WO2015169815A1

WO2015169815A1 - Hydrogen-storing component from a melt

Info

Publication number: WO2015169815A1
Application number: PCT/EP2015/059882
Authority: WO
Inventors: Antonio Casellas; Klaus Dollmeier; Eberhard Ernst
Original assignee: Gkn Sinter Metals Engineering Gmbh
Priority date: 2014-05-05
Filing date: 2015-05-05
Publication date: 2015-11-12
Also published as: DE102014006376A1

Abstract

The invention relates to a strip-shaped, metal-containing, preferably metal form of a component of a hydrogen store, wherein the form assumes one of the following primary functions in the hydrogen store: thermal conduction, gas feed-through, insulation, and/or hydrogen storage, wherein the strip-shaped, metal-containing, preferably metal form is rolled. The invention further relates to a method for production and to a device for production.

Description

Hydrogen-storing component from a melt

The present invention relates to a hydrogen storage component, a method for manufacturing as well as an apparatus for producing such a component.

Hydrogen stores are often made from powder materials. But the powder has its peculiarities, since it can be distributed loosely in the hydrogen storage, especially according to its particle size distribution segregation in the use of the hydrogen storage by hydrogenation and dehydrogenation together with associated volume change undergoes.

Object of the present invention is to provide a better fixable hydrogenatable component of a hydrogen storage.

This object is achieved with a band-shaped, metal-containing, preferably metal form of a component of a hydrogen storage with the features of claim 1, a method for producing a hydrogen storage component of a hydrogen storage by creating the band-shaped, metal-containing, hydrogenatable shape with the features of claim 14 and with a Device solved with the features of claim 21. Advantageous features, embodiments and further developments will become apparent from the following description, the figures as well as from the claims, wherein individual features of an embodiment are not limited to these. Rather, one or more features of one embodiment can be linked to one or more features of another embodiment to form further embodiments. Also, the formulations of independent claims 1, 14 and 21 in their filed form serve only as a first draft of the formulations of the claimed subject-matter. One or more features of the formulations can therefore be exchanged as well as omitted, but also be supplemented in addition. The features cited with reference to a specific exemplary embodiment can also be generalized or likewise used in other exemplary embodiments, in particular applications.

It becomes a band-shaped, metal-containing, preferably metal, shape of a component of a hydrogen storage device, wherein the shape performs at least one of the following primary functions in the hydrogen storage: heat conduction, insulation, gas transmission. leadership and / or hydrogen storage, wherein the band-shaped, metal-containing, preferably metallic shape is rolled.

By means of rolling, it is possible, on the one hand, preferably to achieve a three-dimensional design of the shape, ie in the sense of the invention, that the shape has received a change in shape, in particular a change in shape by means of calendering. Thus, preferably a change in thickness, for example, but also a surface change is produced by means of calendering. Also, by means of calendering, a lamination or joining of different materials can take place, which are used together in the hydrogen storage. The calendering in particular allows, for example, pourable materials such as powder, particles, fibers or the like can be pressed into another material and fixed. For example, a semifinished product can be used as preform, for example a sheet-like material. However, calendering also makes it possible to combine pourable materials which are fed to the calender as poured layers. For this purpose, for example, a binder material miteingesetzt be used to connect the pourable material together and to fix. The binding material may remain in the form in the hydrogen storage or else be later removed from the mold, for example by means of solvents, heating and evaporation or by burnout. For example, a polymer can be used as a binder. The binder may also be supplied as a pourable material, for example in the form of particles, fibers or other geometries, or be present as a semi-finished product, for example as a film material, as a layer or in rod form. In addition to impressing a pressure in the adjustable calender nip, at least one calender roll, preferably at least two adjacent calender rolls, which form a common calender nip, can preferably be tempered. An embodiment provides that both calender rolls to an equal temperature or an approximately equal temperature range, which preferably has + -5 ° deviation up and down around a temperature center has. Also, a different temperature can be present. Thus, one roll can be tempered to a temperature above 100 ° C and the other roll to a temperature below 100 ° C. It is also possible that at least one roller of the calender is cooled, for example, to keep a temperature difference permanently. By means of tempering, it is possible, for example, to heat the binder at least to the extent that it at least softens or has an adhesive property. Thus, the binder can be used to achieve a caking, allowing a stable shape formation in the calender. Also The binder can be melted to form one for molding

Calender gap to create adaptable shape or to fix materials together. The calender can in particular have a temperature control in the form of a cooling, if it is fed to a preform, which itself already has a sufficiently high temperature to allow calendering the desired shape. The calender itself can not only have a calender nip but also a plurality of calender nips arranged one behind the other and also arranged parallel to one another. So more than two calender rolls can be used. Also, several calenders can be arranged one behind the other to achieve the desired shape. The calender can have at least one smooth roller, for example two smooth rollers, which form a calender gap opposite one another. The calender may additionally or alternatively alternatively have at least one roller with a surface profile, by means of which, for example, a profiling, perforation, or other additional geometry creation is possible. Thus, for example by means of a channel formation, a corrugation and / or a perforation, a gas guide, a gas permeability, in particular a gas feedthrough be created.

