WO2001053550A1 - Composite hydrogen storage material of hydrogen storage alloy/carbon nanotube and producing method thereof - Google Patents

Composite hydrogen storage material of hydrogen storage alloy/carbon nanotube and producing method thereof Download PDF

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Publication number
WO2001053550A1
WO2001053550A1 PCT/CN2000/000484 CN0000484W WO0153550A1 WO 2001053550 A1 WO2001053550 A1 WO 2001053550A1 CN 0000484 W CN0000484 W CN 0000484W WO 0153550 A1 WO0153550 A1 WO 0153550A1
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hydrogen storage
alloy
storage material
type
titanium
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PCT/CN2000/000484
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French (fr)
Chinese (zh)
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Xueping Gao
Xue Qin
Feng Wu
Shihai Ye
Hong Liu
Huatang Yuan
Deying Song
Panwen Shen
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Nankai University
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Priority to AU2001215126A priority Critical patent/AU2001215126A1/en
Publication of WO2001053550A1 publication Critical patent/WO2001053550A1/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

Definitions

  • the present invention relates to a hydrogen storage material, particularly a hydrogen storage alloy / carbon nanotube composite hydrogen storage material, and the present invention also relates to a method for preparing the composite hydrogen storage material. Background technique
  • Hydrogen storage alloys that reversibly absorb and release hydrogen under mild conditions have been continuously researched and developed since they were discovered in the late 1960s. Especially, the hydrogen storage alloy electrode materials used in nickel-hydrogen batteries have been industrialized. Hydrogen storage alloys are generally divided into four categories: rare earth nickel series (AB 5 type), titanium nickel and titanium iron series (type AB), magnesium-based alloys (type A 2 B) and zirconium-based and titanium-based Laves phase series (AB 2 Type). Under certain conditions (such as temperature and pressure), hydrogen is in contact with the surface of the hydrogen storage alloy, and hydrogen molecules (H 2 ) are adsorbed on the surface of the alloy and catalyzed to dissociate into hydrogen atoms (H) into the alloy lattice space for storage.
  • AB 5 type rare earth nickel series
  • type AB titanium nickel and titanium iron series
  • magnesium-based alloys type A 2 B
  • zirconium-based and titanium-based Laves phase series AB 2 Type
  • the hydrogen storage alloy can be prepared by metal melting method, powder metallurgy method, mechanized alloy method, chemical reduction diffusion method and co-deposition chemical reduction diffusion method.
  • Carbon nanotube hydrogen storage research has only been reported in the last two years (Dillon AC, et al., Nature, 386 (1997) 377; Chen P., et al., Science, 285 (1999) 91; Liu C., et al. ., Science, 286 (1999) 1127).
  • Hydrogen molecules enter carbon nanotubes for storage under certain conditions. Due to different conditions, the reported hydrogen storage capacities vary, ranging from 4wt% to 20wt%.
  • carbon nanotubes have the following shortcomings in hydrogen storage: high hydrogen absorption pressure (greater than 12MFa), difficulty in dehydrogenation, and lack of platform characteristics for hydrogen storage.
  • the hydrogen absorption reaches 4.3wt% under 12MPa hydrogen pressure, and only 2/3 of the hydrogen absorption amount can be released under mild conditions, that is, 3wt3 ⁇ 4.
  • the catalysts are metals such as Co, Ni, Fe, and Y and their mixtures. Disclosure of invention
  • An object of the present invention is to provide a composite hydrogen storage material, which combines the advantages of two types of hydrogen storage materials: hydrogen storage alloy and carbon nanotubes (high catalytic activity of hydrogen storage alloys and high hydrogen storage capacity of carbon nanotubes) Hydrogen storage alloy / carbon nanotube composite hydrogen storage material, which overcomes the shortcomings of the prior art;
  • Another object of the present invention is to provide a first method for preparing the composite hydrogen storage material; another object of the present invention is to provide a second method for preparing the composite hydrogen storage material; another object of the present invention A third method for preparing the composite hydrogen storage material is provided; another object of the present invention is to provide a fourth method for preparing the composite hydrogen storage material.
  • the hydrogen storage alloy / carbon nanotube composite hydrogen storage material of the present invention includes a hydrogen storage alloy and a carbon nanotube, wherein the weight content of the hydrogen storage alloy ranges from 1 to 90%.
  • the hydrogen storage alloy according to the present invention is a rare earth nickel-based AB 5 type, a zirconium-based or titanium-based or a rare-earth nickel-based Laves phase AB 2 type, a titanium nickel-based or titanium iron-based AB type, a magnesium-based alloy A 2 B type, or a non- Any one or two or more kinds of crystalline alloys.
  • the composition of the rare earth nickel-based AB 5 type alloy in the hydrogen storage alloy is LNi n — xz Co x N y M z , where L is a mixed rare earth metal, La, Ce, Nd, Pr, Y, and N and M are M ⁇ , V, Cr, Al, Fe, Cu, Zn, Sn, 4 ⁇ n ⁇ 6, 0 ⁇ x ⁇ 2, 0 ⁇ y ⁇ 2, 0 ⁇ z ⁇ 2; Zirconium-based or titanium-based or rare-earth nickel-based Laves phase system
  • the composition of type AB 2 alloy is KNi a — b — c — J d , where K is Zr, Ti, Hf, mixed rare earth metal, La, Ce, Nd, Pr, Y, G, and J, and J is Co, Mn.
  • the carbon nanotubes in the present invention are single-walled nanotubes or multi-walled nanotubes, and the outer diameter of the carbon nanotubes is 0.5 to 150 nm.
  • Hydrogen storage alloys are used as catalysts to produce hydrogen storage alloy / carbon nanotube composite hydrogen storage materials by cracking hydrocarbons (or CO).
  • the hydrogen storage alloy used as the catalyst can be selected from rare earth nickel series (AB 5 type), zirconium-based or titanium-based La Ves phase series (AB 2 type), titanium nickel series and titanium iron series (AB type), and magnesium-based alloy ( A 2 B type) and amorphous alloy (or two or more) binary or multiple hydrogen storage alloys.
  • Surface-treated (such as alkaline solution or inorganic salt solution) hydrogen storage alloy can obtain nano-scale catalytic sites, the reaction gas is CH 4 , C 2 H 2 , C 2 H 4 , C 6 H 6 or C0.
  • the preparation of the hydrogen storage alloy / carbon nanotube composite hydrogen storage material is performed on a fixed bed gas continuous flow reaction device.
  • a certain amount of catalyst is heated to 523K ⁇ 1073K under a hydrogen stream, maintained for 10 ⁇ 70 minutes, then adjusted to 673K ⁇ 1273K, replaced with a reaction gas, and the flow rate is 2 ⁇ 40ml / cm 2.
  • Min> Stop heating after 10 ⁇ 70 minutes And cool down 'to collect the product.
  • SEM Sccanning Electron Microscope
  • XRD X-Diffraction
  • TEM Transmission Electron Microscopy
  • a certain amount of catalyst precursors Ni0, Co0, FeO, CuO, etc., or a mixture of several metal oxides are placed in a fixed-bed gas continuous flow reactor, and the temperature is raised under a hydrogen stream To 523K ⁇ 1073K, keep it for 0.5 ⁇ 5 hours, then adjust the temperature to 673K ⁇ 1273K, change to the reaction gas, flow rate 2 ⁇ 40ml / cm 2 .min, stop heating and cool down after 10 ⁇ 70 minutes, the reaction gas is CH 4 , C 2 H 2 , C 2 H 4 , C 6 H 6 etc. or C0.
  • the mixture of the prepared carbon nanotubes and the catalyst metal is thoroughly mixed with a measured amount of Mg powder or Ti powder, and placed in a pressure-resistant reactor under a Ar atmosphere of 0.2 to 0.8 MPa at a constant temperature of 723K to 1273K for 1 to 6 hours.
  • the catalyst metal is formed into a hydrogen storage alloy or a hydrogen storage alloy mixture such as Mg 2 Ni or Mg 2 Cu or TiNi, Ti 2 Ni or TiFe, so as to obtain a hydrogen storage alloy / carbon nanotube composite hydrogen storage alloy material.
