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WO2015169746A1 - Dispositif de fabrication d'élément de stockage d'hydrogène, procédé associé et élément de stockage d'hydrogène - Google Patents

Dispositif de fabrication d'élément de stockage d'hydrogène, procédé associé et élément de stockage d'hydrogène Download PDF

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Publication number
WO2015169746A1
WO2015169746A1 PCT/EP2015/059716 EP2015059716W WO2015169746A1 WO 2015169746 A1 WO2015169746 A1 WO 2015169746A1 EP 2015059716 W EP2015059716 W EP 2015059716W WO 2015169746 A1 WO2015169746 A1 WO 2015169746A1
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WO
WIPO (PCT)
Prior art keywords
hydrogen storage
cavity
storage element
materials
filling
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2015/059716
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German (de)
English (en)
Inventor
Antonio Casellas
Klaus Dollmeier
Eberhard Ernst
Thomas Schupp
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
GKN Powder Metallurgy Engineering GmbH
Original Assignee
GKN Sinter Metals Engineering GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by GKN Sinter Metals Engineering GmbH filed Critical GKN Sinter Metals Engineering GmbH
Publication of WO2015169746A1 publication Critical patent/WO2015169746A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
    • C01B3/0078—Composite solid storage mediums, i.e. coherent or loose mixtures of different solid constituents, chemically or structurally heterogeneous solid masses, coated solids or solids having a chemically modified surface region
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/004—Filling molds with powder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/02—Compacting only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/02—Compacting only
    • B22F3/04—Compacting only by applying fluid pressure, e.g. by cold isostatic pressing [CIP]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/002—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of porous nature
    • 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
    • C01B3/0084—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
    • 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 element manufacturing apparatus comprising a cavity which can be filled with a flowable material for the production of a hydrogen storage element blank. Further, the invention relates to a feeder for use in the hydrogen storage element manufacturing apparatus, a method for producing a hydrogen storage element blank and a hydrogen storage element blank, preferably composite material. It is known that for a hydrogen storage in addition to hydrogen storage material and thermally conductive material is required because when using the hydrogen storage endothermic as well as exothermic reactions occur. This invention has for its object to simplify the production of a hydrogen storage element.
  • a hydrogen storage element production device comprising a cavity to be filled, at least a first material supply of a first material and a second material supply of a second material, wherein the first and the second material supply are arranged separately from one another, with a supply device for feeding the at least two materials in the cavity.
  • hydrogen storage describes a reservoir in which hydrogen can be stored.
  • conventional methods for storage and storage of hydrogen may be used, such as.
  • As storage of compressed gas ie storage in pressure vessels by compression with compressors or liquefied gas storage or storage in liquefied form by cooling and compression.
  • Other alternative forms of hydrogen storage are based on solids or liquids, for example, metal hydride storage, ie, the principle of storage as a chemical bond between hydrogen and a metal or alloy, or adsorptive storage; H . adsorptive storage of hydrogen in highly porous materials.
  • hydrogen storage is also possible for storage and transport of hydrogen, which temporarily bind the hydrogen to organic substances, with liquid, pressure-less storable compounds (so-called "chemically bound hydrogen”) arise.
  • layers describes that preferably one material, but also two or more materials are arranged in one layer and this can be delimited as a layer from its direct environment. For example, different materials can be poured one after another loosely one over the other, so that adjacent layers touch each other directly.
  • the layer of hydrogenatable material (hydrogenatable layer) may be arranged immediately adjacent to a thermally conductive layer. Such an arrangement allows the resulting heat in the hydrogen absorption and / or the required heat in the hydrogen release from the hydrogenatable material can be discharged directly from the adjacent layer or absorbed by the latter.
  • primary hydrogen storage By at least one of the following functions "primary hydrogen storage”, “primary heat conduction”, “primary expansion compensation” and / or “primary gas feedthrough” is meant that the respective layer perceives at least this as a major task in the second region of the composite material.
  • a layer is used primarily for hydrogen storage, but at the same time is also able to provide at least some thermal conductivity.
  • at least one other layer is present, which primarily assumes heat conduction, that is to say via which the major part of the heat quantity is derived from or fed to the compressed composite material.
  • the primary gas-permeable layer can be used, through which, for example, the hydrogen is conducted into the material composite but also, for example, channeled out. In this case, heat energy can also be transported via the fluid flowing through.
  • the hydrogenatable material can take up the hydrogen and release it again when needed.
  • the material comprises particulate materials in any 3-dimensional configuration, such as particles, granules, fibers, preferably cut fibers, flakes and / or other geometries.
  • the material may also be plate-shaped or powder-like. It is not necessary that the material has a uniform configuration. Rather, the design may be regular or irregular. Particles in the sense of the present invention are, for example, approximately spherical particles as well as particles with an irregular, angular outer shape.
  • the surface may be smooth, but it is also possible that the surface of the material is rough and / or has bumps and / or depressions and / or elevations.
  • a hydrogen storage may comprise the material in only one specific 3-dimensional configuration, so that all particles of the material have the same spatial extent.
  • a hydrogen storage it is also possible for a hydrogen storage to comprise the material in different configurations / geometries.
  • the material can be used in a variety of different hydrogen storage.
  • the material comprises hollow bodies, for example particles with one or more cavities and / or with a hollow mold, for example a hollow fiber or an extrusion body with a hollow channel.
  • the term hollow fiber describes a cylindrical fiber which has one or more continuous cavities in cross-section.
  • the hydrogenatable material preferably has a bimodal size distribution. In this way, a higher bulk density and thus a higher density of the hydrogenatable material in the hydrogen storage can be made possible, whereby the hydrogen storage capacity, that is, the amount of hydrogen that can be stored in the memory is increased.
  • the hydrogenatable material may comprise at least one hydrogenatable metal and / or at least one hydrogenatable metal alloy, preferably consisting thereof.
  • hydrogenatable materials can also be used: - alkaline earth metal and alkali metal alanates,
  • MOF's Metal-Organic-Frameworks
  • Metal-Organic Frameworks Metal-Organic Frameworks
  • the material according to the invention may also comprise non-hydrogenatable metals or metal alloys.
  • the hydrogenatable material according to the invention may comprise a low-temperature hydride and / or a high-temperature hydride.
  • the term hydride refers to the hydrogenatable material, regardless of whether it is present in the hydrogenated form or the non-hydrogenated form.
  • Low-temperature hydrides preferably hydrogen in a temperature range between -55 ° C to 180 ° C, in particular between -20 ° C and 150 ° C, especially between 0 ° C and 140 ° C.
  • High-temperature hydrides preferably store hydrogen in a temperature range from 280 ° C and more, in particular from 300 ° C and more. At the stated temperatures, the hydrides can not only store hydrogen but also give off, so they are functional in these temperature ranges.
  • Hydrogenatable materials in their hydrogenated or nonhydrogenated form can be used according to the invention in the production of hydrogen storages.
  • the hydrogen storage can take place at room temperature.
  • the hydrogenation is an exothermic reaction.
  • the resulting heat of reaction can be dissipated.
  • energy must be supplied to the hydride in the form of heat for dehydration.
  • Dehydration 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 mixed in a layer of a second region.
  • These can also be arranged separately from one another in different layers or regions, in particular also in different second regions.
  • a first region is arranged between these second regions.
  • a further embodiment provides that a first region has a mixture of low and high temperature hydride distributed in the matrix.
  • different first regions have 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 comprise a metal alloy comprising at least one of said metals.
  • the hydrogenatable material comprises at least one metal alloy which is at a temperature of 150 ° C or less, in particular in a temperature range from -20 ° C to 140 ° C, in particular from 0 ° C to 100 ° C in is able to store and release hydrogen.
