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WO2010029407A1 - Accumulateur d'hydrogène - Google Patents

Accumulateur d'hydrogène Download PDF

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Publication number
WO2010029407A1
WO2010029407A1 PCT/IB2009/006787 IB2009006787W WO2010029407A1 WO 2010029407 A1 WO2010029407 A1 WO 2010029407A1 IB 2009006787 W IB2009006787 W IB 2009006787W WO 2010029407 A1 WO2010029407 A1 WO 2010029407A1
Authority
WO
WIPO (PCT)
Prior art keywords
hydrogen
pressure
metal
hydrides
hydrogen storage
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/IB2009/006787
Other languages
German (de)
English (en)
Other versions
WO2010029407A8 (fr
Inventor
Ferdi SCHÜTH
Michael Felderhoff
Borislav Bogdanovic
Weidenthaler Claudia
Andre Pommerin
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.)
Studiengesellschaft Kohle gGmbH
Original Assignee
Studiengesellschaft Kohle gGmbH
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 Studiengesellschaft Kohle gGmbH filed Critical Studiengesellschaft Kohle gGmbH
Publication of WO2010029407A1 publication Critical patent/WO2010029407A1/fr
Publication of WO2010029407A8 publication Critical patent/WO2010029407A8/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
    • 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
    • C01B3/0031—Intermetallic compounds; Metal alloys; Treatment thereof
    • C01B3/0047—Intermetallic compounds; Metal alloys; Treatment thereof containing a rare earth metal; Treatment thereof
    • C01B3/0057—Intermetallic compounds; Metal alloys; Treatment thereof containing a rare earth metal; Treatment thereof also containing nickel
    • 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 invention relates to a hydrogen storage, comprising a metal hydride and a pressure-resistant container.
  • the hydrogen can also be stored in chemical form in a hydride-forming alloy or chemical compound.
  • typical hydride-forming alloys are TiFe or C14-Laves phases hydrides, which have a storage capacity of about 1.5% by weight of hydrogen, based on the hydride-forming alloy.
  • complex metal hydrides such as NaAlH 4
  • NaAlH 4 have significantly higher hydrogen storage capacities (NaAlH 4 5.6 wt%), they also need to be significantly increased to ensure a sufficiently long range for mobile applications.
  • Patent DE 35 14 500 discloses a process for storing hydrogen under a pressure of 100-300 bar in combination with a hydride-forming alloy.
  • a hydride-forming alloy As hydridnduende alloys TiFe or C14 Lavesphasen hydrides are called, which can store a maximum of 1.9 wt.% Hydrogen.
  • the free gas volume within the storage tank should also be used for hydrogen storage. Even with this system, the achievable storage capacities are not sufficient to ensure high ranges for mobile systems (automobiles). Rather, the gravimetric storage densities of the overall system are in the order of only 1 wt .-%. That alone weighs that
  • Hydrogen storage system approx. 500 kg for the storage of approx. 5 kg of hydrogen.
  • the object of the invention was to optimize the weight-related storage capacity for hydrogen. As a result, based on the weight unit of storage, more hydrogen than previously stored.
  • the present invention is a hydrogen storage comprising a metal hydride and a pressure-resistant container, characterized in that the metal hydride is selected from low temperature of the general formula I.
  • Me 1 is selected from Sc, Ti, Zr, V 1 Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Nb, Mo, La, Ce, Pr and Nd, or when x> 2, also a mixture may be of several metals, and x is a number from 1 to 3, y is a number from 1 to 2, z is a number from 4 to 7 and n is a number from 1 to 7.
  • Cryogenic hydrides are generally understood as meaning those hydrides which have an equilibrium hydrogen pressure ⁇ 1 bar at temperatures 50 ⁇ T ⁇ -30 ° C. Expanding the definition of Buchner, complex low-temperature hydrides are understood to mean those compounds whose hydrogen equilibrium pressure is significantly greater than 1 bar at room temperature, preferably between 50 and 900 bar.
  • complex aluminum metal hydrides are those compounds consisting of hydride ions, an aluminum metal (AI) and at least one electropositive metal (Me). They have the general form Me 1 x Al y H z .
  • such hydrides are not thermodynamically stable under standard conditions (298 K, 1 bar), but can only be produced in a pressure vessel under elevated hydrogen pressure (> 50 bar).
  • metal-aluminum hydrides for example metal-aluminum hydrides (metal alanates) can be used, which have a gravimetric storage densities up to 9 wt.% Hydrogen.
  • metal-aluminum hydrides with their hydrogen storage densities are shown in Figure 1. The list is exemplary and not to be considered as complete.
