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WO2007066219A2 - Compositions de li3n dopes avec des composes metalliques pour adsorption/desorption de l'hydrogene - Google Patents

Compositions de li3n dopes avec des composes metalliques pour adsorption/desorption de l'hydrogene Download PDF

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Publication number
WO2007066219A2
WO2007066219A2 PCT/IB2006/003537 IB2006003537W WO2007066219A2 WO 2007066219 A2 WO2007066219 A2 WO 2007066219A2 IB 2006003537 W IB2006003537 W IB 2006003537W WO 2007066219 A2 WO2007066219 A2 WO 2007066219A2
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hydrogen
composition
metal compound
group
composition according
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WO2007066219A3 (fr
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Jizhong Luo
Ziyi Zhong
Yook Si Loo
Jianyi Lin
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Agency for Science Technology and Research Singapore
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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
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/0602—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with two or more other elements chosen from metals, silicon or boron
    • 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
    • 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 metal compound doped compositions capable of for use in hydrogen storage devices.
  • the invention also relates to various processes by which these compositions are obtainable
  • Hydrogen is a clean energy carrier made from diverse resources such as water, renewable energy, nuclear energy, and fossil energy. Hydrogen, as an energy carrier, is superior to other chemical energy sources since it exhibits the highest heating value per mass of all chemical fuels. Furthermore, hydrogen is regenerative and environmentally friendly as it is one of the cleanest of the currently known energy sources as it reacts cleanly with air producing water as sole product so that the product of the hydrogen combustion contains neither greenhouse gases nor other air pollutants.
  • the second difficulty with hydrogen as an energy carrier is its low critical temperature of 33 K, i.e. hydrogen is a gas at ambient, temperature, so that both for mobile and in many cases also for stationary applications the volumetric and gravimetric density of hydrogen in a storage material is either not sufficient or is difficult to realize.
  • hydrogen can be stored using six different methods and phenomena: (1) high-pressure gas cylinders (up to 800 bar), (2) liquid hydrogen in cryogenic tanks (at 21 K), (3) adsorbed hydrogen on materials . with a large specific surface area, (4) absorbed on interstitial sites in a host metal, (5) chemically bonded in covalent and ionic compounds, or (6) through oxidation of reactive metals, e.g. Li, Na, Mg, Al, Zn with water.
  • reactive metals e.g. Li, Na, Mg, Al, Zn with water.
  • Liquid hydrogen is stored in cryogenic tanks at 21.2 K and ambient pressure. Due to the low critical temperature of hydrogen (33 K), liquid hydrogen can only be stored in open systems.
  • Hydrogen can also be stored indirectly in reactive metals such as Li, Na, Al or Zn. These metals easily react with water to the corresponding hydroxide and liberate the hydrogen from the water. Since water is the product of the combustion of hydrogen with either oxygen or air, it can be recycled in a closed loop and react with the metal.
  • reactive metals such as Li, Na, Al or Zn.
  • Hydrogen stored in a solid is desirable since it can be released or desorbed under appropriate temperature and pressure conditions, thereby providing a controllable source of hydrogen. It has been desirable to maximize the hydrogen storage capacity in a material or hydrogen content released from the material at relatively low temperatures and pressures.
  • Lithium nitride is usually employed as an electrode, or as a starting material for the synthesis of binary or ternary nitrides.
  • Y. Kojima et a/ disclose the hydrogen storage of metal nitride, e.g. U 3 N, by a mechanochemical reaction (Chem. Commun., 2004, 2210-2211), while H. Y. Leng et al.
  • Li 3 N possesses disadvantages such as high heat generation, low stability and a propensity to sinter.
  • the temperature required to release the hydrogen at usable pressures is too high for practical applications.
  • the present invention provides a composition capable of absorbing and/or desorbing hydrogen, comprising Li 3 N and at least one kind of a metal compound which is obtainable by various methods.
