EP2215010A1 - Hydrogen-storing composite materials - Google Patents
Hydrogen-storing composite materialsInfo
- Publication number
- EP2215010A1 EP2215010A1 EP08849758A EP08849758A EP2215010A1 EP 2215010 A1 EP2215010 A1 EP 2215010A1 EP 08849758 A EP08849758 A EP 08849758A EP 08849758 A EP08849758 A EP 08849758A EP 2215010 A1 EP2215010 A1 EP 2215010A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- hydrogen
- alkaline earth
- composite material
- periodic table
- alkali metal
- 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.)
- Withdrawn
Links
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
- C01B3/0078—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C23/00—Auxiliary methods or auxiliary devices or accessories specially adapted for crushing or disintegrating not provided for in preceding groups or not specially adapted to apparatus covered by a single preceding group
- B02C23/18—Adding fluid, other than for crushing or disintegrating by fluid energy
-
- 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 hydrogen-storing composite materials which are substantially reversibly convertible between a storage state and a non-storage state, and a process for producing the same.
- Hydrogen energy storage has become increasingly important in recent years.
- Today there are various techniques for storing hydrogen in which a distinction can be made between storage in gaseous, liquid or in the form of metal hydrides in a chemically bound state.
- the storage of gaseous or liquid hydrogen often leads to security problems.
- Hydrogen storage systems in which hydrogen is stored in the form of metal hydrides in chemically bonded state are therefore advantageous.
- Such metal hydride hydrogen storage devices have a storage state and a non-storage state, between which they can be converted substantially reversibly.
- NaAlH 4 alkali metal alkanoates NaAlH 4 , LiAlH 4 , Li 3 AlH 6 , LiNa 2 AlH 6 , CaAlH 5 and borohydrides such as LiBH 4 , NaBH 4 , Mg (BH 4 ) 2 , Ca (BH 4 ) 2 due to their relatively high mass-based hydrogen storage capacity.
- NaAlH 4 hydrogen is liberated, for example, in the following reaction steps:
- reaction step (I) the equilibrium temperature at 1 bar of hydrogen is 33 ° C., which corresponds to the measured reaction enthalpy of about 37 kJ / mol of H 2 , and for reaction step (II) HO 0 C, which corresponds to the measured reaction enthalpy of about 47 kJ / mol H 2 .
- reaction enthalpy changes when sodium is replaced by another alkali metal or an alkaline earth metal and / or aluminum by another element of the third main group of the periodic table of the elements.
- a hydrogen-storing composite material which is substantially reversible between a storage state and a non-storage state, and in the storage state, at least one complex metal hydride of alkali metal or alkaline earth metal and an element of the third main group of the Periodic Table of the Elements and at least one complex metal halide of alkali metal or alkaline earth metal and an element of the third main group of the Periodic Table of the Elements or in the storage state at least one complex metal halide of alkali metal or alkaline earth metal and an element of the third main group of the Periodic Table of the Elements and in the non-storage state at least one alkali metal or Alkaline earth metal halide and a metal of the third main group of the Periodic Table of the Elements contains.
- the halide is preferably selected from the group consisting of fluoride, chloride, bromide and mixtures thereof.
- the element of the third main group of the periodic table is preferably selected from the group consisting of boron, aluminum and mixtures thereof.
- the alkali metal is preferably selected from the group consisting of lithium, sodium, potassium and mixtures thereof.
- the alkaline earth metal is preferably selected from the group consisting of beryllium, magnesium, calcium and mixtures thereof.
- hydrogen-storing composite materials which, when loaded, comprise at least one complex metal hydride of lithium, sodium, magnesium and / or calcium, and aluminum or boron, and at least one complex metal halide of lithium, sodium, magnesium and / or calcium, and also aluminum or Boron containing, for example, composite materials containing Na 3 AlH 6 and Na 3 AlF 6 , Li 3 AlH 6 and Li 3 AlF 6 , NaAlH 4 and NaAlCl 4 , NaBH 4 and NaBF 4 , LiBH 4 and LiBF 4 , Ca (BH 4 ) 2 and Ca (BF 4 ) 2 , Ca (AlH 4 ) 2 and Ca (AlF 4 ) 2 , and / or Mg (BH 4 ) 2 and Mg (BF 4 ) 2 .