Using a calender also allows one or more pre-made films to be calendered together. The band-shaped metal-containing shape may be formed, for example, by various films calendered together. Also, other preforms may be calendered together with one or more films to provide the proposed shape. For example, a graphite foil can be used, an aluminum foil and / or foils of other materials. The film is, for example, pre-rolled. For example, a graphite foil may be used as an insulator over another material, for example between aluminum and a magnesium material to prevent poisoning, as well as a heat conductor.

Furthermore, there is the possibility that calendering takes place under protective gas. For this purpose, the calender can have one or more inert gas feeds. As a result, it is possible, for example, to prevent oxidation of a surface, in particular of a hydrogen-storing material, which would either still have to be calendered or is being calendered or calendered. Preferably, the band-shaped, metal-containing, preferably metal shape is arranged in a hydrogen storage in which the band-shaped, metal-containing shape is installed. The band-shaped, metal-containing shape has a height extent, wherein along at least one side of the band-shaped metal-containing shape, a top or bottom, a functional layer of the hydrogen storage directly connected, wherein the functional layer having a different primary function than the band-shaped, metal-containing shape is provided for the hydrogen storage, wherein the primary function is selected from the group comprising a heat conduction, a gas feedthrough, an insulation and / or a hydrogen storage. The vertical extent preferably results exclusively from the deformation in the calender. However, a subsequent additional processing in terms of achieving a vertical extent is not excluded. The height extent of the band-shaped, metal-containing shape results for example from the fact that the band-shaped metal-containing shape is rolled into a tortuous shape, wherein the winding shape is preferably helical, helical and / or wavy. The height extension is therefore to be understood as an extension in the height or depth, which adjusts to a flat, planar material.

An embodiment provides that the band-shaped metal-containing shape has a powder material which is rolled into the continuous, band-shaped, three-dimensional shape. The powder can consist entirely of particles. However, fibers or other geometries may also be contained in the powder. The powder may contain a mixture of different materials, for example a mixture of different powders. There is also the possibility that the powder has only one material, for example an alloy.

Furthermore, it can be provided that the band-shaped, metal-containing shape is such that the powder material is rolled into a band-shaped preform of the band-shaped, metal-containing shape, wherein preferably the powder material forms a layer along the band-shaped metal-containing shape. The layer may be closed or broken. Preferably, the layer is fluid-permeable, in particular so porous that a fluid can flow through. But it can also be created a fluid-impermeable layer. It is preferably provided that the powder material forms a heat conductor on a surface of the band-shaped metal-containing shape.

A further development provides that several layers are rolled, wherein preferably at least one layer is arranged as an insulation layer between two materials of the band-shaped, metal-containing shape, one of the two materials preferably being a high-temperature hydrogen-storing material, in particular a high-temperature hydride, preferably one Layer comprising graphite forms an insulating layer between the high-temperature hydride, in particular a magnesium material as a hydrogen storage and an aluminum material as a heat conductor.

An additional development provides that the band-shaped, metal-containing shape has an additional surface structuring in addition to a shape to the shape that has been introduced when rolling in the surface of the band-shaped, metal shape.

Preferably, the band-shaped, metal-containing shape has a hydrogenatable metal, which preferably has undergone storage of hydrogen prior to rolling. However, the metal may also be late, i. be hydrogenated after installation in the heat storage.

A further embodiment further provides that the band-shaped, metal-containing shape of powder material is rolled. It may be wholly or even partially rolled from one or more powder materials.

Alternatively, as in addition, the band-shaped, metal-containing shape may comprise a prefabricated band-shaped material, preferably a metal material, which has been rolled into the shape. For example, a film, a foil, a metal sheet, a rod or other semi-finished product can be used.

A further development provides that the band-shaped, metal-containing shape as described above and also described below comprises a polymer material with hydrogen-storing metal contained in the polymer. The hydrogen storage material may be present as particles, fiber or the like. The polymer may form a matrix for preferably the hydrogenatable material, the matrix being deformed by calendering. In addition to the at least one polymer, 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. Preferably, the matrix comprises only one polymer. In particular, the matrix itself may be hydrogen storage. For example, ethylene (polyethylene, PE) can be used. Preferably, a titanium-ethylene compound is used. This can, according to a preferred embodiment, store up to 14% by weight of hydrogen.

The term polymer describes a chemical compound of chain or branched molecules, so-called macromolecules, which in turn consist of identical or similar units, the so-called constitutional repeating units or repeating units. Synthetic polymers are usually plastics.