  • This mixture is fully mixed with the measured amount of 3 or Ca, and the temperature is raised to 973 ⁇ in an argon stream: ⁇ 1273K, held for 1 to 5 hours, cooled to room temperature, and the resulting product is washed with water-13 ⁇ 4 acetic acid washed-washed with water to neutrality, Vacuum drying to obtain a hydrogen storage alloy / carbon nanotube composite material.
  • Hydrogen storage alloys can be selected from rare earth nickel series (AB 5 type), zirconium-based or titanium-based Laves phase series (AB 2 type), titanium nickel series and titanium iron series (AB type), magnesium-based alloys (A 2 B type), and Any one (or two or more) amorphous alloys of binary or multiple hydrogen storage alloys.
  • Hydrogen storage alloy particle size ⁇ 7 ( ⁇ 0 !.
  • Surface treatment such as alkaline solution or inorganic salt solution
  • carbon nanotubes under vacuum or argon or hydrogen atmosphere or mechanical ball milling under treatment solution (including alkaline solution, inorganic salt solution or organic solution, etc.) complex. Mechanical milling time is controlled between 10 minutes and 3 hours.
  • Carbon nanotubes are prepared by using any one of metals such as Ni, Co, Fe, Cu, or a mixture of metals as a catalyst, the hydrocarbons are cracked, and the reaction gases are CH 4 , C 2 H 2 , C 2 H 4 , 6 and the like. After SEM or XRD and TEM (transmission electron microscopy, the sample is ultrasonically treated) analysis and test, the product is a hydrogen storage alloy / carbon nanotube composite hydrogen storage material.
  • the alkali solution according to the present invention includes an aqueous solution of K0H or NaOH, and the solution concentration is 0.5 to 8 mol.
  • L- The solution contains borohydride (K or Na), and the concentration of borohydride (K or Na) is 0.0 ⁇ 2mol.
  • the inorganic salt solution includes anions containing: fluoride ion, chloride ion, sulfate ion, nitrate ion, citrate ion, and hypophosphite ion, and the cations are H +, K +, Na +, NH 4 +, Ni 2+ , Co 2 —, Fe 2+ , Cu 2+ or Fd 2+ inorganic salt solution, wherein the anion concentration is 0.01 ⁇ 2mol. L- 1 , the cation concentration is 0.01 ⁇ 2mol. L—
  • the organic solution is tetrahydrofuran, cyclohexadiene, cyclohexene, cyclohexane, toluene, benzene, and the like. The best way to implement the invention
  • the hydrogen storage alloy / carbon nanotube composite hydrogen storage material is prepared on a fixed-bed gas continuous flow reaction type device. After lg alloy catalyst under a hydrogen atmosphere heated to 873K, stable for 20 minutes, into a flow rate 10ml / cm 2. Min methyl embankment, reaction was stopped after 60 minutes, cooled to room temperature under an atmosphere of ⁇ 2, product was collected, carbon The yield of nanotubes was 0.2 g. 5wt3 ⁇ 4 ⁇ Its gas-solid hydrogen storage performance was measured in a standard Sievert's reaction device, and its hydrogen storage capacity was 2.5 wt.
  • Example 2 The 2mol.L- 1 NiCl 2 ⁇ 2mol Shang - 1 LaCl 3 solution volume ratio of 5: 1 mixed, was slowly added under constant stirring 1.5mol.L- 1 Na 2 C0 3 solution, a precipitate formed. The secondary distilled water was repeatedly used to wash until the water layer was free of chloride ions. After filtration, the sample was dried at 373K in an oven to obtain a prepared catalyst precursor sample. The carbon nanotubes were prepared on a fixed-bed gas continuous flow reaction apparatus. 5g of catalyst was heated to 923K in a hydrogen atmosphere. After being stable for 30 minutes, methane with a flow rate of 20ml / cm 2 .min was introduced. After 30 minutes of reaction, the reaction was stopped.
  • the product was collected, and the mass ratio of this product to CaH 2 was 1: 1.1.
  • Mixed into a fixed-bed gas continuous flow reaction device for reaction the temperature was raised to 1223K in a hydrogen atmosphere, and the temperature was maintained for 4 hours.
  • the product was quickly cooled to room temperature and collected.
  • the product was washed with distilled water to neutrality and dried under vacuum to obtain a product.
  • the weight ratio of the hydrogen storage alloy to the carbon nanotubes was 2/1.
  • the gas-solid hydrogen storage performance was measured in a standard Sievert's reaction device, and its hydrogen storage capacity was 4.5wt3 ⁇ 4.
  • the ZrV 0 2 Mn 0 6 Co 0 ! Ni, 2 smelted by the electric arc furnace was pulverized to 10 ⁇ ! ⁇ 20 ⁇ m, and then treated with 0.5mol ⁇ -1 NiF 2 / NH 4 F solution at 343K for 0.5 hours to obtain the prepared alloy catalyst sample.
  • the preparation of the hydrogen storage alloy / carbon nanotube composite hydrogen storage material is performed on a fixed-bed gas continuous flow reaction type device.
  • the lg catalyst was heated to 873K in a hydrogen atmosphere, and after being stable for 10 minutes, methane with a flow rate of 15ml / cm 2 .min was introduced, and the reaction was stopped after 60 minutes.
  • the temperature was reduced to room temperature in an H 2 atmosphere, and the product was collected.
  • the yield of carbon nanotubes 0.4g. Its gas-solid hydrogen storage performance was measured in a standard Sievert's reaction device, and its hydrogen storage capacity was 3.8 wt%.
  • the Mg 2 Ni alloy was pulverized to 50 ⁇ m to 70 ⁇ m, and then the sample was prepared by ball milling under an argon atmosphere for 70 hours.
  • the preparation of the hydrogen storage alloy / carbon nanotube composite hydrogen storage material is performed on a fixed-bed gas continuous flow reaction device.
  • the lg catalyst was heated to 823 K under a hydrogen atmosphere, and acetylene was passed at a flow rate of 30 ml / cm 2 .min. The reaction was stopped after 60 minutes. The temperature was lowered to room temperature in an H 2 atmosphere, and the product was collected.
  • the yield of carbon nanotubes was 0.6 g.
  • the gas-solid hydrogen storage performance was measured in a standard Sievert's reaction device, and its hydrogen storage capacity was 5.2 wt%.
  • the ZrV 0 2 Mn 0 6 N 2 alloy was pulverized to 50 ⁇ -70 ⁇ , and then ball-milled in a 0.5mol.L- 1 NiF 2 / NH 4 F solution for 40 hours to obtain the prepared ultrafine alloy sample.
  • the carbon nanotubes are 5-20 nm, the weight ratio of the hydrogen storage alloy to the carbon nanotubes is 1/2, the ball milling time is 30 minutes, and the product is vacuum dried after washing.
  • the product was tested for its gas-solid hydrogen storage performance in a pseudo-Sievert's reaction device, and its hydrogen storage capacity was 3.4 wt%.
  • the hydrogen storage alloy / carbon nanotube composite hydrogen storage material of the present invention combines the advantages of the existing two types of hydrogen storage materials, that is, the high catalytic activity of the hydrogen storage alloy and the high hydrogen storage capacity of the carbon nanotube, and its performance is stable.
  • a new type of high-capacity composite hydrogen storage material which can be widely used in large-scale storage and transportation of hydrogen, hydrogen sources for fuel cells, nickel-metal hydride batteries, hydrogen purification, and organic hydrogenation catalysis. .

Abstract

The present invention relates to a composite hydrogen storage material, which contains hydrogen storage alloy and carbon nanotube, wherein content range of the hydrogen storage alloy is 1-90 % by weight, said hydrogen storage alloy is one or more of rare earth metal-nickel system AB5 type, zirconium base, titanium base or rare earth metal-nickel base Laves-phase system AB2 type, titanium-nickel or titanium-iron system AB type, magnesium base alloy A2B type or amorphous alloy. The present invention also relates to a method for producing the hydrogen storage alloy, which is the method of catalytic cracking or mechanical complex. The composite hydrogen storage material of the present invention has high capacity, property stability and wide use.