  • the at least one metal alloy is preferably selected from an alloy of the AB 5 type, the AB type and / or the AB 2 type.
  • a and B respectively denote metals different from each other, wherein 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 respective alloy Alloys according to the invention may be doped with foreign atoms.
  • the degree of doping may according to the invention up to 50 atomic%, in particular up to 40 atomic% or up to 35 atomic%, preferably up to 30 atomic% or up to 25 atomic%, especially up to 20 atomic% or until to 15 at%, preferably up to 10 at% or up to 5 at% of A and / or B.
  • the doping can be carried out, 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 easily activated, that is, the conditions that are necessary for activation, similar to those in the operation of the hydrogen storage. They also have a higher ductility than alloys of the AB or AB 2 type. By contrast, alloys of the AB 2 or the AB type have a higher mechanical stability and hardness compared to alloys of the AB 5 type.
  • the hydrogenatable material (hydrogen storage material) comprises a mixture of at least two hydrogenatable alloys, wherein at least one AB 5 -type alloy and the second alloy is an AB-type and / or AB 2 -type alloy.
  • the proportion of the alloy of the AB 5 type is in particular 1 wt .-% to 50 wt .-%, in particular 2 wt .-% to 40 wt .-%, particularly preferably 5 wt .-% to 30 wt .-% and in particular 5% by weight to 20% by weight, based on the total weight of the hydrogenatable material.
  • the hydrogenatable material is preferably present in particulate form (particles, particles).
  • the particles have a particle size x 50 of from 20 pm to 700 pm, preferably from 25 pm to 500 pm, especially from 30 pm to 400 pm, in particular from 50 pm to 300 pm.
  • x 50 means that 50% of the particles have an average particle size that is equal to or less than the stated value.
  • Particle size was determined by laser diffraction but can also be done for example by sieve analysis.
  • the mean particle size here is the weight-based particle size, wherein the volume-based particle size is the same here.
  • Indicated here is the particle size of the hydrogenatable material before it is subjected for the first time to hydrogenation. While the hydrogen storage stresses in the material occurs, which may cause during a plurality of cycles occurs a reduction in the particle size of x 50.
  • the hydrogenatable material is so firmly integrated in the matrix that it comminutes when storing hydrogen. Preference is therefore given to using particles as a hydrogenatable material, which breaks up, while the matrix remains at least predominantly undestroyed. This result is surprising, since it was considered that the matrix would tend to rupture when stretched by volume increase of the hydrogenatable material during storage of hydrogen when high elongation due to volume growth occurs. It is currently believed that the external forces acting on the particles from the outside as a result of the attachment in the matrix in the increase in volume together with the tensions within the particles due to the volume increase lead to a breakup. A break-up of the particles could be found particularly clearly when incorporated into polymer material in the matrix.
  • a binder content may preferably be between 2% and 3% by volume of the matrix volume.
  • a particle size change due to breakage of the particles occurs by the storage of hydrogen by a factor of 0.6, more preferably by a factor of 0.4, based on the x 50 particle size at the beginning and after 100 times of storage.
  • a carbon matrix in which the low-temperature hydride is embedded can be used as the matrix material.
  • At least one component of the composite material can be produced in a sintering process.
  • a sintering process fine-grained, ceramic or metallic materials are heated, but the temperatures remain below the melting temperature of the main components of the substance, so that the shape of the workpiece is maintained. It usually comes to a shrinkage, because the particles of the starting material compact and pore spaces are filled.
  • solid phase sintering and liquid phase sintering, which also results in a melt.
  • the sintered product receives its final properties, such as hardness, strength or thermal conductivity, which are required in the respective application only by the temperature treatment.
  • an open-pored matrix can be created in this way, in which the hydrogenatable material is embedded. It is also possible in this way to create channel structures which are, for example, gas-conducting and can be used in the hydrogen storage element.
  • the cavity to be filled is preferably round and preferably a contact element with a contact surface is provided which, at least on the surface of the at least first and / or second material filled into the cavity.
  • movable and along this is movable, more preferably in the at least first and / or second material movable and within this or this is movable.
  • the feeder is movable in different directions, be it in a Cartesian coordinate system or other orthogonal coordinate system as well as, for example, a polar coordinate system.
  • the supply device and / or the cavity to be filled can be moved in a controlled manner so that a desired material deposit takes place.
  • the feed device of the hydrogen storage element production device has an orifice cross section with at least one first region for the first material and with a second region for the second material different therefrom, for preferably parallel, locally separate filling of the cavity, wherein the first region is preferably at least partially, particularly preferably completely embedded in the second region.
  • a matrix in a wide variety of geometries can also be formed in this way.
  • the matrix includes, for example, a hydrogen-storing material, but is otherwise also thermally conductive and / or preferably porous.
  • a further embodiment of the hydrogen storage element production device according to the invention provides that the device has at least one drive, by means of which at least one controlled relative movement between the cavity to be filled and the supply device is made possible. For example, a trajectory can be preset by the controller.
  • a computerized control of the movement is provided.
  • This can preferably be integrated into a corresponding control unit which controls or regulates the hydrogen storage production device, in particular, for example, also with regard to the filling of the cavities.
  • a further development of the hydrogen storage element production device provides that the supply device (or filler) and / or the cavity is or are arranged to be rotatable relative to one another.
  • the proposed hydrogen storage element manufacturing device In addition to filling the cavity (the die of a press) with only a single material, in particular a powder, now allows the proposed hydrogen storage element manufacturing device to lead the same material in the first and in the second supply line, but for example, with different grain size. As a result, for example, a targeted gradient can be produced in the hydrogen storage element. Furthermore, it is possible to provide for a better distribution of the material, in particular a powder, for example, the feeding device with one or more stripping elements. This can be done, for example, an alignment of the material. In particular, it is possible to replace a layer structure by a uniform helical structure or even to supplement. Furthermore, it is also possible to make the layer structure in the machine axis perpendicular extent uneven.
  • the invention thus not only allows a layered structure of preferably powder layers, wherein the layer structure perpendicular to the machine axis can be regarded as constant. Rather, at least two or more layers can be produced at the same time, in particular in each case from different materials.
  • the cavity to be filled of the hydrogen storage element production device has a die cavity and the feed cavity.
  • Device is a filler and the hydrogen storage element manufacturing device comprises a press for compressing the at least first and second material in the Matrizenkavtician.
  • the press is formed by a lower punch as well as an upper punch.
  • Another hydrogen storage element manufacturing apparatus which may also be constructed according to the proposal, is, for example, a 3-D printer.
  • This may, for example, have a rotating filler with a plurality of chambers for different materials, in particular powders.
  • a material feeding concept is provided in which the filler rotates about the machine longitudinal axis (i.e., about the axis along which upper and / or lower punches shift / shift).
  • a material reservoir, preferably for powder is in this case subdivided into at least two segments, wherein each segment can optionally be filled with different powder. The design of the individual segments in shape, size and position is not defined here.
  • a solidification can follow the filling process, for example by means of a laser beam in shafts of a feed device provided for this purpose.
  • a feeding device for use in a hydrogen storage device having an orifice cross-section with at least a first region for the first material and a second region separated therefrom for the second material for preferably parallel spatially separate filling of the cavity Area is preferably at least partially, particularly preferably completely embedded in the second area.
  • the feeding device is designed such that it has a material feed for the first material and a material supply for the second material separate therefrom, wherein a mixing zone feed is provided. is along which the first and the second material is miscible and feedable.
  • a gradient but above all a matrix, can also be formed.
  • matrix as used above describes a composite of two or more interconnected materials. In this case, one material preferably takes on another. In the present case, the hydrogenatable material is embedded in the matrix.
  • the matrix can be porous as well as closed. Preferably, the matrix is porous.
  • connection takes place, for example, by material or positive connection or a combination of both.
