DE102012221417A1 - Tubular metal air cell e.g. high temperature combined metal air electrolysis fuel cell, for e.g. photovoltaic plant, has storage electrode layer with oxidizable and reducible material reversible between metallic form and oxidic form - Google Patents

Abstract

The cell (10) has a functional layer system comprising an electrolyte layer formed between an air electrode layer (12) and a storage electrode layer (13). The storage electrode layer has an oxidizable and reducible material (131) reversible between a metallic form and an oxidic form. A tubular support structure (11) has a portion (111) made of gastight, oxygen ion-conductive material, which serves as the electrolyte layer of the layer system or a portion made a gas-permeable porous ceramic material, on which an outer side or an inner side the layer system is applied. Independent claims are also included for the following: (1) a method for manufacturing a tubular metal air cell (2) a power system.

Description

The present invention relates to a tubular metal-air cell, a process for their preparation, their use and an energy system.

State of the art

Wind and solar energy have strong fluctuations due to weather changes and day-night changes. To be able to compensate for such fluctuations, there is a great interest in solutions for the conversion of electrical energy into a storable medium.

Excess energy, which can neither be consumed nor fed into the grid, can be transformed into a storable medium with the help of high-performance solid oxide electrolysis cells (SOEC) and so-called metal-air cells.

High-temperature electrolysis cells (SOEC) split carbon dioxide (CO ₂ ) and water (H ₂ O) into carbon monoxide (CO), hydrogen (H ₂ ) and oxygen (O ₂ ) according to the equation: CO ₂ + H ₂ O → CO + H ₂ + (O ₂ ). If required, carbon monoxide (CO) and hydrogen (H ₂ ) can then be converted back into electricity using a high-temperature fuel cell (SOFC, Solid Oxide Fuel Cell).

Another variant of a possible application is the storage of energy in a metal-air cell, in which a metal oxide is reduced to the metallic form for energy storage and re-oxidized for energy release.

According to the current state of the art, tubular electrochemical cells are produced by extruding or pressing one of their electrodes, for example their air electrode (anode) or their fuel gas electrode (cathode), as a tube, which in a complex subsequent process with the thin electrolyte and the thin counter electrode is coated. Due to the process, the tube must be made quite thick-walled, because the electrode material has only a low strength due to the high porosity.

When closed tubes are made, they are conventionally closed by extrusion after extrusion. This creates so-called weld lines at the closing points, which represent weak points in the operational thermo-mechanical stresses and have a limiting effect on the service life.

The current dissipation is usually realized in anode-supported cells by means of metallic interconnectors. In order to combine the material properties corrosion resistance and electrical conductivity, high-chromium materials are generally used for this purpose.

The fuel gas and air space must be separated from each other in a gas-tight manner, which is achieved by means of glass solders at the usual operating temperatures of 650-950 ° C. In planar concepts, the glass seal usually also takes over the electrical insulation between the cells.

Due to the oxygen storage in the metal storage electrode of a metal-air cell, there is a strong, based on an oxidation of the metal volume increase. As a result, the storage electrode is highly porous and brittle, so that the electrical connection over the life can not be guaranteed.

The pamphlets WO 01/80335 A3 describes a metal-air cell with a liquid metal-metal oxide anode.

Disclosure of the invention

The present cell relates to a tubular metal-air cell comprising a tubular support body and a storage electrode layer of a material, in particular solid, reversibly oxidizable and reducible between a metallic form and an oxidic form.

A tubular or tubular or hollow-cylindrical body or section may, in particular, be understood as meaning a substantially hollow-cylindrical body or body portion whose base or top surface / s may basically be substantially round, in particular circular or ovaloid (oval-shaped), as well as polygonal. In particular, a tubular or tubular or hollow-cylindrical body or section may have a circular base or cover surface / s. A tubular or tubular body may be open at one end and closed at the other end, as well as open at both ends.

A material reversibly oxidizable and reducible between a metallic form and an oxidic form can be understood in particular to mean a material which retains the given shape even after at least 25 redox cycles, for example at least 250 or 500 redox cycles.

The reversibility of the reversibly oxidizable and reducible material may in particular be based on a special microstructure, which can be achieved in particular by special production methods known to the person skilled in the art.

The storage electrode layer is in particular part of a, in particular sandwich-like, functional layer system comprising an air electrode layer, the storage electrode layer and an electrolyte layer formed between the air electrode layer and the storage electrode layer.

Under air can be understood in particular a gas containing oxygen. Therefore, the term air in addition to conventional atmospheric air, for example, with 21 vol .-% O ₂ , 78 and Vol .-% N ₂ , including pure oxygen and oxygen-containing gas mixtures, which have a different composition than conventional atmospheric air.

By virtue of the fact that the storage electrode comprises a reversibly oxidizable and reducible material, it is advantageously possible to effectively store electrical energy in the material, which is not possible with conventional electrode materials, for example fuel cells, since these already show degradation phenomena such as cracking and cracking after a few redox cycles Electrode material loss, for example in the form of blasting show. Surprisingly, however, it has been found that materials designed specifically for the reversible redox use, despite their special microstructure, are nevertheless suitable for effectively catalyzing a fuel cell reaction and / or an electrolysis reaction. This advantageously makes it possible to operate the metal-air cell not only as a metal-air cell but also as an electrolytic cell and / or fuel cell and, in particular, to combine all these functions in a combined metal-air-electrolysis fuel cell. A combined metal-air electrolysis fuel cell has the advantage of individually adjustable and flexible electrical energy either in the material of the storage electrode and / or chemically store by electrolysis reaction and also retrieve individually and flexibly again from the material of the storage electrode or by means of fuel cell reaction , This in turn makes it possible to intercept fluctuations in the power network much better and more precisely than is possible by means of an electrochemical cell designed only as a metal-air cell, only as an electrolysis cell or only as a fuel cell.

As a result of the fact that the storage electrode is designed in the form of a flat layer and, for example, is not represented by a compact volume, the storage electrode advantageously has a large surface area. This in turn has the advantage that the volume change of the material, when it changes between oxidized and reduced state, which can be about 30%, distributed over a large area, so that substantially local volume changes occur and in particular a deformation of the total material of the storage electrode at least significantly reduced or even avoided at a local volume change of the material. In addition, the electrical properties of the cell can be improved by a storage electrode in the form of a layer, since in this case the oxidizable and reducible material has a comparatively large interface to the electrolyte layer. In addition, the large surface has the advantage that the cell can also, in particular effectively, be operated as an electrolysis cell and / or fuel cell.

The fact that a solid oxidizable and reducible material is used, moreover, advantageously the handling of the metal-air cell, in particular compared with liquid materials, can be significantly improved.

In particular, two spaces, namely an interior of the tubular carrier body, can be spatially separated from one another by a space surrounding the outside of the tubular carrier body by the tubular carrier body. Since the storage electrode and the air electrode are layered, the interior of the tubular support body is advantageously not completely filled, so that, in particular in the central region of the tubular support body, a free space remains, which at least allows a gas supply to the interior and in particular additionally - in this respect the storage electrode layer is arranged in the interior of the tubular support body, the reversibly reducible and oxidizable material provides an expansion space in which the material can expand during the oxidation, without mechanically burdening the tubular support body or even destroy. One of the two spaces spatially separated from each other by the tubular support body can serve in particular as airspace and the other as expansion space. For the combined metal-air-electrolysis fuel cell operation, the expansion space can additionally be used as a gas space for the gas, hereinafter referred to as fuel gas, which is required in the electrolysis, for example water (H ₂ O) and / or carbon dioxide (CO ₂ ), or which arises during the electrolysis, for example hydrogen (H ₂ ) and / or carbon monoxide (CO), and / or which is required in the fuel cell reaction, for example hydrogen (H ₂ ) and / or carbon monoxide (CO), or which arises in the fuel cell reaction, for example water (H ₂ O) and / or carbon dioxide (CO ₂ ) serve. In particular, the interior of the tubular carrier body as Expansion space and optionally additionally serve as a gas space for the fuel gas.

In the context of one embodiment (electrolyte-supported concept), the tubular carrier body has a section of a gas-tight, oxygen-ion-conductive, in particular ceramic, material which serves as the electrolyte or electrolyte layer of the functional layer system. Since the tubular support body is formed at least in the hollow cylindrical intermediate portion of the gas-tight, oxygen ion conductive electrolyte serving as a material, such a cell may be referred to as at least partially (solid) electrolyte-supported cell. In this case, at least partially electrolyte-supported refers to the fact that the tubular support body may also have portions which may be formed of a material other than the electrolyte material. As explained later, although the reversibly oxidizable and reducible material of the storage electrode layer can have a layer thickness which, in particular in its oxidic form, is greater than the wall thickness of the section of the tubular carrier body formed from the gas-tight, oxygen-ion-conductive material, owing to - compared to FIG gas-tight, oxygen-ion-conductive material - low mechanical stability of the reversibly oxidizable and reducible material in the layer thickness ratios explained later, the supporting function can still be essentially taken over by the tubular carrier body, which is why the cell can be referred to in this aspect as, in particular at least partially, electrolyte-supported ,

In the context of the electrolyte-supported concept, the storage electrode layer and the air electrode layer can be arranged, in particular, on opposite sides of the portion of the tubular carrier body formed from the gas-tight, oxygen-ion-conductive material. For example, the storage electrode layer on the inside and the air electrode layer on the outside, or vice versa, the air electrode layer on the inside and the storage electrode layer on the outside of the formed from the gas-tight, oxygen ion conductive material portion of the tubular support body may be arranged. In the context of the electrolyte-supported concept, the tubular carrier body may be formed both partially and completely from the gas-tight, oxygen-ion-conductive, in particular ceramic, material.