Description

储氢合金 /碳纳米管复合储氢材料及其制备方法 技术领域  Hydrogen storage alloy / carbon nanotube composite hydrogen storage material and preparation method thereof
本发明涉及一种储氢材料， 特别是储氢合金 /碳纳米管复合储 氢材料， 本发明还涉及该复合储氢材料的制备方法。 背景技术  The present invention relates to a hydrogen storage material, particularly a hydrogen storage alloy / carbon nanotube composite hydrogen storage material, and the present invention also relates to a method for preparing the composite hydrogen storage material. Background technique
在温和条件下可逆吸放氢的储氢合金自二十世纪 60 年代末发 现以来， 人们进行了不断的研究和开发， 特別是用于镍氢电池的储 氢合金电极材料已经实现了产业化。 储氢合金一般分为四类： 稀土 镍系 （AB5型） 、 钛镍和钛铁系 （AB型） 、 镁基合金 （A2B型） 和锆 基和钛基 Laves 相系 （AB2型） 。 在一定条件 （如溫度和压力） 下， 氢与储氢合金表面接触， 氢分子 （H2) 被吸附到合金表面并催化解 离为氢原子 （H) 进入到合金晶格间隙中储存起来， 当改变外界条 件 （如溫度或 /和压力） 时， 氢原子从合金晶格间隙中扩散到合金 表面并复合成氢分子释放出来。 各类储氢合金理论储氢容量分别 为 ： 八85合金 （以 LaNi5H6为例） 约为 1.4wt%、 AB合金 （以 TiFel^ 9 为例） 为 1.8wt%、 A2B 合金 （以 Mg2Ni 为例） 为 3.6wt¾ . AB2合金 (以 ZrV2H4 5为例） 为 2.0wt%。 储氢合金制备方法可通过金属熔炼 法、 粉末冶金法、 机械化合金法、 化学还原扩散法和共沉积化学还 原扩散法等。 Hydrogen storage alloys that reversibly absorb and release hydrogen under mild conditions have been continuously researched and developed since they were discovered in the late 1960s. Especially, the hydrogen storage alloy electrode materials used in nickel-hydrogen batteries have been industrialized. Hydrogen storage alloys are generally divided into four categories: rare earth nickel series (AB 5 type), titanium nickel and titanium iron series (type AB), magnesium-based alloys (type A 2 B) and zirconium-based and titanium-based Laves phase series (AB 2 Type). Under certain conditions (such as temperature and pressure), hydrogen is in contact with the surface of the hydrogen storage alloy, and hydrogen molecules (H 2 ) are adsorbed on the surface of the alloy and catalyzed to dissociate into hydrogen atoms (H) into the alloy lattice space for storage. When external conditions (such as temperature or / and pressure) are changed, hydrogen atoms diffuse from the interstitial space of the alloy to the surface of the alloy and are compounded into hydrogen molecules and released. Various kinds of hydrogen-absorbing alloy theoretical hydrogen storage capacity were: Eight 85 alloy (an example in LaNi 5 H 6) about 1.4wt%, AB alloy (In Case TiFel ^ 9) is 1.8wt%, A 2 B alloy (Taking Mg 2 Ni as an example) is 3.6wt¾. AB 2 alloy (taking ZrV 2 H 4 5 as an example) is 2.0wt%. The hydrogen storage alloy can be prepared by metal melting method, powder metallurgy method, mechanized alloy method, chemical reduction diffusion method and co-deposition chemical reduction diffusion method.
碳纳米管储氢研究最近两年才有报道 （Dillon A. C.， et al .， Nature, 386(1997)377； Chen P. , et al . , Science, 285(1999)91； Liu C.， et al. , Science , 286(1999)1127) 。 氢分子 (H2) 在一 定条件下进入到碳納米管储存起来， 因条件不同， 报道的储氢容量 有所差异， 从 4wt% j 20wt%。 但碳納米管储氢存在以下缺点， 即吸 氢压力高 （大于 12MFa) 、 脱氢困难和缺少储氢的平台特征等。 最 好的结果为 12MPa氢压下吸氢达 4.3wt%， 在温和条件下只能释放吸 氢量的 2/3 , 即 3wt¾。 碳納米管的制备主要有三种方法： 电弧放电 法、 化学气相沉积法和脉沖激光蒸发法， 催化剂为 Co、 Ni 、 Fe和 Y 等金属及其混合物。 发明的公开 Carbon nanotube hydrogen storage research has only been reported in the last two years (Dillon AC, et al., Nature, 386 (1997) 377; Chen P., et al., Science, 285 (1999) 91; Liu C., et al. ., Science, 286 (1999) 1127). Hydrogen molecules (H 2 ) enter carbon nanotubes for storage under certain conditions. Due to different conditions, the reported hydrogen storage capacities vary, ranging from 4wt% to 20wt%. However, carbon nanotubes have the following shortcomings in hydrogen storage: high hydrogen absorption pressure (greater than 12MFa), difficulty in dehydrogenation, and lack of platform characteristics for hydrogen storage. Most A good result is that the hydrogen absorption reaches 4.3wt% under 12MPa hydrogen pressure, and only 2/3 of the hydrogen absorption amount can be released under mild conditions, that is, 3wt¾. There are three main methods for preparing carbon nanotubes: arc discharge, chemical vapor deposition, and pulsed laser evaporation. The catalysts are metals such as Co, Ni, Fe, and Y and their mixtures. Disclosure of invention
本发明的一个目的是提供了一种复合储氢材料， 该储氢材料是 结合储氢合金和碳纳米管两类储氢材料优点 （储氢合金高催化活性 和碳納米管高储氢容量） 的储氢合金 /碳纳米管复合储氢材料， 其 克服了现有技术的不足；  An object of the present invention is to provide a composite hydrogen storage material, which combines the advantages of two types of hydrogen storage materials: hydrogen storage alloy and carbon nanotubes (high catalytic activity of hydrogen storage alloys and high hydrogen storage capacity of carbon nanotubes) Hydrogen storage alloy / carbon nanotube composite hydrogen storage material, which overcomes the shortcomings of the prior art;
本发明的另一目的是提供了所述复合储氢材料的第一种制备方法； 本发明的又一目的是提供了所述复合储氢材料的第二种制备方法； 本发明的又一目的是提供了所述复合储氢材料的第三种制备方法； 本发明的再一目的是提供了所述复合储氢材料的第四种制备方法。 本发明储氢合金 /碳納米管复合储氢材料包括储氢合金和碳纳 米管， 其中储氢合金的重量含量范围为 1〜90%。  Another object of the present invention is to provide a first method for preparing the composite hydrogen storage material; another object of the present invention is to provide a second method for preparing the composite hydrogen storage material; another object of the present invention A third method for preparing the composite hydrogen storage material is provided; another object of the present invention is to provide a fourth method for preparing the composite hydrogen storage material. The hydrogen storage alloy / carbon nanotube composite hydrogen storage material of the present invention includes a hydrogen storage alloy and a carbon nanotube, wherein the weight content of the hydrogen storage alloy ranges from 1 to 90%.
本发明所述储氢合金是稀土镍系 ΑΒ5型、 锆基或钛基或稀土镍 基 Laves相系 AB2型、 钛镍系或钛铁系 AB型、 镁基合金 A2B型或者 非晶合金的任一种或两种以上的二元或多元储氢合金。 The hydrogen storage alloy according to the present invention is a rare earth nickel-based AB 5 type, a zirconium-based or titanium-based or a rare-earth nickel-based Laves phase AB 2 type, a titanium nickel-based or titanium iron-based AB type, a magnesium-based alloy A 2 B type, or a non- Any one or two or more kinds of crystalline alloys.