- thermodynamic reaction equilibrium of the transfer between a storage state and a non-storage state at a temperature of about -4o 0 C to 300 0 C, more preferably about -4o 0 C and 8O 0 C, in particular about 15 0 C to 4O 0 C, more preferably about 2O 0 C to 35 0 C and most preferably about 2O 0 C to 3O 0 C and a pressure of about 0.1 to 20 bar absolute, more preferably 1 to 10 bar absolute, even more preferably 5 to 8 bar absolute.
- Certain complex metal hydrides and / or complex metal halides of alkali metal or alkaline earth metal and an element of the third main group of the Periodic Table of the Elements have a perovskite structure.
- the composite materials according to the invention may contain further constituents, such as alkali metal or alkaline earth metal halides and / or metals of the third main group of the Periodic Table of the Elements and / or further complex hydrides.
- the reaction enthalpy of transfer between a storage state and a non-storage state is preferably 25 to 40 kJ / mol H 2 , preferably 25 to 35 kJ / mol, and more preferably about 30 kJ / mol H 2 .
- the hydrogen-storing composite materials according to the invention are preferably prepared by a process in which an alkali metal halide compound and / or an alkaline earth metal halide compound is mixed with a metal powder of an element of the third main group of the Periodic Table of the Elements and mechanically stressed, for example ground.
- a metal powder of an element of the third main group of the Periodic Table of the Elements and mechanically stressed for example ground.
- ball mills eg vibrating mills, attritors, etc.
- the milled mixture can then be hydrogenated.
- the molar ratio of alkali metal halide or alkaline earth metal halide to metal powder of an element of the third main group of the Periodic Table of the Elements is preferably 0.01: 1 to 100: 1, more preferably 0.1: 1 to 10: 1, and especially 0.5: 1 to 3: 1 and in particular about 1: 1.
- the grinding preferably takes place in an oxygen-poor and dry atmosphere, preferably ter a nitrogen atmosphere, an argon atmosphere, a hydrogen atmosphere, or under vacuum, more preferably at a pressure of 0.00001 mbar absolute to 10 bar absolute, preferably at a pressure of ambient pressure to 20 mbar above ambient pressure.
- the grinding preferably takes place at temperatures between 77 K and 115 0 C, preferably between 15 0 C and 35 0 C, more preferably 2O 0 C to 25 0 C instead.
- the hydrogenation is preferably carried out after introducing the alloy into a pressure vessel under conditions for which the pressure vessel is designed, preferably at a temperature between -4O 0 C and 300 0 C, more preferably between 15 0 C and 15O 0 C and a hydrogen pressure of 1 to 800 bar, preferably 5 to 100 bar, more preferably 10 to 50 bar.
- NaF and Al powders were mixed in a molar ratio of 1: 1 and ground for five hours in a planetary ball mill under inert gas (argon). Subsequently, the milled material was hydrogenated at 145 bar and 14O 0 C for eight hours. The hydrogenated material was dehydrated at 35O 0 C.
- Figure 1 shows an X-ray diffraction spectrum of the reaction product after five hours of grinding (upper spectrum), after hydrogenation at 14O 0 C and 145 bar (middle spectrum) and after the renewed dehydrogenation at 35O 0 C (lower spectrum).
- NaF and Al before the hydrogenation, NaF and Al are present as the only phase.
- the spectrum additionally shows a perovskite phase similar to Na 3 AlH 6 and Na 3 AlF 6 .
- After renewed dehydration again only NaF- and Al- Phases are detected.
- the material is thus substantially reversible between a memory state and a non-memory state can be transferred.