In the context of another embodiment (inertly supported concept), the tubular carrier body has a section of a gas-permeable porous, in particular inert or electrochemically inactive or non-oxygen-ion-conducting, for example electrically weakly conducting or electrically insulating, ceramic material. Under an inert or electrochemically inactive material may be understood in particular a material which does not serve as an electrode or electrolyte, and in particular does not participate in the electrochemical reaction of the cell. The material of the gas-permeable porous portion of the tubular support body may also be particularly electrically weakly conductive or electrically insulating. This has the advantage that in this way the electrical insulation or interconnection of the cell can be simplified.

In the context of the inertially supported concept, the functional layer system, in particular in the form of a functional layer system package, is applied on the outside or on the inside thereof. Gas can pass through one of the gas-permeable pores of the tubular support body to one side or an electrode layer of the functional layer system. The electrolyte layer of the functional layer system is formed from a gas-tight, oxygen ion-conductive, in particular ceramic, material. Such a cell may be referred to in particular as inertgeträgert. In the context of the inertly supported concept, the functional layer system, and thus both the storage electrode layer and the air electrode layer and the electrolyte layer formed therebetween, can be arranged on one side of the section of the tubular carrier body formed from the gas-permeable porous ceramic material. In this case, the functional layer system can be arranged both on the inside and on the outside of the formed from the gas-permeable porous, ceramic material portion of the tubular support body. In this case, the functional layer system can rest against both the air electrode layer and the storage electrode layer on the portion of the tubular carrier body formed from the gas-permeable, porous, ceramic material. In the context of the inertly supported concept, those sections of the carrier body which are not provided with the functional layer system are preferably formed from a gas-tight, in particular non-oxygen ion-conducting or inert or electrochemically inactive, ceramic material. Suitable non-oxygen ion conductive or inert or electrochemically inactive, in particular ceramic, materials which can be made both gas-permeable porous and gas-tight, are explained in more detail later.

The fact that the supporting function is at least essentially taken over by the tubular carrier body, has the advantage that the reduced mechanical stress on the electrode layers or the mechanical stability of the functional layer system during the volume change of the reversibly oxidizable and reducible material can be improved, which can be advantageous to the life of the cell, in particular the storage electrode, impact. In addition, this allows the air electrode layer significantly thinner walled, for example, with a layer thickness of about 50 microns or less, as in the case of electrode-carrying cells, which has an advantageous effect, inter alia, on the electrical properties, gas diffusion, the cost and weight of the cell. In particular, it is thus advantageously possible to achieve a high gas production in the electrolysis operation.

The electrolyte-supported concept (ESC, English: Electrolyte Supported Cell) and the inertly supported concept, in particular from a thermomechanical point of view, have a higher robustness, in particular breaking strength, than the electrode-supported concept. The electrolyte-supported concept and the inert-supported concept also offer the advantage of a comparatively high redox stability of the carrier material. Furthermore, the electrolyte-supported concept and the inert-based concept offer advantages in terms of electrical insulation and interconnection. By means of the inertially supported concept, furthermore, particularly high power densities in electrolysis operation and in fuel cell operation can advantageously be achieved. In addition, the inert-supported concept makes it possible, for example, to configure the electrolyte layer of the functional layer system substantially thinner than in the electrolyte-supported concept. In addition, the inertly supported concept makes it possible to set the layer thicknesses of the air electrode layer and the storage electrode layer and of the electrolyte layer independently of one another and matched to the desired use. In this case, it is easier to realize thin electrolyte layers with the inert-supported concept than with the electrolyte-supported concept.

During operation of the metal-air cell, in particular high-temperature metal-air cell, can advantageously energy in the storage electrode (metal-metal oxide anode), in particular in serving as a storage medium, reversibly oxidizable and reducible metal or metal / metal oxide system stored and can be recalled if needed. During the charging process or in the energy storage operation, in particular the reversibly reducible and oxidizable material of the storage electrode can be transferred from the oxidized to the reduced form by supplying electrons, oxygen ions being transported through the electrolyte to the air electrode and oxidized to oxygen molecules. During the discharge process or in the energy recovery operation, in particular oxygen molecules can be reduced at the air electrode to oxygen ions and transported through the electrolyte to the storage electrode, wherein the reversibly reducible and oxidizable material of the storage electrode is oxidized to release electrons.

For example, the reversibly reducible and oxidizable material of the storage electrode may comprise or be a material selected from the group consisting of titanium / titanium oxide (Ti / TiO ₂ ), chromium / chromium oxide (Cr / CrO ₂ ), manganese / manganese oxide (Mn / Mn ₂ O ₃ ), iron / iron oxide (Fe / FeO), nickel / nickel oxide (Ni / NiO), copper / copper oxide (Cu / Cu ₂ O), molybdenum / molybdenum oxide (Mo / MoO ₂ ), cobalt / cobalt oxide ( Co / CoO), tungsten / tungsten oxide (W / WO ₃ ) and mixtures thereof.

The reversibly reducible and oxidizable material of the storage electrode or electrode layer sections formed therefrom can have, for example, a, in particular maximum, layer thickness, in particular in oxidized form, of ≥ 200 μm or ≥ 250 μm or ≥ 300 μm ≥ or 350 μm, for example ≥ 400 μm or ≥ 500 μm. In particular, the reversibly reducible and oxidizable material of the storage electrode or electrode layer sections formed therefrom may have a, in particular maximum, layer thickness, in particular in oxidized form, in a range of ≥ 200 μm to ≦ 2500 μm. For example, the reversibly reducible and oxidizable material of the storage electrode or electrode layer sections formed therefrom may have a, in particular maximum, layer thickness, in particular in oxidized form, for example in a range of 200 μm or ≥ 250 μm or ≥ 300 μm or ≥ 350 μm or ≥ 400 μm or ≥ 500 μm or ≥ 700 μm and / or (bis) ≤ 2500 μm or ≤ 2000 μm or ≤ 1500 μm or ≤ 1200 μm or ≤ 1000 μm or ≤ 900 μm.

The air electrode may in particular comprise an oxygen-ion-conductive and / or mixed-conducting (oxygen-ion and electron-conductive) material, as electrochemically active material or at least one electrode layer section formed therefrom, for example a multiplicity of electrode layer sections formed therefrom. The electrochemically active or oxygen-ion-conductive and / or mixed-conducting, in particular ceramic, material of the air electrode can include, for example, lanthanum strontium manganese oxide (LSM), lanthanum strontium cobalt ferrite (LSCF), lanthanum strontium ferrite (LSF), lanthanum strontium cobalt oxide (LSC), lanthanum iron iron ferrite (LNF) or a mixture thereof be. Optionally, these materials can be used as a mixture with an oxygen ion conductive material, for example, electrolyte material used

The, in particular electrochemically active, electrode layer sections of the air electrode can, for example, a, in particular maximum, layer thickness of less than or equal to 200 .mu.m, in particular of less than or equal to 100 .mu.m, for example in a range of 10 .mu.m to .ltoreq.100 .mu.m, for example of .gtoreq.10 .mu.m or ≥ 15 μm or ≥ 20 μm or ≥ 25 μm to ≤ 200 μm or ≤ 100 μm, for example of approximately 50 μm. Thus, advantageously, a high gas diffusion can be achieved.

The electrolyte layer may in particular be formed from a gas-tight, oxygen-ion-conductive, in particular ceramic, material. For example, the gas-tight, oxygen-ion-conductive, in particular ceramic, material of the electrolyte layer may be selected from the group consisting of (highly) doped zirconium oxides (ZrO ₂ ), for example with 6.5 wt .-% or more doped zirconium dioxides, in particular rare earth doped, for example with Scandium (Sc), yttrium (Y), cerium (Ce) terbium (Tb), praseodymium (Pr), samarium (Sm), europium (Eu), gadolinium (Gd) and / or dysprosium (Dy) doped zirconium dioxides Example scandium-, yttrium-, and / or cerium-doped zirconium dioxides ,. Lanthanum strontium gallates and / or manganates (LSGM), undoped or, for example, samarium (Sm), gadolinium (Gd) and / or terbium (Tb) doped cerium oxides and mixtures thereof.