所述储氢合金中稀土镍系 AB5型合金組成为 LNin— x zCoxNyMz , 其中 L为混合稀土金属、 La、 Ce、 Nd、 Pr、 Y， Ν和 Μ分别为 Μη、 V、 Cr、 Al、 Fe、 Cu、 Zn、 Sn， 4≤n≤6 , 0<x≤2 , 0<y<2 , 0≤z<2； 锆 基或钛基或稀土镍基 Laves相系 AB2型合金组成为 KNia— b— c— Jd， 其中 K为 Zr、 Ti、 Hf、 混合稀土金属、 La、 Ce、 Nd、 Pr、 Y , G和 J 分另' J为 Co、 Mn、 Cr、 Al、 Fe、 Cu、 Zn、 Sn ' 1 .2<a<2 .8 , 0≤b<2 , 0<c<2， 0≤d≤2 ;钛镍系或钛铁系 AB型合金組成为
Figure imgf000003_0001
，其中 H为 Zr、 Hf , P为 Co、 Mn、 V、 Cr、 Al、 Cu、 Zn、 Sn， 0 .6<m<l .5 , 0<k<l .5 , 0≤j<l；镁基合金 A2B型合金组成为
Figure imgf000004_0001
其中 E为 Ca、 Zr、 Ti、 Hf 、 混合稀土金属、 La、 Ce、 Nd、 Pr、 Y , T为 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 composition of the rare earth nickel-based AB 5 type alloy in the hydrogen storage alloy is LNi n — xz Co x N y M z , where L is a mixed rare earth metal, La, Ce, Nd, Pr, Y, and N and M are Mη, V, Cr, Al, Fe, Cu, Zn, Sn, 4≤n≤6, 0 <x≤2, 0 <y <2, 0≤z <2; Zirconium-based or titanium-based or rare-earth nickel-based Laves phase system The composition of type AB 2 alloy is KNi a — b — c — J d , where K is Zr, Ti, Hf, mixed rare earth metal, La, Ce, Nd, Pr, Y, G, and J, and J is Co, Mn. , Cr, Al, Fe, Cu, Zn, Sn '1.2 <a <2 .8, 0≤b <2, 0 <c <2, 0≤d≤2; Titanium nickel system or titanium iron series AB type Alloy composition is
Figure imgf000003_0001
, Where H is Zr, Hf, P is Co, Mn, V, Cr, Al, Cu, Zn, Sn, 0.6 <m <l .5, 0 <k <l .5, 0≤j <l; the composition of the magnesium-based alloy A 2 B type alloy is
Figure imgf000004_0001
Where E is Ca, Zr, Ti, Hf, mixed rare earth metals, 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.
所述非晶合金为包括以上稀土镍系 八85型、 锆基或钛基 Laves 相系 AB2型、 钛镍系和钛铁系 AB型、 镁基合金 A2B型的任一种或两种以上的 二元或多元非晶合金。 The eight 85-type amorphous alloy, titanium-based or zirconium-based Laves phase AB 2 type-based, nickel-based and titanium-based AB-type ilmenite, magnesium based alloy either A or B is a rare earth-nickel comprising 2 or more Two or more binary or polycrystalline amorphous alloys.
本发明所述碳納米管是单壁納米管或多壁纳米管， 碳納米管外 径为 0 .5-150nm。  The carbon nanotubes in the present invention are single-walled nanotubes or multi-walled nanotubes, and the outer diameter of the carbon nanotubes is 0.5 to 150 nm.
本发明提供的储氢合金 /碳納米管复合储氢材料的制备方法有 如下几种：  There are several methods for preparing the hydrogen storage alloy / carbon nanotube composite hydrogen storage material provided by the present invention:
1 ) 以储氢合金为催化剂， 碳氢化合物 （或 CO) 裂解制备储氢 合金 /碳納米管的复合储氢材料。  1) Hydrogen storage alloys are used as catalysts to produce hydrogen storage alloy / carbon nanotube composite hydrogen storage materials by cracking hydrocarbons (or CO).
作为催化剂的储氢合金可选稀土镍系（ A B 5型）、锆基或钛基 L a V e s 相系 （AB2型） 、 钛镍系和钛铁系 （AB 型） 、 镁基合金 （A2B 型） 和 非晶合金的任一种 （或两种以上） 二元或多元储氢合金。 储氢合金粒 度<7(^111。 经表面处理 （如碱溶液或无机盐溶液） 的储氢合金可获得 納米級的催化点， 反应气体为 CH4、 C2H2、 C2H4、 C6H6或 C0。 The hydrogen storage alloy used as the catalyst can be selected from rare earth nickel series (AB 5 type), zirconium-based or titanium-based La Ves phase series (AB 2 type), titanium nickel series and titanium iron series (AB type), and magnesium-based alloy ( A 2 B type) and amorphous alloy (or two or more) binary or multiple hydrogen storage alloys. Hydrogen storage alloy particle size <7 (^ 111. Surface-treated (such as alkaline solution or inorganic salt solution) hydrogen storage alloy can obtain nano-scale catalytic sites, the reaction gas is CH 4 , C 2 H 2 , C 2 H 4 , C 6 H 6 or C0.
储氢合金 /碳纳米管的复合储氢材料的制备在固定床气体连续 流动式反应装置上进行。 将一定量的催化剂在氢气流下升温至 523K〜1073K， 保持 10〜70 分钟后调溫到 673Κ〜1273Κ， 换成反应 气体， 流速 2〜40ml/cm2. min > 反应 10〜70分钟后停止加热并降溫' 收集产物。 经 SEM (扫描电镜） 或 XRD ( X-衍射） 和 TEM (透射电镜， 样品经超声波处理） 分析測试， 产物为储氢合金 /碳納米管的复合 储氢材料。 The preparation of the hydrogen storage alloy / carbon nanotube composite hydrogen storage material is performed on a fixed bed gas continuous flow reaction device. A certain amount of catalyst is heated to 523K ~ 1073K under a hydrogen stream, maintained for 10 ~ 70 minutes, then adjusted to 673K ~ 1273K, replaced with a reaction gas, and the flow rate is 2 ~ 40ml / cm 2. Min> Stop heating after 10 ~ 70 minutes And cool down 'to collect the product. After SEM (Scanning Electron Microscope) or XRD (X-Diffraction) and TEM (Transmission Electron Microscopy, samples are ultrasonically treated) analysis and testing, the product is a hydrogen storage alloy / carbon nanotube composite hydrogen storage material.
2) 以 Ni、 Co、 Fe、 Cu 等金属任一种或金属混合物为催化剂， 碳氢化合物 （或 CO) 裂解制备碳納米管， 再将催化剂金属与镁、 钛、 锆稀土金属或混合稀土金属等反应制备成储氢合金得到储氢合金 / 碳纳米管的复合储氢材料。 2) Using any metal or metal mixture such as Ni, Co, Fe, Cu as a catalyst, cracking hydrocarbons (or CO) to prepare carbon nanotubes, and then combining the catalyst metal with magnesium, titanium, zirconium rare earth metal or mixed rare earth metal And other reactions to prepare hydrogen storage alloys to obtain hydrogen storage alloys / Carbon nanotube composite hydrogen storage material.
