WO2010080541A2 - Procédé de préparation d'un hydrure double de lithium et d'aluminium dopé au ti pour un stockage de l'hydrogène très performant - Google Patents

Procédé de préparation d'un hydrure double de lithium et d'aluminium dopé au ti pour un stockage de l'hydrogène très performant Download PDF

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Publication number
WO2010080541A2
WO2010080541A2 PCT/US2009/068583 US2009068583W WO2010080541A2 WO 2010080541 A2 WO2010080541 A2 WO 2010080541A2 US 2009068583 W US2009068583 W US 2009068583W WO 2010080541 A2 WO2010080541 A2 WO 2010080541A2
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Prior art keywords
doped
hydrogen storage
mol
preparing
lialh
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PCT/US2009/068583
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English (en)
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WO2010080541A3 (fr
Inventor
Gerard Sean Mcgrady
Craig M. Jensen
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Hsm Systems, Inc.
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Publication of WO2010080541A2 publication Critical patent/WO2010080541A2/fr
Publication of WO2010080541A3 publication Critical patent/WO2010080541A3/fr

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    • 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
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
    • C01B6/24—Hydrides containing at least two metals; Addition complexes thereof
    • C01B6/243—Hydrides containing at least two metals; Addition complexes thereof containing only hydrogen, aluminium and alkali metals, e.g. Li(AlH4)
    • 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
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the invention relates to processing of materials that store hydrogen in general and particularly to systems and methods that employ solvents having boiling points below room temperature and high dipole moments.
  • the invention features a method of preparing a hydrogen storage material.
  • the method comprises the steps of: preparing a doped hydrogenated composition containing comprising a metal that exhibits a unipositive oxidation state and a metal that exhibits a tripositive oxidation state, the doped hydrogenated composition comprising a transition metal dopant; dehydrogenating the doped hydrogenated composition to provide a dehydrogenated doped composition; subjecting the dehydrogenated doped composition to a source of hydrogen and to a solvent having a boiling point below room temperature to produce a doped rehydrogenated composition; and removing the solvent having a boiling point below room temperature by pumping while holding the doped rehydrogenated composition at a temperature below 50 0 C to provide a doped rehydrogenated composition substantially free of solvent having a boiling point below room temperature.
  • the metal that exhibits a unipositive oxidation state is lithium and the metal that exhibits a tripositive oxidation state is aluminum.
  • the transition metal dopant is titanium.
  • a concentration of the titanium dopant is between 0.01 to 0.5 mol %.
  • the step of preparing a doped hydrogenated composition comprises ball milling the hydrogenated composition containing comprising a metal that exhibits a unipositive oxidation state and a metal that exhibits a tripositive oxidation state with a salt of the transition metal.
  • the solvent having a boiling point below room temperature is Me 2 O.
  • the step of removing the solvent having a boiling point below room temperature is performed at substantially room temperature.
  • FIG. 1 is a schematic diagram that illustrates exemplary thermochemical relationships for generating LiAlH 4 and decomposing that material to provide free H 2 which exist in one embodiment described herein.
  • FIG. 2 is a diagram showing XRD patterns Of LiAlH 4 samples: (a) International
  • Centre for Diffraction Data (ICDD) reference plot (b) ball milled (2.0 mol% TiCl 3 ); (c) fully dehydrogenated (0.2 mol% TiCl 3 ); (d) rehydrogenated (2.0 mol% TiCl 3 ); and (e) rehydrogenated (0.2 mol% TiCl 3 ).
  • FIG. 3 is a diagram in which curve (a) is the XRD spectrum of a ball milled sample before hydrogenation; curve (b) is the XRD spectrum of 0 mol% Ti doped after hydrogenation; curve (c) is the XRD spectrum of 0.05 mol% Ti doped after hydrogenation; curve (d) is the XRD spectrum of 0.2 mol% Ti doped after hydrogenation; curve (e) is the
  • curve (f) is the XRD spectrum of 1 mol% Ti doped after hydrogenation
  • curve (g) is the XRD spectrum of 2 mol% Ti doped after hydrogenation
  • curve (h) is an XRD spectrum of a LiAlH 4 standard material after hydrogenation.
  • FIG. 4 is a diagram showing XRD patterns OfLiAlH 4 milled with various Ti concentrations: (a) 2.0 mol% TiCl 3 ; (b) 1.0 mol% TiCl 3 ; (c) 0.5 mol% TiCl 3 ; (d) 0.2 mol%
  • FIG. 5 is a diagram showing XRD patterns of fully dehydrogenated LiAlH 4 containing various Ti concentrations: (a) 2.0 mol% TiCl 3 ; (b) 1.0 mol% TiCl 3 ; (c) 0.5 mol%
  • FIG. 6 is a diagram showing XRD patterns of rehydrogenated LiAItLt containing various Ti concentrations: (a) 2.0 mol% TiCb; (b) 1.0 mol% TiCl 3 ; (c) 0.5 mol%
  • FIG. 7 is a diagram showing DSC curves for hydrogenated LiH/Al with various
  • FIG. 8 shows a DSC curve (upper panel) and a TGA curve (lower panel) of 0.5 mol % Ti-doped LiAlH 4 as it releases hydrogen.
  • FIG. 9 is a diagram showing temperature-programmed desorption (TPD) plots for LiAlH 4 samples: (a) as-received; (b) milled with 2.0 mol% TiCl 3 ; (c) rehydrogenated (2.0 mol% TiCl 3 ); (d) rehydrogenated (1.0 mol% TiCl 3 ); (e) rehydrogenated (0.5 mol% TiCl 3 ); and
  • FIG. 10 is a schematic diagram of an illustrative process flowsheet for making hydrogenated material without depressurizing the reactor.
  • FIG. 11 is a diagram that illustrates the relationship of Well-To-Tank (WTT)