- FIG. 2 shows a spectrum of the sample after hydrogenation (upper spectrum) recorded by means of synchrotron diffractometry and the associated calculated bands (lower spectrum). This shows the presence of NaF, Al, Na 3 AlH 6 , Na 3 AlF 6 and NaAlH 4 phases.
- FIG. 3 shows the result of simultaneous TGA-DTA and MS measurements in the hydrogen region on hydrogenated material according to Example 1
- FIG. 4 shows the result of simultaneous TGA-DTA and MS measurements in the hydrogen region on pure NaAlH 4 .
- the TGA signal in Figure 3 shows that in the temperature range of 170-300 0 C, a mass loss occurs.
- the MS signal shows that this is hydrogen. Detection in the range of F 2 and HF showed no signs of release of fluorine atoms.
- FIG. 3 also shows that the reaction enthalpy for the decomposition of both phases NaAlH 4 and Na 3 AlH 6 is approximately the same.
- FIG. 5 shows the hydrogen uptake and release of NaH + NaF + 2 Al using the TiCl 4 catalyst measured by an Sievert's apparatus.
- FIG. 5 shows that reversible hydrogen absorption is possible.
- FIG. 6 shows the X-ray diffractometric measurement of the material after mixing and grinding, as well as after hydrogen absorption and renewed hydrogen desorption.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Food Science & Technology (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Fuel Cell (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102007054843A DE102007054843B4 (en) | 2007-11-16 | 2007-11-16 | Hydrogen-storing composite materials |
PCT/EP2008/064721 WO2009062850A1 (en) | 2007-11-16 | 2008-10-30 | Hydrogen-storing composite materials |
Publications (1)
Publication Number | Publication Date |
---|---|
EP2215010A1 true EP2215010A1 (en) | 2010-08-11 |
Family
ID=40405014
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP08849758A Withdrawn EP2215010A1 (en) | 2007-11-16 | 2008-10-30 | Hydrogen-storing composite materials |
Country Status (7)
Country | Link |
---|---|
US (1) | US8926861B2 (en) |
EP (1) | EP2215010A1 (en) |
JP (1) | JP2011502938A (en) |
CN (1) | CN101910051A (en) |
CA (1) | CA2707987A1 (en) |
DE (1) | DE102007054843B4 (en) |
WO (1) | WO2009062850A1 (en) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20110180753A1 (en) * | 2008-02-22 | 2011-07-28 | Toyota Motor Engineering & Manufacturing North America, Inc. | Destabilized and catalyzed borohydride for reversible hydrogen storage |
DE102007054843B4 (en) | 2007-11-16 | 2012-04-12 | Helmholtz-Zentrum Geesthacht Zentrum für Material- und Küstenforschung GmbH | Hydrogen-storing composite materials |
JP2011005485A (en) * | 2009-06-16 | 2011-01-13 | Toyota Motor Engineering & Manufacturing North America Inc | Destabilized and catalyzed borohydride for reversible hydrogen storage |
GB2472458B (en) * | 2009-08-07 | 2011-08-03 | Ilika Technologies Ltd | Hydrogen storage materials |
US20180162881A1 (en) * | 2015-04-02 | 2018-06-14 | Albemarle Germany Gmbh | Highly reactive metal hydrides, process for their preparation and use |
EP3307440A1 (en) * | 2015-06-15 | 2018-04-18 | NETZSCH Trockenmahltechnik GmbH | Method for comminuting material to be ground and mill therefor |
CN109103498B (en) * | 2018-08-27 | 2020-12-18 | 中国电子新能源(武汉)研究院有限责任公司 | Sodium ion battery electrolyte and preparation method and application thereof |
CN109081766A (en) * | 2018-08-29 | 2018-12-25 | 湖北航天化学技术研究所 | A kind of Al-NaF hybrid fuel and its preparation method and application |
