US20170044011A1 - Hydrogen Storage Element for a Hydrogen Store - Google Patents

Hydrogen Storage Element for a Hydrogen Store Download PDF

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Publication number
US20170044011A1
US20170044011A1 US15/307,142 US201515307142A US2017044011A1 US 20170044011 A1 US20170044011 A1 US 20170044011A1 US 201515307142 A US201515307142 A US 201515307142A US 2017044011 A1 US2017044011 A1 US 2017044011A1
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hydrogen storage
heat
hydrogen
conducting
storage element
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US15/307,142
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Inventor
Antonio Casellas
Klaus Dollmeier
Eberhard Ernst
Rene Lindenau
Anastasia OZKAN
Lars Wimbert
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GKN Powder Metallurgy Engineering GmbH
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GKN Sinter Metals Engineering GmbH
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Assigned to GKN SINTER METALS ENGINEERING GMBH reassignment GKN SINTER METALS ENGINEERING GMBH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ÖZKAN, ANASTASIA, CASELLAS, ANTONIO, DOLLMEIER, KLAUS, LINDENAU, René, WIMBERT, LARS, ERNST, EBERHARD
Publication of US20170044011A1 publication Critical patent/US20170044011A1/en
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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
    • C01B3/0005—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
    • C01B3/0078—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
    • 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
    • C01B3/0021—Carbon, e.g. active carbon, carbon nanotubes, fullerenes; 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
    • C01B3/0084—Solid storage mediums characterised by their shape, e.g. pellets, sintered shaped bodies, sheets, porous compacts, spongy metals, hollow particles, solids with cavities, layered solids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • C09K5/14—Solid materials, e.g. powdery or granular
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage

Definitions

  • the present invention relates to a hydrogen storage means comprising a hydrogen-permeable structure and to a process for producing a layer structure.
  • This mixture is pressed, for example, axially to give cylinders or sheets or blocks or slabs, and inserted into a vessel, especially a tank.
  • a mixture of expanded graphite having very low density is mixed with the hydrogenatable metal or the metal hydride, such that the expanded graphite becomes aligned transverse/at right angles to the pressing direction through the axial pressing. This gives rise to high thermal conductivity transverse to pressing direction.
  • EP-A-1 348 527, EP-A-2 221 131, EP-A-1 407 877 and JP-A-60162702 disclose processes and apparatuses for production of components using shaping molds, in which powders of at least two different compositions are introduced into a shaping mold or into a cavity of a shaping mold. Further processes of this kind are known, for example, in DE-B-10 2009 005 859, DE-A-10 2010 015 016, DE-T-60 2004 005 070 and WO-A-2013/036982.
  • the hydrogen storage element comprises a heat-conducting material in thermal contact with the first material having hydrogen storage capacity.
  • these two materials intermesh, meaning that they do not take the form of mere layers alongside one another.
  • the heat-conducting second material projects into the first material having hydrogen storage capacity in subregions, i.e. has different three-dimensional distribution in this respect within the hydrogen storage element. This three-dimensional distribution may itself in turn have regular repeating structures, but this need not necessarily be the case.
  • the second material is a film or ribbon which projects out of the plane or the film or ribbon in sections.
  • the heat-conducting second material thus extends within the compact both in the X and Y directions, i.e. in the direction of the second material, and in the Z direction, i.e. in the direction of the succession of several layers of first and second material.
  • a hydrogen storage means having a hydrogen-permeable structure, preferably a porous structure, which is present as a compressed component in the hydrogen storage means and serves for flow of a hydrogenous gas.
  • the invention especially relates to a layered structure of hydrogen storage means, especially metal hydride storage means having graphite laminas of good thermal conductivity, such that the graphite can remove the large amounts of heat in the hydrogenation of the hydrogen storage means and supply them in the dehydrogenation.
  • One of the layers of the layered structure has mainly at least one of the following functions: primary hydrogen storage, primary heat conduction and/or primary gas conduction.