Within the scope of a further embodiment, the electrolyte layer has a layer thickness or, in the electrolyte-supported concept, the hollow-cylindrical intermediate section has a wall thickness in a range of ≥ 15 μm or ≥ 20 μm or ≥ 50 μm to ≦ 300 μm. In particular, the electrolyte layer can have a layer thickness or, in the electrolyte-supported concept, the hollow cylindrical intermediate section has a wall thickness in a range of ≥ 15 μm or ≥ 20 μm or ≥ 50 μm, for example ≥ 100 μm or ≥ 120 μm, up to ≦ 300 μm, for example ≦ 250 μm or ≤ 200 μm or ≤ 180 μm, for example about 150 μm. It has been found to be particularly advantageous to set the electrolyte layer thickness or wall thickness not as thin as possible, but in particular to ≥ 15 μm or ≥ 20 μm or ≥ 50 μm, for example ≥ 100 μm, in order to achieve high mechanical stability, in particular with regard to to achieve the resulting in the volume change of the reversibly oxidizable and reducible material mechanical stresses. Such an electrolyte minimum layer thickness or wall thickness has also proven to be advantageous from the aspect of the combined electrolysis operation, since it has been found that high demands have to be met in the electrolysis, in particular for high-temperature steam electrolysis, with regard to the ion diffusion of the electrolyte, in particular which higher than at fuel cell are. This is due to the fact that in the case of an electrolysis cell, the gradient of the oxygen partial pressure (pO ₂ ) across the electrolyte is significantly greater than in the case of a fuel cell, which can lead to stronger degradation phenomena over the life of the cell. It has been found that such degradation phenomena can advantageously be counteracted by the fact that the electrolyte layer is not designed as thinly as possible, but at least with a layer thickness or wall thickness of ≥ 15 μm or ≥ 20 μm or ≥ 50 μm, for example ≥ 100 μm becomes. With regard to a sufficiently high realizable current density, on the other hand, it has also proved to be advantageous if the layer thickness or wall thickness of the electrolyte layer is ≦ 300 μm. Overall, it is thus advantageously possible to provide a metal-air cell with a long service life, which is also suitable for electrolysis operation. Since the cell also meets the low requirements for fuel cell operation requirements, such a metal-air cell can also be used as a fuel cell and in particular as a combined metal-air-cell-electrolysis fuel cell.

In the context of the electrolyte-supported concept, such wall thicknesses of the hollow-cylindrical intermediate section serving as the electrolyte layer can be produced-if appropriate directly-by (ceramic) injection molding with a small wall thickness. In the context of the electrolyte-supported concept, if appropriate, the wall thickness of a body produced by (ceramic) injection molding can additionally be adjusted by abrading treatment, for example grinding, of the (ceramic) injection-molded body.

As part of the inertially supported concept, an electrolyte layer having such a layer thickness can be produced, for example, by a printing technique. The electrode layers of the functional layer system can likewise be produced by a printing technique. The tubular carrier body can be produced by (ceramic) injection molding analogously to the electrolyte-supported concept, whereby the tubular carrier body can likewise be provided with the functional layer system during production by means of film injection molding (IML, English: Inmould Labeling). In the context of the inertly supported concept, the hollow-cylindrical intermediate section can have, for example, a wall thickness in a range of ≥ 250 μm to ≦ 2000 μm or ≦ 1500 μm or ≦ 1000 μm, for example of approximately 500 μm. Voryugsweise, the gas-permeable porous material has a porosity of 40%.

In particular, the tubular carrier body can be a (ceramic) injection-molded body. In contrast to extrusion, (ceramic) injection molding advantageously offers the process-related possibility of producing tubular hollow bodies with complex geometries, for example by means of a specially developed injection molding tool and, for example-as explained in more detail below-form the end section of the tubular support body directly in the form of a mounting flange or gas connection flange or cap and in particular to inject directly from another material to the hollow cylindrical intermediate section. So again, advantageously, a good functional integration can be achieved. A (ceramic) injection-molded body may in particular have a microstructure characteristic of injection molding, for example texture and / or flow lines.

Optionally, in particular within the framework of the electrolyte-supported concept, at least the section formed from the gas-tight, oxygen-ion-conductive material, in particular the hollow-cylindrical intermediate section explained below, can have a polished outer surface or be ground externally. The grinding or external cylindrical grinding can in particular be accompanied by characteristic machining marks in transverse or longitudinal grinding.

In the context of a special embodiment, the tubular support body may have a hollow-cylindrical intermediate section and two end sections.

In the context of the electrolyte-supported concept, the storage electrode layer and the air electrode layer can be arranged in particular on opposite sides of the hollow cylindrical intermediate section. For example, the storage electrode layer on the inside and the air electrode layer on the outside, or conversely, the air electrode layer on the inside and the storage electrode layer may be arranged on the outside of the hollow cylindrical intermediate portion.

In the context of the electrolyte-supported concept, the functional layer system can be arranged on one side of the hollow-cylindrical intermediate section. In this case, the functional layer system can be arranged both on the inside and on the outside of the hollow cylindrical intermediate portion. In this case, the functional layer system can rest against the hollow cylindrical intermediate section both with the air electrode layer and with the storage electrode layer.

In the context of one embodiment, at least one of the end sections of the tubular support body is designed for mounting the cell.

A cell designed exclusively as a metal-air cell with a storage electrode layer facing the interior of the tubular carrier body can have both an open and a closed end section designed for mounting. The other end portion can also be designed to be closed. Inasmuch as a cell (designed exclusively as a metal-air cell) has an open end section designed for mounting, it is possible to mount the cell over it on a, in particular closed, carrier element, for example carrier plate. In this case, in particular the environment on the outside of the tubular carrier body can represent an airspace. Optionally, air can be supplied by means of a gas line to this air space and / or be discharged therefrom. If appropriate, an inert gas atmosphere may be provided in the interior of the tubular support body.

In the context of a preferred embodiment, however, at least one of the end sections of the tubular carrier body is designed for mounting the cell, in particular on a gas line or a gas line system. For example, the at least one end section designed for mounting can be designed for mounting the cell on a carrier element, for example a carrier plate, in particular with a continuous opening, of a gas line system. In particular, the at least one end section designed for mounting can be designed for gas-conducting installation / connection of the cell and / or open. For example, the at least one end section designed for mounting can be designed as a gas connection flange. In this case, the designed for mounting, in particular gasanschlussflanschförmige, end portion in particular directly to the gas line or the gas line system, for example, the support member of the gas line system, are connected. The mechanical connection can be realized for example by a clamping ring or through bolts. In particular, during the connection, the end face of the end section designed for mounting, in particular gas connection flange-shaped, end section can be applied to a section of the gas line or the gas line system surrounding a continuous opening.

In principle, it is possible to design both end sections as open end sections designed for mounting, for example as gas connection flanges. The tubular carrier body can in particular be open tube on both sides be designed. Such a cell may be referred to in particular as a tubular cell open on both sides.

In a further embodiment, however, the other end portion closes the tubular carrier body and can be referred to, for example, as caps, dome, Tubusdom. In particular, the other end portion of the tubular carrier body is designed as a closed cap or dome. The tubular support body is thus configured as a closed tube on one side. Such a cell with a gas connection flange-shaped end section and a cap-shaped end section or with a tube closed on one side can be referred to in particular as a unilaterally closed, tubular cell. Tubular cells closed on one side advantageously allow a simple gas recirculation in the system, whereby advantageously, in particular by means of a metal-air electrolysis fuel cell, a high degree of efficiency in electrochemical current storage can be achieved with demand-based reconversion.

In the context of a further embodiment, the hollow cylindrical intermediate section is the section formed from the gas-tight, oxygen-ion-conductive material (electrolyte-supported concept) or the section formed from the gas-permeable porous, in particular inert, ceramic material (inertly supported concept).

In the context of the electrolyte-supported concept, one of the two end sections, in particular the cap-shaped end section or both end sections, can be formed from the same material as the hollow cylindrical intermediate section, ie also from the gas-tight, oxygen ion-conductive, in particular ceramic, material. However, as explained in more detail below, in the electrolyte-supported concept, one or both end sections may also be formed from another, in particular ceramic, material, such as the hollow-cylindrical intermediate section.

In the context of a further embodiment (of the electrolyte-supported concept as well as of the inert-supported concept), the at least one end section and / or the cap-shaped end section designed for mounting is formed from another, in particular ceramic, material than the hollow-cylindrical intermediate section. The materials may differ in particular in their composition and / or porosity or density.

For example, in the context of the inertially supported concept, the material of the mounting, in particular gasanschlussflanschförmigen, end portion or the cap-shaped end portion have the same composition as the material of the hollow cylindrical intermediate portion, but differ from the material of the hollow cylindrical intermediate portion in that the material is gas-tight and not gas permeable is porous.

Characterized in that the designed for mounting, in particular gasanschlussflanschförmige, end portion and / or the cap-shaped end portion is not formed of the same material as the hollow cylindrical intermediate portion and in particular inert or electrochemically inactive and not oxygen ion conductive (electrolyte-supported concept) or porous (inertgeträgertes concept) must be, the material can be advantageously selected from a wider range of materials. This makes it possible, inter alia, to use a less expensive material and / or an electrically weakly conductive or electrically insulating material for this purpose.

Characterized in that an electrically weakly conductive, in particular electrically insulating material is used for the gasanschlussflanschförmigen end, can advantageously by the gasanschlussflanschförmigen end portion and an electrical insulation between the electrochemically active components of the cell and the gas line or the support plate of the gas line system, which as such metallic and to be electrically conductive can be guaranteed.

In a further embodiment, the at least one designed for mounting, in particular gasanschlussflanschförmige, end portion and / or the cap-shaped end portion of a gas-tight, in particular non-oxygen conductive or inert or electrochemically inactive, in particular ceramic material is formed.

In particular, the at least one designed for mounting, in particular gasanschlussflanschförmige, end portion and / or the cap-shaped end portion of a gas-tight, non-oxygen conductive or inert or electrochemically inactive, electrically weakly conductive or electrically insulating, in particular ceramic material may be formed.