  • those electropositive metals are used which are selected from the metals of the subgroups of the periodic table as well as the rare earth metals.
  • alkali metal and / or alkaline-earth aluminum hydrides (alkali metal or alkaline earth metal anates) of the general formula II
  • Me 2 is selected from Li, Na, K, Mg and Ca, or when x> 2, may also be a mixture of several metals, and a is a number from 1 to 3, b is a number from 1 to 2, c is a number from 4 to 7 and m is a number from 1 to 7, may be included.
  • the complex metal-aluminum hydride compound CaAIH 5 may be mentioned here.
  • mixed complex aluminum hydrides can also be used.
  • the compound NaMg (AIH 4 J 3 is listed as an example.
  • a further increase in the storage capacity can be achieved, for example, by virtue of the fact that the pressure-tight container has a size in addition to the storage materials, such as a hydrogen-storing complex metal hydride or a hydride-forming metal or a hydride-forming alloy has free volume, which can be used in the high-pressure tank for storing hydrogen.
  • the storage materials such as a hydrogen-storing complex metal hydride or a hydride-forming metal or a hydride-forming alloy has free volume, which can be used in the high-pressure tank for storing hydrogen.
  • the remaining degree of filling can be determined towards the end of emptying (C).
  • the storage of hydrogen is carried out for the most part in a complex cryogenic metal hydride at a hydrogen pressure which is between 50 and 900 bar, in particular between 50 and 350 bar hydrogen pressure.
  • the storage takes place in a pressure vessel.
  • pressure vessels made of composite materials, for example carbon fiber wrapped metal vessels, are used.
  • the pressure-resistant container should be designed so that it can be pressurized to a pressure of 50 to 900 bar
  • such pressure vessels are used, which have an integrated heat exchanger, so that the released during loading reaction and compression heat can be dissipated.
  • such pressure vessels are used which contain a highly porous metal foam for better heat exchange.
  • a metal foam for producing such metal foams, composites of a metal and a blowing agent (often titanium hydride) are generally used. After compression to a starting material, this is heated to a temperature above the melting point of the metal used. In the process, the metal hydride decomposes, releases hydrogen and foams the mixture.
  • This metal foam may consist of aluminum, aluminum alloys or other porous metal foams.
  • Another object of the present invention is a process for storing hydrogen in which a metal alloy capable of forming metal hydrides of general formula I is formed
  • Me is selected from Sc, Ti, Zr, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Nb, Mo, La, Ce, Pr and Nd, or when x> 2, also a mixture of may be a plurality of metals, x is a number from 1 to 3, y is a number from 1 to 2, z is a number from 4 to 7 and n is a number from 1 to 7, is pressurized in a pressure vessel under pressure with hydrogen.
  • Another object is a method for releasing hydrogen, in which a metal hydride of the general formula I.
  • Me is selected from Sc, Ti, Zr, V, Cr, Mn, Fe, Co, Ni, Cu, Zn 1 Y, Nb, Mo, La, Ce, Pr and Nd, or when x> 2, also a mixture of a number from 1 to 3, y is a number from 1 to 2, z is a number from 4 to 7 and n is a number from 1 to 7, is kept under hydrogen pressure in a pressure vessel, and the release of the
  • Hydrogen occurs by reducing the pressure.
  • the inventive method for storing hydrogen is used.
  • aluminum metal and one or more other metals or metal hydrides are used as the solid starting compounds and H 2 is used under high pressure as the gaseous component, wherein the storage of hydrogen takes place in solid form in a complex metal aluminum hydride.
  • other complex metal hydrides eg transition metal borohydrides
  • the prerequisite is that their hydrogen equilibrium pressure is between 50 and 900 bar at room temperature.
  • metal alloys or metal mixtures are used to form the metal (mixture) aluminum hydride.
  • catalysts preferably transition metal catalysts
  • These catalysts improve the hydrogenation and dehydrogenation properties of the hydrogen storage materials.
  • the catalysts can be added to the storage material in the form of metals, metal compounds or as alloy constituents of the metals used.
  • the transition metal catalysts are selected from transition metal compounds of the group B to VB of the periodic table as well as Fe, Co, Ni and compounds of rare earth metals or combinations thereof, in particular their alkoxides, halides, hydrides, organometallic and intermetallic compounds, such as TiAl. 3