  • Other components of the matrix may be, for example, materials for the heat conduction and / or the gas feedthrough.
  • the matrix may have one or more further components, such as, for example, materials for the heat conduction and / or the gas feedthrough.
  • the matrix may comprise one or more polymers according to the invention and is therefore referred to as a polymeric matrix.
  • the matrix may therefore comprise a polymer or mixtures of two or more polymers.
  • the matrix comprises only one polymer.
  • the matrix itself may be hydrogen storage.
  • ethylene polyethylene, PE
  • PE polyethylene
  • a titanium-ethylene compound is used. This can, according to a preferred embodiment, store up to 14% by weight of hydrogen.
  • polymer describes a chemical compound of chain or branched molecules, so-called macromolecules, which in turn consist of or similar units, the so-called constitutional repetitive units or repeating units.
  • Synthetic polymers are usually plastics.
  • good optical, mechanical, thermal and / or chemical properties can be assigned to the material by the matrix.
  • the hydrogen storage by the polymer may have good temperature resistance, resistance to the surrounding medium (oxidation resistance, corrosion resistance), good conductivity, good hydrogen uptake and storage ability, or other properties such as mechanical strength, which would otherwise be absent the polymer would not be possible.
  • polymers which, for example, do not allow storage of hydrogen but permit high elongation, such as, for example, polyamide or polyvinyl acetates.
  • the polymer may be a homopolymer or a copolymer.
  • Copolymers are polymers composed of two or more different monomer units. Copolymers consisting of three different monomers are called terpolymers.
  • the polymer may also comprise a terpolymer.
  • the polymer preferably has a monomer unit which preferably contains at least one heteroatom selected from sulfur, oxygen, nitrogen and phosphorus in addition to carbon and hydrogen, so that the polymer obtained is not completely nonpolar in contrast to, for example, polyethylene.
  • at least one halogen atom selected from chlorine, bromine, fluorine, iodine and astatine may be present.
  • the polymer is a copolymer and / or a terpolymer in which at least one monomer unit in addition to carbon and hydrogen further at least one heteroatom selected from sulfur, oxygen, nitrogen and phosphorus and / or at least one halogen atom selected from chlorine, bromine , Flour, Iodine and Astatine, is present. It is possible that two or more monomer units 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 thus forms a matrix that stably adheres to the hydrogen storage material even under conditions such as those encountered during hydrogen storage.
  • the adhesive properties of the polymer enable stable incorporation of the material into a hydrogen reservoir and positioning of the material at a defined location in the hydrogen reservoir for as long a period as possible, ie, over several cycles of hydrogen storage and hydrogen release.
  • One cycle describes the process of a single hydrogenation and subsequent dehydration.
  • the hydrogen storage material should preferably be stable over at least 500 cycles, in particular over at least 1000 cycles, in order to be able to use the material economically.
  • Stable in the sense of the present invention means that the amount of hydrogen that can be stored and the rate at which the hydrogen is stored, even after 500 or 1000 cycles, substantially corresponds to the values at the beginning of the use of the hydrogen storage.
  • stable means that the hydrogenatable material is maintained at least approximately at the position within the hydrogen storage where it was originally placed in the reservoir.
  • Stable in particular, is to be understood as meaning that no demixing effects occur during the cycles in which finer particles separate and remove themselves from coarser particles.
  • the hydrogen storage material of the present invention is particularly a low-temperature hydrogen storage material.
  • hydrogen storage which is an exothermic process, temperatures of up to 150 ° C occur.
  • a polymer which is used for the matrix of a corresponding hydrogen storage material must be stable at these temperatures.
  • a preferred polymer therefore does not decompose to a temperature of 180 ° C., in particular up to a temperature of 165 ° C., in particular of up to 145 ° C.
  • the polymer is a polymer having a melting point of 100 ° C or more, especially 105 ° C or more, but less than 150 ° C, especially less than 140 ° C, especially 135 ° C or less.
  • the density of the polymer, determined according to ISO 1183 at 20 ° C. is preferably 0.7 g / cm 3 or more, in particular 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 , in particular 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, in particular in the range from 15 MPa to 90 MPa, particularly preferably in the range from 15 MPa to 80 MPa.
  • the tensile modulus according to ISO 527 is preferably in the range from 50 MPa to 5000 MPa, in particular in the range from 55 MPa to 4500 MPa, particularly preferably in the range from 60 MPa to 4000 MPa.
  • the polymer is selected from EVA, PMMA, EEAMA and mixtures of these polymers.
  • EVA ethyl vinyl acetate
  • Typical EVA are solid at room temperature and have a tensile elongation of up to 750%.
  • EVA are resistant to stress cracking.
  • EVA has the following general formula (I): (Formula (I))
  • EVA preferably has a density of 0.9 g / cm 3 to 1.0 g / cm 3 (according to ISO 1183).
  • the yield stress according to ISO 527 is in particular from 4 to 12 MPa, preferably from 5 MPa to 10 MPa, especially from 5 to 8 MPa.
  • Particularly suitable are those EVA which have a tensile strength (according to ISO 527) of more than 12 MPa, in particular more than 15 MPa, and less than 50 MPa, in particular less than 40 MPa, in particular of 25 MPa or less.
  • the elongation at break (according to ISO 527) is in particular> 30% or> 35%, especially> 40% or 45%, preferably> 50%.
  • the tensile modulus of elasticity is preferably in the range from 35 MPa to 120 MPA, especially from 40 MPa to 100 MPa, preferably from 45 MPa to 90 MPa, in particular from 50 MPa to 80 MPa.
  • Suitable EVA are registered names, for example, by the company axalta Coating Systems LLC under the Han Coathylene ® CB 3547 sold.
  • Polymethyl methacrylate is a synthetic, transparent, thermoplastic material having the following general structural formula (II):
  • the glass transition temperature is dependent on the molecular weight at 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 distinguished due to its resistance to weather, light and UV radiation.
  • PMMA preferably has a density of 0.9 to 1.5 g / cm 3 (according to ISO 1183), in particular from 1.0 g / cm 3 to 1.25 g / cm 3 .
  • Particularly suitable are those PMMA which have a tensile strength (according to ISO 527) of more than 30 MPa, preferably of more than 40 MPa, in particular more than 50 MPa, and less than 90 MPa, in particular less than 85 MPa, especially of 80 MPa or have less.
  • the elongation at break (according to ISO 527) is in particular ⁇ 10%, especially ⁇ 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, in particular from 2000 MPa to 4000 MPa.
  • Suitable PMMA are offered for example by the company Ter Hell Plastics GmbH, Bochum, Germany, under the trade name 7M Plexiglas ® granules.
  • EEAMA is a terpolymer of ethylene, acrylic ester and maleic anhydride monomer units.
  • EEAMA has a melting point of about 102 ° C, depending on the molecular weight. 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 EEAMA be marketed under the trade name Coathylene ® TB3580 by the company axalta Coating Systems LLC.
  • the composite material essentially comprises the hydrogen storage material and the matrix.
  • the weight fraction of the matrix based on the total weight of the composite material is preferably 10% by weight or less, in particular 8% by weight or less, more preferably 5% by weight or less, and is preferably at least 1% by weight and in particular at least 2 wt .-% to 3 wt .-%. It is desirable to keep the proportion by weight of the matrix as low as possible.
  • the matrix is capable of storing hydrogen, the hydrogen storage capacity is still not as pronounced as that of the hydrogen storage material itself. However, the matrix is necessary to minimize or completely avoid any oxidation of the hydrogen storage material that may occur and to prevent hydrogen storage Cohesion between the particles of the material to ensure.
  • the matrix is a polymer having a low crystallinity.
  • the crystallinity of the polymer can significantly change the properties of a material.