  • the functions of “primary hydrogen storage”, “primary heat conduction” and/or “primary gas conduction” are understood to mean that the respective layer fulfills at least one of these functions as a main object in one region of the composite material compact.
  • a layer is utilized primarily for hydrogen storage, but is simultaneously also capable of providing at least a certain thermal conductivity. It may be the case here that at least one other layer is present which assumes the primary task of heat conduction, which means that the majority of the amount of heat is dissipated from the compressed material composite via this layer.
  • the primarily gas-conducting layer through which, for example, the hydrogen can be passed into the material composite or else, for example, conducted out of it. In this case, the flowing fluid can also entrain heat.
  • hydrogen storage means describes a reservoir vessel in which hydrogen can be stored by means of hydrogen-storing elements or components which for the most part remain intrinsically dimensionally stable and are in the form, for example, of sheets, blocks, tablets or pellets. This can be done using conventional methods of saving and storage of hydrogen, for example compressed gas storage, such as storage in pressure vessels by compression with compressors, or liquefied gas storage, such as storage in liquefied form by cooling and compression. Further alternative forms of storage of hydrogen are based on solids or liquids, for example metal hydride storage means, such as storage as a chemical compound between hydrogen and a metal or an alloy, or adsorption storage, such as adsorptive storage of hydrogen in highly porous materials. In addition, for storage and transport of hydrogen, there are also possible hydrogen storage means which temporarily bind the hydrogen to organic substances, giving rise to liquid compounds that can be stored at ambient pressure, called “chemically bound hydrogen”.
  • Element and “component” each refer to a component of any geometry having hydrogen storage capacity, for example in sheet, cylinder, block or slab form or the like.
  • One or more prefabricated hydrogen storage components of this kind are positioned in the (pressure) vessel of a hydrogen storage means.
  • layers means that preferably one material, but also two or more material laminas, are in an arrangement and these material laminas can be delimited from their direct environment. For example, it is possible for different materials to be poured in successively in loose form, such that adjacent layers are in direct contact with one another.
  • the hydrogenatable layer is arranged directly adjacent to a thermally conductive layer, such that the heat that arises on absorption of hydrogen and/or release of hydrogen can be released from the hydrogenatable material directly to the adjacent layer.
  • a layer preferably surface-coated fibers are combined to form bundles. These bundles are, for example, stretched and then cut in order to obtain, for example, a layer comprising short fibers.
  • the surface coating is preferably hydrogen-permeable. If the material of the fibers is hydrogen-storing, the coating can especially form protection against oxidation.
  • a hydrogen storage means comprising a first material and a second material at separate locations from one another, each of which form separate layers adjacent to one another, preferably abutting one another, the first material comprising a primarily hydrogen-storing material and the second material being a primarily heat-conducting material, with the primarily heat-conducting material extending preferably from the interior of the hydrogen storage element outward.
  • a gradient is formed between the first and second layers, along which a transition from the first to the second layer is accomplished via a change in the respective material content (density content) of the first and second materials.
  • a gradient can be brought about, for example, by moving a bar, in the case of several bars by means of a comb, or generally by means of a contact element having a different geometry, in the materials of the first and second layers, when they are yet to be further processed, for example yet to be laid down with compression together.
  • a bar in the case of several bars by means of a comb, or generally by means of a contact element having a different geometry, in the materials of the first and second layers, when they are yet to be further processed, for example yet to be laid down with compression together.
  • a further configuration of the hydrogen storage means has components in the form of a core-shell structure, in which the core comprises a first material and the shell comprises a different second material, the first material and/or the second material comprising a hydrogen-storing material, the components preferably being selected from the group comprising powders, granules, flakes, fibers and/or other geometries.
  • the hydrogen storage element comprises the second material of the shell in the form of a polymer configured so as to be at least hydrogen-permeable.
  • the hydrogen storage component has a structure in which the core comprises a primarily heat-conducting material and the shell a primarily hydrogen-storing material.