  • the present invention provides a process for preparing a composition capable of absorbing and/or desorbing hydrogen, said composition comprising Li 3 N and at least one kind of a metal compound, said process comprising doping Li 3 N with at least one kind of a metal compound.
  • the present invention provides a process for reversely absorbing hydrogen comprising:
  • composition capable of absorbing and/or desorbing hydrogen with hydrogen at a suitable absorption temperature for a suitable period of time thereby absorbing hydrogen, wherein said composition comprises Li 3 N and at least one kind of a metal compound;
  • Fig. 1 shows a graph illustrating the High Pressure Differential
  • Fig. 2 shows a graph illustrating the HP-DSC profiles for hydrogenation process over pristine Li 3 N and Li 3 N doped by aluminium isopropoxide.
  • Doping method ball milling. Reaction condition: 30 bar H 2 , heating rate: 5°C min "1 .
  • Fig. 3 shows a graph illustrating the HP-DSC profiles for hydrogenation process over Li 3 N doped by metallic aluminium, AIF 3 and AICI 3 , respectively.
  • Doping method ball milling. Reaction condition: 30 bar H 2 , heating rate: 5 0 C min '1 .
  • Fig. 4 shows a graph illustrating the HP-DSC profiles for hydrogenation process over Li 3 N doped by Al isopropoxide and Ti isopropoxide, respectively.
  • Doping method ball milling under 300 rpm for 10 hours. Reaction conditions: 30 bar H 2 , heating rate: 5 0 C min "1 .
  • Fig. 5 shows a graph illustrating the HP-DSC profile for hydrogenation process over Li 3 N doped by Al ethoxide and Ti ethoxide, respectively.
  • Doping method ball milling under 300 rpm for 10 hours, Reaction conditions: 30 bar H 2 , heating rate: 5°C min "1 .
  • Fig. 6 shows a graph illustrating the H 2 signal of Temperature Programmed Desorption (TPD) over hydrogenated Li 3 N and Li 3 N doped by Al isopropoxide. Doping method: ball milling under 300 rpm for 10 hours.
  • TPD Temperature Programmed Desorption
  • Fig. 7 shows a graph illustrating the hydrogen absorption over Li 3 N doped by AICI 3 at 150 0 C. Hydrogenation condition: 50 bar H 2 .
  • Fig. 8 shows a graph illustrating the hydrogen absorption over Li 3 N doped by Al isopropoxide at 170 0 C. Hydrogenation condition: 50 bar H 2 .
  • Fig. 9 shows a graph illustrating the hydrogen absorption over Li 3 N doped by Ti ethoxide at 170 0 C. Hydrogenation condition: 50 bar H 2 .
  • Fig. 10 shows a graph illustrating the hydrogen absorption over Li 3 N doped by Ti isopropoxide at 170 0 C. Hydrogenation condition: 50 bar H 2 .
  • Fig. 11 shows a graph illustrating the HP-DSC profile for Li 3 N doped by CaCI 2 .
  • Hydrogenation conditions 30 bar H 2 , heating rate: 5°C min "1
  • compositions comprising Li 3 N and at least one kind of a metal compound are capable of absorbing and/or desorbing hydrogen at lower temperatures and/or pressures than known compounds and therefore can be used as, for example, hydrogen storage materials.
  • the hydrogen storage ability of these compositions is a reversible process, i.e. hydrogen can be stored and released again. Therefore these compositions can be used repeatedly in applications where hydrogen supply is needed.
  • the term “comprising” means including, but not limited to, whatever follows the word “comprising”. Thus, use of the term “comprising” indicates that the listed elements are required or mandatory, but that other elements are optional and may or may not be present.
  • metal compound refers to compounds which are composed of a metal atom and one or more ligands.
  • the metal compound can be selected from any metal of the Periodic Table of the Elements.
  • the metal atom of the metal compound may be selected from the group consisting of a metal compound of Group I, Group II, Group III, Group Ib, Group lib, Group IVb, and Group Vb to Group VIIIb.