  • the properties of a semi-crystalline material are determined by both the crystalline and the amorphous regions of the polymer. This shows a certain correlation with composite materials, which are also made up of several substances. For example, as the density increases, the stretchability of the matrix decreases.
  • the matrix can also be in the form of prepregs.
  • Prepreg is the English short form for preimpregnated fibers (American: preimpregnated fibers), in English: "preimpregnated fibers”.
  • Prepregs are semi-finished with a polymer pre-impregnated (semi-finished), which are cured for the production of components under temperature and pressure.
  • Suitable polymers are those having a high viscosity but not polymerized thermoset plastic matrix.
  • the preferred polymers according to the present invention may also be in the form of a prepreg.
  • the fibers contained in the prepreg can be in the form of a pure unidirectional layer, as a fabric or a scrim.
  • the prepregs according to the invention can also be comminuted and processed as flakes or chips together with the hydrogenatable material to form a composite material.
  • the polymer can either be in the form of a liquid which is brought into contact with the hydrogenatable material. Liquid means that either the polymer is melted. However, according to the invention, it is also included that the polymer is dissolved in a suitable solvent, the solvent being removed again after preparation of the composite material, for example by evaporation. However, it is also possible that the polymer is in the form of a granulate which is mixed with the hydrogenatable material. By compacting the composite material, the polymer softens, allowing it to form the matrix comes, in which the hydrogenatable material is embedded.
  • the polymer is used in the form of particles, ie as granules, they preferably have an x 50 particle size (volume-based particle size) in the range from 30 ⁇ m to 60 ⁇ m, in particular from 40 ⁇ m to 45 ⁇ m.
  • the x 90 particle size is 90 m or less, preferably 80 m or less.
  • the feeding device with an additional unit for feeding strip, strip or plate-shaped material over which a strip of material can be guided into the mouth cross-section.
  • a fabric, a nonwoven fabric, a film, laminates of multiple materials, or other strip material may be supplied with the other at least two materials, preferably parallel to the feeding of the first and second materials.
  • fibers, wires or other materials to be embedded can also be supplied via a corresponding design of the feeder and mitabrob
  • a method of making a hydrogen storage element blank by means of at least a first material comprising a hydrogen storage material and a second material having thermal conductivity, wherein a first material supply of the first material over a first region a feed device and a second material supply of the second material parallel to the first material supply via a second region of the feed device, wherein at least the first and the second material together form a composite material of the hydrogen storage element.
  • composite material here describes that various materials are used in the hydrogen storage element, in addition to hydrogenatable material and other materials may be arranged with other functionalities.
  • the composite material is made, for example, from individual components components, such as the matrix and the individual layers. For example, material properties and geometries of the components are important for the properties of the composite material.
  • the composite material is preferably compacted.
  • a development of the method provides that at least one of the two materials, preferably the first and the second material, pourable, free-flowing and thus flowable, preferably supplied in powder form.
  • the supply device is rotated, the first and the second material from the supply device thereby emerge in parallel, and a composite material is formed as a hydrogen storage element.
  • the at least two materials are preferably arranged one above the other in a layered manner, with a material, for example, being arranged in a helical or wavy manner at least in one section. It is advantageous in this case that the helical geometry in the composite material is supported as a structure by the material surrounding the helix.
  • the layers in this way extend adjacent to one another in the Z direction of the extension, preferably arranged around an axis of rotation.
  • inner layers can be built on top of each other, which co-curl upwards about an axis, while an outer area forms a cylinder enclosure of the inner layers.
  • the first and second materials form a continuous porous structure in the hydrogen storage element, preferably one or more channels in the composite material are made by means of one or more mandrels, free holders and / or material to be removed.
  • one or more channels in the composite material are made by means of one or more mandrels, free holders and / or material to be removed.
  • a further embodiment provides that the cavity is formed by a container of the hydrogen storage.
  • other compacting can be effected under the simultaneous influence of heat and / or of, for example, a gas.
  • a suction for example for suction of binder, which is possibly arranged in a first and / or in a second region of the composite body.
  • the binder can be completely or partially removed from the composite, for example, to provide a porous structure.
  • one binder may be arranged in one of the two regions and no binder in another of the two regions.
  • Different binders can also be used, for example by introducing a different binder in the first area than in the second area.
  • a hydrogen storage element comprising a composite material having at least a first and a second material
  • the first material comprises a hydrogen-storing material
  • the second material comprises a heat-conducting material
  • the hydrogen storage element preferably with a production device and / or Method is prepared as described above. It has proved to be advantageous if in the hydrogen storage element, the second material extends from an interior of the composite material to an exterior of the composite material, wherein the first and the second material are arranged at least in a region separated from each other.
  • the composite material preferably has a matrix in the first material.
  • further components may be contained in the matrix.
  • These components have at least one of the following functions: primary hydrogen storage, primary heat conduction and / or primary gas feedthrough.
  • primary hydrogen storage By this is meant that the respective component performs at least this function as the main task in the composite. So it is possible that a component is used primarily for hydrogen storage, but at the same time is also able to provide at least some thermal conductivity available. However, it is provided that at least one other component is present, which primarily assumes a heat conduction, which means that over this the largest amount of heat is derived compared to the other components of the compressed composite material.
  • the primary gas-carrying component can be used, through which, for example, hydrogen (fluid) is introduced into the composite of materials but is also conducted out, for example.
  • heat can also be taken along via the fluid flowing through.
  • the fluid flowing through in the sense of the present invention is hydrogen or a gas mixture which contains hydrogen in a proportion of 50% by volume or more, preferably of 60% by volume or more, in particular of 70% by volume or more, preferably of 80% by volume or more, especially 90% by volume or 95% by volume or more.
  • the hydrogenatable material stores only hydrogen, so that even when using gas mixtures as a fluid substantially only hydrogen is stored.
  • the hydrogen storage device preferably has at least 2, preferably more than 2, mutually different layers, one layer of the composite material and one layer different therefrom being at least one of the following Features primary hydrogen storage, primary heat conduction and / or primary gas feedthrough.
  • layers describes that preferably one material, but also two or more materials are arranged in one layer and this can be delimited as a layer from a direct environment. For example, different materials can be poured one after another loosely one over the other so that adjacent layers are in direct contact.
  • the hydrogenatable layer can be arranged directly adjacent to a thermally conductive layer, so that the resulting heat in the hydrogen uptake and / or release of hydrogen from the hydrogenatable material can be delivered directly to the adjacent layer.
  • At least one of the following functions of primary hydrogen storage, primary heat conduction and / or primary gas feedthrough is to be understood as meaning that the respective layer perceives at least one of these as a main task in the second region of the composite material.
  • a layer is used primarily for hydrogen storage, but at the same time is also able to provide a thermal conductivity available.
  • at least one other layer is present, which primarily assumes a heat conduction, which means that the largest amount of heat is derived from the compressed composite material in this layer over the other layers in the hydrogen storage.
  • the primary gas-carrying layer can be used, through which, for example, hydrogen (fluid) is introduced into the composite of materials but is also conducted out, for example. In this case, however, heat can also be taken along via the fluid flowing through.
  • a thermally conductive layer according to the invention may comprise at least one thermally conductive metal and / or graphite. These materials can also be used as a heat-conducting component.
  • the thermally conductive material should be a good thermal conductivity on the one hand, on the other hand, but also a have as low a weight as possible to keep the total weight of the hydrogen storage as low as possible.
  • the metal preferably has a thermal conductivity ⁇ of 100 W / (m-K) or more, in particular of 120 W / (mK) or more, preferably of 180 W / (mK) or more, especially of 200 or more.
  • the heat-conducting metal according to the invention may also be a metal alloy or a mixture of different metals.