  • the core comprises a primarily hydrogen-storing material and the shell a primarily heat-conducting material, the heat-conducting material being hydrogen-permeable.
  • the hydrogen-storing material has a hydrogen-permeable coating which prevents oxidation of the hydrogen-storing material, the coating preferably being hydrogen-storing.
  • This coating can alternatively be used to prevent oxidation or else additionally serve for coherence, i.e. for mechanical bonding of the hydrogenatable material present, for example, in particulate form.
  • the matrix can impart good optical, mechanical, thermal and/or chemical properties to the material.
  • the hydrogen storage means by virtue of the polymer, may have good thermal stability, resistance to the surrounding medium (oxidation resistance, corrosion resistance), good conductivity, good hydrogen absorption and storage capacity or other properties, for example mechanical strength, which would otherwise not be possible without the polymer.
  • polymers which, for example, do not enable storage of hydrogen but do enable high expansion, for example polyamide or polyvinyl acetates.
  • the polymer may be a homopolymer or a copolymer.
  • Copolymers are polymers composed of two or more different types of monomer unit. Copolymers consisting of three different monomers are called terpolymers.
  • the polymer for example, may also comprise a terpolymer.
  • the polymer has a monomer unit which, as well as carbon and hydrogen, preferably additionally includes at least one heteroatom selected from sulfur, oxygen, nitrogen and phosphorus, such that the polymer obtained, in contrast to polyethylene, for example, is not entirely nonpolar. It is also possible for at least one halogen atom selected from chlorine, bromine, fluorine, iodine and astatine to be present.
  • the polymer is a copolymer and/or a terpolymer in which at least one monomer unit, in addition to carbon and hydrogen, additionally includes at least one heteroatom selected from sulfur, oxygen, nitrogen and phosphorus and/or at least one halogen atom selected from chlorine, bromine, fluorine, iodine and astatine is present. It is also possible that two or more monomer units have a corresponding heteroatom and/or halogen atom.
  • the polymer preferably has adhesive properties with respect to the hydrogen storage material. This means that it adheres well to the hydrogen storage material itself and hence forms a matrix having stable adhesion to the hydrogen storage material even under stresses as occur during the storage of hydrogen.
  • the adhesive properties of the polymer enable stable penetration of the material into a hydrogen storage means and the positioning of the material at a defined point in the hydrogen storage means over a maximum period of time, i.e. over several cycles of hydrogen storage and hydrogen release.
  • a cycle describes the operation of a single hydrogenation and subsequent dehydrogenation.
  • the hydrogen storage material should preferably be stable over at least 500 cycles, especially over at least 1000 cycles, in order to be able to use the material economically. “Stable” in the context of the present invention means that the amount of hydrogen which can be stored and the rate at which the hydrogen is stored, even after 500 or 1000 cycles, corresponds essentially to the values at the start of use of the hydrogen storage means.
  • “stable” means that the hydrogenatable material is kept at least roughly at the position within the hydrogen storage means where it was originally introduced into the storage means. “Stable” should especially be understood to the effect that no separation effects occur during the cycles, where finer particles separate and are removed from coarser particles.
  • the hydrogen storage material of the present invention is especially a low-temperature hydrogen storage material.
  • temperatures of up to 150° C. therefore occur.
  • a polymer which is used for the matrix of a corresponding hydrogen storage material therefore has to be stable at these temperatures.
  • a preferred polymer therefore does not break down up to a temperature of 180° C., especially up to a temperature of 165° C., especially up to 145° C.
  • the polymer is a polymer having a melting point of 100° C. or more, especially of 105° C. or more, but less than 150° C., especially of less than 140° C., particularly of 135° C. or less.
  • the density of the polymer, determined according to ISO 1183 at 20° C. is 0.7 g/cm 3 or more, especially 0.8 g/cm 3 or more, preferably 0.9 g/cm 3 or more, but not more than 1.3 g/cm 3 , preferably not more than 1.25 g/cm 3 , especially 1.20 g/cm 3 or less.