By using at least one polymer, good optical, mechanical, thermal and / or chemical properties can be assigned to the material by the matrix. For example, 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. 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.

In the invention, 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. For example, according to the invention, the polymer may also comprise a terpolymer. The polymer (homopolymer) preferably has a monomer unit which, in addition to carbon and hydrogen, furthermore preferably has at least one heteroatom selected from among sulfur, oxygen, nitrogen and phosphorus, so that the polymer obtained in the For example, polyethylene is not completely non-polar. Also, at least one halogen atom selected from chlorine, bromine, fluorine, iodine and astatine may be present. Preferably, 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, fluorine , Iodine and astatine, is present. It is possible that two or more monomer units have a corresponding heteroatom and / or halogen atom. The polymer preferably has adhesive properties with respect to the hydrogen storage material. This means that it adheres well to the hydrogen storage material itself and thus forms a matrix which stably adheres to the hydrogen storage material even under conditions such as occur 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. In particular, 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 that there are no segregation effects during the cycles in which finer particles separate and remove coarser particles.

The hydrogen storage material of the present invention is particularly a low-temperature hydrogen storage material. In the hydrogen storage, which is an exothermic process, therefore, 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 decomposes not up to a temperature of 180 ° C, in particular up to a temperature of 165 ° C, in particular up to 145 ° C.

In particular, 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. Preferably, the density of the polymer, determined according to ISO 1 183 at 20 ° C, 0.7 g / cm ³ or more, in particular 0.8 g / cm ³ or more, preferably 0.9 g / cm ³ or more maximum 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. Surprisingly, it has been found that polymers with these mechanical properties are particularly stable and easy to process. In particular, they allow stable cohesion between the matrix and the hydrogenatable material embedded therein so that the hydrogenatable material remains in the same position within the hydrogen storage for many cycles for a long time. This allows a long life of the hydrogen storage.

For the purposes of the present invention, the polymer is selected from EVA, PMMA, EEAMA and mixtures of these polymers. EVA (ethyl vinyl acetate) refers to a group of copolymers of ethylene and vinyl acetate which have a vinyl acetate content in the range of 2% to 50% by weight. Lower levels of vinyl acetate result in the formation of hard films, while higher levels result in greater polymer adhesiveness. Typical EVA are solid at room temperature and have a tensile elongation of up to 750%. In addition, EVA are stress cracking resistant. EVA has the following general formula (I):

(Formula (I))

For the purposes of the present invention, EVA preferably has a density of 0.9 g / cm ³ to 1.0 g / cm ³ (according to ISO 1 183). 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%. In this case, 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 sold for example by the company axalta Coating Systems LLC under the trade name Coathylene ^® CB 3547th Polymethyl methacrylate (PMMA) is a synthetic, transparent, thermoplastic material having the following general structural formula (II):

(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 1 10 ° C. The thermoplastic copolymer is characterized by its resistance to weathering, light and UV radiation.

For the purposes of the present invention, PMMA preferably has a density of 0.9 to 1.5 g / cm ³ (according to ISO 1 183), in particular from 1.0 g / cm ³ to 1.25 g / cm ³ . Especially 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 less exhibit. The elongation at break (according to ISO 527) is in particular <10%, especially <8%, preferably <5%. In this case, 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 EEAMA for example, offered by the company Ter Hell Plastics GmbH, Bochum, Germany, under the trade name 7M Plexiglas ^® granulate 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 281 1) 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.

Preferably, 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. Even though the matrix is capable of storing hydrogen, the hydrogen storage capacity is nevertheless not as pronounced as that of the hydrogen storage material itself. However, the matrix is necessary in order to minimize or completely avoid any possible oxidation of the hydrogen storage material and to ensure a cohesion between the particles of the material.

It is preferable that 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 extensibility 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 German: "preimpregnated fibers". "prepregs" are polymer preformed semi-finished products which are cured under temperature and pressure to produce components suitable polymers are those having a high viscosity but not polymerized thermoset plastic matrix Invention preferred polymers 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. According to the invention, the prepregs can also be comminuted and processed as flakes or chips together with the hydrogenatable material to form a composite material.

According to the invention, 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, resulting in the formation of the matrix in which the hydrogenatable material is embedded. If the polymer is used in the form of particles, that is to say as granules, these preferably have an x ₅₀ particle size (volume-based particle size) in the range from 30 μm to 60 μm, in particular from 40 μm to 45 μm. The x ₉₀ particle size is in particular 90 μηι or less, preferably 80 μηι or less.