  • the thermally conductive metal is selected from silver, copper, gold, aluminum and mixtures of these metals or alloys comprising these metals.
  • Silver is particularly preferred since this has a very high thermal conductivity of more than 400 W / (mK).
  • Aluminum is also preferred since, in addition to the high heat conductivity of 236 W / (m-K), it has a low density and thus a low weight.
  • graphite comprises both expanded and unexpanded graphite.
  • expanded or expandable graphite is used.
  • carbon nanotubes single-walled, double-walled or multi-walled
  • they also have a very high thermal conductivity. Due to the high cost of the nanotubes, it is preferable to use expanded graphite or mixtures of expanded graphite and unexpanded graphite. If mixtures are present, more unexpanded graphite is used by weight than expanded graphite.
  • metal hydride-based hydrogen storage preferably uses graphite grades based on expanded graphite. This is produced in particular from natural graphite and has a significantly lower density than unexpanded graphite, but adheres well in the composite, so that a stable composite material can be obtained. However, if one were to use exclusively expanded graphite in uncompacted form, the volume of the hydrogen storage medium could become too large to be able to operate it economically. Therefore, preferably, mixtures of expanded and unexpanded Graphite used.
  • expanded graphite results in an oriented layer which can conduct heat particularly well.
  • the graphite layers (hexagonal planes) in expanded graphite are shifted by the pressure during pressing against each other, so that lamellae or layers form. These hexagonal planes of the graphite are then transverse (approximately perpendicular to the compression direction during an axial pressing operation), so that the hydrogen can then be easily introduced into the composite material and the heat can be well in or out.
  • the expanded graphite can be processed, for example, by means of calendar rolls into films. These films will then be ground again. The flakes or flakes thus obtained can then be used as a heat-conducting material. Due to the rolling, a preferred direction in the carbon lattice results here, as a result of which a particularly good transfer of heat and fluid is made possible.
  • graphite is used as the heat-conducting material, for example when a high-temperature hydride is contained as a hydrogenatable material in the composite material.
  • a heat-conducting metal in particular aluminum, is preferred.
  • this combination is particularly preferred when the two layers directly adjoin one another.
  • a first layer which represents the first area
  • the composite material according to the invention comprising a high-temperature hydride
  • a second layer comprising graphite.
  • This second layer can in turn immediately adjoin a third layer, comprising a heat-conducting metal, which in turn adjoins a fourth, graphite-containing layer.
  • a first layer, comprising the composite material, can then be directly connected to this fourth layer.
  • Any layer sequences are according to the invention possible.
  • “comprising” means that not only the said materials but also other constituents can be contained; preferred means comprise but consist of.
  • the density of the hydrogenatable material in the matrix and in the layers has a gradient, for example such that a gradient or an increase in the amount and / or density of the hydrogenatable material is present, for example depending on the fluid, which flows through the hydrogen storage element. It is preferably provided that a gradient is formed between the first and the second material, along which a transition takes place from the first to the second layer.
  • the hydrogen storage element comprises components in the form of a core-shell structure in which the core comprises a first material and the shell comprises a second material different therefrom, wherein the first material and / or the second material comprise a hydrogen-storing material , For example, this is preferably as layers of the composite material.
  • the second material of the shell comprises a polymer, which is at least hydrogen-permeable.
  • the core has a heat-conducting material and the jacket has a hydrogen-storing material. Again, it can be provided that the core has a primary hydrogen-storing material and the jacket is a primary heat-conducting material, wherein the heat-conductive material is hydrogen-permeable.
  • the method for producing the hydrogen storage element can provide that separate layers of a hydrogen storage material and a thermally conductive material are filled in a pressing tool and these are pressed together to produce a sandwich structure, wherein the heat conductive material when using the sandwich structure for hydrogen storage, a heat conduction preferably takes over in the direction of the layer extension. Between the separated layers and / or adjacent, one or more matrices may be arranged so that the composite material thereby obtains first and second regions.
  • a metal powder and / or normal natural graphite are used as heat-conducting material, wherein when using the normal natural, lenticular graphite or, for example, flakes of expanded graphite during filling are preferably aligned horizontally, so that a heat conduction in the direction of aligned hexagonal lattice structure in the sandwich structure can be used.
  • one or more layers of foils of a rolled expanded graphite, of flakes of a rolled expanded graphite and / or a graphite fabric are introduced as heat-conducting material in the sandwich structure.
  • the composite material of the hydrogen storage element is porous. Thereby, a hydrogen gas guide can be facilitated.
  • a third material is provided, which forms a functional position in the hydrogen storage element, in particular a porous, gas-permeable layer.
  • a matrix and at least one layer each have carbon.
  • the matrix and / or a layer comprise a mixture of different types of carbon including, for example, expanded natural graphite as one of the carbon species.
  • Non-expanded graphite is preferably used together with expanded natural graphite. wherein weight-related more unexpanded graphite is used as expanded graphite.
  • the matrix may comprise expanded natural graphite in which, for example, a hydrogenatable material is arranged.
  • the composite material has an extensibility, preferably an elastic property in at least one area. In this way it can be ensured that the hydrogenatable material can expand, for example, when taking up hydrogen, without damaging or excessively stressing the composite material.
  • the feeding device also called filling device, filling shoe or filler
  • the feeding device can rotate in the machine longitudinal axis
  • it can be provided, for example, to position the filler for filling the Matrizenkavmaschine on this, the upper side of the lower punch terminates with the upper side of the die.
  • the filler rotates around the machine axis as the materials are dispensed.
  • the layer thicknesses can be controlled by the design of the chambers, the speed of rotation and the speed of the lower punch.
  • the proportion of the individual layers perpendicular to the machine longitudinal axis is determined essentially by the structure and the division of the chambers.
  • different internals may be accommodated in the chambers, which influence the flow behavior of the powder or similar properties. These may be, for example, radial spokes or else gratings or other geometries.
  • the basic structure of a pressing tool is not limited in this case. Several tool levels and mandrels can still be used.
  • An additional embodiment of the invention provides a structure of three functional layers, wherein, for example, an outer layer of the heat supply or heat dissipation is used, a middle layer serves as a storage medium, and an inner layer of the supply or removal of the medium to be stored is used.
  • the outer layer for heat transfer as graphite Be performed layer
  • the middle layer as a metal hydride for storing hydrogen
  • the inner layer of another material in particular metal alloy, preferably chromium-nickel powder, which serves to supply and removal of hydrogen.
  • the filler is filled outside the Matrizen- filling position.
  • the filler rotates during the filler filling process, whereas it does not necessarily rotate during the filling of the matrix cavity.
  • a rotation of the filler when filling the die may be useful, for example, to counteract filling differences that can occur in cavities for the production of components with teeth.
  • a sucking filling of the die is not absolutely necessary, but may be useful so as to prevent uncontrollable mixing of the individual powders. For example, it is possible to fill the filler in the outer region with a different powder than in the inner region, with reference to the center axis or the axis of rotation of the filler.
  • the filler has three or more chambers, wherein the inner and the outer region is filled with a powder, is introduced into the pressing aid, preferably in the middle region, a powder is introduced without pressing aid. Since the pressing aid serves to reduce the friction between powder and tool components, pressing aids can be dispensed with in the middle range. Furthermore, the addition of pressing aids, despite its low density always means a reduction in part density. This partial density reduction can thus be further reduced without reducing the lubricating function between tool components and powder.
  • the described three- or multi-chamber filler consisting of an inner region and at least two surrounding annular regions, it is thus possible, for example, to press a gear with an inner bore, in which the die cavity is filled by the described filler structure, that the pressing aid is only used in internal and external rich, so in the area of the mandrel and the external toothing is present.