  • the tensile strength according to ISO 527 is preferably in the range from 10 MPa to 100 MPa, especially in the range from 15 MPa to 90 MPa, more preferably in the range from 15 MPa to 80 MPa.
  • the tensile modulus of elasticity according to ISO 527 is preferably in the range from 50 MPa to 5000 MPa, especially in the range from 55 MPa to 4500 MPa, more preferably in the range from 60 MPa to 4000 MPa. It has been found that, surprisingly, polymers having these mechanical properties are particularly stable and have good processibility. More particularly, they enable stable coherence between the matrix and the hydrogenatable material embedded therein, such that the hydrogenatable material remains at the same position within the hydrogen storage means over several cycles. This enables a long lifetime of the hydrogen storage means.
  • the polymer is selected from EVA, PMMA, EEAMA and mixtures of these polymers.
  • EVA ethyl vinyl acetate
  • EVA ethyl vinyl acetate
  • Typical EVAs are solid at room temperature and have tensile elongation of up to 750%.
  • EVAs are resistant to stress cracking.
  • EVA has the following general formula (I):
  • EVA in the context of the present invention preferably has a density of 0.9 g/cm 3 to 1.0 g/cm 3 (according to ISO 1183).
  • Yield stress according to ISO 527 is especially 4 to 12 MPa, preferably in the range from 5 MPa to 10 MPa, particularly 5 to 8 MPa.
  • Elongation at break (according to ISO 527) is especially >30% or >35%, particularly >40% or 45%, preferably >50%.
  • the tensile modulus of elasticity is preferably in the range from 35 MPa to 120 MPa, particularly from 40 MPa to 100 MPa, preferably from 45 MPa to 90 MPa, especially from 50 MPa to 80 MPa.
  • Suitable EVAs are sold, for example, by Axalta Coating Systems LLC under the Coathylene® CB 3547 trade name.
  • Polymethylmethacrylate (PMMA) is a synthetic transparent thermoplastic polymer having the following general structural formula (II):
  • the glass transition temperature is about 45° C. to 130° C.
  • the softening temperature is preferably 80° C. to 120° C., especially 90° C. to 110° C.
  • the thermoplastic copolymer is notable for its resistance to weathering, light and UV radiation.
  • PMMA in the context of the present invention preferably has a density of 0.9 to 1.5 g/cm 3 (according to ISO 1183), especially of 1.0 g/cm 3 to 1.25 g/cm 3 .
  • Elongation at break is especially ⁇ 10%, particularly ⁇ 8%, preferably ⁇ 5%.
  • the tensile modulus of elasticity is preferably in the range from 900 MPa to 5000 MPa, preferably from 1200 to 4500 MPa, especially from 2000 MPa to 4000 MPa.
  • Suitable PMMAs are sold, for example, by Ter Hell Plastics GmbH, Bochum, Germany, under the trade name of 7M Plexiglas® pellets.
  • EEAMA is a terpolymer formed from ethylene, acrylic ester and maleic acid anhydride monomer units.
  • EEAMA has a melting point of about 102° C., depending on the molar mass. It preferably has a relative density at 20° C. (DIN 53217/ISO 2811) of 1.0 g/cm 3 or less and 0.85 g/cm 3 or more.
  • Suitable EEAMAs are sold, for example, under the Coathylene® TB3580 trade name by Axalta Coating Systems LLC.
  • the composite material comprises essentially the hydrogen storage material and the matrix.
  • the proportion by weight of the matrix based on the total weight of the composite material is preferably 10% by weight or less, especially 8% by weight or less, more preferably 5% by weight or less, and is preferably at least 1% by weight and especially at least 2% by weight to 3% by weight. It is desirable to minimize the proportion by weight of the matrix.
