A1, CN00100500.7).But should see that the storage of 1～4.5wt% of carbon nanotube that can be repeated to verify or carbon nano fiber, and one-dimensional nano carbon at present hydrogen also needs the above original pressure of 10MPa.
Summary of the invention
The purpose of this invention is to provide one-dimensional nano carbon high-performance hydrogen storage material of a kind of hydrogen storage metal or hydrogen storage alloy modification and preparation method thereof.
The hydrogen storage material of realizing the object of the invention is through the hydrogen storage material that mixes on the unidimensional nanocarbon surface of microwave plasma-etching or deposition hydrogen storage metal or hydrogen storage alloy are made.Adopt the method for microwave plasma-etching that etching is carried out on the surface of one-dimensional nano carbon, thereby from outward appearance to inner essence increase and increase the diffusion admittance of hydrogen, make more hydrogen enter into the inside of one-dimensional nano carbon, afterwards, on the unidimensional nanocarbon surface of over etching, mixing or deposition hydrogen storage metal or hydrogen storage alloy.The main effect of hydrogen storage metal or hydrogen storage alloy is by catalysis, absorption or sorption hydrogen molecule to be transformed hydrogen atom, to accelerate hydrogen to one-dimensional nano carbon internal divergence speed, reduce the diffusional resistance of hydrogen, not only improve the hydrogen storage property of 1-dimention nano carbon material, and under room temperature, 5～7MPa condition, the storage of hydrogen, set level platform and turn for the better.Therefore, hydrogen storage metal or hydrogen storage alloy modification one-dimensional nano carbon high-performance hydrogen storage material have remedied to a certain extent because of using the deficiency of one-dimensional nano carbon or alloy material storing hydrogen storage hydrogen separately.
One-dimensional nano carbon of the present invention is carbon nanotube or carbon nano fiber, or the mixture of the two.Wherein, carbon nanotube is Single Walled Carbon Nanotube or multi-walled carbon nano-tubes.Single Walled Carbon Nanotube adopts the preparation of hydrogen arc electric discharge, and multi-walled carbon nano-tubes and carbon nano fiber all prepare by catalystic pyrolysis.The present invention is equally applicable to the 1-dimention nano carbon material of other method preparation.
Microwave plasma-etching of the present invention mainly carries out on microwave plasma generation device.The s main working parameters of this device is: etching power is generally 0.3～3Kw, and 300～1500 ℃ of etching temperatures are handled air pressure 6.0 * 10
2～6.0 * 10
3Pa, etching gas are hydrogen, and condition gas is nitrogen or argon gas or the gas mixture of the two.Under nitrogen or argon gas condition, the hydrogen ratio is greater than 80%, and nitrogen or argon gas are less than 20%; For mixing condition gas, the summation of nitrogen and argon gas is not more than 20%.
Hydrogen storage metal of the present invention comprises IA in the periodictable～IVB family heat release lysotype metal, the heat absorption lysotype metal of VB～VIII family except that heat release lysotype metal Pd.Described hydrogen storage alloy is that crystalline state rare earth nickel is AB
5Type alloy, zirconium base or titanium base Laves are AB
2Type alloy, nickel titante series and ferrotianium are AB type alloy, magnesium base A
2The Type B alloy; Or any one or two kinds of above binary or the polynary amorphous hydrogen storage alloys of above-mentioned hydrogen storage alloy.
Hydrogen storage alloy rare earth nickel described in the present invention is AB
5Type consists of 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, and 4≤n≤6≤x≤, 02,0≤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 be Zr, Ti, Hf, norium, La, Ce, Nd, Pr, Y, G and J be 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-iF
eKP
i, H is Zr, Hf, P be Co, Mn, V, Cr, Al, Cu, Zn, Sn,, 0.6≤m1.5,0≤k≤1.5,0≤j≤1, Magnuminium A
2The Type B alloy composition is Mg
G-fE
fNi
F-p-gCo
pT
q, E is Ca, Zr, Ti, Hf, norium, La, Ce, Nd, Pr, Y, Ti 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.
The 1-dimention nano carbon material of hydrogen storage metal of the present invention or alloy can be used method preparations such as chemical coprecipitation reduction method, vacuum deposition method, sputtering method or CVD method.
The concrete preparation technology of hydrogen storage material of the present invention is as follows:
1, the preparation of 1-dimention nano carbon material.Single Walled Carbon Nanotube mainly adopts the preparation of hydrogen arc electric discharge, and purity is greater than 50%; Multi-walled carbon nano-tubes or carbon nano fiber are prepared by catalystic pyrolysis, and its purity is all greater than 70%.
2, the pre-treatment of 1-dimention nano carbon material.Put into NaOH solution after the monodimension nanometer material grinding with preparation, reflux and ultra-sonic oscillation are handled, to improve the dispersiveness of one-dimensional nano carbon; Afterwards, one-dimensional nano carbon is carried out oxide treatment,, just prepare purity greater than 90% one-dimensional nano carbon through deionized water wash, drying.After oxide treatment, the specific surface area of one-dimensional nano carbon increases to some extent, and carbon nanotube (caliber＞0.4nm) the most fullerenes cage in two ends is opened, and helps the internal reservoir that hydrogen enters pipe.