The end portions may be formed both from the same material and from a different material. In particular, however, the end portions may be formed of the same material. For example, the cap-shaped end section can thus be formed from the same material as the end section designed for mounting, in particular gas connection flange-shaped.

In particular, the designed for mounting, in particular gasanschlussflanschförmige, end portion and / or the cap-shaped end portion, in particular in the adjacent to the hollow cylindrical intermediate portion subsection, a greater wall thickness (d112 ', d113'), for example by at least a factor of 1.1 or 1, 2 or 1.5 or 2, for example by at least the factor 3 or 4 or 10, greater wall thickness (d112 ', d113') than the hollow cylindrical intermediate portion (d). Thus, advantageously, a high mechanical stability of the cell as such and, in the case of the gas connection flange-shaped end section, a high mechanical stability of the connection of the cell to the gas line or the carrier element of the gas line system can be achieved. Since the wall thickness of the gas connection flange-shaped end section or of the cap-shaped end section does not influence the electrochemical reaction, it is also advantageously possible to use materials which, as such, have a lower mechanical stability than the construction of the gas inlet flange-shaped end section and / or the cap-shaped end section have the material of the hollow cylindrical intermediate portion, in which the low mechanical stability of the material, but compensated by the increased wall thickness or even overcompensated, so that even with the use of a mechanically unstable material overall may even have a higher mechanical stability than the hollow cylindrical intermediate portion , The gas connection flange-shaped end section can have, in addition to the lower section adjacent to the hollow cylindrical intermediate section, at least one further subsection, for example in the form of a projection, which serves, for example, for mechanically connecting the cell and which, in particular, has an even greater wall thickness (d112 ") than that of FIG The sub-section (d112 ', d113') adjacent to the hollow-cylindrical intermediate section may have.

At operating temperatures of 650 ° C to 950 ° C, the connection between the designed for mounting, in particular gasanschlussflanschförmigen, end portion and a gas line or a support member of a gas line system can be sealed by means of a, in particular electrically insulating, glass solder. Since glass solders are not fully temperature resistant, it has proven to be advantageous to provide the end face of the designed for mounting, in particular gasanschlussflanschförmigen, end portion and possibly also the connection portion of the gas line or the support element of the gas line system with a flat grinding. Thus, advantageously, a glass solder-free sealing can be realized.

The gas-permeable porous or gas-tight, non-oxygen ion conductive or inert or electrochemically inactive, especially electrically weakly conductive or electrically insulating material, such as the material of the designed for mounting, in particular gasanschlussflanschförmigen, end portion and / or the material of the cap-shaped end portion and / or the material of the gas-permeable porous hollow cylindrical intermediate section may in particular be selected from the group consisting of low-doped zirconium dioxides, that is with less than 3 wt .-% doped zirconia, undoped zirconia, magnesium silicates, especially forsterite (Mg ₂ SiO ₄ ), alumina, alumina Zirconia mixtures, spinels, for example, magnesium aluminate (MgAl ₂ O ₄ ), zirconia-glass mixtures, zinc oxide, and mixtures thereof.

In particular, can be used as the gas-permeable porous or gas-tight, non-oxygen ion conductive or inert or electrochemically inactive, in particular electrically insulating material magnesium silicate, in particular forsterite. Forsterite is based essentially on the general empirical formula Mg ₂ SiO ₄ . Forsterite may advantageously be highly electrically and ionically highly insulating and, for example, have a specific electrical resistance of 10 ¹¹ Ωm at 20 ° C. and a specific electrical resistance of 10 ⁵ Ωm at 600 ° C. Thus, it is advantageously possible to avoid electrical and ionic short circuits and to dispense with one or more additional insulation layers. Further advantages of Forsterit are its sintering behavior and its thermal expansion coefficient. Thus, forsterite can have advantageous shrinkage properties and an advantageous shrinkage kinetics. The thermal expansion coefficient of Forsterit can also substantially correspond to the thermal expansion coefficient of the materials of the functional layer system and can be about 10 to 11 · 10 ^-6 K ^-1 , which has an advantageous effect on a simultaneous sintering (co-sintering) of the tubular support body and the functional layer system , In addition, forsterite can be obtained via a reaction sintering from inexpensive raw materials, such as talc and magnesium oxide, which further contributes to cost savings in the production.

As part of a further embodiment, a toothing is formed between the designed for mounting, in particular gasanschlussflanschförmigen, end portion and the hollow cylindrical intermediate portion. In particular, the teeth may be tongue and groove-like or wave-shaped and, for example, have an at least partially circumferential extension. In the area of the toothing between the end portion designed for mounting, in particular gas connection flange, and the hollow cylindrical intermediate portion, the hollow cylindrical intermediate portion may be substantially convex and the gas terminal flange end portion particularly substantially concave. In this way it can advantageously be achieved that the electrochemically active surface or gas diffusion is not or only slightly affected by the gearing.

As part of a further embodiment, between the cap-shaped end portion and the hollow cylindrical intermediate portion, a, in particular tongue and groove-like, toothing, in particular with an at least partially circumferential extent, formed. In particular, in this case too, the teeth can be tongue and groove-like or wave-shaped and, for example, have an at least partially circumferential extent. In the region of the toothing between the cap-shaped end section and the hollow-cylindrical intermediate section, the hollow-cylindrical intermediate section may in particular be substantially convex and the cap-shaped end section may in particular be substantially concave-shaped. In this way it can advantageously be achieved that the electrochemically active surface or gas diffusion is not or only slightly affected by the toothing.

In the context of a further embodiment, the cap-shaped end section has at least three, in particular circumferentially distributed, indents and / or (inner) struts. The indentations and / or struts can in particular be rotationally symmetrical to one another. In particular, the rotational symmetry axis may correspond to the longitudinal axis of the tubular carrier body. In particular, the indents and / or struts may define a clearance extending therebetween the diameter of which decreases along the axis of symmetry / longitudinal axis of the tubular support body from the hollow cylindrical intermediate portion towards the center of the cap-shaped end portion. These indentations and / or struts can in particular be injected into the cap-shaped end section or produced in the context of (ceramic) injection molding of the tubular carrier body. Such trained struts or indentations can, in particular as Zentrierungs- and / or stabilizing elements, for centering and / or stabilizing a insertable into the interior of the tubular cell gas lance, for example, fuel gas lance serve. Thus, by means of a further functional integration, an exact, both radial and axial positioning and fixing of the gas lance can advantageously be achieved and a precise and reproducible gas conduction over the service life can be ensured. In particular, the cap-shaped end portion may have three such indents and / or struts. This has turned out to be advantageous for centering and fixing.

The air electrode layer and the storage electrode layer may, in the context of the electrolyte-supported concept, cover the entire outer side or the entire inner side of the hollow cylindrical intermediate section.

As part of the inertially supported concept, the functional layer system package can cover the entire outside or the entire inside of the hollow cylindrical intermediate section. In the context of the inertly supported concept, those sections of the carrier body which are not provided with the functional layer system are preferably formed from a gas-tight, in particular non-oxygen ion-conducting or inert or electrochemically inactive, ceramic material. Suitable non-oxygen ion conductive or inert or electrochemically inactive, in particular ceramic, materials which can be made both gas-permeable porous and gas-tight, are explained in more detail later.

In particular, the end sections, in particular the gas connection flange-shaped end section or the cap / dome-shaped end section, can not be coated with the electrode layers (electrolyte-supported concept) or the functional layer system (inertly supported concept).

The air electrode layer and / or the storage electrode layer may (at least) comprise at least one interconnector made of an electrically conductive material, in particular which electrically contacts at least one, in particular electrochemically active, electrode layer section of the (respective) electrode layer. If appropriate, an interconnector can connect at least two, in particular electrochemically active, electrode layer sections of the (respective) electrode layer to one another in an electrically conductive manner.

The interconnectors of the air electrode layer and / or the storage electrode layer can be both (fully) flat or web-shaped or combined (fully) flat and designed web-shaped.

In this case, the interconnectors of the air electrode layer and the storage electrode layer can be formed both from the same material and from different materials.

In principle, the interconnectors of the air electrode layer and the storage electrode layer can be formed of a porous or gas-permeable as well as of a dense or gas-tight material or partially gas-tight and partially gas-permeable porous.

Within the scope of an embodiment, the air electrode layer and / or the storage electrode layer (in each case) has at least one flat, in particular full-surface, interconnector. For example, the air electrode layer and / or the storage electrode layer may have a flat, in particular full-surface interconnector, for example of a gas-permeable material, which is applied to the, in particular electrochemically active, electrode layer sections of the (respective) electrode layer.

In the context of another alternative or additional embodiment, the air electrode layer and / or the storage electrode layer (in each case) has at least one or a plurality of web-shaped interconnect / s on which at least two electrode layer sections of the (respective) electrode layer are arranged. The web-shaped interconnect (s) can be formed both from a gas-permeable and from a gas-tight material.

The air electrode layer may in particular comprise an oxygen ion conductive and / or mixed conductive (oxygen ion and electron conductive), in particular ceramic, material as electrochemically active material or at least one formed, in particular electrochemically active, electrode layer section, for example a plurality of, in particular electrochemically active, electrode layer sections ,

The, in particular electrochemically active, electrode layer sections of the air electrode layer may comprise, for example, lanthanum strontium manganese oxide (LSM), lanthanum strontium cobalt ferrite (LSCF), lanthanum strontium ferrite (LSF), lanthanum strontium cobalt oxide (LSC), lanthanum nickel ferrite (LNF) or a mixture thereof. Optionally, these materials may be used as a mixture with an oxygen ion-conductive material, for example, electrolyte material.