(A) 将一定量催化剂前驱体 Ni0、 Co0、 FeO、 CuO 等中的任一 种金属氧化物或几种金属氧化物的混合物， 放在固定床气体连续流 动式反应裝置中， 在氢气流下升溫至 523K〜1073K， 保持 0 . 5〜5 小 时后调溫至 673Κ〜1273Κ , 换成反应气体， 流速 2〜40ml/cm2. min， 反应 10〜70分钟后停止加热并降温， 反应气体为 CH4、 C2H2、 C2H4、 C6H6等或 C0。 将制得碳納米管和催化剂金属的混合物与计量的 Mg 粉或 Ti粉充分混合， 放入耐压反应器中， 在 0.2〜0 .8MPa 的 Ar 气 氛下， 723K〜1273K 恒溫扩散 1〜6 小时， 使催化剂金属形成 Mg2Ni 或 Mg2Cu或 TiNi、 Ti2Ni或 TiFe等储氢合金或储氢合金混合物， 从 而获得储氢合金 /碳纳米管的复合储氢合金材料。经 SEM、 XRD和 TEM(A) A certain amount of catalyst precursors Ni0, Co0, FeO, CuO, etc., or a mixture of several metal oxides are placed in a fixed-bed gas continuous flow reactor, and the temperature is raised under a hydrogen stream To 523K ~ 1073K, keep it for 0.5 ~ 5 hours, then adjust the temperature to 673K ~ 1273K, change to the reaction gas, flow rate 2 ~ 40ml / cm 2 .min, stop heating and cool down after 10 ~ 70 minutes, the reaction gas is CH 4 , C 2 H 2 , C 2 H 4 , C 6 H 6 etc. or C0. The mixture of the prepared carbon nanotubes and the catalyst metal is thoroughly mixed with a measured amount of Mg powder or Ti powder, and placed in a pressure-resistant reactor under a Ar atmosphere of 0.2 to 0.8 MPa at a constant temperature of 723K to 1273K for 1 to 6 hours. The catalyst metal is formed into a hydrogen storage alloy or a hydrogen storage alloy mixture such as Mg 2 Ni or Mg 2 Cu or TiNi, Ti 2 Ni or TiFe, so as to obtain a hydrogen storage alloy / carbon nanotube composite hydrogen storage alloy material. SEM, XRD and TEM
(透射电镜， 样品经超声波处理） 分析測试证实为储氢合金 /碳納 米管复合储氢合金材料。 (Transmission electron microscope, the sample was ultrasonically treated) Analysis and test confirmed that it is a hydrogen storage alloy / carbon nanotube composite hydrogen storage alloy material.
( B ) 以共沉淀还原法制备储氢合金的前驱体 La203.10NiO、 Mm203.10NiO、 Ti02.NiO、 Ti02-0 .5NiO 和 Ti02-Fe203 等复合金属氧化 物为制备碳纳米管催化剂前驱体。 同 （A) 所述步骤进行， 得到碳 納米管和催化剂金属 Ni、 CO或 Fe及 La203或 Mm203或 Ti02混合物。 将此混合物与计量的 3 或 Ca充分混合，在氩气流中升溫至 973}：〜 1273K , 保温 1〜5 小时， 冷却至室温， 所得产物经水洗—— 1¾醋酸 洗一一水洗至中性， 真空干燥， 得到储氢合金 /碳纳米管复合材料。 经 SEM、 XRD和 TEM (透射电镜， 样品经超声波处理） 分析測试证实 为储氢合金 /碳纳米管复合材料。 (B) Preparation of La 2 0 3 .10NiO, Mm 2 0 3 .10NiO, Ti0 2 .NiO, Ti0 2 -0.5 NiO, Ti0 2 -Fe 2 0 3 and other composites by coprecipitation reduction method Metal oxides are precursors for the preparation of carbon nanotube catalysts. Perform the same steps as in (A) to obtain a mixture of carbon nanotubes and catalyst metals Ni, CO or Fe and La 2 0 3 or Mm 2 0 3 or Ti 0 2 . This mixture is fully mixed with the measured amount of 3 or Ca, and the temperature is raised to 973} in an argon stream: ~ 1273K, held for 1 to 5 hours, cooled to room temperature, and the resulting product is washed with water-1¾ acetic acid washed-washed with water to neutrality, Vacuum drying to obtain a hydrogen storage alloy / carbon nanotube composite material. SEM, XRD, and TEM (transmission electron microscopy, samples were ultrasonically treated) analysis and testing confirmed the hydrogen storage alloy / carbon nanotube composite.
3) 储氢合金与碳納米管直接机械复合制备储氢合金 /碳納米管 的复合储氢材料。  3) Direct mechanical compounding of hydrogen storage alloys and carbon nanotubes to prepare hydrogen storage alloy / carbon nanotube composite hydrogen storage materials.
储氢合金可选稀土镍系 （AB5型） 、 锆基或钛基 Laves相系 （AB2 型） 、 钛鎳系和钛铁系 （AB 型） 、 镁基合金 （A2B 型） 和非晶合金 的任一种（或两种以上）二元或多元储氢合金。储氢合金粒度<7(^0!。 经表面处理 （如碱溶液或无机盐溶液） 的储氢合金后与碳納米管在 真空或氩气或氢气气氛下或在处理溶液 （包括碱溶液、 无机盐溶液 或有机溶液等） 下机械球磨复合。 机械球磨时间控制在 10分钟至 3 小时之间 。 碳納米管制备采用 Ni、 Co、 Fe、 Cu 等金属任一种或金 属混合物为催化剂， 碳氢化合物裂解， 反应气体为 CH4、 C2H2、 C2H4、 6 等。 经 SEM 或 XRD 和 TEM (透射电镜， 样品经超声波处理） 分 析測试， 产物为储氢合金 /碳納米管的复合储氢材料。 Hydrogen storage alloys can be selected from rare earth nickel series (AB 5 type), zirconium-based or titanium-based Laves phase series (AB 2 type), titanium nickel series and titanium iron series (AB type), magnesium-based alloys (A 2 B type), and Any one (or two or more) amorphous alloys of binary or multiple hydrogen storage alloys. Hydrogen storage alloy particle size <7 (^ 0 !. Surface treatment (such as alkaline solution or inorganic salt solution) of hydrogen storage alloy and carbon nanotubes under vacuum or argon or hydrogen atmosphere or mechanical ball milling under treatment solution (including alkaline solution, inorganic salt solution or organic solution, etc.) complex. Mechanical milling time is controlled between 10 minutes and 3 hours. Carbon nanotubes are prepared by using any one of metals such as Ni, Co, Fe, Cu, or a mixture of metals as a catalyst, the hydrocarbons are cracked, and the reaction gases are CH 4 , C 2 H 2 , C 2 H 4 , 6 and the like. After SEM or XRD and TEM (transmission electron microscopy, the sample is ultrasonically treated) analysis and test, the product is a hydrogen storage alloy / carbon nanotube composite hydrogen storage material.
本发明所述所述碱溶液包括 K0H 或 NaOH 的水溶液， 溶液浓度 为 0 .5〜8mol . L- 溶液中含有硼氢化物 （K 或 Na) ， 硼氢化物 （K 或 Na) 的浓度为 0.0〜2mol . L- 1； 所述无机盐溶液包括含有阴离子 为 ： 氟离子、 氯离子、 硫酸根离子、 硝酸根离子、 柠檬酸根离子或 和次亚磷酸根离子， 阳离子为 H+、 K+、 Na+、 NH4+、 Ni2+、 Co2—、 Fe2+、 Cu2+或 Fd2+离子的无机盐溶液， 其中阴离子浓度为 0 .01〜2mol . L一1， 阳离子浓度为 0.01〜2mol . L— 所述有机溶液是四氢呋喃、 环己二 烯、 环己烯、 环己烷、 甲苯、 苯等。 实现本发明的最佳方式 The alkali solution according to the present invention includes an aqueous solution of K0H or NaOH, and the solution concentration is 0.5 to 8 mol. L- The solution contains borohydride (K or Na), and the concentration of borohydride (K or Na) is 0.0 ~ 2mol. L- 1 ; The inorganic salt solution includes anions containing: fluoride ion, chloride ion, sulfate ion, nitrate ion, citrate ion, and hypophosphite ion, and the cations are H +, K +, Na +, NH 4 +, Ni 2+ , Co 2 —, Fe 2+ , Cu 2+ or Fd 2+ inorganic salt solution, wherein the anion concentration is 0.01 ~ 2mol. L- 1 , the cation concentration is 0.01 ~ 2mol. L— The organic solution is tetrahydrofuran, cyclohexadiene, cyclohexene, cyclohexane, toluene, benzene, and the like. The best way to implement the invention
实施例 1  Example 1
将高频炉冶炼的 LaNi4 5Fe0 5粉碎至 ΙΟμπ！〜 20μηι， 在 6mol . L- 1 K0H溶液中室溫下处理 30分钟后， 真空干燥， 即得所制备的合金催 化剂试样。 储氢合金 /碳纳米管复合储氢材料的制备是在固定床气 体连续流动反应式装置上进行。 将 l g 合金催化剂在氢气气氛下升 温至 873K , 稳定 20分钟后， 通入流速 10ml/cm2. min的甲垸， 反应 60 分钟后停止， 在 Η2 气氛下降温至室溫， 收集产物， 碳納米管产 量为 0.2g。 在标准 Sievert' s 反应装置中測定其气固储氢性能， 其 储氢容量为 2 . 5wt¾。 Crush LaNi 4 5 Fe 0 5 smelted in a high-frequency furnace to 10 μπ! ~ 20μηι, treated in a 6mol. L- 1 KOH solution at room temperature for 30 minutes, and dried in vacuum to obtain the prepared alloy catalyst sample. The hydrogen storage alloy / carbon nanotube composite hydrogen storage material is prepared on a fixed-bed gas continuous flow reaction type device. After lg alloy catalyst under a hydrogen atmosphere heated to 873K, stable for 20 minutes, into a flow rate 10ml / cm 2. Min methyl embankment, reaction was stopped after 60 minutes, cooled to room temperature under an atmosphere of Η 2, product was collected, carbon The yield of nanotubes was 0.2 g. 5wt¾。 Its gas-solid hydrogen storage performance was measured in a standard Sievert's reaction device, and its hydrogen storage capacity was 2.5 wt.