  • the chamber structure can be arbitrarily complex and is independent of the components to be pressed. It is even possible to use different powders for, for example, breakthroughs. In this case, only the position when transferring the filler into the filling position of the die must be positioned sufficiently accurately. Different filling of the component cavity makes it possible to produce different component properties, depending on the requirements of the individual component regions or functional surfaces of the component.
  • a gear it is possible for a gear to produce the component area between internal teeth and external teeth with a powder that is compacted to a very low density, so as to ensure the damping properties of the porous structure and further necessary for the high load on the inner and outer regions to ensure high density.
  • the proposed filler can also be used to create a wide variety of complex geometries for the hydrogen storage element.
  • the top of the lower punch is not with the top of the die in a plane, but below it.
  • a layer of preferably powder on lower punch which need not be a single powder from a single chamber.
  • powders from a plurality of chambers as a first layer into the die cavity or other materials as described above.
  • a filler may be composed of three chambers, one chamber filled with graphite, one with a metal hydride and another with a powder intended for gas supply.
  • the shape of the component is not produced by the pressing of powders and / or shreds or flakes, but by extruding different extrusion media into a mold by rotating the same or by rotating the inlet geometry into a non-rotating one Shape.
  • a press with a material is added filling cavity and proposed with a movable by means of a displacement device of the press comb, wherein the traversing device can move the comb in the material and on this.
  • a programmable control of the displacement device is present, which converts a predeterminable path into a movement of the comb.
  • a smoothing, in particular an alignment of a material, at least in the region of a surface thereof, can be effected by means of the comb or even a strip or one or more prongs.
  • a gradient can be introduced into the layers by means of the comb or other components.
  • the comb is at least partially interchangeable. This allows the device to remain as such.
  • an adapted comb, a strip or a prong or the like is used.
  • the comb may have a plurality of prongs.
  • the comb has at least one prong which has a widening for contacting the material. This allows to set targeted gradients by means of, for example, different broadening.
  • a further embodiment provides that a distance between two prongs of the comb is variable. This can be done, for example, during operation, i. during contact of the tines with the material. As a result, helical patterns can be generated, for example, as well as different gradient distances, for example adapted to a helix. It is further preferred if two or more combs are movable in parallel.
  • At least two materials are provided for the disposal of the cavity of the sintering press, wherein the comb is movable so far that it enters at least in the filled first material, preferably in the first and the second material.
  • the comb performs a movement contacting the material. It is also possible that the comb is immersed in the filled material and is moved in the cavity. For example, the comb can dip in different depths. Furthermore, there is the possibility that the comb is immersed in the filling of the cavity with first and second material at least in one of the two first and second materials and is moved.
  • the combs can be integrated into the filler geometry.
  • FIGS. 45 to 54 show in principle the procedure when filling a Matrizenkavmaschine with a rotary filler
  • Fig. 1 shows a filler 11 with two equal chambers 5, 6 for two different powders 1, 2, and the corresponding compact. 9
  • FIG. 2 shows a filler 11 with three chambers 5, 6, 7, the areal distribution of the three chambers 5, 6, 7 being different in each case, and the corresponding compact 9.
  • FIG. 3 shows a filler 11 similar to that of FIG. 2 but with four chambers 5, 6, 7, 8 instead of three chambers, and the associated compact 9.
  • Fig. 4 shows a possible chamber structure of a filler 11 for three powders 1, 2, 3, with which four layers of the compact 9 also shown are produced, wherein the material in the center of the compact 9 is homogeneous and a helical structure is present on the outside.
  • FIG. 5 shows a filler 11 for three different materials, material 1 enclosing the helix of the compact 9 also shown formed by the materials 2 and 3.
  • Fig. 6 shows a filler 11 and the compact 9, which by means of a normal filling on the top and bottom and with a helical structure in the middle whereby it is possible to completely seal off the internal materials, in this case material 2 and material 3, to the outside, here by material 1, material 4 and material in the chamber 5, and the filler 11 for producing the middle segment of the compact 9 in the form of a helix is used.
  • FIG. 7 shows a further embodiment of a filler 11 and the compact 9 which can be produced with it.
  • FIG. 8 shows a next embodiment of a filler 11 and the compact 9 that can be produced with it.
  • Figs. 1 through 8 In the filler top views on the left in Figs. 1 through 8 are filler port outlet port arrangements which result in a helical layered layup of powder material in a press cavity when the filler rotates in its fill position above the press cavity and the bottom of the cavity attaches Relative twist from the filler farther and farther away.
  • the outlet openings of at least two chambers are arranged offset in the radial direction and rotational direction of the filler considered, thus sweeping concentric surface areas that overlap or one of which is disposed within the other.
  • Fig. 9 to FIG. 28 show the basic procedure when filling a die cavity with two fillers.
  • the filler 18 is filled with the material 1, filler 24 with material 2.
  • the example shows a 4-layer structure in which two layers of powder 1 and two layers of powder 2 are pressed.
  • the number, the order and the thickness of the layers can be made free due to the properties to be achieved. Below we briefly describe the respective process in each figure.
  • FIG. 9 The lower punch 10 has moved downwards by the respective path, which corresponds to the height of the partial filling space 12 (the cavity 14) for the first material 16.
  • the first filler 18 moves over the cavity 14.
  • Fig. 10 The first (powder) material 16 falls by gravity into the die cavity 14.
  • FIG. 11 The filler 18 returns to the starting position and wipes the (powder) material 16 in the die cavity 14 at the level of the die top 20 off.
  • Fig. 12 The lower punch 10 moves downwards, thus providing the one further partial filling space 12 '(the cavity 14) for a second (powder) material 22.
  • FIG. 13 The second filler 24 moves over the cavity 14.
  • Fig. 14 The (powder) material 22 falls by gravity into the Matrizenkavmaschine 14 on the (powder) material 16th
  • Fig. 15 The filler 24 moves back to the starting position and thereby strips the (powder) material 22 at the height of the die top 20 from.
  • Fig. 16 The lower punch 10 gradually moves further downwards, thus providing a further partial filling space 12 "for the next layer of first (powder material 16), which is then the second layer of (powder material 16, FIG The filler 18 moves over the die cavity 14.
  • Fig. 18 The (powder) material 16 falls from the filler 18 by gravity into the Matrizenkavmaschine 14 on the (powder) material 22.
  • Fig. 19 The filler 18 is moved back to the starting position.
  • FIG. 20 The lower punch 10 continues to move stepwise downwards, thus providing a further partial filling space for the next layer of second (powder material 22).
  • FIG. 21 The filler 24 moves over the cavity 14.
  • Fig. 22 The (powder) material 22 falls by gravity into the Matrizenkavmaschine 14 on the upper (powder) material sixteenth
  • Fig. 23 The filler 24 moves back to the starting position and thereby strips the (powder) material 22 at the height of the die top 20 from.
  • Fig. 24 The Matrizenkavtician 14 is filled with two layers of two materials which are alternately stacked.
  • FIG. 25 The upper punch 26 moves toward the lower punch 10.
  • the lower punch 10 can be driven down slightly before the compression of the material layers in the cavity 14 by the upper punch, as shown here (to produce a so-called underfilling).
  • Fig. 26 The upper punch 26 compresses the four layers to the desired density and then moves back to the starting position.
  • the lower stamp 10 remains in the previously assumed position.
  • the lower punch 10 moves after immersion of the upper punch 26 in the Matrizenkavtician 14 on the upper punch 26.
  • the die cavity 14 it is also possible for the die cavity 14 to be moved linearly in the machine longitudinal axis 30, whereby it is preferably moved in the same direction as the upper punch 26 at a fixed lower punch 10 at half the punching rate.
  • Fig. 27 After the pressing operation, the compact 32 is ejected from the die 28 by the lower punch 10.