The electrode layer sections of the air electrode layer may in particular have a layer thickness of less than or equal to 200 μm of less than or equal to 100 μm, for example in a range of ≥ 10 μm to ≤ 100 μm, for example of ≥ 10 μm or ≥ 15 μm or ≥ 20 μm or ≥ 25 microns to ≤ 200 microns or ≤ 100 microns, for example, from about 50 microns have. Thus, advantageously, a high gas diffusion can be achieved.

The interconnectors of the air electrode layer and / or the storage electrode layer may be formed from one, in particular redox-stable, ceramic or metallic, in particular ceramic, material.

A redox-stable material may, in particular, be understood as meaning a material which, under the conditions to which it is exposed during operation of the cell, is electrochemically and / or chemically stable, in particular undergoes no reduction reactions and oxidation reactions, so-called redox reactions. The assessment of the redox stability can be carried out in particular with regard to the conditions to which the material is exposed during operation of the tubular cell.

As explained in more detail in connection with the method according to the invention, a tubular cell can advantageously be equipped in a particularly simple and cost-effective manner with a ceramic, electrically conductive and redox-stable material by means of (ceramic) injection molding and / or film injection molding. In addition, a ceramic material may be more temperature-resistant and / or less expensive compared to a metallic material.

By way of example, the interconnector material may comprise or be formed from at least one material selected from the group consisting of lanthanum chromates (LaCrO ₃ ), lanthanum strontium manganese oxides (LSM), in particular scandium-doped lanthanum strontium manganese oxide (LSSM), lanthanum iron iron compounds (LNF), metals, in particular precious metals and / or others, especially high temperature stable metals and mixtures thereof. In this context, high-temperature-stable metals may be understood as meaning metals which have a melting point of at least 1000 ° C. and are chemically stable, in particular under a reducing and / or oxidizing atmosphere, in particular under the atmosphere under which they are operated.

In order to realize both good corrosion resistance and high electrical conductivity, it is possible, for example, to use materials containing chromium, in particular high chromium, such as lanthanum chromium oxide (LaCrO ₃ ).

Within the scope of a further embodiment, the storage electrode layer faces the interior of the tubular support body and the air electrode layer faces the outer environment around the tubular support body.

In the context of another embodiment, the air electrode layer faces the interior of the tubular carrier body and the storage electrode layer of the external environment faces the tubular carrier body.

The storage electrode layer of the outer environment to form the tubular carrier body, has the advantage that in the interior of an air supply lance are received and an advantageous gas recirculation system can be formed.

However, the storage electrode layer facing the interior of the tubular carrier body has the advantage, in particular in the case of unstructured storage electrode layers, that slight pressure is exerted on the storage electrode layer during expansion of the storage electrode material due to the circumference decreasing in the direction of the central region of the tubular carrier body which cracking in the storage electrode layer can be avoided. Alternatively or additionally, however, crack formation in the storage electrode layer can also be at least significantly reduced or avoided by using the expanded form of the storage electrode material during the production of the metal-air cell and / or by a fin structure explained in more detail below. the outer environment facing storage electrode can be advantageously realized.

As an alternative or in addition to the interconnectors, the tubular metal-air cell may have at least one rib structure formed from an electrically conductive and redox-stable material. In this case, in particular, the material of the storage electrode can be formed between the ribs of the rib structure.

In the context of a further embodiment, therefore, the storage electrode layer has a rib structure formed from an electrically conductive and redox-stable material, wherein the reversibly oxidizable and reducible material of the storage electrode layer is formed between the ribs of the rib structure.

In principle, the air electrode can be an areal contiguous electrode, in particular not segmented by a rib structure. Alternatively or additionally, it is also possible to form the material of the air electrode between the ribs of the rib structure or a further rib structure made of an electrically conductive and redox-stable material. Optionally, therefore, the air electrode layer may also have a rib structure formed of an electrically conductive and redox-stable material, wherein the electrochemically active material of the air electrode layer is formed between the ribs of the rib structure.

Interconnect materials, which are used for the electrical interconnection of electrochemical cells and, for example, have already been explained above, are electrically conductive and, moreover, can in particular also be redox-stable. The rib structure of the storage electrode layer and / or the air electrode layer can therefore be formed, for example, from an interconnector material, in particular from an interconnector material described above.

For example, on the inside and / or on the outside, in particular on the inside, of the tubular carrier body or of the functional layer system, a rib structure (rib-shaped elevations) may be formed from an electrically conductive and redox-stable material or an interconnector material.

The reversibly reducible and oxidizable material of the storage electrode layer or the electrochemically active material of the air electrode layer can be formed or incorporated, for example, between the ribs of the (respective) rib structure, in particular in intermediate spaces between the ribs of the (respective) rib structure. In particular, the reversibly reducible and oxidizable material of the storage electrode layer or the electrochemically active material of the air electrode layer can be applied between the ribs of the (respective) rib structure, for example in interspaces between the ribs, on the tubular carrier body and / or on the electrolyte layer.

By forming the material of the storage electrode layer or the air electrode layer between the ribs of the rib structure, advantageously both the electrical connection and the mechanical stability of the storage electrode layer or the air electrode layer, in particular over the Life of the tubular metal-air cell, to be improved.

In this case, the rib structure also makes it possible in particular to ensure good electrical connection of the material, for example redox reaction-induced and / or temperature-induced volume changes, for example an alternating volume increase and decrease in volume, of the reversibly oxidizable and reducible material of the storage electrode layer or of the electrochemical active material of the air electrode. This is particularly advantageous for metal-air cells, since their reversibly oxidizable and reducible material have a relatively high layer thickness and its redox reaction-induced volume changes can be particularly strong. The reversibly oxidizable and reducible material can also be highly porous in its oxidized form and in particular lose its own mechanical stability, the rib structure then advantageously mechanically stabilize the reversibly oxidizable and reducible material or solidify from the outside and can ensure sufficient mechanical stability of the overall arrangement.

In particular, the rib structure can additionally serve as an interconnector.

Overall, it is thus advantageously possible to realize a long service life of the tubular metal-air cell.

In a further embodiment, the rib structure of the storage electrode layer and / or the air electrode layer, in particular the storage electrode layer, ribs which extend in the longitudinal direction of the tubular support body or at least substantially in the longitudinal direction of the tubular support body. Such a rib structure can advantageously be produced particularly easily.

In the context of a further alternative or additional embodiment, the rib structure of the storage electrode layer and / or the air electrode layer, in particular the storage electrode layer, ribs which extend in the circumferential direction of the tubular support body or at least substantially in the circumferential direction of the tubular support body. In essence, it may be understood in particular that deviations of approximately ± 20 ° should be included.

In one embodiment, the rib structure of the storage electrode layer and / or the air electrode layer, in particular the storage electrode layer, ribs (rib-shaped elevations) which differ from the longitudinal direction and / or circumferential direction of the tubular support body or deviating from the longitudinal and / or circumferential direction of the tubular Carrier body (ceramic body) are aligned. For example, the ribs may extend in one direction, which deviate by more than 20 ° from the longitudinal direction and / or the circumferential direction of the tubular carrier body. The rib structure of the storage electrode layer and / or the air electrode layer, in particular the storage electrode layer, may be formed, for example, grid-shaped. Thus, advantageously, a particularly good electrical and mechanical connection of the reversibly oxidizable and reducible material of the storage electrode layer or of the electrochemically active material of the air electrode layer can be achieved.

In particular, the ribs of the rib structure of the storage electrode layer and / or the air electrode layer, in particular the storage electrode layer, have a height which is greater than or equal to, in particular maximum, layer thickness of the reversibly oxidizable and reducible material, in particular in oxidic form, the storage electrode or the electrochemically active Material of the air electrode is. In this case, the maximum layer thickness can be understood as the maximum possible layer thickness which the material can achieve under the operating conditions, for example due to a temperature and / or redox-induced increase in volume. Thus, advantageously, a particularly good mechanical stabilization, in particular a storage electrode, can be achieved. In this case, at least in one form of the reversibly oxidizable and reducible material of the storage electrode or of the electrochemically active material of the air electrode, in which the layer thickness is less than its maximum layer thickness, for example in an at least partially reduced form, a cavity is present, in particular which is bounded laterally by the ribs of the rib structure.

In particular, the ribs of the rib structure may have a height of the storage electrode layer and / or the air electrode layer, in particular the storage electrode layer, which greater, in particular maximum, layer thickness of the reversibly oxidizable and reducible material of the storage electrode, in particular in oxidic form, or the electrochemically active material Air electrode is. In this case, in a form of the reversibly oxidizable and reducible material of the storage electrode or of the electrochemically active material of the air electrode, in which its layer thickness is maximum, for example in the oxidized form, a cavity, in particular which is bounded laterally by the ribs of the rib structure.

For example, the ribs of the rib structure of the storage electrode layer and / or the air electrode layer, in particular the storage electrode layer, may have a height which is at least 10%, for example at least 20%, in particular at least 30%, higher than, in particular minimum, layer thickness of the reversibly oxidizable and reducible material of the storage electrode, in particular in reduced or metallic form, or of the electrochemically active material of the air electrode. In this case, the minimum layer thickness can be understood as the layer thickness which the respective material can have in its form with the lowest volume, for example in reduced or metallic form, at room temperature.