The hydrogenatable material can take up the hydrogen and release it again when needed. In a preferred embodiment, the material comprises particulate materials in any 3-dimensional configuration, such as particles, granules, fibers, preferably cut fibers, flakes and / or other geometries. In particular, the material may also be formed plate-shaped or powdery. 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. According to the invention, a hydrogen storage may be the material in only one specific 3-dimensional configuration have, so that all particles of the material have the same spatial extent. However, it is also possible that a hydrogen storage comprises the material in different configurations / geometries. By a variety of different geometries or configurations of the material, the material can be used in a variety of different hydrogen storage.

Preferably, 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. By using a hollow fiber, several hollow fibers can be combined to form a hollow fiber membrane, whereby absorption and / or release of the hydrogen from the material can be facilitated due to the high porosity. 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. According to the invention, the hydrogenatable material may comprise at least one hydrogenatable metal and / or at least one hydrogenatable metal alloy, preferably consisting thereof.

As hydrogenatable materials can also be used:

- alkaline earth metal and alkali metal alanates,

Alkaline earth metal and alkali metal borohydrides,

- Metal-Organic-Frameworks (MOF's) / Metal-Organic Frameworks, and / or

clathrates,

as well as of course respective combinations of the respective materials.

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 store hydrogen at a temperature Temperature range between -55 ° C to 180 ° C, especially 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 temperatures mentioned, the hydrides can not only supply hydrogen but also give off, ie they are able to function in these temperature ranges.

If "hydrides" are described in this context, this is to be understood as meaning the hydrogenatable material in its hydrogenated form as well as in its non-hydrogenated form. Hydrogenatable materials in their hydrogenated or nonhydrogenated form can be used according to the invention in the production of hydrogen storages.

With regard to hydrides and their properties, reference is made to Tables 1 to 4 in S. Sakietuna et al, International Journal of Energy, 32 (2007), pp. 1 121-1 140 within the scope of the disclosure.

The hydrogen storage (hydrogenation) can take place at room temperature. The hydrogenation is an exothermic reaction. The resulting heat of reaction can be dissipated. In contrast, energy must be supplied to the hydride in the form of heat for dehydration. Dehydration is an endothermic reaction.

For example, it can be provided that a low-temperature hydride is used together with a high-temperature hydride. Thus, according to one embodiment, it can be provided that, for example, 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. For example, it may be provided that 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. There is also the possibility that different first regions have either a low-temperature hydride or a high-temperature hydride.

Preferably, 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. Particularly preferably, the hydrogenatable material (hydrogen storage material) comprises at least one metal alloy capable of at a temperature of 150 ° C or less, in particular in a temperature range of - 20 ° C to 140 ° C, in particular from 0 ° C to 100 ° C. is 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. In this case, A and B denote each other different metals, 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. The alloys according to the invention may be doped with foreign atoms. The degree of doping can according to the invention up to atom%, 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 up 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. The doping can take place with one or more different foreign atoms. 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. By way of example, mention may be made here of FeTi as the AB-type alloy, TiMn ₂ as the AB ₂ -type alloy, and LaNi ₅ as the AB ₅ -type alloy.

Particularly preferably, 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 (hydrogen storage material) is preferably present in particulate form (particles, particles). The particles have in particular a particle size x ₅₀ of 20 μηι to 700 μηι, preferably from 25μηι to 500 μηι, especially from 30μηι to 400 μηι, in particular from 50 μηι to 300 μηι on. In this case, x50 means that 50% of the particles have an average particle size that is equal to or less than the stated value. The particle size was determined by means of 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 to hydrogenation for the first time. 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.

Preferably, the hydrogenatable material is so firmly integrated in the matrix that it comminutes upon storage of 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. The matrix of polymer material was able to hold the thus broken up paticles stable stationary.

Incidentally, tests have shown that, when a binder, in particular an adhesive binder, is used in the matrix for fixing these particles, a particularly good stationary positioning within the matrix is made possible. A binder content may preferably be between 2% and 3% by volume of the matrix volume.

Preferably, 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 x50 particle size at the beginning and after 100 times of storage.

Surprisingly, it has been found that materials of this size show particularly good properties in hydrogen storage. When storing and dispensing Hydrogen causes an elongation (in the hydrogenation) or shrinkage (in the dehydrogenation) of the material. This volume change can be up to 30%. As a result, mechanical stresses occur on the particles of the hydrogenatable material, ie on the hydrogen storage material. Repeated loading and unloading (hydrogenation and dehydrogenation) with hydrogen has been shown to break the particles. If the hydrogenatable material now has, in particular, a particle size of less than 50 μm, in particular less than 30 μm and in particular less than 25 μm, a finer powder may form during use which may no longer be able to store hydrogen effectively. In addition, the distribution of the material in the hydrogen storage itself may change. Beds containing particles of material of very small diameters of a few nanometers can collect at the lowest point of the hydrogen storage. When charged with hydrogen (hydrogenation), high mechanical stresses occur on the walls of the hydrogen storage at this point due to the expansion of the hydrogen storage material. By choosing suitable particle sizes for the material, this can be at least partially avoided. On the other hand, a smaller particle size results in a larger number of contact points at which the particles interact with the matrix and adhere to it, resulting in improved stability, which is the case for particles with a size of more than 700 μm. in particular of more than 500 μηι can not be achieved.