  • the terms Group I, Group II, Group 111, Group Ib, Group lib, Group IVb, and Group Vb to Group VIIIb as used herein refer to the Groups of the Periodic Table of the Elements and stand for the corresponding metal.
  • the metal atom of the metal compound may be, but is not limited to, at least one of Li, Na, K, Mg, Ca, Al, Cu, Zn, Ti, Cr, Mn, Fe, Co and Ni to name just a few.
  • Ligand in the context of the present invention is any compound which is linked to the metal atom of the metal compound.
  • the number of ligands depends on the respective metal atom, i.e. the metal atom and the ligand(s) should typically constitute an uncharged and neutral compound.
  • the metal is coordinated with/bound to 3 or 4 ligands.
  • the number of ligands is typically within 1 to 6.
  • the one or more ligands can be one or more organic compounds (or residue), or one or more inorganic compounds or atoms. It is of course also possible that the metal atom has both organic and inorganic ligands.
  • the ligand on the metal atom may be one or more organic compound.
  • organic compound may be an alkyl, an alkoxy, an alkenyl, an alkynyl, an aryl, a heteroaryl known in the prior art.
  • the organic compound may have at least 1 to 15 or 20 carbon atoms. Further, the organic compound may have at least 1 to 10 carbon atoms, for example at least 1 to 6 carbon atoms.
  • an alkyl group may be, but not limited to, groups having 1 to 15 or 20 or, for example, 1 to 10 main chain carbon atoms such as methyl, ethyl, iso-propyl, n-butyl, tert.-butyl, cyclopentyl and cyclohexyl, all may be optionally substituted.
  • alkoxy groups may be, but not limited to, methoxy, ethoxy, isopropoxy, n-butoxy and tert.-butoxy, all may be optionally substituted.
  • alkenyl groups may be, but not limited to, ethylene, propylene and isobutylene, all may be optionally substituted.
  • Suitable alkynyl groups may be, but not limited to, ethyne, propyne and butyne, all may be optionally substituted.
  • An aryl group according to the present invention may be any compound having aromaticity, such as for example benzene, toluene, naphthalene, anthracene, cyclopentadienyl (Cp), cyclooctatetraene all may be optionally substituted.
  • a heteroaryl group may be an aryl group wherein at least one carbon atom is replaced by nitrogen, oxygen and sulphur.
  • heteraryl groups may be, but not limited to, pyrrole, pyridine, piperidine thiophene, pyrazole, imidazole, pyrimidine, indol, thiazole, furan and tetrahydrofuran, all may be optionally substituted.
  • the metal compound consists of a metal atom and one or more organic ligands.
  • Optionally substituted in the context of the present invention means that at least one hydrogen atom of the above compounds may be replaced by F, Cl, Br, OH, CN, NO 2 , NH 2 , SO 2 or an alkyl group or an aryl group as defined above.
  • the metal atom may also contain one or more inorganic ligand(s).
  • an inorganic ligand may be, but is not limited to, NH 2 , F, Cl, Br or I.
  • the metal compound is composed of a metal atom and one or more organic ligands and one or more inorganic ligands.
  • the metal compound may be in the form of a salt wherein the metal atom is the cation and the one or more inorganic ligand is the respective anion of the salt.
  • the metal compound may be NaF, NaCI, NaBr, NaI, LiF, LiCI, LiBr, LiI, or mixtures thereof.
  • Further examples may be MgCb, CaCI 2 , ZnCI 2 , FeCI 3 , NiCI 2 , CoCI 2 , CuCI 2 , CuCI, and SrCI 2 or mixtures thereof.
  • Still further examples of the halogen anion salt may be AIF 3 , AICI 3 , AIBr 3 , SnCI 2 , SnCI 4 , or TiCU or mixtures thereof.
  • the metal compound can be a compound of any of the general formulas (I) to (IV),
  • metals in the oxidation state M + ' include copper, lithium, sodium and potassium, and examples of metals in the oxidation state M + " include magnesium, calcium, iron, cobalt, copper, nickel, zinc, tin to name just a few.
