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WO2008032774A1 - Matériau de stockage d'hydrogène et son procédé de fabrication - Google Patents

Matériau de stockage d'hydrogène et son procédé de fabrication Download PDF

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Publication number
WO2008032774A1
WO2008032774A1 PCT/JP2007/067819 JP2007067819W WO2008032774A1 WO 2008032774 A1 WO2008032774 A1 WO 2008032774A1 JP 2007067819 W JP2007067819 W JP 2007067819W WO 2008032774 A1 WO2008032774 A1 WO 2008032774A1
Authority
WO
WIPO (PCT)
Prior art keywords
hydrogen storage
storage material
tin
magnesium
hydrogen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2007/067819
Other languages
English (en)
Japanese (ja)
Inventor
Shinji Oshima
Hayao Imamura
Yoshihisa Sakata
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eneos Corp
Yamaguchi University NUC
Original Assignee
Nippon Oil Corp
Yamaguchi University NUC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Oil Corp, Yamaguchi University NUC filed Critical Nippon Oil Corp
Publication of WO2008032774A1 publication Critical patent/WO2008032774A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0408—Light metal alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C2202/00—Physical properties
    • C22C2202/04—Hydrogen absorbing
    • 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 and a method for manufacturing the same, and more specifically, a hydrogen storage material for storing hydrogen gas expected to be used in fuel cell vehicles, hydrogen internal combustion engines, and the like, and a method for manufacturing the same. About.
  • Examples of conventional representative hydrogen storage alloys include AB type compounds such as LaNi and CaNi.
  • Laves phase structure alloy such as gold, MgCu, MgNi and TiCr alloy, V TiNi, etc.
  • Patent Document 1 listed below discloses a Mg Ni crystal region as a magnesium-based hydrogen storage material.
  • non-crystalline region (metastable phase) of Mg Ni composition become nanostructured on the nanometer scale
  • a hydrogen storage material is disclosed.
  • M B, Al, Si, Ca, Ti, V, Cr, Mn, Fe, Co, Cu, Zn, Sr, Y, Zr).
  • Nb, Mo, Pd, Ag, Sn, Ba, Hf, Ta, La, Ce, Pr, Nd, Sm) A method for producing an amorphous magnesium nickel-based hydrogen storage alloy in which a melted alloy is made amorphous by mechanical alloying is disclosed.
  • Patent Document 1 JP 11 61313 A
  • Patent Document 2 JP-A-11 269572
  • Magnesium-nickel alloys such as those disclosed in Patent Documents 1 and 2 are expected as hydrogen storage materials that have a large amount of hydrogen storage per unit mass and are lightweight and capable of storing a large amount of hydrogen. Yes.
  • these magnesium-nickel alloys and the conventional hydrogen storage materials described above still have problems with high hydrogen release temperatures! / ,! The Therefore, it is desired to develop a hydrogen storage material capable of lowering the hydrogen release temperature while maintaining a sufficiently high hydrogen storage amount.
  • the present invention has been made in view of the above-described problems of the prior art, and provides a hydrogen storage material having a sufficiently high hydrogen storage amount and a sufficiently low hydrogen release temperature, and a method for producing the same.
  • the purpose is to do.
  • the present invention provides a hydrogen storage material characterized by containing substantially only magnesium and tin as metal elements.
  • a magnesium-nickel alloy hydrogen storage material As a conventional hydrogen storage material, as described above, a magnesium-nickel alloy hydrogen storage material is generally used. However, the present inventors have intensively researched on magnesium that uses nickel. On the other hand, by combining tin alone, it was found that the hydrogen release temperature can be greatly reduced compared with the case of using nickel. That is, according to the hydrogen storage material of the present invention, by containing substantially only magnesium and tin as metal elements, the hydrogen storage temperature is sufficiently maintained due to the presence of tin while sufficiently maintaining a high hydrogen storage amount by magnesium. It can be made low enough. Furthermore, the effect of lowering the hydrogen release temperature can be sufficiently obtained by adding a small amount of tin to the hydrogen storage material of the present invention. Therefore, the ratio of magnesium in the hydrogen storage material can be kept sufficiently high, and accordingly, a sufficiently high hydrogen storage amount can be obtained.
  • the hydrogen storage material of the present invention contains the magnesium as particles containing substantially only the magnesium as a metal element, and the tin is essentially only the tin as a metal element. It is preferable to contain as the particle
  • the content of the tin is preferably 1 to 40 mol% based on the total content of the magnesium and the tin. As a result, a high level of hydrogen storage and a low hydrogen release temperature can be achieved at a higher level.