According to a further aspect of the invention, which may be used independently as well as with the other embodiments of the invention, a method for producing a hydrogen storage component of a hydrogen storage by means of creating the band-shaped, metal-containing, hydrogenatable shape is proposed with the following steps:

a. Creating a preform of the band-shaped, metal-containing, hydrogenatable shape,

b. Rolling the preform into a band-shaped, metal-containing, hydrogenatable form, wherein the preform undergoes a three-dimensional design to the band-shaped, metal-containing, hydrogenatable shape, preferably in a helix or screw shape, as a wound roll, as a folded and / or superimposed one documents,

c. Inserting the band-shaped, metal-containing, hydrogenatable shape as a component or part thereof into a hydrogen storage.

A further development provides that the production includes the following steps: a) producing a liquid melt comprising the hydrogenatable metal, b) preparing a preform for the component, preferably a layer, from the liquid phase.

It is further provided that the liquid melt is a polymer melt in which the hydrogenatable metal is located.

It is preferable that the preform is rolled by means of a calender so that the rolled shape peeled off the calender is bent to the three-dimensional shape. An exemplary embodiment provides, for example, that the preform is guided by a calender comprising at least two rolls, wherein the two rolls have different roll speeds and / or different roll shapes in the calender nip, and the component thereby obtains an unequal stretch, which leads to a bending of the component , preferably for generating a helical geomerism.

A further embodiment provides that the production proceeds as an in-line process, wherein the preform is guided and pressed by the calender comprising at least two rolls, preferably for reducing a thickness of the component and / or for producing a structure, preferably a profiling on the surface during rolling, in particular a microstructure on the surface.

The method may further provide that the preform is rolled together with a second material, preferably wherein the second material will primarily perform a thermally conductive function in the hydrogen storage. However, the material may also have another primary function alternatively as well as in addition. Thus, for example, a material can be used on the one hand thermally conductive as on the other hand, gas permeable. Another possibility is that the material is used thermally conductive but also insulating, for example, a graphite material arranged between a high-temperature hydrogen storage material and aluminum. According to a further aspect of the invention, which can be used independently as well as with the other embodiments of the invention, a device for producing a hydrogen storage component comprising a band-shaped, metal-containing, hydrogenatable shape with a three-dimensional design is proposed, wherein the device Calender, which brings the band-shaped, metal-containing, hydrogenatable shape in a three-dimensional design, preferably in a helical or helical shape, as a wound roll, as a folded and / or adjacent layer. A further embodiment provides that the calender has different rollers, by means of which the three-dimensional design can be achieved. It is preferably provided that the calender has a control unit by means of which different rollers of the calender can be operated with mutually different speeds. It can also be provided that at least one further feed for an additional material is provided for the common calendering of the preform of the band-shaped, metal-containing, hydrogenatable shape and the additional material. It is further preferred that a powder bed is arranged in front of the calender for feeding a pourable material, in particular for producing the preform to be calendered the band-shaped, metal-containing, hydrogenatable design. Alternatively, as well as in addition, a semifinished product, in particular a film feed to the calender, may be provided,

A further embodiment provides that a cooled roller is provided, on which the hydrogenatable, to be calendered metal is deposited before the calender from a melt.

A method for producing a hydrogen-storing component of a hydrogen storage unit is furthermore proposed with the following steps: a) producing a liquid melt comprising a hydrogenatable metal, b) preparing a component, preferably a layer, from the liquid phase, c) inserting the component, in particular capable of storing in a hydrogen storage. Furthermore, the liquid melt is produced as a metallic alloy with a molten, hydrogenatable metal, preferably under protective gas. The term hydrogen storage describes a reservoir in which hydrogen can be stored. In this case, conventional methods for storing and storing hydrogen can be used, for example compressed gas storage, such as storage in pressure vessels by compression with compressors or liquefied natural gas storage, such as storage in liquefied form by cooling and compression. Other alternative forms of storage of hydrogen are based on solids or liquids, such as metal hydride storage, such as storage as a chemical link between hydrogen and a metal or alloy, or adsorption storage, such as adsorbed storage of hydrogen in highly porous materials. Furthermore, hydrogen storage is also possible for storage and transport of hydrogen, which temporarily bind the hydrogen to organic substances, whereby liquid, pressure-less storable compounds arise, so-called "chemically bonded hydrogen". According to one embodiment, the component is subjected to a rapid cooling, preferably the liquid phase is guided as a layer on a cooled surface, preferably for producing a nanocrystalline structure of the component.