  • metals of oxidation state M + '" include aluminium, iron, cobalt and examples of metals of oxidation state M +Iv include titanium, manganese, or tin, to name just a few.
  • such compounds may be
  • AIX n R 3- n (formula Ilia) or
  • X can be an inorganic ligand such as F, Cl, Br or I; and R may be an organic ligand with 1 to 20 carbon atoms as explained above.
  • R may be an alkyl such as methyl, ethyl, iso-propyl, n-butyl, tert.-butylhexyl, cyclohexyl, phenyl or benzyl, or an alkoxy such as methoxy, ethoxy, isopropoxy, n-butoxy and tert.-butoxy.
  • n can be an integer from 0 to 3 and m can be an integer from 0 to 4. In one embodiment of the present invention n is 0. In a further embodiment of the present invention m is 0.
  • the metal compound may be, but is not limited to, LiCH 3 , CpLi, Na(OCH 3 ), Na(OC 2 H 5 ), Na(OC 3 H 7 ), K(OCH 3 ), K(OC 2 H 5 ), K(OC 3 H 7 ) Mg(CH 3 ) 2 , Mg(OCH 3 ) 2 , Mg(OC 2 H 5 ) 2 , (C 6 H 6 )MgCI, AI(OCH 3 ) 3 , AI(OC 2 Hg) 3 , AI(OC 3 H 7 ) 3 (Al isopropoxide), AI(OC 4 Hg) 3 (Al n-butoxide), AI[(OC(CH 3 ) 3 ] 3 (Al tert.-butoxide), AI(CH 3 ) 3 , AI(C 2 Hs) 3 , AICI(CHa) 2 , AICI 2 (CH 3 ), Ti(OCH 3 ) 4 , Ti(OC 2 H
  • a composition of the present invention comprises Li 3 N and at least one kind of a metal compound. It is thus also possible that a composition of the invention comprises Li 3 N in combination with two or more different metal compounds as given above. For example, combinations of Li 3 N with an aluminium compound and a titanium compound such as- AI(OC 3 Hy) 3 and Ti(OC 3 Hy) 4 or AI(OC 3 Hy) 3 and Ti(OC 2 Hs) 4 may be used. Furthermore, combinations of different metal compounds of Al such as, for example, AI(OC 2 H 5 ) 3 and AI(OC 3 Hy) 3 or different metal compounds of Ti such as, for example, Ti(OC 2 H 5 ) 4 and Ti(OC 3 Hy) 4 or different compounds of any other metal may also be used in the present invention.
  • the metal compound is present in the composition in a range of O to 40 wt.% with respect to the total weight of the composition. In some embodiment the metal compound is present in the composition in a range of O to 20 wt.% with respect to the total weight of the composition or in a range of O to 10 wt.% with respect to the total weight of the composition. In some purely illustrative embodiments, the total weight of the composition is in the range of about 5 to about 15 g, such as 10 g.
  • a composition of the invention is prepared by doping the Li 3 N with at least one kind of a metal compound referred to as "dopant".
  • dopant a metal compound referred to as "dopant”.
  • Li 3 N is contacted, optionally or typically after mixing, with the metal compound for a suitable amount of time such that a certain amount of the metal is incorporated into Li 3 N.
  • Doping means that a metal compound is present and that a metal atom and/or any substituent or counter ion can be identified in a composition comprising Li 3 N by any qualitative or quantitative analytical method and especially by a spectroscopic method, such as mass spectroscopy, nuclear magnetic resonance (NMR), infrared (IR) spectroscopy, atom spectroscopy, inductively coupled plasma (ICP), X-ray photoelectron spectroscopy (XPS), X-ray fluorescence (XRF), energy dispersive spectroscopy (EDX) and ion scattering Spectroscopy (ISS).
  • mass spectroscopy nuclear magnetic resonance (NMR), infrared (IR) spectroscopy, atom spectroscopy, inductively coupled plasma (ICP), X-ray photoelectron spectroscopy (XPS), X-ray fluorescence (XRF), energy dispersive spectroscopy (EDX) and ion scattering Spectroscopy (ISS).