  • the present invention also includes magnesium alone and / or magnesium compound and tin alone and
  • a method for producing a hydrogen storage material characterized in that the hydrogen storage material according to the present invention is obtained by ball milling with a tin compound in a vacuum, an inert gas atmosphere or a hydrogen gas atmosphere.
  • the hydrogen storage amount of the present invention can be efficiently and reliably produced with a sufficiently high hydrogen storage amount and a sufficiently low hydrogen release temperature.
  • S can.
  • magnesium alone and / or magnesium compound and tin alone and / or tin compound to direct ball milling without alloying by melting or the like, particles containing substantially only magnesium as a metal element; A hydrogen storage material containing particles containing substantially only tin as a metal element can be produced efficiently and reliably.
  • the ball milling is performed in the presence of an organic solvent.
  • an organic solvent it is preferable that the milling effect between the magnesium simple substance and / or the magnesium compound and the tin simple substance and / or the tin compound can be enhanced, and both the hydrogen storage amount and the hydrogen release temperature of the obtained hydrogen storage material can be stabilized more stably. It ’s good.
  • the hydrogen storage material of the present invention is characterized by containing substantially only magnesium and tin as metal elements.
  • substantially containing only magnesium and tin as metal elements means that metal elements other than magnesium and tin are not intentionally added to the hydrogen storage material. That is, the metal element as an impurity contained in the raw material, the metal element generated in the manufacturing process of the hydrogen storage material such as a ball milling process, etc. are within the range of the hydrogen storage material as long as the effects of the present invention are not impaired. It may be mixed in.
  • the hydrogen storage material contains an element other than a metal element without any particular limitation. For example, an element other than a metal element such as hydrogen, carbon, or halogen may be contained.
  • the total content of magnesium and tin in the hydrogen storage material of the present invention is preferably 70% by mass or more based on the total amount of metal elements contained, and is 85% by mass or more. It is more preferably 90% by mass or more, and particularly preferably 99% by mass or more. Further, in this specification, the “metal element” is a concept including a key element.
  • magnesium and tin may be alloyed or not alloyed, or may be partially alloyed but preferably not alloyed.
  • the hydrogen storage material of the present invention preferably contains magnesium as particles containing substantially only magnesium as a metal element, and contains tin as particles containing substantially only tin as a metal element. .
  • the particles containing substantially only magnesium as the metal element and the particles containing substantially only tin as the metal element exist in a mixed state while adhering to each other. In this case, the particles that substantially contain only magnesium as the metal element and the particles that substantially contain only tin as the metal element are adhered to each other without being alloyed to form a composite particle.
  • particles containing substantially only magnesium as a metal element means particles to which no metal element other than magnesium is intentionally added
  • substantially containing only tin as a metal element means a particle to which no metal element other than tin is intentionally added. That is, the metal element as an impurity contained in the raw material, the metal element generated in the manufacturing process of the hydrogen storage material such as the ball milling process, etc. are within the range of each particle as long as they do not impair the effects of the present invention. It may be mixed in.
  • each particle contains an element other than a metal element without any particular limitation. For example, an element other than a metal element such as hydrogen or halogen may be contained.
  • the content of tin is preferably 1 to 40 mol% based on the total content of magnesium and tin. A force is preferable. If the tin content is less than mol%, the effect of lowering the hydrogen release temperature tends to decrease, and if it exceeds 40 mol%, the hydrogen storage amount tends to decrease.
  • the hydrogen storage material of the present invention is preferably in a powder form.
  • the crystallite size of the hydrogen storage material measured by XRD analysis is preferably 30 nm or less, more preferably lOnm or less, from the viewpoint of obtaining the effects of the present invention more sufficiently.