Furthermore, it can be provided that the component is connected to a second material, wherein the second material will perform a heat-conducting function in the hydrogen storage.

There is also the possibility that the component receives a profiling on the surface during the manufacturing process.

A development provides that the production proceeds as an in-line process, wherein the component is guided and pressed by a calender having at least two rollers, preferably for reducing a thickness of the component and / or for producing a structure, in particular one Microstructure on the surface.

It can also be provided that the component is guided by a calender having at least two rollers, wherein the two rollers have different roller speeds in the calendering gap, and the component thereby receives an uneven stretching, which leads to a bending of the component, preferably for generating a helical Geomerie. It is also possible that the component is further processed into a film layer, which is connected to a thermally conductive film and inserted into a container of the hydrogen storage. A further embodiment provides that the component has a coating, in particular an electrochemical coating.

Furthermore, it can be provided that a laminate with the hydrogenatable metal is prepared from the liquid phase, wherein the laminate is deposited in a helical or helical form, in a wound roll, as folded or superimposed layers.

According to a further aspect of the invention, an apparatus for producing a hydrogen storage component of a hydrogen storage is proposed, wherein a container is provided for receiving a liquid melt containing hydrogenatable metal, with a protective gas to cover the liquid melt with inert gas to prevent oxidation of the melt, with an opening through which the liquid melt exits, with a tray on which the liquid melt is applied, and with a further processing unit, which is in connection with a storage unit.

Preferably, the melt flows out of the opening under protective gas.

A development provides that the tray is a cooled roller, which is located directly below the opening. But other shelves, and refrigerated shelves are possible.

A further embodiment provides that the further processing unit has a calender for reducing the thickness and / or surface structuring of the gas line.

Furthermore, it is provided, for example, that a laminate station is provided, by means of which a supplied layer is connected to the hydrogenatable metal.

According to a further aspect of the invention, a component is proposed as described above, and a laminate, preferably produced by a method according to one of claims 14 to 20, in particular preferably produced by a device according to one of claims 21 to 26, comprising at least one first location with a hydrogenatable metal and a second layer with a thermally conductive material, wherein the laminate is used in a hydrogen storage.

A development of the laminate provides that at least the first layer of the laminate has a surface profiling.

Furthermore, it can be provided that the laminate is arranged in a container of a hydrogen storage, wherein the laminate forms the hydrogen storage at least partially.

A further embodiment provides that the laminate is arranged helically in the container, in a wound structure and / or stacked on top of one another.

It can also be provided that the hydrogen storage 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 is a hydrogen-storing material exhibit. For example, this is preferably provided in the layers of the composite material. An embodiment provides that the second material of the shell comprises a polymer, which is at least designed hydrogen-permeable. A further embodiment provides that the core has a heat-conducting material and the jacket 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.

Furthermore, a surface treatment of the component can be provided, of hydrogen-storing materials preferably metallic materials by degreasing, cleaning and "pickling" or targeted chemical attack for later facilitated activation, or what should be avoided in most cases, aside from the hydrogen storage, but here the aim is already to introduce hydrogen into the metal surface by pickling.

Furthermore, any type of heat treatment, if possible integrated into the production process, can be provided, for example formation of intermetallic phases, crystallite or grain coarsening, recrystallization of amorphous regions. Further advantageous embodiments as well as features will become apparent from the following figures and the associated description. The resulting from the figures and the description of individual features and embodiments are exemplary only and not limited to the particular embodiment. Rather, from one or more figures, one or more features may be combined with other features from the above description to form further embodiments. In particular, the features are not limiting but exemplified. Show it:

1 shows an exemplary production device with a calender,

Fig. 2 is a closer view of the shape design, and

Fig. 3 shows an exemplary embodiment with respect to an insertion of a helical / helical shape in a hydrogen storage.