  • the doping of Li 3 N with at least one kind of a metal compound is performed by milling a mixture of Li 3 N and, for example, one or more of the metal compounds described above in a ball mill.
  • the ball mill technology is quite mature in industry and has broad application in material technology, geology and mineralogy, ceramics, biology, medicine, pharmacology, and chemistry. Easy scale up is one of the advantages for this technology.
  • Ball mills are mills typically used for micro-milling or homogenisation.
  • Ball mills are typically cylindrical rotating grinding devices used to grind or mix materials such as chemicals, ceramics and paints. They consist of a rotating grinding beaker in which the grist to be milled is inserted together with balls of different materials. Materials typically used for the grinding include, for example, ceramics balls, flint pebbles or stainless steel balls of different sizes.
  • the ball mill process can be used for lab scale preparations as well as industrial scale preparations.
  • the milling process may be carried out at any suitable temperature and any suitable pressure.
  • the temperature may be in the range of about -196 to about 50 0 C.
  • the pressure may be in the range of from about 0.1 to about 20 bar.
  • the process can be carried out at any suitable velocity of the mill, for example at a velocity of about 150 to about 400 rpm, or of about 200 to about 250 rpm.
  • the process may be completed in any suitable time, for example within about 100 hours, or within about 80 hours, or within about 50 hours.
  • the process may be carried out for about 10 hours, or about 8 hours, or about 2 hours, or even about 0.5 hours.
  • the milling process is carried out for about 10 hours at a velocity of about 300 rpm.
  • the velocity of the ball mill should in some embodiments, however, not be lower than 150 rpm, since no promoting effect may be observed no matter how long the milling process is carried out at a velocity below 150 rpm.
  • the above explained doping process can also be used for the preparation of the compounds of the present invention if volatile metal containing compounds are used for doping U 3 N.
  • the ball mill may be additionally filled with an inert gas, for example N 2 or Ar, in the range of about 1 to about 20 bar, for example about 2 to about 10 bar or about 4 to about 8 bar, such as 6 bar.
  • an inert gas for example N 2 or Ar
  • the volatilization of these otherwise volatile compounds will be depressed.
  • “Volatile” in this respect means that the respective chemical compound has a high enough vapor pressure under normal conditions to significantly vaporize and enter the atmosphere.
  • the compositions of the invention can be prepared by calcination.
  • Calcination is the well-know process of heating a substance to a high temperature, which is below the melting or fusing point of the respective substance/composition, in order to achieve at least partial thermal decomposition or a phase transition in the physical or chemical constitution of the substance/composition.
  • the temperature, time, heating and cooling rate, and the atmosphere, etc. have to be considered.
  • heating of the mixture of U 3 N and one or more metal compounds is typically carried out in the temperature range of about 200 to about 700 0 C.
  • calcination is carried out in the temperature range of about 300 to about 600 C for a suitable amount of time.
  • the determination of the suitable calcination conditions is within the knowledge of the person of average skill in the art and can be determined empirically.
  • the compositions of the invention can be prepared by a wet chemical process.
  • the starting compounds i.e. Li 3 N and the metal containing compound are dispersed or dissolved and then mixed (thoroughly) in a respective solvent by means of a mechanical stirrer, such as a magnetic stirrer.
  • the so obtained solution or dispersion may be mixed for any suitable time, for example, for about 1 to about 20 hours, or for about 2 to about 10 hours or about 2 to about 5 hours.
  • the solution or dispersion may be heated up to the boiling point of the respective solvent. Any solvent that is inert under the reaction conditions may be used for the purpose of the present invention.
  • the solvent may be, but is not limited to, pentane, hexane, heptane, benzene, toluene, tetrahydrofuran, diethylether, CHCI 3 or CH 2 CI 2 , to name only a few. After removal of the solvent the compositions of the invention can be obtained.
  • compositions of the present invention are obtainable by one of the preparation methods as given above.