  • the hydrogen storage material of the present invention described above has a sufficiently high hydrogen storage amount and a sufficiently low hydrogen release temperature. By using such a power and hydrogen storage material, it is possible to store hydrogen gas, which is expected to be used in fuel cell vehicles, hydrogen internal combustion engines, etc., at high density.
  • the method for producing a hydrogen storage material of the present invention includes ball milling a magnesium simple substance and / or a magnesium compound and a tin simple substance and / or a tin compound in a vacuum, an inert gas atmosphere or a hydrogen gas atmosphere. This is a method characterized in that the hydrogen storage material of the present invention is obtained.
  • the magnesium simple substance and the magnesium compound are preferably in the form of powder, and the average particle diameter is preferably 100 m or less, and more preferably 10 m or less.
  • magnesium compound examples include MgH and the like.
  • the average particle size is 100,1 m or less, and the force S is preferable, and 10 m or less is more preferable.
  • the tin compounds include SnCl, SnCl, SnO, SnO, SnO, SnS and so on.
  • organotin compounds examples include Bu Sn, Bu
  • the organotin compound may be in a liquid form.
  • the active material finally produced after milling is a simple substance of tin, it is preferable to use a simple substance of tin among simple substances of tin and tin compounds.
  • the atmosphere when ball milling the object is a vacuum S, an inert gas atmosphere or a hydrogen gas atmosphere S, an inert gas atmosphere or a hydrogen gas atmosphere is preferred.
  • a gas atmosphere is more preferable.
  • Nitrogen gas is preferred as an inert gas, among which nitrogen gas and argon gas can be cited.
  • the pressure of the atmosphere gas is preferably 0.05 to lMPa, more preferably 0 to; 0.5 to 0.5 MPa. It is preferable. When this pressure is less than 0.05 MPa, the hydrogen release temperature tends to increase. On the other hand, when the pressure exceeds IMPa, the effect of further increasing the pressure tends to be small.
  • ball milling of magnesium alone and / or magnesium compound and tin alone and / or tin compound is preferably performed in the presence of an organic solvent.
  • an organic solvent By adding an organic solvent during ball milling, the milling effect can be enhanced, and the hydrogen storage capacity and hydrogen release temperature of the resulting hydrogen storage material can both be stabilized and improved. S can.
  • the organic solvent is not particularly limited, and examples thereof include benzene, cyclohexane, tetrahydrofuran (THF), and toluene.
  • cyclohexane is preferable from the viewpoint of further improving the milling effect.
  • the addition amount of the organic solvent is preferably 0.7 to 5 mL with respect to magnesium alone and / or magnesium compound lg 0.7 to 5 mL. Is more preferable.
  • Ball milling is preferably performed using a planetary ball mill.
  • Preferred examples of the ball mill container and ball material include stainless steel, chrome steel, zircoure, menor, and tandastain carbide, with zircoyu being particularly preferred!
  • the ball milling under the condition that the powdery hydrogen storage material having the above-mentioned average particle diameter is obtained.
  • the container is rotated at 200 to 900 rpm for 1 to 10 hours. It is preferable to do it under conditions.
  • the hydrogen storage material of the present invention has a sufficiently high hydrogen storage amount and a sufficiently low hydrogen release temperature. Can be manufactured.
  • MgH powder (Wako Pure Chemical Industries, purity 98%) lg, Sn powder
  • MgH powder (Wako Pure Chemical Industries, purity 98%) lg, SnCl powder (
  • MgH powder (Wako Pure Chemical Industries, purity 98%) lg, Sn powder
  • Example 4 In a nitrogen gas atmosphere, MgH powder (manufactured by Wako Pure Chemical Industries, Ltd., purity 98%) lg, tetrabutyl
  • MgH powder (Wako Pure Chemical Industries, purity 98%) lg, planetary ball mill (Kurimoto
  • Zircoure container manufactured by Kogyo Co., Ltd. (with a volume of 170 mU together with 55 mL of 2 mm diameter zirconium balls), filled with nitrogen gas as an inert gas at atmospheric pressure, sealed and sealed.
  • This container was placed on the base of a planetary ball mill apparatus, and the powder rotation rate was 863 rpm, and ball milling was performed for 2 hours. A powdered hydrogen storage material was obtained.
  • Example 2 For the hydrogen storage materials obtained in! ⁇ 2 and Comparative Example 1! /, And using a TPD device, the peak temperature of hydrogen release was measured in a vacuum at a rate of 2 ° C / min. . The results are shown in Table 1. In the hydrogen storage material of Example 2, hydrogen release was separated into two peaks, and the hydrogen release amount at both peaks was approximately 1: 1.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Analytical Chemistry (AREA)
  • Powder Metallurgy (AREA)
  • Hydrogen, Water And Hydrids (AREA)