实施例 2 将 2mol.L— 1 NiCl2^ 2mol丄—1 LaCl3水溶液按体积比 5:1 混合均 匀， 在不断搅拌下緩慢加入 1.5mol.L— 1 Na2C03溶液， 生成沉淀。 反 复采用二次蒸馏水洗涤至水层无氯离子， 过滤后， 于烘箱中在 373K 下烘千， 即得所制备的催化剂前驱体试样。 碳纳米管的制备在固定 床气体连续流动反应式装置上进行。 将 5g 催化剂在氢气气氛下升 温至 923K, 稳定 30分钟后， 通入流速 20ml/cm2.min 的甲烷， 反应 30 分钟后停止， 收集产物， 将此产物与 CaH2按质量比为 1:1.1 混 合放入固定床气体连续流动反应式装置进行反应， 在氢气气氛下升 温至 1223K, 恒溫 4 个小时。 迅速冷却产物至室温， 收集产物。 将 此产物用蒸馏水洗涤至中性， 真空千燥， 得到产物， 储氢合金与碳 纳米管重量比为 2/1。 在标准 Sievert's 反应装置中測定其气固储 氢性能， 其储氢容量为 4.5wt¾。 Example 2 The 2mol.L- 1 NiCl 2 ^ 2mol Shang - 1 LaCl 3 solution volume ratio of 5: 1 mixed, was slowly added under constant stirring 1.5mol.L- 1 Na 2 C0 3 solution, a precipitate formed. The secondary distilled water was repeatedly used to wash until the water layer was free of chloride ions. After filtration, the sample was dried at 373K in an oven to obtain a prepared catalyst precursor sample. The carbon nanotubes were prepared on a fixed-bed gas continuous flow reaction apparatus. 5g of catalyst was heated to 923K in a hydrogen atmosphere. After being stable for 30 minutes, methane with a flow rate of 20ml / cm 2 .min was introduced. After 30 minutes of reaction, the reaction was stopped. The product was collected, and the mass ratio of this product to CaH 2 was 1: 1.1. Mixed into a fixed-bed gas continuous flow reaction device for reaction, the temperature was raised to 1223K in a hydrogen atmosphere, and the temperature was maintained for 4 hours. The product was quickly cooled to room temperature and collected. The product was washed with distilled water to neutrality and dried under vacuum to obtain a product. The weight ratio of the hydrogen storage alloy to the carbon nanotubes was 2/1. The gas-solid hydrogen storage performance was measured in a standard Sievert's reaction device, and its hydrogen storage capacity was 4.5wt¾.
实施例 3  Example 3
将电弧炉冶炼的 ZrV0 2Mn0 6Co0 !Ni, 2粉碎至 ΙΟμπ！〜 20μπι， 然后 在 343Κ下 0.5mol丄—1 NiF2/NH4F溶液中处理 0.5 小时即得所制备的 合金催化剂试样。 储氢合金 /碳纳米管复合储氢材料的制备在固定 床气体连续流动反应式装置上进行。 将 lg 催化剂在氢气气氛下升 溫至 873K, 稳定 10分钟后， 通入流速 15ml/cm2.min 的甲烷， 反应 60 分钟后停止， 在 H2 气氛下降溫至室温， 收集产物， 碳納米管产 量为 0.4g。 在标准 Sievert's 反应装置中測定其气固储氢性能， 其 储氢容量为 3.8wt%。 The ZrV 0 2 Mn 0 6 Co 0 ! Ni, 2 smelted by the electric arc furnace was pulverized to 10 μπ! ~ 20μm, and then treated with 0.5mol 丄-1 NiF 2 / NH 4 F solution at 343K for 0.5 hours to obtain the prepared alloy catalyst sample. The preparation of the hydrogen storage alloy / carbon nanotube composite hydrogen storage material is performed on a fixed-bed gas continuous flow reaction type device. The lg catalyst was heated to 873K in a hydrogen atmosphere, and after being stable for 10 minutes, methane with a flow rate of 15ml / cm 2 .min was introduced, and the reaction was stopped after 60 minutes. The temperature was reduced to room temperature in an H 2 atmosphere, and the product was collected. The yield of carbon nanotubes 0.4g. Its gas-solid hydrogen storage performance was measured in a standard Sievert's reaction device, and its hydrogen storage capacity was 3.8 wt%.
实施例 4  Example 4
将电弧炉冶炼制备的 TiFe。 9Ni。 , 合金粉碎至 50μπ！〜 70μπι, 然 后在 0.5mol.L- 1 NiF2/NH4F/NaH2P02溶液中球磨 （行星式球磨机） 70 小时即得所制备的超细合金催化剂试样。 储氢合金 /碳纳米管复合 储氢材料的制备在固定床气体连续流动反应式装置上进行。 将 lg 催化剂在氢气气氛下升溫至 973K, 稳定 10 分钟后 ， 通入流速 25ml/cm2.min 的甲烷， 反应 60 分钟后停止， 在 112气氛下降溫至室 温， 收集产物， 碳納米 产量为 0.3g。 在标准 Sievert's 反应装置 中测定其气固储氢性能， 其储氢容量为 3.1wt¾。 TiFe prepared by arc furnace smelting. 9 Ni. , The alloy is crushed to 50μπ! ~ 70μm, and then ball milling (planetary ball mill) in a 0.5mol.L- 1 NiF 2 / NH 4 F / NaH 2 P0 2 solution for 70 hours to obtain the prepared ultrafine alloy catalyst sample. The preparation of the hydrogen storage alloy / carbon nanotube composite hydrogen storage material is performed on a fixed-bed gas continuous flow reaction type device. The lg catalyst was heated to 973K in a hydrogen atmosphere. After being stable for 10 minutes, the flow rate was passed in. 25ml / cm 2 .min methane, reaction was stopped after 60 minutes, cooled to room temperature under an atmosphere of 112, the product was collected, yield of carbon nano 0.3g. The gas-solid hydrogen storage performance was measured in a standard Sievert's reaction device, and its hydrogen storage capacity was 3.1wt¾.
实施例 5  Example 5
将 Mg2Ni 合金粉碎至 50μπι〜70μπι, 然后在氩气气氛条件下球磨 70 小时即得所制备的非晶合金催化剂试样。 储氢合金 /碳納米管的 复合储氢材料的制备在固定床气体连续流动反应式装置上进行。 将 lg 催化剂在氢气气氛下升温至 823K， 通入流速 30ml/cm2.min 的乙 炔， 反应 60 分钟后停止， 在 H2气氛下降温至室溫， 收集产物， 碳 納米管产量为 0.6g。 在标准 Sievert's 反应装置中測定其气固储氢 性能， 其储氢容量为 5.2wt%。 The Mg 2 Ni alloy was pulverized to 50 μm to 70 μm, and then the sample was prepared by ball milling under an argon atmosphere for 70 hours. The preparation of the hydrogen storage alloy / carbon nanotube composite hydrogen storage material is performed on a fixed-bed gas continuous flow reaction device. The lg catalyst was heated to 823 K under a hydrogen atmosphere, and acetylene was passed at a flow rate of 30 ml / cm 2 .min. The reaction was stopped after 60 minutes. The temperature was lowered to room temperature in an H 2 atmosphere, and the product was collected. The yield of carbon nanotubes was 0.6 g. The gas-solid hydrogen storage performance was measured in a standard Sievert's reaction device, and its hydrogen storage capacity was 5.2 wt%.