  • a metal atom alone or together with its substituent(s)/ ligands e.g., Mg(CH 3 ) 2 , Mg(OCH 3 ) 2 , Mg(OC 2 Hs) 2 (Ti(OC 2 H 5 ) 4 , Ti(OC 3 Hz) 4 , AI(OC 3 Hr) 3 , AICI 3 or TiCI 4
  • substituent(s)/ ligands e.g., Mg(CH 3 ) 2 , Mg(OCH 3 ) 2 , Mg(OC 2 Hs) 2 (Ti(OC 2 H 5 ) 4 , Ti(OC 3 Hz) 4 , AI(OC 3 Hr) 3 , AICI 3 or TiCI 4
  • the composition of the invention may be present as a mixture of Li 3 N (having incorporated some of the active atom) and the respective metal compound which with Li 3 N is contacted.
  • the composition may substantially consist of Li 3 N (with some of the active atom incorporated therein).
  • the composition of the invention is usually present as a mixture if a solid and chemically stable dopant (for example, a compound such as Na(OCH 3 ), or AI(OC 2 H 5 ) 3 ) is used. If a volatile dopant or a dopant that is susceptible to decomposition is used, then the composition may essentially consist of only the doped Li 3 N since (at least under atmospheric pressure), since the dopant will typically be released after the doping process (in which the dopant has been brought into contact with Li 3 N) is completed.
  • a solid and chemically stable dopant for example, a compound such as Na(OCH 3 ), or AI(OC 2 H 5 ) 3
  • a volatile dopant or a dopant that is susceptible to decomposition is used, then the composition may essentially consist of only the doped Li 3 N since (at least under atmospheric pressure), since the dopant will typically be released after the doping process (in which the dopant has been brought into contact with Li 3 N) is completed.
  • the absorption of hydrogen by the composition of the present invention is temperature and pressure dependent, as already mentioned above.
  • the absorption temperature may be within the range of about 0 0 C to about 25O 0 C.
  • the absorption temperature can be within the range of about 50 0 C to about 220 0 C, or about 100 to about 150°C.
  • the absorption temperature is about 100°C.
  • the absorption pressure may be in the range of about 1 bar to about 200 bar H 2 , or about 5 bar to about 100 bar H 2 , or about 5 to about 50 bar H 2 .
  • the onset temperature indicating the beginning of the hydrogen absorption is typically in the range of about 50°C to about 12O 0 C, or about 8O 0 C to about 100 0 C
  • the above-mentioned temperature dependency of the compositions of the present invention is not the only parameter when considering the storage ability of those compositions.
  • the total quantity of hydrogen which is actually absorbed during the absorption process provides an indication of the storage capability of the inventive compositions.
  • the total quantity of hydrogen that is capable of being reversibly absorbed by the compositions may be about 1 to 10.4 wt.%, or about 1 to 9.36 wt.%, or about 1 to 8.32 wt.%.
  • Table 1 below shows some illustrative examples of the hydrogen capacity (wt%) of Li 3 N doped by Al and Ti compounds at different temperatures.
  • 10 wt% of the dopant Ti(OC 2 H 5 ) 4 ⁇ Ti(OC 3 Hr) 4 or AI(OC 3 Hr) 3
  • X 90% 9.36 wt%
  • the on-set temperature for the hydrogenation of Li 3 N is 200 0 C, i.e. below 200 0 C pristine Li 3 N cannot absorb any hydrogen at all (indicated as "0" in Table 1).
  • the results in Table 1 indicate that at lower temperatures, for example at 17O 0 C 1 all three tested compounds, i.e. Ti(OC 2 Hs) 4 , Ti(OC 3 Hr) 4 and AI(OC 3 Hr) 3 -Li 3 N are capable of absorbing about 100% of the theoretical hydrogen amount contrary to the inability of pristine Li 3 N to absorb any hydrogen at this temperature.
  • composition of the present invention is that the absorption of hydrogen can occur in shorter times, when compared to the absorption of pristine L1 3 N, i.e. that the reaction rate is fast.