  • FIG. 12 is a diagram that illustrates the cycle performance of hydrogenated 0.05 mol% Ti-doped LiAlH 4 in which curve (a) represents Cycle-1; curve (b) represents Cycle-2; and curve (c) represents Cycle-3.
  • FIG. I illustrates a simple, effective, efficient single-stage procedure for direct re-H of Ti-doped LiAlH 4
  • the Ti- doped LiAlH 4 can operate as a reversible H 2 storage material (>7.5 wt.% H, hydrogen evolving starting at approximately 80 0 C).
  • the Ti-doped LiAlH 4 material can be recharged quantitatively under remarkably mild conditions using Me 2 O.
  • Ti-doped LiH/Al can be directly hydrogenated into LiAlH 4 and the XRD peaks of un-reacted LiH/AI tend to decrease with decreasing Ti content.
  • the catalyst activates both hydrogen uptake and release lower Ti content is favorable to the formation and stability Of LiAlH 4 .
  • This also can be confirmed by following TGA results.
  • An un-doped sample can not be hydrogenated into LiAlH 4 indicating a very small amount of a dopant such as TiCl 3 plays an important role in the hydrogenation reaction. It should be pointed out that the diffraction peaks of LiH are invisible because LiH becomes amorphous after ball billing and/or its peaks are overlapped by those of
  • LiAlH 4 and NaAlH 4 each release hydrogen in two stages, as described in Eq. 1 and Eq. 2, and as shown in FIG. 7 and FIG. 8:
  • FIG. 7 is a diagram showing DSC curves for hydrogenated LiH/Al with various
  • the upper panel of FIG. 8 is a DSC curve of 0.5 mol % Ti-doped LiAlH 4 shows two endothermic peaks at 112 C and 195 C.
  • the two-step dehydrogenations were also noticeably observed in the TGA curve shown in the lower panel of FIG. 8.
  • the first dehydrogenation LiAlH 4 to Li 3 AlH 6
  • the second dehydrogenation Li 3 AlH 6 to LiH and Al
  • the two obvious mass losses can be assigned to the two-step dehydrogenation reactions.
  • the first endothermic peak corresponds to the direct decomposition of solid LiAlH 4 to Li 3 AlH 6 , which means Ti-doped LiAlH 4 can absorb some heat to directly decompose and form Li 3 AlH 6 without melting.
  • the second endothermic peak at 195 C reflects the decomposition of Li 3 AlH 6 to LiH and Al.
  • the enthalpy of Eq. 1 is dominated for Li by the high lattice energy of L13AIH6, with its small cations and triply-charged anion.
  • the implication for LiAlH 4 is that Eq. 1 as written is thermodynamically irreversible under all practical conditions.
  • it contains over 40% more hydrogen by weight than its Na congener it appears to have been widely accepted that LiAlH 4 cannot be recharged, and there have been no reports of its use for reversible hydrogen storage.
  • the unfavorable thermodynamics of Eq. 1 may be altered by carrying out the reaction in solution, with the solvation Of LiAlH 4 contributing to an (ideally) endothermic ⁇ H value.
  • Ashby et al. reported that a mixture of LiH and activated Al in THF or diglyme solvent reacted with 350 bar H 2 at 120 0 C to produce LiAlH 4 .
  • the THF reaction has been improved recently by Graetz et al, using Ti doping to significantly lower the pressure and temperature required.
  • Ritter et ah employing high energy ball milling of a LiH/Al/H 2 mixture in the presence of THF.
  • LiAlH 4 from LiH, Al and H 2 they demand a large energy investment in the temperature, pressure and/or mechanical energy required, as well as for the removal of THF solvent (for example, by vacuum drying at 60 0 C for several hours). Ashby noted that it is very difficult to remove the final vestiges of THF; however, his attempts to prepare LiAlH 4 in Et20 met with no success. The prolonged baking in vacuo required to remove THF will necessarily compromise the integrity of a Ti-activated product, which as noted above is only kinetically stable.
  • the reaction is carried out in an autoclave at ambient temperature (room temperature, or approximately in the range of 20 - 25 0 C), and the volatile solvent can be vented easily on completion of reaction along with excess H 2 to leave a fine, dry powder product that requires no further processing, and which releases large amounts of H 2 rapidly and at moderate temperatures.
  • ambient temperature room temperature, or approximately in the range of 20 - 25 0 C
  • LiAlH 4 Alfa Aesar, 95%) and TiCl 3 (Aldrich, 99.999%) were used as received.
  • Ti-doped LiAlH 4 was prepared by ball milling the appropriate stoichiometrics Of LiAlH 4 and T1CI 3 (T1CI 3 : 0.2, 0.5, 1.0, and 2.0 mol%).
  • T1CI 3 0.2, 0.5, 1.0, and 2.0 mol%.
  • 5 g OfLiAlH 4 and the corresponding amount of TiCl 3 was loaded in a 250 mL stainless steel milling vessel containing five stainless steel balls (about 162 g).
  • the powder mixtures were mechanically milled at room temperature in a N 2 atmosphere at a rotational speed of 300 rpm for 2 h using a Retsch PM 100 planetary ball mill. After every 15 min of milling there was a 30 s pause and the rotation was automatically reversed. More recent information indicates that TiCb doping as low as 0.01 mol% is also effective.
  • Powder X-ray diffraction was performed on a Rigaku MiniFlex diffractometer with Cu K a radiation source. Samples for XRD analysis were mounted on a
  • FIG. 4, FIG. 5 and FIG. 6 are diagrams showing XRD patterns of ball milled, fully decomposed, and rehydrogenated Ti-doped LiAlH 4
  • TPD Temperature-programmed desorption
  • Ti-doped LiAlH 4 can operate as a reversible hydrogen storage material, which can be recharged almost quantitatively under remarkably mild conditions in the presence of the low-boiling ether solvent Me 2 O.
  • Preliminary desorption studies indicate rapid release of ca. 7 wt% of the hydrogen thus absorbed at onset temperatures around 80 0 C, and with excellent kinetics.
  • We are currently exploring in detail how the extended cycling behavior of Ti-doped LiAlH 4 produced in this manner is affected by the provenance and concentration of the dopant, and by the recharging conditions and handling procedures employed.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Powder Metallurgy (AREA)