In the case of an air electrode layer, the height of the rib structure may be a smaller percentage than that in the case of a storage electrode layer. For example, the height of ribs for an air electrode layer may only be at least 10% or 20% higher than the layer thickness of the electrochemically active material of the air electrode layer, since the electrochemically active material of air electrodes perform a smaller volume change, in particular a substantially only temperature-induced volume change.

The reversibly reducible and oxidizable material of the storage electrode or electrode layer sections formed therefrom can have, for example, a, in particular maximum, layer thickness, in particular in oxidized form, of ≥ 200 μm or ≥ 250 μm or ≥ 300 μm or ≥ 350 μm, for example ≥ 400 μm or ≥ 500 μm. In particular, the reversibly reducible and oxidizable material of the storage electrode

or the electrode layer sections formed therefrom have a, in particular maximum, layer thickness, in particular in oxidized form, in a range of ≥ 200 μm to ≦ 2500 μm. For example, the reversibly reducible and oxidizable material of the storage electrode or electrode layer sections formed therefrom may have a, in particular maximum, layer thickness, in particular in oxidized form, for example in a range of ≥ 200 μm or ≥ 250 μm or ≥ 300 μm or ≥ 350 μm or ≥ 400 μm or ≥ 500 μm or ≥ 700 μm, and / or (bis) ≤ 2500 μm or ≤ 2000 μm or ≤ 1500 μm or ≤ 1200 μm or ≤ 1000 μm or ≤ 900 μm.

The ribs of the rib structure of the storage electrode layer may, for example, have a height, where appropriate, in a range ≥ 200 μm or ≥ 220 μm or ≥ 250 μm or ≥ 275 μm or ≥ 300 μm or ≥ 330 μm or ≥ 350 μm or ≥ 400 μm or ≥ 450 μm or ≥ 500 μm or ≥ 550 μm or ≥ 700 μm or ≥ 750 μm, and / or (to) ≤ 4000 μm or ≤ 3500 μm or ≤ 3250 μm or ≤ 3000 μm or ≤ 2750 μm or ≤ 2500 μm or ≤ 2250 μm or ≤ 2000 μm or ≤ 1750 μm or ≤ 1500 μm or ≤ 1350 μm or ≤ 1200 μm or ≤ 1000 μm.

The ribs of the rib structure of the air electrode may, for example, have a height, optionally in a range of ≥ 20 μm or ≥ 50 μm or ≥ 60 μm or ≥ 100 μm or ≥ 120 μm or ≥ 150 μm or ≥ 200 μm, and / or ( to) ≤ 500 μm or ≤ 400 μm or ≤ 300 μm.

In the context of the electrolyte-supported concept, the ribbed structure of the storage electrode layer can be arranged or applied on the inside or on the outside, in particular on the inside, of the section formed from the gas-tight, oxygen-ion-conductive material, in particular hollow-cylindrical intermediate section of the tubular carrier body. In this case, the air electrode layer can be arranged or applied on a side of the tubular carrier body which is opposite to the storage electrode layer, for example on the outside or on the inside, in particular on the outside. Insofar as the air electrode layer has a rib structure, its rib structure can be arranged or applied on the outside or on the inside, in particular on the outside, of the tubular carrier body, in particular on the side of the tubular carrier body opposite the storage electrode. The reversibly oxidizable and reducible material of the storage electrode layer or the electrochemically active material of the air electrode layer may in particular be applied between the ribs of the rib structure or the further rib structure on the formed of the gas-tight, oxygen ion conductive material portion, in particular hollow cylindrical intermediate portion of the tubular carrier body and / or be introduced into intermediate spaces between the ribs of the rib structure and, for example, serving as the electrolyte portion, in particular hollow cylindrical intermediate portion of the tubular carrier body. In this case, the reversibly oxidizable and reducible material of the storage electrode layer or the electrochemically active material of the air electrode layer can in particular adjoin the section serving as the electrolyte, in particular the hollow cylindrical intermediate section, of the tubular carrier body.

In the context of the inertially supported concept, the ribbed structure of the storage electrode layer can lie against the section formed by the gas-permeable porous, in particular inert, ceramic material, in particular the hollow cylindrical intermediate section, of the tubular carrier body, as well as be open. On the other hand, in both cases, the rib structure may rest against the electrolyte layer in particular. In particular, in both cases, the reversibly oxidizable and reducible material of the storage electrode layer between the ribs of the rib structure of the storage electrode layer can be applied to the electrolyte layer. The air electrode layer may be applied to a side of the electrolyte layer opposite the storage electrode layer. Insofar as the air electrode layer has a rib structure, its rib structure can be arranged or applied on the opposite side of the electrolyte layer. The reversibly oxidizable and reducible material of the storage electrode layer or the electrochemically active material of the air electrode layer can be applied in particular between the ribs of the rib structure or the further rib structure on the electrolyte layer and / or introduced into spaces between the ribs of the rib structure and, for example, the electrolyte layer.

For example, the rib structure of the storage electrode layer on the one hand on the formed from the gas-permeable porous, especially inert, ceramic material portion, in particular hollow cylindrical intermediate portion of the tubular carrier body and on the other hand abut the electrolyte layer. The air electrode layer and, if appropriate, its rib structure can be open on the one hand and rest against the opposite side of the electrolyte layer on the other hand.

Or the ribbed structure of the storage electrode may on the one hand be open and, on the other hand, abut against the electrolyte layer. In this case, the air electrode layer and optionally its rib structure on the one hand on the gas permeable porous, especially inert, ceramic material formed portion, in particular hollow cylindrical intermediate portion of the tubular support body abut and on the other hand abut the opposite side of the electrolyte layer.

Within the scope of a specific embodiment of the inertly supported concept, in particular in which the rib structure of the storage electrode rests against the tubular support body, at least in one form of the reversibly oxidizable and reducible material of the storage electrode layer, in which its layer thickness is less than its maximum layer thickness, for example in one at least partially reduced form, between the reversibly oxidizable material of the storage electrode layer and the gas permeable porous, especially inert, ceramic material formed portion, in particular hollow cylindrical intermediate portion of the tubular support body before a cavity. In particular, the cavity can be delimited laterally by the ribs of the rib structure of the storage electrode layer. Thus, the material of the storage electrode layer can advantageously expand with an increase in volume into the cavity and fill it, for example in the form of maximum layer thickness, in particular in oxidized form. In particular, in a form of the reversibly oxidizable and reducible material of the storage electrode layer, in which its layer thickness is maximum, for example in the oxidized form, a cavity, in particular which is bounded laterally by the ribs of the rib structure of the storage electrode layer. Thus, it can advantageously be ensured with particular reliability that the reversibly oxidizable and reducible material of the storage electrode layer can expand to a maximum, in particular without generating mechanical stresses. This is advantageous in particular when the material of the storage electrode layer is arranged between the tubular carrier body and the electrolyte layer.

The electrochemical cell may, for example, be a metal-air cell and / or an electrolysis cell and / or a fuel cell, in particular a metal-air cell or a combined metal-air-electrolysis fuel cell. The cell may include, for example, a high-temperature metal-air cell and / or a high-temperature electrolysis cell and / or a high-temperature fuel cell, in particular a high-temperature metal-air cell or a combined high-temperature metal-air electrolysis fuel Cell, his. The electrochemical cell can be produced, for example, by the process according to the invention explained below.

With regard to further technical features and advantages of the cell according to the invention, reference is hereby explicitly made to the explanations in connection with the method according to the invention, the uses according to the invention, the energy system according to the invention and to the description of the figures and the figures.

A further subject of the present invention is a process for producing a tubular metal-air cell, in particular a tubular metal-air cell according to the invention.

The method may in particular comprise a (ceramic) injection molding process, in particular a multi-component (ceramic) injection molding process, for example a two-component (ceramic) injection molding process. In particular, the injection molding process can be part of a so-called in-mold labeling process (IML) or a film (rear) injection.

In the context of the method, in particular, a storage electrode layer is applied, which is a reversibly oxidizable and reducible material between a metallic form and an oxidic form, or a material precursor, which. For example, thermally, in particular in the process step d) explained later, is convertible into a reversibly oxidizable and reducible material between a metallic form and an oxidic form

Manufacture by means of (ceramic) injection molding has the advantage that tying seam-free, closed tubular bodies can thereby be produced, which can not be achieved by conventional methods based on a subsequent extrusion of extruded tubes. Thus, it is advantageously possible to avoid weak points which could break or break during thermomechanical stresses during operation and would otherwise reduce the service life of the cell.

In particular, the method may comprise the method step a) of providing an injection molding tool having a cavity and an injection mold core insertable into the cavity, wherein a tubular cavity can be formed by introducing the injection molding tool core into the cavity. In particular, the tubular cavity may have a hollow-cylindrical intermediate section and two end sections. At least one of the end sections of the tubular cavity of the injection molding tool can be designed, in particular, to form a, in particular open, mounting (end) section, for example a gas connection flange. The other end portion may be designed to form a closed cap or possibly another, in particular open, mounting (end) section, for example a gas connection flange.