  • the matrix is capable of storing hydrogen, the hydrogen storage capacity is not as significant as that of the hydrogen storage material itself. However, the matrix is needed in order firstly to keep any oxidation of the hydrogen storage material that occurs at a low level or prevent it entirely and to assure coherence between the particles of the material.
  • the matrix is a polymer having low crystallinity.
  • the crystallinity of the polymer can considerably alter the properties of a material.
  • the properties of a semicrystalline material are determined both by the crystalline and the amorphous regions of the polymer.
  • composite materials which are likewise formed from two or more substances. For example, the expansion capacity of the matrix decreases with increasing density.
  • the matrix may also take the form of prepregs.
  • Prepreg is the English abbreviation of “preimpregnated fibers”.
  • Prepregs are semifinished textile products preimpregnated with a polymer, which are cured thermally and under pressure for production of components.
  • Suitable polymers are those having a highly viscous but unpolymerized thermoset polymer matrix.
  • the polymers preferred according to the present invention may also take the form of a prepreg.
  • the fibers present in the prepreg may be present as a pure unidirectional layer, as a fabric or scrim.
  • the prepregs may, in accordance with the invention, also be comminuted and be processed as flakes or shavings together with the hydrogenatable material to give a composite material.
  • the polymer may take the form of a liquid which is contacted with the hydrogenatable material.
  • liquid is that the polymer is melted.
  • the invention also encompasses dissolution of the polymer in a suitable solvent, in which case the solvent is removed again after production of the composite material, for example by evaporation.
  • the polymer takes the form of pellets which are mixed with the hydrogenatable material. As a result of the compaction of the composite material, the polymer softens, so as to form the matrix into which the hydrogenatable material is embedded. If the polymer is used in the form of particles, i.e.
  • pellets these preferably have an x 50 particle size (volume-based particle size) in the range from 30 ⁇ m to 60 ⁇ m, especially 40 ⁇ m to 45 ⁇ m.
  • the x 90 particle size is especially 90 ⁇ m or less, preferably 80 ⁇ m or less.
  • the hydrogenatable material can absorb the hydrogen and, if required, release it again.
  • the material comprises particulate materials in any 3-dimensional configuration, such as particles, pellets, fibers, preferably cut fibers, flakes and/or other geometries. More particularly, the material may also take the form of sheets or powder. In this case, the material does not necessarily have a homogeneous configuration. Instead, the configuration may be regular or irregular. Particles in the context of the present invention are, for example, virtually spherical particles, and likewise particles having an irregular, angular outward shape. The surface may be smooth, but it is also possible that the surface of the material is rough and/or has unevenness and/or depressions and/or elevations.
  • the material comprises hollow bodies, for example particles having one or more cavities and/or having a hollow shape, for example a hollow fiber or an extrusion body with a hollow channel.
  • hollow fiber describes a cylindrical fiber having one or more continuous cavities in cross section.
  • the hydrogenatable material has a bimodal size distribution.
  • a higher bulk density and hence a higher density of the hydrogenatable material in the hydrogen storage means can be enabled, which increases the hydrogen storage capacity, i.e. the amount of hydrogen which can be stored in the storage means.
  • the hydrogenatable material may comprise, preferably consist of, at least one hydrogenatable metal and/or at least one hydrogenatable metal alloy.
  • the material may also include non-hydrogenatable metals or metal alloys.
  • the hydrogenatable material may comprise a low-temperature hydride and/or a high-temperature hydride.
  • the term “hydride” refers to the hydrogenatable material, irrespective of whether it is in the hydrogenated form or the non-hydrogenated form.
  • Low-temperature hydrides store hydrogen preferably within a temperature range between ⁇ 55° C. and 180° C., especially between ⁇ 20° C. and 150° C., particularly between 0° C. and 140° C.
  • High-temperature hydrides store hydrogen preferably within a temperature range of 280° C. upward, especially 300° C. upward. At the temperatures mentioned, the hydrides cannot just store hydrogen but can also release it, i.e. are able to function within these temperature ranges.