  • the upper punch 26 acts during the ejection of the compact 32 with a small force on the compact 32 and moves back only after the complete ejection of the compact 32 to the starting position.
  • Fig. 28 shows the ejected compact 32 and the machine components in starting position.
  • the compact 32 can be removed.
  • the working cycle can start from the beginning to produce a next compact.
  • Fig. 29 to 44 show the basic sequence of filling with a (single) filler 18 with two chambers 34, 36, which can thus store two different powders. It is also possible that more than two different chambers are used for correspondingly more than two powders.
  • Fig. 30 The filler 18 is located with its first chamber 34 above the Matrizenkavmaschine 14 and the (powder) material 16 has fallen from the chamber 34 into the Matrizenkavmaschine.
  • FIG. 31 The filler 18 is moved further until its chamber 36 with the (powder) material 22 is above the die cavity 14.
  • Fig. 32 The lower punch 10 is moved down until the filling level for the second layer of (powder) material 22 is reached.
  • Fig. 33 The (powder) material 22 falls from the chamber 36, during the lowering of the lower punch 10, in the Matrizenkavtician 14 and thus forms the second layer.
  • the lower punch 10 can just as well have shut down (completely) when the chamber 36 is above the cavity 14.
  • Fig. 34 The filler 18 is moved until the chamber 34 with the (powder material 16 is above the Matrizenkavtician 14.
  • Fig. 35 The lower punch 10 is moved down until the filling level for the third layer is reached.
  • Fig. 36 The (powdery) material 16 falls out of the chamber 34, during the lowering of the lower punch 10 in the Matrizenkavtician 14 and thus forms the third layer.
  • Fig. 37 The filler 18 is moved on until the chamber 36 with the (powder) material 22 is above the die cavity 14.
  • Fig. 38 The lower punch 10 is moved down until the filling level for the second layer is reached.
  • the (powdery) material 22 drops out of the chamber 36 during lowering of the lower punch 10 into the Matrizenkavtician 14, thus forming the fourth layer.
  • Fig. 39 The filler 18 is moved to the starting position.
  • Fig. 40 The upper punch 26 is moved in the axial direction in the direction of the lower punch 10 in order to press the individual layers.
  • Fig. 41 The upper punch 26 and lower punch 10 are in Pressend ein.
  • Fig. 42 The upper punch 26 is moved to the starting position and the lower punch 10 ejects the compact 32 from.
  • Fig. 43 The tool components are in their home position with ejected compact 32.
  • FIGS. 45 to FIG. 54 show the basic procedure for filling the cavity with a rotary filler with two or more chambers. In this case, the filler only needs to rotate during the downward movement of the lower punch or during the filling of the cavity. However, it is also conceivable that the filler rotates permanently.
  • Fig. 45 The rotary filler 18 'is moved over the Matrizenkavmaschine 14.
  • FIG. 46 The rotary filler 18 'is located above die cavity 14.
  • Rotary filler 18 rotates about machine longitudinal axis 30 as lower punch 10 moves down machine longitudinal axis 30 to gradually release cavity 14 for introduction of material.
  • Fig. 48 The lower punch 10 is in its lower filling position.
  • the rotary filler 18 'no longer rotates.
  • Fig. 49 The rotary filler 18 'is moved back to the starting position.
  • Fig. 50 The rotary filler 18 'is located between the filling position and the starting position.
  • Fig. 51 The upper punch 26 moves toward the lower punch 10 with the rotary filler 18 'not shown.
  • FIG. 52 Upper punch 26 and lower punch 10 press the (powder material, which is double helix-shaped in cavity 14) into a compact 32.
  • the rotary filler 18 ' is not shown.
  • Fig. 53 The upper punch 26 moves to its starting position. Also, the lower punch 10 moves to the starting position and ejects the compact 32 from. The rotary filler 18 'is also not shown here.
  • Fig. 54 The compact 32 is removed. Subsequently, the cycle can restart, in which case the unillustrated rotary filler 18 'again comes into action.
  • the press 100 for producing a blank of, in this case, three different powder materials which are twisted into each other and helically arranged in the blank.
  • the press 100 has a die 110 with a cavity 112.
  • the cavity 112 is formed in this embodiment as a through hole of the die 110 and is closed at its bottom by an axially along the center axis 114 movable lower punch 116.
  • the upper punch 119 can also be moved back and forth along the center axis 114 of the cavity 112. In this way, as is generally known, powder material introduced into the cavity 112 can be pressed into a blank (possibly with the additional use of heat).
  • fillers 118 are used, which can also generally be referred to as filling devices 120.
  • the filling device 120 includes a rotary filler 118 which, when located above the opening 122 of the cavity 112, rotates about the central axis 114 relative to the cavity 112.
  • the rotary filler 118 is shown in its filling position in Fig. 55, in which in this embodiment three free-flowing (eg powder) materials 124, 126, 128 are introduced into three separate chambers 130, 132, 134 of the rotary filler 118.
  • the rotary filler 118 is filled during its movement and in particular during the dispensing of material.
  • the material supply lines are moved translationally with the rotary filler 118 in order to be able to top up the rotary filler 118 during the discharge of material.
  • the rotary filler 118 is located above the cavity 112 (filling position) and fills therein the three powder materials under rotation.
  • the lower punch 116 is initially in its uppermost position.
  • the lower punch 116 is then moved downward accordingly, so that he releases so per unit time exactly the Kavticianssteilvolumen, which is filled by powder material from the rotary filler 118 into the cavity 112.
  • the more detailed construction of the embodiment of the rotary filler 118 described herein is shown in Figs. 57 and 58 are shown.
  • the rotary filler 118 rotationally driven by a driver 136 has a substantially cylindrical outer shape similar to a sleeve.
  • the filler 118 has an inlet opening arrangement 138 with three concentric inlet openings 140, 142, 144 in this exemplary embodiment.
  • the central opening 144 is penetrated by the axis of rotation and is concentric with this.
  • the two openings 140 and 142 extend annularly around each other and are therefore arranged concentrically.
  • the three chambers 130, 132, 134 are delimited from each other by chamber walls 146, 148, 150 and limited to the outside, wherein these three chamber walls 146, 148, 150 form concentric rings in the region of the inlet opening arrangement 138.
  • the inner chamber walls 148, 150 are deformed to the lower, the cavity 112 facing outlet end, so that in this embodiment at the lower end of the rotary filler 118, the Auslrawö Stammsan extract 152 results according to FIG. D.
  • the outer chamber wall 146 is substantially cylindrical along its entire axial length, while the next inner chamber wall 148 has a neck 154 (similar to a heart shape) at the outlet end of the rotary filler 118.
  • the V-shaped constriction 154 points toward the center of the rotary filler 118 and thus to the innermost chamber wall 134, which has a radially extending forming collar at the outlet end of the rotary filler 118.
  • an outlet opening 156 of the chamber 130 is formed, while the next inner chamber 132 has an outlet opening 158 formed by the chamber wall 148 with constriction 154 on the one hand and by the chamber wall 134 with its radially elongated shape.
  • the third, innermost chamber 134 has an outlet opening 160 which is directed radially outwardly and extends partially around the center axis 162 of the filler 118.
  • the chamber Walls or comb structures 164, 166 serve to grade the powder materials exiting the chambers at their respective interfaces.
  • the rotary filler 118 may be used to deposit into the cavity 112 three powder materials that form three intertwined partial or full helical assemblies.
  • the powder material 126 emerging from the middle chamber 132 is present in the blank or in the cavity 112 as the middle helix 168 (see FIG. 59).
  • the powder material 124 exiting the outer chamber 130 forms a cylindrical shape with a helix extending inside the cylinder wall.
  • the powder material 128 emerging from the inner chamber 134 is located in the core of the blank as a solid cylinder with an external helical projection. The situation is shown for a partial section of the blank in FIG. 59.