In the context of the electrolyte-supported concept, the hollow cylindrical intermediate portion of the tubular cavity can in particular be designed such that a hollow cylindrical intermediate portion of an injection molded body formed therein has a wall thickness of less than or equal to 500 .mu.m, in particular of less than or equal to 400 .mu.m, for example of less than or equal to 360 .mu.m Example of less than or equal to 240 microns, and isbesondere greater than or equal to 20 microns, for example, greater than or equal to 60 microns or greater or equal to 120 microns, having.

In the context of the inertially supported concept, the hollow cylindrical intermediate section of the tubular cavity can in particular be configured such that a hollow cylindrical intermediate section of an injection molded body formed therein has a wall thickness of less than or equal to 2400 μm, for example less than or equal to 1800 μm or less than or equal to 1200 μm / or in particular of greater than or equal to 300 microns, for example of about 600 microns, having.

Since a shrinkage of the injection-molded body of about 20% can occur in the context of sintering, the desired wall thicknesses of the hollow-cylindrical intermediate section can be achieved by injection molds designed in this way.

Furthermore, the method may comprise a method step b) in which at least one electrode layer, in particular a storage electrode layer and / or an air electrode layer, optionally in the form of a, in particular sandwich-like, functional layer system package comprising an air electrode layer, a storage electrode layer and an electrolyte layer formed between the air electrode layer and the storage electrode layer is applied to a cavity-limiting part of the injection-molding tool, in particular to a part of the injection-molding tool which delimits the cavity in the region of the hollow-cylindrical intermediate section.

The application of the storage electrode layer and / or the air electrode layer or the functional layer system package to the cavity-limiting parts of the injection molding tool can be carried out in method step b) by, for example, using a printing technique, for example screen printing, with the storage electrode layer or the air electrode layer or is provided with the functional layer system, is applied to the tool core and / or on an inner wall of the cavity (in-mold labeling / film injection). Within the scope of process step b), in particular variants b1), b2) and b3) explained later are possible, the variants b1) and b2) being designed for producing an electrolyte-supported cell and variant b3) for producing an inert-supported cell.

After process step b), it is possible in particular for process step c): injection of at least one injection-molding component into the tubular cavity. The at least one Injection molding component can be designed in particular for forming a gas-tight or gas-permeable porous, in particular ceramic, material. In this case, the at least one injection-molding component can be converted into a gas-tight or gas-permeable, porous, in particular ceramic, material, in particular by the thermal treatment, in particular sintering, in process step d) and / or g) explained below. In this case, in particular the electrode layer (s) applied in method step b) or the functional layer system package applied in method step b) can be injection-molded with the at least one injection-molding component, which is also referred to as in-mold labeling or film-hit spraying. Specific embodiments of method step c) are explained in the context of the following explanations concerning the variants b1), b2) and b3) of method step b) and in the context of the explanations on multicomponent injection molding.

The injection-molded body produced in process step c), in particular connected to the electrode layer (s) or the functional layer system, can in particular be thermally treated, in particular sintered, and optionally thermally debinded in a process step d).

Within the scope of the first variant b1) of method step b), which is used in particular for producing an electrolyte-supported cell, the method comprises the method step b1): applying a storage electrode layer or an air electrode layer, in particular a storage electrode layer, to the tool core or to an inner wall of the cavity, especially on the tool core. In the context of this variant, initially only one electrode layer, optionally the storage electrode layer or the air electrode layer, is selectively applied to the tool core or to the inner wall of the cavity. The other, in particular corresponding, electrode layer, in particular the air electrode layer or the storage electrode layer, is then in a process step e) following process step d), in particular on the side opposite the electrode layer applied in process step b1), in particular outside or inside, of Injection molded body applied. Within the scope of the first variant b1) of process step b), in step c) at least in the electrode layer applied in step b1), in particular storage electrode layer or air electrode layer, limited section, in particular hollow cylindrical intermediate section, of the tubular cavity of the injection mold an injection molding component for forming a gas-tight, oxygen ion-conductive, in particular ceramic, (electrolyte) material injected.

Insofar as the electrode layer, in particular the storage electrode layer or the air electrode layer, is applied to the tool core in method step b1), this electrode layer serves to form an electrode layer on the inside of the injection molded body (support body) to be formed in the tubular cavity. In method step e), the other electrode layer, in particular air electrode layer or storage electrode layer, can then be applied to the outside of the injection molded body (carrier body). This can be done in method step e), for example by printing, in particular by a printing technique, for example screen printing, and / or doctoring and / or dipping.

Insofar as the electrode layer, in particular the storage electrode layer or air electrode layer, is applied to the inner wall of the cavity in method step b1), this electrode layer serves to form an electrode layer on the outside of the injection molded body (carrier body) to be formed in the tubular cavity. In method step e), the other electrode layer, in particular air electrode layer or storage electrode layer, can then be applied to the inside of the injection-molded body (carrier body). In addition, the process may also include process step f) in the context of process variant b1) after process step e): thermal treatment, in particular (post) sintering (postfiring) of the body from process step e).

The method variant b1) has the advantage that different methods can be used for applying the two electrode layers, for example in process step b1) in-mold labeling or film injection and in process step e) doctoring, dipping or printing to apply the respective electrode layer. Thus, for example, a very thin, for example air electrode layer, and by doctoring, dipping or printing a significantly thicker electrode layer, for example, storage electrode layer can be formed by in-mold labeling or film injection. In addition, method variant b1) after method step d) and before method step e) allows a method step e0) to be carried out, in which the side opposite the electrode layer applied in method step b1), in particular outside or inside, of the injection-molded body is subjected to ablative treatment, in particular abraded , for example externally ground, becomes. In this case, the wall thickness of the injection-molded body can be reduced. In addition to the side, in particular outer side, of the hollow-cylindrical intermediate section, in step e0) the outside of one or both end sections of the injection-molded body formed in the end sections of the injection molding tool can also be at least partially removed, in particular sanded off. However, in order to achieve a particularly high mechanical stability of the cell, it may be advantageous to remove only the hollow-cylindrical intermediate section and optionally at most only a part of the cap-shaped end section, in particular to abrade it. In method step e), the electrode layer can then be applied in particular to the abraded or abraded side, in particular outside or inside, of the injection-molded body, in particular of the hollow-cylindrical intermediate section of the injection-molded body.

In the context of a second variant of method step b), which also serves in particular for producing an electrolyte-supported cell, the method comprises the method step b2): applying a storage electrode layer on the tool core and an air electrode layer on an inner wall of the cavity opposite the tool core, or vice versa, ie In that an air electrode layer is applied to the tool core and a storage electrode layer is applied to an inner wall of the cavity opposite the tool core. In the second variant, consequently, both the storage electrode layer and the air electrode layer are applied on opposite parts of the injection molding tool in method step b2). Within the scope of the second variant b2) of method step b), an injection-molded component is also formed in method step c) at least in the electrode layers applied by method step b2), in particular the storage electrode layer and the air electrode layer, limited section, in particular hollow cylindrical intermediate section, of the tubular cavity of the injection molding tool for the formation of a gas-tight, oxygen ion-conductive, in particular ceramic, (electrolyte) material is injected.

The process variant b2) has the advantage that in this way an electrolyte-supported metal-air cell can be produced with a few process steps and in a particularly simple and time-saving manner.

In the context of a third variant, which is used in particular for producing an inertly supported cell, the method comprises the following step: b3) applying a functional layer system comprising a storage electrode layer comprising an air electrode layer, a storage electrode layer and an electrolyte layer formed between the air electrode layer and the storage electrode layer to the tool core or Inner wall of the cavity. In the third variant, consequently, in process step b3), the entire functional layer system comprising the storage electrode layer, the electrolyte layer and the air electrode layer is applied directly to a part of the injection molding tool. Within the scope of the third variant b3) of process step b), in process step c), at least in the functional layer system, limited section, in particular hollow cylindrical intermediate section, of the tubular cavity of the injection molding tool is an injection-molded component for forming a gas-permeable porous, in particular inert , ceramic material injected.

The process variant b3) on the one hand has the advantage that in this way an inert-supported metal-air cell can be produced with a few process steps and in a particularly simple and time-saving manner. On the other hand, the layer thicknesses can be set independently of each other in this way. This makes it possible in particular to achieve a thin layer thickness of the air electrode layer and an optimum layer thickness of the electrolyte layer and thus to realize a high efficiency and performance of the cell. On the other hand, the storage electrode layer can also be produced in the context of this process variant b3) with a large layer thickness, which is why the process variant b3) combines many advantages in itself.

To form the designed for mounting, in particular gasanschlussflanschförmigen, end portion and / or the cap-shaped end portion of the injection molded body of a different material than the hollow cylindrical intermediate portion, process step c) as a multi-component (ceramic) injection molding process, for example, a two-component - (ceramic) injection molding process, done. In particular, an injection molding tool with two or more tool units can be used.

In this case, in step c) in the at least one assembly (end) section-forming, in particular gasanschlussflanschbildenden, end portion and / or the cap-forming end portion of the tubular cavity of the injection mold, in particular a different injection-molded component are injected. In particular, in process step c), both in process variants b1) and b2) and process variant b3), in the at least one assembly (end) section-forming, in particular gasanschlussflanschbildenden, end portion and / or the cap-forming end portion of the tubular cavity of the injection mold one to form a gas-tight, non-oxygen ion conductive or inert or electrochemically inactive and / or electrically weakly conductive or electrically insulating, in particular ceramic, material to be injected.