CN113998988A (en) * | 2021-11-09 | 2022-02-01 | 上海超高环保科技股份有限公司 | Method for manufacturing sheet, block, tubular and special-shaped material for hydrogen storage |
CN113845688B (en) * | 2021-11-22 | 2022-12-13 | 上海超高环保科技股份有限公司 | Method for manufacturing ice slush-structured hydrogen storage material |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0815273B1 (en) | 1995-02-02 | 2001-05-23 | Hydro-Quebec | NANOCRYSTALLINE Mg-BASED MATERIALS AND USE THEREOF FOR THE TRANSPORTATION AND STORAGE OF HYDROGEN |
CA2217095A1 (en) | 1997-10-22 | 1999-04-22 | Hydro-Quebec | Activated interface nanocomposites prepared by mechanical grinding of magnesium hydrides and their use for hydrogen storage |
DE10012794A1 (en) * | 2000-03-16 | 2001-09-20 | Studiengesellschaft Kohle Mbh | Process for the reversible storage of hydrogen comprises using reversible hydrogen-storage materials containing mixtures of aluminum metal with alkali metals and/or alkali metal hydrides |
US20060194695A1 (en) * | 2004-08-27 | 2006-08-31 | Westinghouse Savannah River Co., Llc | Destabilized and catalyzed borohydrided for reversible hydrogen storage |
JP2006142281A (en) * | 2004-10-20 | 2006-06-08 | Toyota Central Res & Dev Lab Inc | Aluminum type nanocomposite catalyst, its manufacturing method and hydrogen occluding composite material using it |
DE102004061286B4 (en) | 2004-12-14 | 2021-09-16 | Helmholtz-Zentrum Geesthacht Zentrum für Material- und Küstenforschung GmbH | Hydrogen-storing composite material as well as a device for the reversible storage of hydrogen |
DE102005003623A1 (en) | 2005-01-26 | 2006-07-27 | Studiengesellschaft Kohle Mbh | Materials for reversible hydrogen storage comprise alkali metal-aluminum hydride or mixtures of aluminum with alkali metals and/or alkali metal hydrides |
US7837976B2 (en) * | 2005-07-29 | 2010-11-23 | Brookhaven Science Associates, Llc | Activated aluminum hydride hydrogen storage compositions and uses thereof |
NO330070B1 (en) | 2006-01-26 | 2011-02-14 | Inst Energiteknik | Hydrogen storage system, process for reversible hydrogen storage and production of material therefor as well as use |
JP2007289877A (en) * | 2006-04-26 | 2007-11-08 | Toyota Central Res & Dev Lab Inc | Hydrogen storage material, manufacturing method thereof and hydride compound material |
DE102007054843B4 (en) | 2007-11-16 | 2012-04-12 | Helmholtz-Zentrum Geesthacht Zentrum für Material- und Küstenforschung GmbH | Hydrogen-storing composite materials |
-
2007
- 2007-11-16 DE DE102007054843A patent/DE102007054843B4/en active Active
-
2008
- 2008-10-30 EP EP08849758A patent/EP2215010A1/en not_active Withdrawn
- 2008-10-30 JP JP2010533533A patent/JP2011502938A/en active Pending
- 2008-10-30 CN CN200880124562XA patent/CN101910051A/en active Pending
- 2008-10-30 US US12/742,504 patent/US8926861B2/en active Active
- 2008-10-30 CA CA2707987A patent/CA2707987A1/en not_active Abandoned
- 2008-10-30 WO PCT/EP2008/064721 patent/WO2009062850A1/en active Application Filing
Non-Patent Citations (2)
Title |
---|
BOGDANOVIC B ET AL: "Metal-doped sodium aluminium hydrides as potential new hydrogen storage materials", JOURNAL OF ALLOYS AND COMPOUNDS, ELSEVIER SEQUOIA, LAUSANNE, CH, vol. 302, no. 1-2, 1 April 2000 (2000-04-01), pages 36 - 58, XP004194367, ISSN: 0925-8388, DOI: DOI:10.1016/S0925-8388(99)00663-5 * |
See also references of WO2009062850A1 * |
Also Published As
Publication number | Publication date |
---|---|
DE102007054843A1 (en) | 2009-05-20 |
US20130187085A1 (en) | 2013-07-25 |