实施例 6  Example 6
将 ZrV0 2Mn0 6N 2合金粉碎至 50μπι-70μπι, 然后在 0.5mol.L- 1 NiF2/NH4F 溶液中球磨 40 小时即得所制备的超细合金试样， 再加入 管径为 5〜20nm的碳纳米管， 储氢合金与碳納米管的重量比为 1/2, 球磨时间为 30分钟， 产物洗涤后真空干燥。 产物在柘准 Sievert's 反应裝置中测定其气固储氢性能， 其储氢容量为 3.4wt%。 工业应用性 The ZrV 0 2 Mn 0 6 N 2 alloy was pulverized to 50 μπι-70 μπι, and then ball-milled in a 0.5mol.L- 1 NiF 2 / NH 4 F solution for 40 hours to obtain the prepared ultrafine alloy sample. The carbon nanotubes are 5-20 nm, the weight ratio of the hydrogen storage alloy to the carbon nanotubes is 1/2, the ball milling time is 30 minutes, and the product is vacuum dried after washing. The product was tested for its gas-solid hydrogen storage performance in a pseudo-Sievert's reaction device, and its hydrogen storage capacity was 3.4 wt%. Industrial applicability
本发明的储氢合金 /碳纳米管复合储氢材料结合了现有的两类 储氢材料的优点， 即储氢合金的高催化活性和碳纳米管的高储氢容 量， 其性能稳定， 是一种新型的高容量复合储氢材料， 可广泛应用 于氢的规模化储运、 燃料电池的氢源、 镍氢电池、 氢的提纯以及有 机加氢催化等方面， 具有很好的工业应用前景。  The hydrogen storage alloy / carbon nanotube composite hydrogen storage material of the present invention combines the advantages of the existing two types of hydrogen storage materials, that is, the high catalytic activity of the hydrogen storage alloy and the high hydrogen storage capacity of the carbon nanotube, and its performance is stable. A new type of high-capacity composite hydrogen storage material, which can be widely used in large-scale storage and transportation of hydrogen, hydrogen sources for fuel cells, nickel-metal hydride batteries, hydrogen purification, and organic hydrogenation catalysis. .

Claims

杈利要求 Profit requirements
1 .一种复合储氢材料， 1. A composite hydrogen storage material,
其特征在于， 该复合储氢材料包括储氢合金和碳纳米管， 其中储氢合金 的重量含量范围为 1〜90%。 It is characterized in that the composite hydrogen storage material includes a hydrogen storage alloy and carbon nanotubes, wherein the weight content of the hydrogen storage alloy ranges from 1 to 90%.
2.根据杈利要求 1的复合储氢材料，  2. The composite hydrogen storage material according to the requirements 1
其特征在于， 所述储氢合金是稀土镍系 AB5型、 锆基或钛基或稀土镍基 Laves相系 AB2型、 钛镍系或钛铁系 AB型、 镁基合金 A2B型、 或者非晶 合金的任一种或两种以上的二元或多元储氢合金； It is characterized in that the hydrogen storage alloy is a rare-earth nickel-based AB 5 type, a zirconium-based or titanium-based or a rare-earth nickel-based Laves phase-based AB 2 type, a titanium-nickel or titanium iron-based AB type, and a magnesium-based alloy A 2 B type. Or any one or two or more binary or multiple hydrogen storage alloys of an amorphous alloy;
储氢合金中稀土镍系 AB5型合金组成为： LNin_x_y— zCoxNyMz， 其中 其中 L为混合稀土金属、 La、 Ce、 Nd、 Pr、 Y， Ν和 Μ分别为 Μη、 V、 Cr、 Al、 Fe、 Cu 、 Zn、 Sn， 4<n<6 , 0<x<2 , 0<y<2 , 0<z<2； 锆基 或钛基或稀土镇基 Laves 相系 AB2型合金组成为： KNia_b— c_dVbGcJd , 其中 K为 Zr、 Ti 、 Hf 、 混合稀土金属、 La、 Ce、 Nd、 Pr、 Y， G和 J 分別为 Co、 Mn、（： r、 Al、 Fe、（： u、 Zn、 Sn , 1 .2<a<2 .8 , 0<b<2 , 0<c<2， 0<d<2； 钛镍系或钛铁系 AB 型合金组成为： HNim— k— d.FekPd， 其中 H 为 Zr、 Hf , P为 Co、 Mn、 V、 Cr、 Al、 Cu、 Zn、 Sn , 0 .6<m≤l .5 , 0<k<l .5 , 0≤j'≤l；镁基合金 A2B型合金组成为：
Figure imgf000009_0001
p— qCopTq，其中 E为 Ca、 Zr、 Ti、 Hf 、 混合稀土金属、 La、 Ce、 Nd、 Fr、 Y , T为 Mn、 V、 Cr、 Al、 Fe、 Cu、 Zn、 Sn， 0.8≤g≤2.5， 0≤f≤l , 0<p<0 .6 , 0<q<0 .6； 非晶合金为包括以上稀土镍系 AB5型、 锆基或钛基 Laves 相系 AB2 型、 钛镍系和钛铁系 AB型、 镁基合金 A2B型的任一种或两种以上的二元 或多元非晶合金。 The composition of the rare earth nickel-based AB 5 type alloy in the hydrogen storage alloy is: LNi n _ x _ y — z Co x N y M z , where L is a mixed rare earth metal, La, Ce, Nd, Pr, Y, Ν and Μ Mn, V, Cr, Al, Fe, Cu, Zn, Sn, 4 <n <6, 0 <x <2, 0 <y <2, 0 <z <2; zirconium or titanium based or rare earth town The composition of the base Laves phase AB 2 alloy is: KNi a _ b — c _ d V b G c J d , where K is Zr, Ti, Hf, mixed rare earth metal, La, Ce, Nd, Pr, Y, G And J are Co, Mn, (: r, Al, Fe, (: u, Zn, Sn, 1.2 <a <2.8, 0 <b <2, 0 <c <2, 0 <d <2; The composition of Ti-Ni-based or TiFe-based AB alloys is: HNi m — k — d. Fe k P d , where H is Zr, Hf, P is Co, Mn, V, Cr, Al, Cu, Zn, Sn, 0.6 <m≤l .5, 0 <k <l .5, 0≤j'≤l; The composition of the magnesium-based alloy A 2 B alloy is:
Figure imgf000009_0001
p — q Co p T q , where E is Ca, Zr, Ti, Hf, mixed rare earth metal, La, Ce, Nd, Fr, Y, and T is Mn, V, Cr, Al, Fe, Cu, Zn, Sn , 0.8≤g≤2.5, 0≤f≤l, 0 <p <0.6, 0 <q <0.6; The amorphous alloy is the above-mentioned rare earth nickel-based AB 5 type, zirconium-based or titanium-based Laves phase system Any one or two or more types of binary or multiple amorphous alloys of the AB 2 type, the titanium nickel system and the titanium iron system AB type, and the magnesium base alloy A 2 B type.
3.根据杈利要求 1的复合储氢材料，  3. According to the requirements of the composite hydrogen storage material 1,
其特征在于， 所述碳纳米管是单壁纳米管或多壁纳米管， 碳納米管外径 为 0.5〜150nm。  It is characterized in that the carbon nanotube is a single-walled nanotube or a multi-walled nanotube, and the outer diameter of the carbon nanotube is 0.5 to 150 nm.