Fig. 1 shows an exemplary embodiment in which by means of a calender 1, a band-shaped, metal-containing shape 2 can be produced. For example, a starting material can be melted via a melting device 3. Here, the melt may comprise a metal, in particular a hydrogenatable metal or metal alloy, a material mixture of solid and liquid material such as a polymer and a metal or the like. The melt can be placed on a tray 4 under a protective gas atmosphere or under atmospheric conditions, for example. Here, for example, the tray is a cooled roller, for example, with a copper surface forming a copper wheel. The material, for example a rapidly solidified metal, in particular a strip, preferably a metallic strip of Mg, can then be further treated in an in-line process. The melting device 3 can also deposit the molten material on a depositing belt, from which further processing takes place. The calender 2, the preform 5 thus prepared can be supplied. There is also the possibility that one or more additional materials are additionally supplied to the calender 1, which are then calendered together. There is the possibility that, for example, calendering also removes a surface layer, in particular an oxidation layer, for example by chipping off. In particular, a shaping takes place in a desired shape. Various shapes are given by way of example, such as a helix / screw structure 2.1, a roller structure 2.2 or schematically indicated a folded / stacked structure 2.3. In the case of calendering, it is in particular also possible to carry out surface treatment by chemical means. Thus, for example, pickling of the surface can take place, a surface treatment by means of acid or another means. Furthermore, FIG. 1 shows an exemplary embodiment of a further processing. This can be done, for example, in a housing 6 under a protective gas atmosphere. The shielding gas is preferably inert, but it may also be hydrogen, which is used as a protective gas against oxidation. The calendering preferably also takes place under protective gas. For this purpose, the calender 1 may also be housed. The calendering may be followed, for example, by a further calendering step, for example, if only a surface treatment is carried out during the first calendering, whereas a final shape is not already produced. Thus, for example, from the first calender 1 and a flat material can be deducted, which is then connected only with another material by means of another calender. Thus, for example, a roll, in particular a film or a film, can be rolled up and fed to the preform from a roll illustrated by way of example. This may, for example, be a graphite foil, a coated aluminum foil, for example anodized or else. For example, the film may be perforated or perforated. After the calendering, not shown in detail, and thus preferably further shaping to the final shape, the shape is introduced, for example, directly into a container 7. The container 7 can be closed, for example with inert gas. Also, this can be filled with hydrogen and then sealed. The container 7 is preferably used later as a hydrogen storage, when the necessary lines have been connected to it.

Fig. 2 shows an example in a schematic view of a sequence, as the desired shape 2 can be created by means of rollers. A flat metal foil 8, for example coming from a belt or a roller, is formed via the roller device 9 into structured or plane, helical / helical structures. As shown, the roller device 8 may have, for example, an angle between the rollers, version A), or the helical / helical shape is created by means of conical rollers, cf. Version B). If a roller has a surface profiling, for example by height and depth profiles, by needling, punching or the like, this can be impressed in addition to the helical / helical design. This is indicated by the different metal foil cross sections 10.1, 10.2, 10.3 and 10.4. A metal foil cross section 10.5, however, has no additional imprint and is therefore flat. Fig. 3 shows a schematic view of an exemplary embodiment of how a shape 2 with a helical / helical structure in a container 7 can be inserted as a later hydrogen storage. The figure 2 can be further processed or as herge represents in the form of one or more components 1 1 are introduced into the container. In the container 7, for example, a porous tube 12 is arranged centrally through which hydrogen can flow in or out. For example, the shape 2 may comprise a primary heat-conductive material such as aluminum, abbreviated to Al, and a high-temperature hydride material, for example Mg. Both are preferably materially isolated from each other, for example by a graphite layer. The component 11 is preferably inserted into the container 7 such that a direct contact between a container wall 13 with the primary heat-conducting material 14 is ensured. For this purpose, as indicated, the primary heat-conducting material before insertion at the edge of the container

7stand and bend over when inserting and thus produce the direct wall contact also over a larger area. The same is also possible on the porous tube or other geometry in the interior of the container 7, for example, for improved heat transfer as well as for stabilization of the component 1 1 in the container. 7

Claims

Expectations

1. Band-shaped, metal-containing, preferably metal shape of a component of a hydrogen storage, the shape performing at least one of the following primary functions in the hydrogen storage: heat conduction, gas passage, insulation and / or hydrogen storage, the band-shaped, metal-containing, preferably metal shape being rolled .

2. Band-shaped, metal-containing, preferably metal shape according to claim 1, with a hydrogen storage in which the band-shaped, metal-containing shape is installed, characterized in that the band-shaped, metal-containing shape has a height extension, being along at least one side of the band-shaped, metal-containing Shape, a top or bottom, a functional layer of the hydrogen storage directly adjoins, the functional layer being provided with a different primary function than the band-shaped, metal-containing shape for the hydrogen storage, the primary function from the group comprising a heat conduction, a gas duct, insulation and/or hydrogen storage is selected.

3. Band-shaped, metal-containing shape according to claim 1 or 2, characterized in that the band-shaped metal-containing shape is rolled into a winding shape, the winding shape preferably being helical, snail-shaped and/or wave-shaped

4. Band-shaped, metal-containing shape according to one of the preceding claims, characterized in that the band-shaped metal-containing shape has a powder material which is rolled into the coherent, band-shaped, three-dimensional shape.

5. Band-shaped, metal-containing shape according to claim 4, characterized in that the powder material is rolled into a band-shaped preform of the band-shaped, metal-containing shape, the powder material preferably forming a layer along the band-shaped metal-containing shape.

