Classifications

• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
  • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
  • F17C11/00—Use of gas-solvents or gas-sorbents in vessels
  • F17C11/005—Use of gas-solvents or gas-sorbents in vessels for hydrogen
• • 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
  • C01B3/0084—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
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
  • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
  • F17C2221/00—Handled fluid, in particular type of fluid
  • F17C2221/01—Pure fluids
  • F17C2221/012—Hydrogen
• • 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 invention relates to a hydrogen storage device and a method for producing a hydrogen storage device.
• the hydrogen storage element is provided by compression molding and comprises a hydrogen-storing material and a thermally conductive material. Such hydrogen storage elements are stacked or arranged geometrically fixed to one another and thus yield a hydrogen storage device. The individual layers of the hydrogen storage elements who aligned with each other and functionally connected to each other, for. B. for heat conduction, for the passage of hydrogen, etc.
• a hydrogen storage device which comprises at least one container with a first volume, wherein a bulk material is arranged in the container.
• the bulk material comprises at least a plurality of press-formed compacts, wherein each compact at least one hydrogen-storage-cherAuses first material and a second material as a binder for the powder before the prespecific preparation present first material to summarizes.
• bulk material refers to a granular or else lumpy mixture which is present in a pourable form.
• the properties of bulk material are determined by grain size and grain distribution, as well as bulk density, angle of repose, moisture and temperature.
• a bed in particular special loose bed, refers to goods that can be freely in a container or are not otherwise secured in their position. An Orientie tion of the components of the bulk material to each other or z. B. to the container with the first volume is not specified.
• a compact is an element made by pressing.
• a powdery first material, here together with the second material, which is also provided in powder form in particular, is filled into a mold and by mutually movable punches under a pressure of at least 50 MPa [MegaPascal], in particular of at least 100 MPa, in particular isosta table pressed into a compact.
• a hot pressing in which temperatures of at least 50 degrees Celsius, in particular of at least 70 degrees Celsius, preferably of at least 100 degrees Celsius are generated in the compact.
• a temperature is set which essentially corresponds to the melting temperature of the second material used or deviates by at most 20 kelvin thereof. Due to the elevated temperature, the second material can be at least partially melted, so that a better connection of the first material and the second material takes place.
• the proportion of the second material is in particular between 1 and 5% by weight.
• the hydrogen storage material is used as a bulk material.
• the bulk material is filled in the almost arbitrarily shaped container and is arranged in it. In this case, gaps are formed between the compacts, which are in the A storage and re-release of hydrogen to compensate for the size change tion of the compacts in terms of their size are variable.
• the hydrogen-storing first material and the second material as a binder are z. B. from WO 2015/169740 Al known.
• As a second material in particular special at least one polymer is used. By using at least one polymer, certain optical, mechanical, thermal and / or chemical properties can be assigned to the compact.
• the polymer may have good temperature resistance, resistance to the surrounding medium (oxidation resistance, corrosion resistance), good conductivity, good hydrogen uptake and storage capability, or other properties such as mechanical strength, which would otherwise be absent from the Po - lymer would not be possible. It is also possible to use 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 monomeric units.
• the polymer preferably has a monomer unit which, in addition to carbon and hydrogen, preferably further contains at least one heteroatom selected from sulfur, oxygen, nitrogen and phosphorus, so that the polymer obtained is not completely non-polar, for example, as compared to polyethylene. Also, at least one halogen atom selected from chlorine, bromine, fluorine, iodine and asi may be present.
• the polymer is a copolymer 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, fluorine, iodine and astatine , is available.
• the polymer preferably has adhesive properties with respect to the first material. This means that it adheres well to the first material itself and thus forms a matrix, which stably adheres to the first material even under loads as they occur during hydrogen storage.
• the adhesive properties of the polymer allow a high stability of the compact over 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 compact should preferably be stable for at least 500 cycles, in particular for 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 ent speaks the values at the beginning of the use of the compact.
• stable means that the first material is held at least approximately at the position within the compact to which it was originally arranged. Stable is to be understood in particular to the effect that no segregation effects occur during the cycles in which finer particles separate from coarser particles (eg from the compact) and remove.