  • the compositions are able to absorb at least 4 wt.% of hydrogen in less than 10 minutes, less than 8 minutes, or in even less than 5 minutes or even within 30 seconds.
  • the compositions of the present invention can absorb at least 9 wt.% of hydrogen with in 60 minutes or even less.
  • the absorption of hydrogen is temperature dependent and the reaction rate is even faster at elevated temperatures. For example, the reaction rate is 2 times faster when the temperature is about 1O 0 C higher.
  • the ideal temperature for optimal hydrogen absorption for any purpose should be as low as possible.
  • the absorption temperature of KCI-U 3 N to be compatible with Proton Exchange Membrane (PEM) fuel cells is about 13O 0 C, which is much lower than the corresponding temperature of the pristine IJ 3 N which is about 230 0 C (but achievable with a composition of the invention).
  • the reaction rate it should be as fast as possible.
  • it should advantageously be not longer than about 10 min, or about 5 min.
  • the temperature should be around 100 0 C and filling time should be less than 5 min.
  • the stored hydrogen can also be released.
  • the desorption takes place at temperatures in the range of about O 0 C to about 25O 0 C, or about 8O 0 C to about 220 0 C, or about 80 to about 18O 0 C or even about 100°C to about 15O 0 C.
  • the onset temperature indicating the beginning of the hydrogen desorption is typically in the range of O 0 C to 100°C, preferably 5O 0 C to 9O 0 C.
  • the compositions of the present invention are typically capable of desorbing about 50% to about 100% or about 60% to about 90% of the absorbed hydrogen.
  • the desorption of hydrogen is temperature dependent and the reaction rate is faster at elevated temperatures, i.e.
  • composition of the present invention is the prolonged life time of the composition of the present invention.
  • pristine LJ 3 N still showed good activity after up to only 10 absorption/desorption cycles, whereas the compositions of the present invention show good activity after up to 100 absorption/desorption cycles, meaning a rather significantly improved life time.
  • the process for reversely absorbing hydrogen comprises: contacting a composition capable of absorbing and/or desorbing hydrogen with hydrogen at a suitable absorption temperature for a suitable period of time thereby absorbing hydrogen, wherein said composition comprises Li 3 N and at least one kind of a metal compound; and (ii) releasing the absorbed hydrogen from the composition at a desorption temperature.
  • the term "reversely absorbing” as used herein means that a quantity of hydrogen is absorbed by the composition at an absorption temperature and subsequently undergoes desorption from the composition at a desorption temperature.
  • the quantity of hydrogen in the desorption step does not have to be identical with the absorbed quantity. Nevertheless, in one embodiment, at least about 50 % to about 100% or about 60% to about 90% of the hydrogen that has been absorbed in the absorption step is released in the desorption step.
  • the desorption process is temperature dependent. The higher the operating temperature, the higher percentage value of desorption. In order to satisfy the US Department of Energy's technical target of 6.0 wt% hydrogen capacity for on-board usage, a presently preferred range of hydrogen desorption should be about 50% to about 100%.
  • the temperatures and pressures used in this process can be as indicated above. After step (i), the absorbed hydrogen can be stored in the composition for the above-mentioned period of time.
  • compositions of the invention can be used in various applications, wherever a hydrogen supply is needed. Accordingly, in some embodiments the compositions of the invention are used as a hydrogen reservoir.
  • a hydrogen reservoir may comprise a unit that contains the composition of the invention.
  • the unit may have an inflow valve and an outflow valve for passing the hydrogen during absorption and desorption through the unit.
  • the unit can also have a single reversible valve to permit both the inflow and outflow of the hydrogen.
  • Li 3 N (80 mesh, 99.5% purity) and metal compounds were purchased from Sigma-Aldrich. The sample handlings were performed inside a glovebox (Mbraun Master 130) filled with purified Ar gas to maintain an inert atmosphere (H 2 O ⁇ 1 PPM, O 2 ⁇ 1 PPM).