6. Band-shaped, metal-containing shape according to claim 4 or 5, characterized in that the powder material forms at least one heat conductor on a surface of the band-shaped metal-containing shape.

7. Band-shaped, metal-containing shape according to one of claims 4, 5 or 6, characterized in that several layers are rolled in, preferably at least one layer being arranged as an insulating layer between two materials of the band-shaped, metal-containing shape, one of the two materials preferably being one High-temperature hydrogen-storing material, in particular a high-temperature hydride, preferably a layer comprising graphite forms an insulating layer between the high-temperature hydride, in particular a magnesium material as a hydrogen storage and an aluminum material as a heat conductor.

8. Band-shaped, metal-containing shape according to one of the preceding claims, characterized in that the band-shaped, metal-containing shape has an additional surface structuring in addition to a shape to the shape that was introduced into the surface of the band-shaped, metal shape during rolling.

9. Band-shaped, metal-containing shape according to one of the preceding claims, characterized in that the band-shaped, metal-containing shape has a hydrogenatable metal, which has preferably undergone storage of hydrogen before rolling.

10. Band-shaped, metal-containing shape according to one of the preceding claims, characterized in that the band-shaped, metal-containing shape is rolled from powder material.

1 1 . Band-shaped, metal-containing shape according to one of the preceding claims 1 to 9, characterized in that the band-shaped, metal-containing shape has a prefabricated band-shaped material, preferably a metal material, which has been rolled into the shape.

12. Band-shaped, metal-containing shape according to one of the preceding claims, characterized in that the band-shaped, metal-containing material comprises a polymer material with hydrogen-storing metal contained in the polymer.

13. Band-shaped, metal-containing shape according to one of the preceding claims, characterized in that a surface of the shape or a preform of the Shape has been subjected to an additional surface treatment, preferably pickling and / or a coating.

14. Process for producing a hydrogen-storing component of a hydrogen storage by creating the band-shaped, metal-containing, hydrogenable

Shape according to one of claims 1 to 13 with the following steps:

b. Rolling the preform into a band-shaped, metal-containing, hydrogenatable shape, the preform undergoing a three-dimensional design into a band-shaped, metal-containing, hydrogenatable shape, preferably in a helix or screw shape, as a wound roll, as a folded roll and/or lying one on top of the other layers,

c. Insertion of the band-shaped, metal-containing, hydrogenatable form as a component or part thereof in a hydrogen storage.

15. The method according to claim 14, characterized in that the production includes the following steps: a) producing a liquid melt comprising the hydrogenatable metal, b) creating a preform for the component, preferably a layer, from the liquid phase.

16. The method according to claim 14 or 15, characterized in that the liquid

Melt is a polymer melt in which the hydrogenatable metal is located.

17. The method according to claim 14, 15 or 16, characterized in that the preform is rolled by means of a calender in such a way that the rolled shape withdrawn from the calender is bent to form a three-dimensional design.

18. The method according to any one of the preceding claims, characterized in that the preform is guided through a calender having at least two rolls, the two rolls having different roll speeds and / or different roll shapes in the calender gap, and the

Component thereby receives an unequal stretching, which leads to bending of the component, preferably to create a helical geometry.

19. The method according to claim 18, characterized in that the production takes place as an in-line process, wherein the preform is guided and pressed through the calender having at least two rollers, preferably to reduce a thickness of the component and / or to create a structure , preferably a profiling on the surface during rolling, in particular a microstructure on the surface.

20. The method according to any one of the preceding claims, characterized in that the preform is rolled together with a second material, wherein preferably the second material will primarily perform a heat-conducting function in the hydrogen storage.

21. Device for producing a hydrogen-storing component having a band-shaped, metal-containing, hydrogenatable shape according to one of claims 1 to 13 with a three-dimensional design, the device comprising a calender which brings the band-shaped, metal-containing, hydrogenatable shape into a three-dimensional shape, preferably into a Helix or screw shape, as a wound roll, as a folded and/or stacked layer.

22. The device according to claim 21, characterized in that the calender has different rollers by means of which the three-dimensional design can be achieved

23. Device according to claim 21 or 22, characterized in that the calender has a control device by means of which different rollers of the calender can be operated at different speeds.

24. The device according to claim 21, 22 or 23, characterized in that at least one further feed for an additional material is provided for joint calendering of the preform of the band-shaped, metal-containing, hydrogenatable shape and the additional material.

25. Device according to one of the preceding claims, characterized in that a powder bed is arranged in front of the calender for supplying a pourable material, in particular for producing the preform to be calendered of the band-shaped, metal-containing, hydrogenatable design.

26. Device according to one of the preceding claims 21 to 25, characterized in that a cooled roller is provided, onto which the hydrogenatable metal to be calendered is deposited from a melt in front of the calender.