• the first material is in particular a low-temperature hydrogen storage material.
• hydrogen storage which is an exothermic process, therefore, temperatures of up to 150 ° C occur.
• a polymer, which is used here as a second material, must be stable at these temperatures. Therefore, a preferred polymer does not decompose to a temperature of 180 ° C, in particular special up to a temperature of 165 ° C, in particular up to 145 ° C.
• the polymer is selected from EVA, PMMA, EEAMA and mixtures of these polymers.
• EVA ethyl vinyl acetate
• EVA ethyl vinyl acetate
• Typical EVA are solid at room temperature and have an elongation at break of up to 750%.
• EVA are stress crack resistant.
• Polymethyl methacrylate is a synthetic, transparent, thermoplastic material.
• the glass transition temperature is dependent on the molar mass at about 45 ° C to l30 ° C.
• the softening temperature is preferably 80 ° C to 120 ° C, especially 90 ° C to 110 ° C.
• the thermoplastic copolymer is distinguished by its resistance to weathering, light and UV radiation.
• EEAMA is a terpolymer (copolymer) of ethylene, acrylic ester and maleic anhydride monomer units.
• EEAMA has a melting point of about 102 ° C, depending on the molecular weight.
• the compact comprises only the first material and the second material, that is, the hydrogen-storable first material and the binder.
• the proportion by weight of the second material, based on the total weight of the pressed article, is preferably at most 10% by weight, in particular at most 5% by weight, preferably at most 2% by weight.
• the weight fraction of the binder on the compact should be as low as possible. Even if the binder is is also hydrogen to store, so the hydrogen storage capacity is still not as pronounced as that of the first material (in particular at most 20% of the hydrogen storage capacity). On the one hand, however, the binder can reduce or completely avoid any oxidation of the first material which occurs, and on the other hand ensures cohesion between the pulverulent particles of the first material in the compact.
• the first material may comprise, preferably consists of, at least one hydrogenatable metal and / or at least one hydrogenatable metal alloy.
• the following materials can also be used as the hydrogenatable first material: alkaline earth metal and alkali metal alanates, alkaline earth metal and alkali metal borohydrides, metal-organic frameworks (MOFs) / metal-organic skeletons, and / or clathrates, and, of course, combinations of these each time materials.
• the first material may also include non-hydrogenatable metals or metal alloys.
• the first material 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 store 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 store hydrogen preferably in a Temperaturbe range from 280 ° C and more, especially from 300 ° C and more. At the stated temperatures, the hydrides can not only store hydrogen, but also released, so they are functional in these temperature ranges.
• hydrogenatable material in its hydrogenated form and in its non-hydrogenated form.
• hydrogenated materials in their hydrogenated or nonhydrogenated form can be used in the production of hydrogen storage.
• the hydrogen storage (hydrogenation) 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 en dothermic reaction.
• the compact In a hydrogenated first state, the compact has a larger second volume than in a dehydrated second state.
• the first material is in particular powdery (ie as particles, particles).
• the particles have a particle size x50 of 20 ⁇ m [micrometre] to 700 ⁇ m, in particular from 50 ⁇ m to 300 ⁇ m.
• x50 means that 50% of the particles have an average particle size that is equal to or less than the stated value.
• the average particle size is present ge weight-based particle size. Indicated here is the particle size (particle size) of the hydrogenatable material before being subjected to hydrogenation for the first time. During hydrogen storage, stresses occur in the material, which may result in a reduction in the x50 particle size over several cycles.
• the second material fixes the particles / particles in the compact.
• the plurality of compacts comprises at least 50% by volume, in particular at least 75% by volume, preferably at least 90% by volume of the bulk material.
• the bulk material may additionally comprise at least one compressible third material arranged at least in spaces between the plurality of pressliners.
• the third material can compensate for volume expansion of the plurality of compacts during uptake of hydrogen by compression.
• the third material comprises z.
• a graphite in particular an ex pandieres graphite.
• at least the second material has a melting temperature which differs from a highest operating temperature of the hydrogen storage device by at most 20 Kelvin, in particular by at most 10 Kelvin.