3, pretreated one-dimensional nano carbon is carried out microwave plasma-etching.The normal power of etching is 0.3～3kW, and 300～1500 ℃ of etching temperatures are handled air pressure 6.0 * 10
2～6.0 * 10
3Pa; Etching gas is a hydrogen, and condition gas is nitrogen or argon gas or the gas mixture of the two.Under nitrogen or argon gas condition, the hydrogen ratio is usually greater than 80%, and nitrogen or argon gas are less than 20%; For mixing condition gas, the summation of nitrogen and argon gas should be not more than 20%.
4, adopt methods such as chemical coprecipitation reduction method, vacuum deposition method, sputtering method or CVD method to prepare the 1-dimention nano carbon composite of hydrogen storage metal or hydrogen storage alloy modification.Afterwards, roasting 1～2h under nitrogen or argon gas, 200～700 ℃ of conditions, it is tightr that the hydrogen storage metal of preparation or hydrogen storage alloy are combined with one-dimensional nano carbon, thereby obtain the one-dimensional nano carbon hydrogen storage material that hydrogen storage metal or hydrogen storage alloy are modified.
Embodiment
Below by embodiment in detail the present invention is described in detail.
Embodiment 1
Adopt the hydrogen arc electric discharge to prepare Single Walled Carbon Nanotube, the single carbon nano pipe purity that makes is 60%, and caliber is 1～40nm, pipe range 10～100 μ m.After its grinding, put into NaOH solution reflux and ultra-sonic oscillation 1h successively, with deionized water wash and dry.Afterwards, Single Walled Carbon Nanotube is placed nitration mixture (dense H
2SO
4: dense HNO
3=3: make oxide treatment 1), reflux 1h, deionized water wash is also dry.Above-mentioned pretreated Single Walled Carbon Nanotube is carried out microwave plasma-etching.Etching gas is a hydrogen, and etching power is 2.5kW, 1200 ℃ of temperature, and etching time 2h handles air pressure 6.0 * 10
2Pa.In hydrogen purity is 99.9999%, and original pressure is under 7MPa and the room temperature condition, and the hydrogen storage capability of etching single wall carbon nano tube is 4wt%.Preparation 200ml PdCl
2Solution, and mix through the Single Walled Carbon Nanotube of etching with 2g and to stir 1h, stirring velocity is 800r/min.Afterwards, logical H
2Reaction, temperature of reaction is 100 ℃.Reaction product is washed, drying, and under 300 ℃, argon gas condition roasting 2h, make palladium and modify Single Walled Carbon Nanotube.Show through TEM, XRD, electron diffraction and power spectrum result of study, have the single particle of metal level and metal on the Single Walled Carbon Nanotube surface, encapsulation ratio is about 55%, and its main component is metal Pd (＞99%), and few part is impurity such as Fe, Co, Ni.Under identical test condition, the hydrogen storage capability of etching single wall carbon nano tube is 5.5wt%.
Embodiment 2
Multi-walled carbon nano-tubes is prepared by catalystic pyrolysis.The multi-walled carbon nano-tubes purity that makes is 75%, and caliber is 10～80nm, pipe range 20～100 μ m.The pre-treatment of multi-walled carbon nano-tubes, microwave plasma-etching technology and storage hydrogen test condition are identical with example 1.Test shows, the hydrogen storage capability of the multi-walled carbon nano-tubes of etching are 2.5wt%.The hydrogen storage capability of palladium modifying multiwall carbon nano-tube is 3.5wt%.Show that through TEM, XRD, electron diffraction and power spectrum result of study the metal of multi-wall carbon nano-tube tube-surface is many to be existed with stratiform or single particle state, encapsulation ratio is about 65%, and its main component is metal Pd (＞98%), and few part is impurity such as Fe, Co, Ni.
Embodiment 3
Carbon nano fiber is prepared by catalystic pyrolysis.The carbon nano fiber purity that makes is 78%, and caliber is 80～100nm, and pipe range is more than the 0.1mm.The pre-treatment of carbon nano fiber, microwave plasma-etching technology and storage hydrogen test condition are identical with example 1.Test shows, the hydrogen storage capability of the carbon nano fiber of etching are 3.8wt%.The hydrogen storage capability of palladium decorated nanometer carbon fiber is 5wt%.Show that through TEM, XRD, electron diffraction and power spectrum result of study the metal on carbon nano fiber surface is many to be existed with stratiform or single particle state, encapsulation ratio is about 50%, and its main component is metal Pd (＞98%), and few part is impurity such as Fe, Co, Ni.