  • Fig. 60 shows the situation when, during the rotation of the filler 118 in its inner chamber 134, there is a mandrel (not shown) as a spacer which holds the center 169 of the blank free of powder material.
  • a mandrel not shown
  • Such an arrangement is advantageous, for example, to provide the blank with a channel for a gas supply.
  • the rotary filler can be used in particular for producing a blank for use as a hydrogen-storing component or a hydrogen-storing component.
  • the material 126 supplied via the middle chamber 132 and recessed into the cavity 112 can be hydrogenated, while the material 124, which passes into the cavity 112 via the outer chamber 130 of the rotary filler 118, has heat-conducting properties.
  • the interior of the blank is then gas-permeable material 128.
  • the inner material of the blank thus provides for the supply and thus the porosity of the blank, so that in this hydrogen can be introduced, which then binds to the hydrogenatable material.
  • the resulting heat is dissipated via the material 124 to the outside.
  • Outside of the hydrogen storage (blank) is located around a (pressure) container, which is in thermal contact with the hydrogen storage component.
  • FIG. 61 shows in perspective or in FIG. 62 from above a further embodiment of a rotary filler 170.
  • the rotary filler 170 on three ring chambers which, however, unlike the Fign. 55 to 60 are arranged substantially continuously concentric.
  • An inner partition wall 172 defines an inner chamber 173, while a centrally located further cylindrical wall 174 defines a second chamber 176. Outside is a third cylindrical wall 178 defining the outer chamber 180.
  • the special feature of the rotary filler 170 is that an additional chamber 182 is formed on the outlet side, into which wall-wet material passes on both sides of the middle chamber wall 174.
  • Flow inlet of the chamber 182 are deflecting elements 184, which provide for a local mixing of the two near-wall material flows.
  • a hydrogen storage element manufacturing apparatus comprising a cavity to be filled, at least a first material supply of a first material and a second material supply of a second material, wherein the first and the second material supply are arranged separately from each other, with a feeding device for supplying the at least first and the second material in the to be filled cavity, wherein the first material is a primary hydrogen storage material, and the second material is a primary heat-conducting material.
  • Hydrogen storage element manufacturing device wherein the cavity to be filled is preferably round and preferably a contact surface is provided which is movable at least on a surface of the at least first and / or second material filled in the cavity and movable along this, particularly preferably in the at least first and / or second material is movable and movable therein.
  • the hydrogen storage element manufacturing apparatus according to item 1 or 2, wherein the supply device has an orifice cross section with at least a first region for the first material and a second region separated therefrom for the second material for preferably parallel, spatially separate filling of the cavity, wherein the first region preferably at least partially, more preferably completely embedded in the second region.
  • a hydrogen storage element manufacturing apparatus according to any one of the preceding figures, wherein the hydrogen storage element manufacturing device has at least one drive by means of which at least one controlled relative movement between the cavity to be filled and the supply device is made possible.
  • Hydrogen storage element production device according to one of the preceding figures, wherein it has an axis of rotation about which the supply device is rotatably arranged and / or that the cavity is rotatable. bar is arranged.
  • a hydrogen storage device manufacturing apparatus wherein the cavity to be filled is a die cavity and the feeder is a filler and the hydrogen storage element manufacturing apparatus comprises a press for compacting the at least first and second materials in the die cavity.
  • a hydrogen storage device manufacturing apparatus according to any one of the preceding figures, which is a 3-D printer.
  • a delivery device for use in a hydrogen storage device manufacturing apparatus having an orifice cross section with at least a first region for the first material and a second region separated therefrom for the second material for preferably parallel, spatially separate filling of the cavity, the first region preferably at least partially, especially preferably completely embedded in the second region.
  • Feeding device wherein it has a material supply for the first material and a separate material supply for the second material, wherein a mixing zone supply is provided, along which the first and the second material is miscible and can be fed.
  • Feeding device according to item 8 or 9, wherein an additional strip feed is provided, over which a strip of material in the mouth cross-section is feasible.
  • Feeding device according to any one of the items 8 to 10, wherein the outlet opening (160) of the first chamber (134) extends transversely to the orientation of the center axis (114), in particular to one side of the center axis (114), and within the outlet opening (158 ) of the second chamber (132) is arranged, which in turn about the center axis (114) extends around.
  • a delivery device according to any one of 8 to 11, wherein the filling means (120) comprises a third chamber (130), the third chamber (130) extending outwardly around the second chamber (132) and having an outlet opening (156) extends around the second outlet opening (158), wherein the second outlet opening (158) has a substantially V-shaped, in the direction of the center axis (114) facing constriction (154).
  • a hydrogen storage element comprising a composite material comprising at least a first and a second material, wherein the first material comprises a hydrogen storage material and the second material comprises a thermally conductive material, wherein the hydrogen storage device preferably with a hydrogen storage manufacturing apparatus and / or a method according to any one of 14 to 20 is made.
  • Hydrogen storage element according to item 21 or 22, wherein the Ver Bundmaterial the hydrogen storage element is porous.
  • Hydrogen storage element according to any one of the numbers 21 to 23, wherein a third material is provided which forms a functional position in the hydrogen storage, in particular a porous, gas-permeable layer.
  • 26. A hydrogen storage device having a plurality of hydrogen storage elements according to any one of items 21 to 25, wherein it has a low-temperature hydride and a high-temperature hydride.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Filling Or Discharging Of Gas Storage Vessels (AREA)

Abstract

L'invention concerne un dispositif de fabrication d'élément de stockage d'hydrogène qui comprend une cavité destinée à être remplie, au moins une première alimentation en un premier matériau et une deuxième alimentation en un deuxième matériau, les première et deuxième alimentations en matériau étant séparées l'une de l'autre et un dispositif d'alimentation étant destiné à amener le premier et le deuxième matériau dans la cavité destinée à être remplie, le premier matériau étant un matériau dont la fonction primaire est d'emmagasiner l'hydrogène et le deuxième matériau étant un matériau dont la fonction primaire est de conduire la chaleur et/ou le gaz.
PCT/EP2015/059716 2014-05-05 2015-05-04 Dispositif de fabrication d'élément de stockage d'hydrogène, procédé associé et élément de stockage d'hydrogène Ceased WO2015169746A1 (fr)

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DE102014006371.2A DE102014006371A1 (de) 2014-05-05 2014-05-05 Wasserstoffspeicher-Herstellvorrichtung nebst Verfahren hierzu und Wasserstoffspeicher
DE102014006371.2 2014-05-05

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CN112212213A (zh) * 2020-11-04 2021-01-12 中国科学院广州能源研究所 一种电动汽车金属氢化物储热供暖系统
CN119594330A (zh) * 2024-12-17 2025-03-11 武汉船用电力推进装置研究所(中国船舶集团有限公司第七一二研究所) 一种储氢粉体网格压合件及其装配方法、固态储氢装置
US12516614B2 (en) 2016-12-23 2026-01-06 Gkn Sinter Metals Engineering Gmbh Green compact of a stator-cover unit

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DE102017100361A1 (de) * 2017-01-10 2018-07-12 Audi Ag Wasserstoffspeichertank und Brennstoffzellensystem sowie Kraftfahrzeug mit einem solchen
EP4254451A1 (fr) * 2022-03-30 2023-10-04 Abb Schweiz Ag Ampoule à vide

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CN112212213A (zh) * 2020-11-04 2021-01-12 中国科学院广州能源研究所 一种电动汽车金属氢化物储热供暖系统
CN119594330A (zh) * 2024-12-17 2025-03-11 武汉船用电力推进装置研究所(中国船舶集团有限公司第七一二研究所) 一种储氢粉体网格压合件及其装配方法、固态储氢装置

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