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Filling Or Discharging Of Gas Storage Vessels (AREA)

Abstract

L'invention concerne un accumulateur d'hydrogène qui comprend un hydrure de métal et un récipient résistant à la pression, l'hydrure de métal étant choisi parmi les hydrures à basse température de formule générale Me1 x(AlyHz)n  (I), dans laquelle Me est choisi parmi Sc, Ti1 Zr, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Nb, Mo, La, Ce, Pr et Nd ou si x = 2, il peut être également un mélange de plusieurs métaux, x étant un nombre de 1 à 3, y un nombre de 1 à 2, z un nombre de 4 à 7 et n, un nombre de 1 à 7. L'utilisation d'hydrures à basse température complexes de formule (I) permet d'augmenter nettement la capacité d'accumulation des accumulateurs d'hydrogène de sorte qu'avec un poids plus faible de l'accumulateur, l'autonomie dans les utilisations automobiles puisse être améliorée.
PCT/IB2009/006787 2008-09-12 2009-09-08 Accumulateur d'hydrogène Ceased WO2010029407A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102008047222A DE102008047222A1 (de) 2008-09-12 2008-09-12 Wasserstoffspeicher
DE102008047222.0 2008-09-12

Publications (2)

Publication Number Publication Date
WO2010029407A1 true WO2010029407A1 (fr) 2010-03-18
WO2010029407A8 WO2010029407A8 (fr) 2010-07-15

Family

ID=41351597

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2009/006787 Ceased WO2010029407A1 (fr) 2008-09-12 2009-09-08 Accumulateur d'hydrogène

Country Status (2)

Country Link
DE (1) DE102008047222A1 (fr)
WO (1) WO2010029407A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4538224A1 (fr) 2023-10-11 2025-04-16 Cyrus S.A. "Lefkippos" Technology Park of Attica - NCSR Technique de compression d'hydrogene

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000007930A1 (fr) * 1998-08-06 2000-02-17 University Of Hawaii Nouveaux materiaux de stockage de l'hydrogene et leur procede de fabrication par homogeneisation a sec
EP1124754B1 (fr) * 1998-10-07 2002-06-12 McGILL UNIVERSITY Composition de stockage d'hydrogene reversible
WO2003048036A1 (fr) * 2001-11-30 2003-06-12 Energy Conversion Devices, Inc. Materiau de stockage d'hydrogene contenant un alliage ti-mn2 modifie
US6726892B1 (en) * 2001-02-14 2004-04-27 Quantum Fuel Systems Technologies Worldwide, Inc. Advanced aluminum alloys for hydrogen storage
DE102005010700A1 (de) * 2005-03-09 2006-09-14 Studiengesellschaft Kohle Mbh Verfahren zur Synthese von Verbindungen

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3514500C1 (de) 1985-04-22 1986-05-22 Daimler-Benz Ag, 7000 Stuttgart Wasserstoffspeicher
DE19526434A1 (de) * 1995-07-19 1997-01-23 Studiengesellschaft Kohle Mbh Verfahren zur reversilben Speicherung von Wasserstoff
US6471935B2 (en) * 1998-08-06 2002-10-29 University Of Hawaii Hydrogen storage materials and method of making by dry homogenation
DE10012794A1 (de) * 2000-03-16 2001-09-20 Studiengesellschaft Kohle Mbh Verfahren zur reversiblen Speicherung von Wasserstoff auf der Basis von Alkalimetallen und Aluminium
US6680043B2 (en) * 2001-11-29 2004-01-20 General Motors Corporation Process for enhancing the kinetics of hydrogenation/dehydrogenation of MAIH4 and MBH4 metal hydrides for reversible hydrogen storage

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000007930A1 (fr) * 1998-08-06 2000-02-17 University Of Hawaii Nouveaux materiaux de stockage de l'hydrogene et leur procede de fabrication par homogeneisation a sec
EP1124754B1 (fr) * 1998-10-07 2002-06-12 McGILL UNIVERSITY Composition de stockage d'hydrogene reversible
US6726892B1 (en) * 2001-02-14 2004-04-27 Quantum Fuel Systems Technologies Worldwide, Inc. Advanced aluminum alloys for hydrogen storage
WO2003048036A1 (fr) * 2001-11-30 2003-06-12 Energy Conversion Devices, Inc. Materiau de stockage d'hydrogene contenant un alliage ti-mn2 modifie
DE102005010700A1 (de) * 2005-03-09 2006-09-14 Studiengesellschaft Kohle Mbh Verfahren zur Synthese von Verbindungen

Also Published As

Publication number Publication date
DE102008047222A1 (de) 2010-04-15
WO2010029407A8 (fr) 2010-07-15
DE102008047222A8 (de) 2010-09-16

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