  • Hydrogen storage can be effected at room temperature. Hydrogenation is an exothermic reaction. The heat of reaction that arises can be removed. By contrast, for the dehydrogenation, energy has to be supplied to the hydride in the form of heat. Dehydrogenation is an endothermic reaction.
  • a low-temperature hydride is used together with a high-temperature hydride.
  • the low-temperature hydride and the high temperature hydride are provided in a mixture in a layer of a second region. It is also possible for these each to be arranged separately in different layers or regions, especially also in different second regions. For example, it may be the case that a first region is arranged between these second regions. In a further configuration, a first region has a mixture of low- and high-temperature hydride distributed in the matrix. It is also possible that different first regions include either a low-temperature hydride or a high-temperature hydride.
  • the hydrogenatable material comprises a metal selected from magnesium, titanium, iron, nickel, manganese, nickel, lanthanum, zirconium, vanadium, chromium, or a mixture of two or more of these metals.
  • the hydrogenatable material may also include a metal alloy comprising at least one of the metals mentioned.
  • the hydrogenatable material comprises at least one metal alloy capable of storing hydrogen and releasing it again at a temperature of 150° C. or less, especially within a temperature range from ⁇ 20° C. to 140° C., especially from 0° C. to 100° C.
  • the at least one metal alloy here is preferably selected from an alloy of the AB 5 type, the AB type and/or the AB 2 type.
  • a and B here each denote different metals, where A and/or B are especially selected from the group comprising magnesium, titanium, iron, nickel, manganese, nickel, lanthanum, zirconium, vanadium and chromium.
  • the indices represent the stoichiometric ratio of the metals in the particular alloy.
  • the alloys here may be doped with extraneous atoms.
  • the doping level may be up to 50 atom %, especially up to 40 atom % or up to 35 atom %, preferably up to 30 atom % or up to 25 atom %, particularly up to 20 atom % or up to 15 atom %, preferably up to 10 atom % or up to 5 atom %, of A and/or B.
  • the doping can be effected, for example, with magnesium, titanium, iron, nickel, manganese, nickel, lanthanum or other lanthanides, zirconium, vanadium and/or chromium.
  • Alloys of the AB 5 type are readily activatable, meaning that the conditions needed for activation are similar to those in the operation of the hydrogen storage means. They additionally have a higher ductility than alloys of the AB or AB 2 type. Alloys of the AB 2 or of the AB type, by contrast, have higher mechanical stability and hardness compared to alloys of the AB 5 type. Mention may be made here by way of example of FeTi as an alloy of the AB type, TiMn 2 as an alloy of the AB 2 type and LaNi 5 as an alloy of the AB 5 type.
  • the hydrogenatable material (hydrogen storage material) comprises a mixture of at least two hydrogenatable alloys, at least one alloy being of the AB 5 type and the second alloy being an alloy of the AB type and/or the AB 2 type.
  • the proportion of the alloy of the AB 5 type is especially 1% by weight to 50% by weight, especially 2% by weight of 40% to weight, more preferably 5% by weight to 30% by weight and particularly 5% by weight to 20% by weight, based on the total weight of the hydrogenatable material.
  • the hydrogenatable material (hydrogen storage material) is preferably in particulate form (particles).
  • the particles especially have a particle size x 50 of 20 ⁇ m to 700 ⁇ m, preferably of 25 ⁇ m to 500 ⁇ m, particularly of 30 ⁇ m to 400 ⁇ m, especially 50 ⁇ m to 300 ⁇ m.
  • x 50 means that 50% of the particles have a median particle size equal to or less than the value mentioned.
  • the particle size was determined by means of laser diffraction, but can also be effected by sieve analysis, for example.
  • the median particle size in the present case is the particle size based on weight, the particle size based on volume being the same in the present case. What is reported here is the particle size of the hydrogenatable material before it is subjected to hydrogenation for the first time. During the storage of hydrogen, stresses occur within the material, which can lead to a reduction in the x 50 particle size over several cycles.