DE102007054843B4 (en) | 2012-04-12 |
CA2707987A1 (en) | 2009-05-22 |
JP2011502938A (en) | 2011-01-27 |
WO2009062850A1 (en) | 2009-05-22 |
CN101910051A (en) | 2010-12-08 |
US8926861B2 (en) | 2015-01-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE102007054843B4 (en) | Hydrogen-storing composite materials | |
Denys et al. | Mg substitution effect on the hydrogenation behaviour, thermodynamic and structural properties of the La2Ni7–H (D) 2 system | |
DE112005002271B4 (en) | Method for storing hydrogen in hydrogen storage systems | |
Denys et al. | LaMg11 with a giant unit cell synthesized by hydrogen metallurgy: crystal structure and hydrogenation behavior | |
EP1824780B8 (en) | Composite material storing hydrogen, and its use in a device for the reversible storage of hydrogen | |
Huot et al. | Structure of nanocomposite metal hydrides | |
DE112005002738T5 (en) | Scaffold borazane lithium hydride hydrogen storage materials | |
WO1997003919A1 (en) | Method for the reversible storage of hydrogen | |
Li et al. | Significantly improved dehydrogenation of LiAlH4 destabilized by K2TiF6 | |
Yang et al. | Multi-hydride systems with enhanced hydrogen storage properties derived from Mg (BH4) 2 and LiAlH4 | |
Pighin et al. | Study of MgH2+ NbF5 mixtures: Formation of MgH2− xFx solid solutions and interaction with hydrogen | |
Zou et al. | Reversible hydrogen storage in a 3NaBH4/YF3 composite | |
CA2636295C (en) | Synthesis of alh3 and structurally related phases | |
Gennari et al. | A Systematic approach to the synthesis, thermal stability and hydrogen storage properties of rare-earth borohydrides | |
Chen et al. | Hydrogen absorption–desorption cycle durability of SmMgNi4 | |
Lv et al. | Niobium fluoride-modified hydrogen evolution reaction of magnesium borohydride diammoniate | |
Remhof et al. | Hydrogen cycling behavior of LiBD4/Al studied by in situ neutron diffraction | |
Xiao et al. | Synthesis and hydriding/dehydriding properties of nanosized sodium alanates prepared by reactive ball-milling | |
Qu et al. | Comparative catalytic effects of NiCl 2, TiC and TiN on hydrogen storage properties of LiAlH 4 | |
Soubeyroux et al. | Phase stability and neutron diffraction studies of Laves phases Zr (Cr1− xMx) 2 with M=(Cu0. 5Ni0. 5) and 0< x< 0.2 and their hydrides | |
Lushnikov et al. | CeNi 3-based Intermetallic hydrides | |
Léon et al. | Investigation of (Mg, Al, Li, H)-based hydride and alanate mixtures produced by reactive ball milling | |
Karimi | zur Erlangung des Doktorgrades des Department Physik der Universität Hamburg | |
Liu et al. | Structural change and hydrogenation behavior of (Sr, Ca) 2Al alloys | |
DE102004064260B3 (en) | Composite material that stores hydrogen and a device for the reversible storage of hydrogen |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20100615 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR |
|
AX | Request for extension of the european patent |
Extension state: AL BA MK RS |
|
RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: BORMANN, RUEDIGER Inventor name: DORNHEIM, MARTIN Inventor name: EIGEN, NICO |
|
DAX | Request for extension of the european patent (deleted) | ||
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: HELMHOLTZ-ZENTRUM GEESTHACHT ZENTRUM FUER MATERIAL |
|
17Q | First examination report despatched |
Effective date: 20110614 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
18D | Application deemed to be withdrawn |
Effective date: 20111228 |