• a second material is selected, which has a melting temperature of at most 70 degrees Celsius.
• the melting temperature of the second material can also be lower than the highest operating temperature.
• the operating temperature can be between 40 and 140 degrees Celsius, in particular between 40 and 80 degrees Celsius.
• significantly higher operating temperatures can also be provided.
• the effect of further segregation of the particles / particles of the first material can thus be counteracted or compensated for.
• the scaled particles would detach from a compact and migrate downwardly within the container with gravity. Possibly.
• gaps between the compacts were filled by the first material, so that a volume expansion of the plurality of compacts during a recording of hydrogen could not be compensated, z. B. by a compression z.
• a third material otherwise provided in the Eisenhoff-. This then not (sufficiently) com pensiere volume expansion could cause local stresses in the container and thus at least lead to damage to the container.
• the second material has a melting temperature that is higher than the highest operating temperature.
• At least one compact of the plurality of compacts may have a cylindrical shape.
• a cylindrical shape is particularly easy to produce by pressing.
• At least one compact in particular a pos as large number of the plurality of compacts, preferably all compacts, have a spherical shape.
• the spherical shape allows a particularly high packing density of the bulk material, so that a particularly effective hydrogen storage pre- direction can be provided.
• a spherical shape is difficult to produce by pressing for known reasons.
• a densest sphere packing (ie the highest packing density of spheres) is the geometrical arrangement of infinitely many spheres of equal size in the 3-dimensional space in such a way that they only touch and do not overlap, leaving the remaining empty space minimal. Such an arrangement results when many balls are stacked in layers. Within each layer, each ball touches six neighboring balls. The packing density of a densest packing is about 74%.
• At least one compact of the plurality of compacts in particular special the largest possible number of the plurality of compacts, preferably all compacts, a mold with a second volume, each point of a surface of the mold at a distance of at most 5%, in particular Höchs - At least 2%, preferably at most 1%, of a diameter of a spherical shape, which also has the second volume, is arranged by the spherical surface of the spherical shape.
• the compact thus has a shape which is as far as possible approximated to a spherical shape.
• each compact of the bulk material in the non-hydrogenated state has a second volume of at least 10 mm 3 [cubic millimeters] and at most 1000 mm 3 .
• a bulk material can be used, in which all compacts each have the same second volume or in which individual compacts are designed with different second volumes.
• the compact comprises at least one hydrogen storable first material and a second material as a binder for the before a presstechni- see production in powder form present first material.
• the comments on the hydrogen storage device apply equally to the compact and vice versa. Furthermore, a method for producing a hydrogen storage device (in particular described above) is proposed. The procedure includes at least the following steps:
• the bulk material comprises at least a plurality of press-formed compacts, wherein each compact at least one hydrogen storage-capable first material and a second Ma material as a binder for before the pressischen Preparation comprises powdered present first material.
• the first volume in step b) may additionally be filled with at least one compressible third material via the opening, wherein the third material is at least in intermediate spaces between the plurality of Arranges compacts.
• the third material may compensate for volume expansion of the plurality of compacts during uptake of hydrogen by compression.
• the reticulated third material can contribute to increasing the thermal conductivity of the bulk material and / or accelerate the kinetics for hydrogen uptake and release.
• a packing density of the plurality of compacts in the first volume may be adjusted by changing a shape of a compact of at least a subset of the plurality of compacts.
• the packing density can be adjusted by a targeted feeding of differently shaped compacts during the bed (ie during filling into the container).
• Fig. 1 a bed of a plurality of compacts
• Fig. 2 a detail of the bed of Fig. 1;
• 3 shows a hydrogen storage device in a side view
• 4 shows a hydrogen storage device in a perspective view on
• Fig. 5 a first embodiment of a form of a compact in one
• FIG. 6 shows a second embodiment of a form of a compact in one
• Fig. 7 a third embodiment of a form of a compact in one
• Fig. 1 shows a bed with a plurality of compacts 5.
• Fig. 2 shows a detail of the bed of Fig. 1. Figs. 1 and 2 are described together sam next.