  • the hydrogenatable material is incorporated in the matrix to such a firm degree that it decreases in size on storage of hydrogen.
  • This result is surprising, since it was expected that the matrix would if anything tend to break up on expansion as a result of the increase in volume of the hydrogenatable material during the storage of hydrogen when there is high expansion because of the increase in volume. It is assumed at present that the outside forces acting on the particles, as a result of the binding within the matrix, when the volume increases, lead to breakup together with the stresses within the particles resulting from the increase in volume. Breakup of the particles was discovered particularly clearly on incorporation into polymer material in the matrix. The matrix composed of polymer material was capable of keeping the particles broken up in this way in a stable fixed position as well.
  • a binder content may preferably be between 2% by volume and 3% by volume of the matrix volume.
  • a low-temperature hydride is used together with a high-temperature hydride.
  • the low-temperature hydride and the high-temperature hydride are provided in a mixture in a layer of a second region of the hydrogen storage element. These may also be arranged separately in different layers, especially also in different regions, of one and the same layer of the hydrogen storage element. For example, it may be the case that another region is arranged between these elements.
  • a region comprises a mixture of low- and high-temperature hydride distributed in a matrix. It is also possible that different regions of the element comprise either a low-temperature hydride or a high-temperature hydride.
  • the hydrogen storage means has a high-temperature hydride vessel and a low-temperature vessel.
  • the high-temperature hydrides may generate temperatures of more than 350° C., which have to be dissipated. This heat is released very rapidly and can be utilized, for example, for heating of a component thermally associated with the hydrogen storage element.
  • High-temperature hydrides utilized may, for example, be metal powders based on titanium.
  • the low-temperature hydride assumes temperatures within a range preferably between ⁇ 55° C. and 155° C., especially preferably within a temperature range between 80° C. and 140° C.
  • a low-temperature hydride is, for example, Ti 0.8 Zr 0.2 CrMn or Ti 0.98 Zr 0.02 V 0.43 Cr 0.05 Mn 1.2 .
  • One configuration envisages transfer of hydrogen from the high-temperature hydride container to the low-temperature hydride container and vice versa, and storage therein in each case.
  • the expanded graphite be very substantially replaced by using a specific filling technique to introduce layers of hydrogen-storing material, preferably a hydride, and a heat-conducting material such as graphite into a shaping mold in order then to give, compressed together, a sandwich structure in which the graphite again assumes the task of heat conduction.
  • a specific filling technique to introduce layers of hydrogen-storing material, preferably a hydride, and a heat-conducting material such as graphite into a shaping mold in order then to give, compressed together, a sandwich structure in which the graphite again assumes the task of heat conduction.
  • a specific filling technique to introduce layers of hydrogen-storing material, preferably a hydride, and a heat-conducting material such as graphite into a shaping mold in order then to give, compressed together, a sandwich structure in which the graphite again assumes the task of heat conduction.
  • filling of the cavity may be undertaken layer by layer, in which case, for example, every new or every second or every third new layer is followed by immediate compaction by means of the upper and lower rams.
  • This allows a particularly close association of, for example, the primarily heat-conducting material and the primarily hydrogen-storing material.
  • a process for producing a hydrogen storage element preferably a hydrogen storage element as described above, wherein separate layers of a hydrogen-storing material and a heat-conducting material are introduced into a press mold and these are compressed together to generate a sandwich structure, the heat-conducting material, on use of the sandwich structure as hydrogen storage element, assuming the task of conducting heat, preferably in a direction transverse to the direction of succession of the layers of the hydrogen storage element.
  • a metal powder and/or normal natural graphite is/are utilized as heat-conducting material, in which case, on utilization of normal natural graphite, the lenticular particles thereof are preferably aligned horizontally in the course of filling, such that conduction of heat in the direction of a hexagonal lattice structure of the graphite structure can be utilized.