Abstract

L'invention concerne des systèmes et des procédés permettant de préparer un hydrure métallique, comme LiAlH4, pouvant être déshydrogéné et réhydrogéné en condition douce. L'hydrure comprend un dopant, par exemple 0,2 % à 0,5 % en mole de titane sous la forme de billes de sel broyées avec l'hydrure. L'hydrogénation est effectuée dans du Me2O, qui est utilisé comme solvant pour H2, sous une pression de H2 d'environ 100 bar à 120 °C. Le solvant Me2O est éliminé à température ambiante pour donner une poudre hydrogénée sèche. L'hydrogène se dégage de la poudre hydrogénée à des températures aussi basses que 80 °C.
PCT/US2009/068583 2008-12-17 2009-12-17 Procédé de préparation d'un hydrure double de lithium et d'aluminium dopé au ti pour un stockage de l'hydrogène très performant WO2010080541A2 (fr)

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US13820708P 2008-12-17 2008-12-17
US61/138,207 2008-12-17

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WO2010080541A3 WO2010080541A3 (fr) 2010-10-14

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106986306A (zh) * 2017-05-27 2017-07-28 河南纳宇滤材有限公司 一种高纯α‑三氢化铝的制备方法
KR20180008448A (ko) * 2015-04-02 2018-01-24 알베마를 저머니 게엠베하 고 반응성 금속 수소화물, 이들의 제조 방법 및 용도

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030099595A1 (en) * 2001-11-29 2003-05-29 Bouziane Yebka Process for enhancing the kinetics of hydrogenation/dehydrogenation of MAIH4 and MBH4 metal hydrides for reversible hydrogen storage
US20040009121A1 (en) * 2002-07-10 2004-01-15 Jensen Craig M. Methods for hydrogen storage using doped alanate compositions
US20050191235A1 (en) * 2004-02-26 2005-09-01 Vajo John J. Regeneration of hydrogen storage system materials and methods including hydrides and hydroxides
US20060013753A1 (en) * 2004-03-26 2006-01-19 Vajo John J Reversible hydrogen storage systems

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030099595A1 (en) * 2001-11-29 2003-05-29 Bouziane Yebka Process for enhancing the kinetics of hydrogenation/dehydrogenation of MAIH4 and MBH4 metal hydrides for reversible hydrogen storage
US20040009121A1 (en) * 2002-07-10 2004-01-15 Jensen Craig M. Methods for hydrogen storage using doped alanate compositions
US20050191235A1 (en) * 2004-02-26 2005-09-01 Vajo John J. Regeneration of hydrogen storage system materials and methods including hydrides and hydroxides
US20060013753A1 (en) * 2004-03-26 2006-01-19 Vajo John J Reversible hydrogen storage systems

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20180008448A (ko) * 2015-04-02 2018-01-24 알베마를 저머니 게엠베하 고 반응성 금속 수소화물, 이들의 제조 방법 및 용도
KR102557065B1 (ko) * 2015-04-02 2023-07-18 알베마를 저머니 게엠베하 고 반응성 금속 수소화물, 이들의 제조 방법 및 용도
CN106986306A (zh) * 2017-05-27 2017-07-28 河南纳宇滤材有限公司 一种高纯α‑三氢化铝的制备方法

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