  • Example 1 Li 3 N-AI(OC 3 H 7 )S
  • Li 3 N doped by AI(OC 3 Hj) 3 has one hydrogenation stage at 164 0 C.
  • the onset temperature is at approx. 100 0 C.
  • the hydrogenation can even occur below 100 0 C.
  • the kinetic reaction rate is fast.
  • Within 10 min 5.0 wt% hydrogen can be absorbed.
  • the hydrogen desorption temperature is reduced to 193 0 C, while the onset temperature is as low as 100 0 C, which is the operating temperature for PEM fuel cell (cf. Fig. 2, Fig. 4, Fig.7 and Fig. 9).
  • the hydrogen absorption temperature is reduced to 192°C (cf. Fig. 3)
  • the hydrogen absorption temperature which is present at two stages, is reduced to 15 TC (the second stage is at 236°C), which is about 7O 0 C lower than that of L1 3 N. Further, the hydrogenation can even occur below 100 0 C. At 150 0 C the kinetic reaction rate is fast. Within 10 minutes 3.7 wt.% hydrogen can be absorbed. At 230 0 C, 9.3 wt.% hydrogen can be absorbed, which is about 100% of the theoretical value (cf. Fig. 3 and Fig. 8).
  • Example 5 Li 3 NTi(OC 3 HT) 4
  • the hydrogen absorption temperature is reduced to 169°C (cf. Fig. 4).
  • the HP-DSC was installed inside a glovebox (Mbraun Master 130) filled with purified Ar gas. Normally, 10 mg sample was used each time. The heating rate was 5°C « min "1 and the H 2 pressure was 30 bar. [0084] The hydrogen absorption temperature is reduced to 172 0 C (cf. Fig. 5).
  • the hydrogen desorption can be measured by TPD. After loading 100 mg sample into the sample ceil, the sample was first hydrogenated under 50 bar hydrogen at 230 0 C and then cooled down to room temperature. After releasing the remaining hydrogen, the carrier gas (Ar 50 ml min "1 ) was switched on. The heating rate was 5°C » min "1 and temperature range was 50 to 500 0 C. [0088] The hydrogen absorption temperature is reduced to 152°C, hydrogenation can even occur below 100 0 C. At 150 0 C the kinetic reaction rate is very fast. Within 10 min. 3.0 wt.% hydrogen can be absorbed. At . 230 0 C, 9.3 wt. % hydrogen can be absorbed, which is about 100% of the theoretical value.
  • the hydrogen absorption temperature is reduced to 130 0 C. B.
  • the on-set temperature for CaCI 2 doped Li 3 N is about 100 0 C 1 which is about 100 ° C lower than that over pristine Li 3 N (200 0 C, Fig. 1).
  • the hydrogen absorption temperature is reduced to 168 0 C.
  • Li 3 N doped by CaCI 2 has two hydrogenation stages at 168°C and 225°C, respectively. Comparative Example 1 :
  • the absorption temperature of pristine Li 3 N occurs at temperatures higher than 200 0 C, approximately about 221 0 C and approximately about 260 0 C, respectively.
  • the two peaks in the graph (cf. Fig. 2) at 221 0 C and 260 0 C correspond to two hydrogenation stages (Li 3 N + H 2 «• Li 2 NH +LiH (1); Li 2 NH + H 2 ⁇ LiNH 2 + LiH (2)).
  • the onset temperature for hydrogenation is at 200 0 C, the desorption temperature at 252 0 C (cf. Fig. 2 and Fig. 7).

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Abstract

Cette invention concerne une composition conçue pour adsorber et/ou désorber l'hydrogène. Cette composition contient du Li3N et au moins un type de composé métallique. La présente invention concerne également divers procédés permettant d'obtenir cette composition.
PCT/IB2006/003537 2005-12-09 2006-12-11 Compositions de li3n dopes avec des composes metalliques pour adsorption/desorption de l'hydrogene Ceased WO2007066219A2 (fr)

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