Abstract

L'invention concerne un matériau de stockage d'hydrogène ayant une quantité de stockage d'hydrogène suffisamment élevée et une température de décharge d'hydrogène suffisamment faible. Le matériau de stockage d'hydrogène contient essentiellement uniquement du magnésium et de l'étain comme éléments métalliques.
PCT/JP2007/067819 2006-09-15 2007-09-13 Matériau de stockage d'hydrogène et son procédé de fabrication Ceased WO2008032774A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2006251296 2006-09-15
JP2006-251296 2006-09-15
JP2007049596A JP5189778B2 (ja) 2006-09-15 2007-02-28 水素吸蔵材料及びその製造方法
JP2007-049596 2007-02-28

Publications (1)

Publication Number Publication Date
WO2008032774A1 true WO2008032774A1 (fr) 2008-03-20

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PCT/JP2007/067819 Ceased WO2008032774A1 (fr) 2006-09-15 2007-09-13 Matériau de stockage d'hydrogène et son procédé de fabrication

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JP (1) JP5189778B2 (fr)
WO (1) WO2008032774A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6295170B2 (ja) * 2014-09-05 2018-03-14 太平洋セメント株式会社 水素化マグネシウムの製造法
JP2024535993A (ja) 2021-09-29 2024-10-04 アイユーシーエフ－エイチワイユー（インダストリー－ユニバーシティー コーオペレイション ファウンデーション ハンヤン ユニバーシティー） 水素化／脱水素化の可逆性が改善された白金担持触媒、及びこれを用いた液体有機水素運搬体ベースの水素貯蔵及び放出方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11269572A (ja) * 1998-03-24 1999-10-05 Japan Metals & Chem Co Ltd 非晶質マグネシウムニッケル系水素吸蔵合金の製造方法
JP2000212676A (ja) * 1999-01-26 2000-08-02 Japan Storage Battery Co Ltd リチウム貯蔵性金属間化合物およびこれを用いたリチウム二次電池
JP2002327230A (ja) * 2001-04-26 2002-11-15 Japan Metals & Chem Co Ltd マグネシウム系水素吸蔵合金
JP2002363682A (ja) * 2001-06-12 2002-12-18 Dowa Mining Co Ltd Ｍｇ、ＮｉおよびＭｎを含有する水素吸蔵合金および水素吸蔵合金粉体並びにその製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11269572A (ja) * 1998-03-24 1999-10-05 Japan Metals & Chem Co Ltd 非晶質マグネシウムニッケル系水素吸蔵合金の製造方法
JP2000212676A (ja) * 1999-01-26 2000-08-02 Japan Storage Battery Co Ltd リチウム貯蔵性金属間化合物およびこれを用いたリチウム二次電池
JP2002327230A (ja) * 2001-04-26 2002-11-15 Japan Metals & Chem Co Ltd マグネシウム系水素吸蔵合金
JP2002363682A (ja) * 2001-06-12 2002-12-18 Dowa Mining Co Ltd Ｍｇ、ＮｉおよびＭｎを含有する水素吸蔵合金および水素吸蔵合金粉体並びにその製造方法

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Publication number Publication date
JP2008095172A (ja) 2008-04-24
JP5189778B2 (ja) 2013-04-24

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