  • one or more films composed of rolled expanded graphite, flakes of a rolled expanded graphite and/or a graphite fabric may be introduced into the sandwich structure as heat-conducting material.
  • one of more layers of a material that remains porous are introduced into the sandwich structure as gas-guiding layers and compressed as well.
  • the layers are compacted by means of a press, for example a rotary press or a revolving press.
  • a press for example a rotary press or a revolving press.
  • the principle of a rotary press is known, for example, from DE-B-10 2010 005 780, and also from DE-B-10 2005 019 132.
  • the apparatuses presented in each case can also be utilized for the production of layers of a hydrogen storage means.
  • the first and second layers are compressed together and form the sandwich structure.
  • the compression can be effected, for example, with the aid of an upper ram and a lower ram by pressure.
  • the compression can be effected via isostatic pressing.
  • the isostatic press method is based on the physical law that pressure in liquids and gases propagates uniformly in all directions and generates forces on the areas subjected thereto, the sizes of which are directly proportional to these areas.
  • the materials to be compressed can be introduced, for example, into the pressure vessel of a pressing system, for example, in a rubber mold. The pressure that acts on the rubber mold on all sides via the liquid in the pressure vessel compresses the enclosed materials (at least the first and second layers) in a uniform manner.
  • a preform comprising at least the first and second layers into the isostatic press, for example into a liquid.
  • high pressures preferably within a range from 500 to 6000 bar, the sandwich structure can be produced.
  • the high pressures in isostatic pressing permit, for example, the creation of new material properties in the composite material.
  • one or more films composed of a rolled expanded graphite, flakes of a rolled expanded graphite and/or a graphite fabric are introduced as heat-conducting material into the sandwich structure.
  • one or more laminas of a material that remains porous are introduced into the sandwich structure as gas-guiding layers and compressed as well.
  • two or more sandwich structures are pressed separately from one another and then arranged in a common vessel.
  • FIG. 1 a schematic view of a section of a hydrogen storage means having alternating layers
  • FIG. 2 a schematic view of a section of another hydrogen storage means or another portion of the hydrogen storage means according to FIG. 1 with a schematic representation of another layer arrangement having a non-planar 3-D form, and
  • FIG. 3 a first and second layer shown in schematic form, having a gradient.
  • FIG. 1 shows a schematic view of a detail of a layer stack of a hydrogen storage means 1 having a plurality of cylindrically repeating layer sequences composed of one or more hydrogen storage components.
  • a first layer 2 , a second layer 3 and a third layer 4 are each arranged in an alternating manner.
  • the first layer 2 comprises, for example, a heat-storing material
  • the second layer 3 a heat-removing material
  • the third layer 4 a gas-permeable material as gas-guiding layer. Compression, especially isostatic compression, makes it possible for there to be very intimate contact between the heat-conducting layer and the hydrogen-storing layer.
  • FIG. 2 shows a detail 5 of another or an identical hydrogen storage means with a schematic representation of another layer arrangement which is non-planar.
  • a material may be supplied in such a way that a relative movement between cavity and material supply is executed.
  • a helical layer is generated in a surrounding support layer. It is also possible to generate other geometries along an axis of the cavity.
  • the helical layer has heat-conducting and/or gas-conducting properties.
  • FIG. 3 shows a detail from a compressed sandwich structure 6 with a first layer 7 and a second layer 8 .
  • a groove 9 has been drawn with the aid of a body pulled through the two layers, which has led to formation of a gradient 10 in the sandwich structure.
  • the gradient formation is indicated by the finer shading. Subsequent compression of these two layers prior to new supply of further layer-forming material results in particularly intensive “safeguarding” of the gradient in the sandwich structure.
US15/307,142 2014-05-05 2015-05-04 Hydrogen Storage Element for a Hydrogen Store Abandoned US20170044011A1 (en)

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US11572272B2 (en) 2023-02-07

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