Embodiment 4
The multi-walled carbon nano-tubes preparation is identical with embodiment 2, and its pre-treatment, microwave plasma-etching technology and storage hydrogen test condition are identical with embodiment 1.With multi-walled carbon nano-tubes and the 20g liquid VCl of 2g through etching
4High-speed stirring, blend, even post-heating to be mixed and logical H
2Reaction.Then, reaction product is moved on in the tube furnace logical H
2Reaction 2h, 1250 ℃ of temperature of reaction.Reaction product is washed, and under 300 ℃, argon gas condition roasting 2h, make the vanadium modifying multiwall carbon nano-tube.Show that through TEM, XRD, electron diffraction and power spectrum result of study the metal of multi-wall carbon nano-tube tube-surface is many to be existed with stratiform or single particle state, encapsulation ratio is about 60%, and its main component is metal V (＞90%), and small part is V
2O
3Impurity such as (being about 9%) and Fe, Co, Ni.The hydrogen storage capability of the multi-walled carbon nano-tubes that V modifies is 3.8wt%.
Embodiment 5
The preparation of carbon nano fiber and embodiment 3, its pre-treatment, microwave plasma-etching technology and storage hydrogen test condition are identical with embodiment 1.NiCl with same concentrations
2And LaCl
35: 1 by volume uniform mixing of solution add the carbon nano fiber of 2g through etching and grinding in mixed solution, fast 500r/min is stirred in electronic stirring, and slowly drips Na
2CO
3Solution is treated complete reaction, through suction filtration, deionized water wash and vacuum drying process, makes the LaNi that is attached to the carbon nano fiber surface
5Precursor La
2O
310NiO.Reaction product is moved in the tube furnace logical H
2Reaction, temperature of reaction is 1000 ℃.Reaction product is washed.And under 300 ℃, argon shield condition roasting 2h, make LaNi
5The decorated nanometer carbon fiber.Show that through TEM, XRD, electron diffraction and power spectrum result of study the metal on carbon nano fiber surface is many to be existed with stratiform or single particle state, encapsulation ratio is about 50%, and its main component is metal LaNi
5(＞98%), few part is impurity such as Fe, Co, Ni.LaNi
5The hydrogen storage capability of decorated nanometer carbon fiber is 4.5wt%.
Claims (7)
1, the one-dimensional nano carbon hydrogen storage material modified of a kind of hydrogen storage metal or hydrogen storage alloy is characterized in that this hydrogen storage material is through the high performance hydrogen storage material that mixes on the unidimensional nanocarbon surface of microwave plasma-etching or deposition hydrogen storage metal or hydrogen storage alloy are prepared into.
2, hydrogen storage material as claimed in claim 1 is characterized in that described～dimension nano-sized carbon is carbon nanotube or carbon nano fiber.
3, hydrogen storage material as claimed in claim 1 is characterized in that described carbon nanotube is single wall or multi-walled carbon nano-tubes.
4, hydrogen storage material as claimed in claim 1 is characterized in that described one-dimensional nano carbon is carbon nanotube or the carbon nano fiber mixture by the arbitrary proportion proportioning.
5, hydrogen storage material as claimed in claim 1, it is characterized in that described hydrogen storage metal be IA in the periodic table of elements～
IVB family heat release lysotype metal, the heat absorption lysotype metal of VB～VIII family except that heat release lysotype metal Pd.
6, hydrogen storage material as claimed in claim 1 is characterized in that described hydrogen storage alloy is that crystalline state rare earth nickel is AB
5Type alloy, zirconium base or titanium base Laves are AB
2Type alloy, nickel titante series and ferrotianium are AB type alloy, magnesium base A
2The Type B alloy.
7, hydrogen storage material as claimed in claim 1 is characterized in that described hydrogen storage alloy is an amorphous alloy, and being selected from rare earth nickel is AB
5Type alloy, zirconium base or titanium base Laves are AB
2Type alloy, nickel titante series and ferrotianium are AB type alloy, magnesium base A
2Any one or two kinds of above binary or the polynary amorphous hydrogen storage alloys of Type B alloy.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100368074C (en) * | 2004-08-31 | 2008-02-13 | 中国科学院金属研究所 | Nano composite hydrogen-storing material and preparing method |
| CN101251228B (en) * | 2008-03-21 | 2010-06-09 | 石锋 | Solid hydrogen-storing conveying apparatus |
| CN107253697A (en) * | 2017-06-16 | 2017-10-17 | 扬州大学 | A kind of multi-walled carbon nanotube that adulterates improves the Li of hydrogen storage property3N hydrogen storage materials and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100368074C (en) * | 2004-08-31 | 2008-02-13 | 中国科学院金属研究所 | Nano composite hydrogen-storing material and preparing method |
| CN101251228B (en) * | 2008-03-21 | 2010-06-09 | 石锋 | Solid hydrogen-storing conveying apparatus |
| CN107253697A (en) * | 2017-06-16 | 2017-10-17 | 扬州大学 | A kind of multi-walled carbon nanotube that adulterates improves the Li of hydrogen storage property3N hydrogen storage materials and preparation method thereof |
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