• the bed shows a bulk material 4 consisting of a large number of compacts 5.
• Each compact 5 comprises a hydrogen-storable first material 6 and a second material 7 as a binder for the first material 6 present in powder form prior to the prespecification.
• the compacts 5 are cohesively connected to one another.
• the second material 7 has a melting temperature which differs by at most 20 Kelvin from a highest operating temperature of the hydrogen storage device 1.
• Such selection of the second material 7 allows the second material 7 to soften at each cycle of hydration and / or dehydration. This softening enables a respective new formation of the cohesive connection between the first material 6 and the second material 7 both within the compact 5 and between the compacts 5.
• the compacts 5 used here all have a cylindrical shape 10 and a respective same second volume 11.
• intermediate spaces 9 are formed, which can be filled in a hydrogen storage device 1 by a compressible third material 8 (see FIGS. 3 and 4).
• FIGS. 3 and 4 will be described together below.
• the hydrogen storage devices 1 each comprise a container 2 with a first volume 3, wherein in the container 2, a bulk material 4 is arranged.
• the bulk material 4 comprises at least a plurality of press-manufactured Pressings 5, wherein each compact comprises at least one hydrogen-storable first material 6 and a second material 7 as a binder for the first material 6 present in powder form prior to the press-technical production.
• the hydrogen-storable first material 6 is not adapted to the shape of the container 2 provided for the arrangement of the hydrogen-storing first material 6, but is provided as bulk material 4.
• the bulk material is filled via an opening 18 in the almost arbitrarily shaped container 2 and is arranged in it. In this case, gaps 9 are formed between the compacts, which are variable in the storage and Wiederivary of hydrogen to compensate for the change in size of the compacts 5 with respect to their size changed.
• the bulk material 4 additionally comprises at least one compressible third material 8, which is arranged in the intermediate spaces 9 between the plurality of compacts 5.
• the third material 8 can compensate for a volumetric expansion of the plurality of compacts 5 during absorption of hydrogen by compression (see FIG. 3).
• the compacts 5 used here all have a cylindrical shape 10 and a respective same second volume 11. In a hydrogenated first state 19, the compact 5 has a larger second volume 11 than in a dehydrier th second state 20. The increase in the second volume is illustrated in the loading container 2 based on a compact 5 and in the sweeping end.
• FIG. 5 shows a first embodiment of a mold 10 of a compact 5 in a side view in section.
• Fig. 6 shows a second embodiment of a mold 10 of a compact 5 in a side view in section.
• 7 shows a third te embodiment of a mold 10 of a compact 5 in a side view in section.
• FIGS. 5 and 7 will be described together below.
• a compact 5 has a spherical shape 16.
• the spherical shape 16 allows a particularly high packing density of the bulk material 4, so that a particularly effective hydrogen storage device 1 can be provided.
• a spherical shape 16 is difficult to adjust forth for reasons known by pressing. Therefore, compacts 5 having a shape 10 and a second volume 11 are produced, wherein each point 12 of a surface 13 of the mold 10 at a distance 14 of at most 5% of a diameter 15 of a spherical shape 16, just if the second volume 11 , is arranged by the spherical surface 17 of the spherical shape 16.
• the compact 5 thus has a shape 10 which is as far as possible approximated to a spherical shape 16 (see FIGS. 5 and 6) with an indicated spherical shape 16 of the same second volume 11.
• Fig. 7 shows a compact 5 with a cylindrical shape 10 in a soan view.
• the compact 5 has a diameter 15 and a second volume 11.

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• 2018
  • 2018-03-02 DE DE102018104830.0A patent/DE102018104830A1/de active Pending
• 2019
  • 2019-02-26 WO PCT/EP2019/054752 patent/WO2019166441A1/de unknown
  • 2019-02-26 CN CN201980029652.9A patent/CN112236386A/zh active Pending
  • 2019-02-26 EP EP19708084.9A patent/EP3759046A1/de active Pending
  • 2019-02-26 US US16/977,544 patent/US20210003257A1/en active Pending
  • 2019-02-26 JP JP2020545694A patent/JP2021515158A/ja active Pending

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