4.杈利要求 1的复合储氢材料的制备方法， 其特征在于， 以合金粒度 <70μπι 的储氢合金为催化剂， 在碱溶液或无机 盐溶液中经表面处理使储氢合金表面获得納米級的催化点； 将催化剂在 氢气流下升溫至 523Κ〜1073Κ， 保持 10〜70 分钟后调溫到 673Κ〜 1273K , 换成反应气体碳氢化合物或 CO , 流速 2〜40ml/cm2. min , 反 应 10〜70 分钟后停止加热并降至室温， 得到储氢合金 /碳纳米管复 合储氢材料。 4. Preparation method of the composite hydrogen storage material according to claim 1, It is characterized in that a hydrogen storage alloy with an alloy particle size of <70 μπι is used as a catalyst, and the surface of the hydrogen storage alloy is obtained with a nano-scale catalytic point by surface treatment in an alkali solution or an inorganic salt solution; After maintaining for 10 ~ 70 minutes, adjust the temperature to 673K ~ 1273K, change to the reaction gas hydrocarbon or CO, and the flow rate is 2 ~ 40ml / cm 2 .min. After 10 ~ 70 minutes of reaction, stop heating and drop to room temperature to obtain a hydrogen storage alloy / Carbon nanotube composite hydrogen storage material.
5.杈利要求 1的复合储氢材料的制备方法，  5. Preparation method of composite hydrogen storage material according to claim 1,
其特征在于， 以含有 Ni、 Co、 Fe、 Cu 金属任一种或金属混合物为催化 剂前驱体， 将该催化剂前驱体放在固定床气体连续流动式反应装置 中， 在氢气流下升温至 523K〜1073K , 保持 0 .5〜5 小时后调温至 673Κ〜 1273K , 换成反应 气体碳氢化合物或 CO , 流速 2〜 40ml/cm2. min ) 反应 10〜70分钟后停止加热并降温， 得到碳納米管 和催化剂金属的混合物， 将该混合物与镁、 钛、 锆或稀土金属或混合 稀土金属粉末直接在 0.2〜0 .8MPa 的 Ar 气氛下， 723K〜： 273K 恒温 扩散 1〜6 小时， 降至室温， 得到储氢合金 /碳納米管的复合储氢材 料。 It is characterized in that it uses any metal or metal mixture containing Ni, Co, Fe, Cu as a catalyst precursor, and the catalyst precursor is placed in a fixed-bed gas continuous flow reaction device, and the temperature is raised to 523K to 1073K under a hydrogen stream. after holding the temperature control until 0 hours .5~5 673Κ~ 1273K, the reaction gas into hydrocarbons or CO.'s, the flow rate 2~ 40ml / cm 2. min) 10~70 minutes heating was stopped the reaction and cooling to obtain a carbon nano Mixture of tube and catalyst metal, directly mix the mixture with magnesium, titanium, zirconium or rare earth metal or mixed rare earth metal powder in an Ar atmosphere of 0.2 ~ 0.8MPa, 723K ~: 273K constant temperature diffusion for 1 ~ 6 hours, reduce to room temperature To obtain a hydrogen storage alloy / carbon nanotube composite hydrogen storage material.
6. 杈利要求 1的复合储氢材料的制备方法，  6. Preparation method of composite hydrogen storage material according to claim 1,
其特征在于，以由包括 La203.10Ni0、Mm203- 10NiO、Ti02.NiO、TiO2.0 .5NiO 和 Ti02.Fe203的复合金属氧化物为催化剂前驱体， 将该催化剂前驱体 放在固定床气体连续流动式反应裝置中， 在氢气流下升温至 523K〜 1073K , 保持 0 .5〜5 小时后调温至 673Κ〜1273Κ， 换成反应气体碳 氢化合物或 CO , 流速 2〜40ml/cm2. min， 反应 10〜70 分钟后停止加 热并降溫， 得到含有碳納米管和催化剂金属 Ni、 Co或 Fe及 La203或 Mm203或 1102金属氧化物的混合物， 将此混合物与计量 3 或 Ca充分混 合， 在氩气流中升溫至 973K〜1273K， 保温 1〜5小时， 降至室温， 所 得产物经水洗—— 1¾醋酸洗——水洗至中性， 真空干燥， 制备得到 储氢合金 /碳纳米管的复合储氢材料。 Wherein, in the including La 2 0 3 .10Ni0, Mm 2 0 3 - 10NiO, Ti0 2 .NiO, TiO 2 .0 .5NiO composite metal oxide and Ti0 2 .Fe 2 0 3 as catalyst precursor, The catalyst precursor was placed in a fixed-bed gas continuous flow reaction device, and the temperature was raised to 523K to 1073K under a hydrogen flow, and the temperature was adjusted to 673K to 1273K after maintaining for 0.5 to 5 hours, and replaced with the reaction gas hydrocarbon or CO. At a flow rate of 2 to 40 ml / cm 2. Min, heating and cooling were stopped after 10 to 70 minutes of reaction to obtain carbon nanotubes and catalyst metals Ni, Co or Fe and La 2 0 3 or Mm 2 0 3 or 110 2 metal oxidation This mixture is thoroughly mixed with meter 3 or Ca, and the temperature is raised to 9 73 K ~ 1 27 3K in an argon stream, the temperature is maintained for 1 ~ 5 hours, and the temperature is lowered to room temperature. The resulting product is washed with water-1¾ acetic acid- It was washed with water to neutrality and dried under vacuum to prepare a hydrogen storage alloy / carbon nanotube composite hydrogen storage material.
7. 根据杈利要求 4、 5或 6的复合储氢材料的制备方法， 7. Preparation method of composite hydrogen storage material according to requirements 4, 5, or 6,
其特征在于， 所述碳氢化合物为 CH4、 C2H2、 C2H4或 C6H6。 It is characterized in that the hydrocarbon is CH 4 , C 2 H 2 , C 2 H 4 or C 6 H 6 .
8 - 杈利要求 1的复合储氢材料的制备方法，  8-Preparation method of composite hydrogen storage material according to claim 1,
其特征在于， 将储氢合金与碳納米管在真空或氩气或氢气气氛下或在碱 溶液或无机盐溶液或有机溶液中机械球磨复合， 机械球磨时间控制在 10 分钟到 3小时之间。 It is characterized in that the hydrogen storage alloy and carbon nanotubes are mechanically ball milled in a vacuum or argon or hydrogen atmosphere or in an alkali solution, an inorganic salt solution or an organic solution, and the mechanical ball milling time is controlled between 10 minutes and 3 hours.
9。 根据杈利要求 4或 8的复合储氢材料的制备方法，  9. According to the method for preparing a composite hydrogen storage material of 4 or 8,
其特征在于， 所述碱溶液是 K0H或 NaOH的水溶液， 溶液浓度为 0.5〜 8mol.L— 溶液中含有硼氢化物（硼氢化钾或硼氢化钠）， 硼氢化物 的浓度为 O.O Smol.L-1, 所述无机盐溶液中包括含有阴离子为 ： 氟 离子、 氯离子、 硫酸根离子、 硝酸根离子、 柠檬酸根离子或和次亚 磷酸二氢根离子， 阳离子为 H+、 K+、 Na+、 NH4+、 Ni2+、 Co2+、 Fe2+、 Cu 或 Pd2+离子的无机盐溶液； 阴离子浓度为 0.01〜2mol.L- 阳离子 浓度为 0.01〜2mol丄一1。 It is characterized in that the alkaline solution is an aqueous solution of K0H or NaOH, and the solution concentration is 0.5 to 8 mol.L—the solution contains borohydride (potassium borohydride or sodium borohydride), and the concentration of borohydride is OO Smol.L -1 . The inorganic salt solution includes anions containing: fluoride ion, chloride ion, sulfate ion, nitrate ion, citrate ion, and hypophosphite ion, and the cations are H +, K +, Na +, NH 4 +, Ni 2+ , Co 2+ , Fe 2+ , Cu or Pd 2+ inorganic salt solution; anion concentration is 0.01 ~ 2mol.L- cation concentration is 0.01 ~ 2mol 丄1 .
10- 根据杈利要求 8的复合储氢材料的制备方法，  10- Preparation method of composite hydrogen storage material according to requirement 8
其特征在于， 所述有机溶液是四氢呋喃、 环己二烯、 环己烯、 环己 烷、 甲苯、 苯。 It is characterized in that the organic solution is tetrahydrofuran, cyclohexadiene, cyclohexene, cyclohexane, toluene, benzene.
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