The injection molding tool can furthermore be designed to have a, in particular tongue and groove-like, toothing, for example with an at least partially circumferential extension, of different injection body sections, for example between a hollow cylindrical intermediate section and an end section designed for assembly, in particular gas connection flange-shaped, end section and / or a cap-shaped To produce end section. In this case, the injection molding tool may for example be designed such that in the region of the toothing of the hollow cylindrical intermediate portion in particular substantially convex and designed for mounting, in particular gasanschlussflanschförmige, end portion or the cap-shaped end portion is in particular substantially concave.

For this purpose, for example, the first tool unit may have a cavity bounded by a structure for forming a part of a toothing, wherein in a first injection molding step a first injection molding component is injected against this structure from one side. For the second injection molding step, the resulting preform can then be transferred to a second tool unit, which has a limited by the toothing part of the preform or limited cavity, wherein injected in a second injection molding step, in particular from the opposite side, a second injection molding component against the toothing part of the preform becomes.

For example, the first tool unit may have a tubular cavity with a hollow-cylindrical intermediate section and a cap-forming end section and a tooth-forming end section and a gate section opening into the cap-forming or assembly end section, in particular opening into the gas connection flange through which the first injection molding component is injected in the first injection molding step. Thus, a preform can arise, which has a hollow cylindrical intermediate portion which merges on the one hand in a cap-shaped or designed for mounting, in particular gasanschlussflanschförmigen, end portion and on the other hand has a part of a toothing. For the second injection molding step, the resulting pre-molded part can then be transferred to a second tool unit, which has a limited by the toothing part of the pre-limb tubular cavity for forming a Montageendabschnittes, in particular Gasanschlussflansches, and a sprue opening therein, through which the second injection molding in the second Injection molded component is injected. In this way, the second injection-molded component can be injected against the toothing part of the pre-molded part and the toothing can be completed. Thus, in particular, an injection-molded body with a toothing, for example, between a hollow cylindrical intermediate portion and designed for mounting, in particular gasanschlussflanschförmigen, end portion can be realized.

By a similar approach, however, an injection molding with two or more gear units, for example, between a hollow cylindrical intermediate portion and a designed for mounting, in particular gasanschlussflanschförmigen, on the one hand and a cap-shaped or optionally further designed for mounting, in particular gasanschlussflanschförmigen On the other hand, the end portion can be realized.

The rib structure of the storage electrode layer and / or the air electrode layer can be produced both by in-mold labeling or film injection, for example by using a film with an already fin-structured electrode layer in process step b), in particular b1), b2) or b3), or by multi-component ( Ceramic) injection molding process can be formed.

For a design of the rib structure of the storage electrode layer and / or the air electrode layer by means of multi-component (ceramic) injection molding, in particular a two-or more tool units, in addition to the formation of the rib structure, can be used in method step a), wherein in process step c) additionally injected into the rib-forming portion of the injection molding tool designed to form an electrically conductive and redox-stable material injection molding component. In the context of this embodiment, the reversibly oxidizable and reducible material of the storage electrode or the electrochemically active material of the air electrode can be applied in a later method step, for example by means of doctoring, between the ribs of the rib structure. In this case, for example, the electrode material or an electrode material precursor, for example in oxidized form, in the form of a corresponding paste be applied for example via a dispenser or the like in depressions or compartments between the ribs of the rib structure and coated with a rotating doctor blade.

With regard to further technical features and advantages of the method according to the invention, reference is hereby explicitly made to the explanations in connection with the cell according to the invention, the uses according to the invention, the energy system according to the invention and to the description of the figures and the figures.

Furthermore, the invention relates to the use of a cell according to the invention or produced according to the invention.

In particular, the cell according to the invention or produced according to the invention can be used as a metal-air cell and / or as an electrolysis cell and / or as a fuel cell, in particular as a metal-air cell and / or as a combined metal-air fuel-electrolysis fuel cell become. For example, the cell according to the invention or produced according to the invention as a high-temperature metal-air cell and / or as a high-temperature electrolysis cell and / or as a high-temperature fuel cell, in particular as a high-temperature metal-air cell and / or as a combined high-temperature metal-air Fuel electrolysis fuel cell, used.

In this case, the cell according to the invention or produced according to the invention can be used, for example, for storing an excess of electricity, for example a photovoltaic system and / or wind energy plant and / or biogas plant or for the production of energy storage systems, in particular for the aforementioned plants. For example, the cell according to the invention or inventively produced in an energy storage and / or -wandleranlagen, for example, a so-called power storage system, for example for a wind turbine and / or photovoltaic system and / or biogas plant, can be used.

With regard to further technical features and advantages of the uses according to the invention, reference is hereby explicitly made to the explanations in connection with the cell according to the invention, the method according to the invention, the energy system according to the invention and to the description of the figures and the figures.

Furthermore, the present invention relates to an energy system, for example an energy storage and / or converter system or a (micro) combined heat and power plant or a heat-coupled energy storage and / or converter plant, for example for a photovoltaic system, a wind turbine, a biogas plant , a residential or commercial building, an industrial plant, a power plant or a vehicle, in particular for a photovoltaic system and / or wind power plant, which / s comprises at least one inventive or inventively manufactured cell and / or used according to the invention. A (micro) combined heat and power plant may, in particular, be understood to mean a plant for the simultaneous generation of electricity and heat from an energy source.

The energy system may further include a gas line system. In this case, the at least one cell can be fastened or fastened on a carrier element, in particular a carrier plate, of the gas line system. In a state fastened to the carrier element, in particular the outer environment around the cell is in a gas-tight manner separated from the interior of the cell.

The gas line system may further comprise at least one gas lance, which, on the one hand, opens into a first gas line, in particular in the form of a channel, extends through a continuous opening in the carrier element and, on the other hand, opens into the interior of the at least one cell. The interior of the cell can open into a second gas line, in particular in the form of a channel, surrounding the gas lance, and in turn surrounded by an opening section, in particular designed for mounting, for example gas connection flange end section , The gas lance can extend through the second gas line. The second gas line can be formed between the first gas line and the carrier element and in particular parallel thereto. In this case, the first and second gas line may have a common wall, in particular which has at least one through opening for inserting the at least one gas lance. The carrier element can form a further wall of the second gas line.

With regard to further technical features and advantages of the energy system according to the invention, reference is hereby explicitly made to the explanations in connection with the cell according to the invention, the method according to the invention, the uses according to the invention and to the description of the figures and the figures.

Further advantages and advantageous embodiments of the subject invention are illustrated by the drawings and explained in the following description. It should be noted that the drawings only descriptive and are not intended to limit the invention in any way. Show it

1 - 4 schematic cross-sections through different embodiments of electrolyte-supported, tubular metal-air cell according to the invention;

5 - 12 schematic cross sections through different embodiments of the invention, inertially supported, tubular metal-air cell;

13 . 14 schematic cross-sections illustrating a toothed configuration of a tubular carrier body of a tubular metal-air cell according to the invention;

15a -C are schematic sections for illustrating special embodiments of a cap-shaped end portion of a tubular support body of a tubular metal-air cell according to the invention;

16a F schematic cross sections to illustrate embodiments of a method according to the invention;

17 a sketch illustrating the operation of a metal-air cell;

18 a schematic cross section illustrating an embodiment of an inventive, operable solely as a metal-air cell electrochemical cell; and

19 a schematic cross-section illustrating an embodiment of an energy system according to the invention, which has an embodiment of a combined metal-air-electrolysis-fuel cell according to the invention.

The 1 to 4 show embodiments of electrolyte-supported, tubular metal-air cells according to the invention. The 1 to 4 illustrate that the tubular metal-air cells 10 a, for example, injection-molded, tubular carrier body 11 having a hollow cylindrical intermediate section 111 and two end sections 112 . 113 having. The hollow cylindrical intermediate section 111 of the tubular carrier body 11 is in the, in the 1 to 4 embodiments shown formed from a gas-tight, oxygen-ion conductive material. The in the 1 to 4 shown metal-air cell 10 may therefore be referred to in particular as electrolyte-supported metal-air cells. In the gas-tight, oxygen-ion conductive material 111 of the tubular carrier body 11 it may be, for example, a rare earth, in particular Sc, Y, Ce, doped zirconia (ZrO ₂ ). Such electrolyte materials may advantageously be gastight after sintering, so that the gas spaces through the tubular support body 11 be separated or along the tubular carrier body 11 stay separated. 1 and 4 also illustrate the circumferential direction U and the longitudinal axis L of the tubular support body 11 ,

The 1 to 4 show that from the two end sections 112 . 113 of the tubular carrier body 11 , the one 113 designed as a cap, which 113 the tubular carrier body 11 closes on one side. The in the 1 to 4 shown cells 10 may therefore be referred to as unilaterally closed cells in particular. The 2 to 4 show that the end section 112 , on the cap-shaped end portion 113 opposite side, is designed as a gas connection flange. The gas connection flange 112 can have a precise surface grinding, by which it can be clamped to a precision-ground counter flange of a gas supply line or a carrier plate (FIG. 20 , please refer 2 and 3 ) is connectable. On a seal of glassy materials can be advantageously dispensed with. However, there are also other, in particular flat, without possibly one or more seals having terminal configuration conceivable.

The 1 to 4 illustrate that on the hollow cylindrical intermediate section 111 of the tubular carrier body 11 a storage electrode layer 13 and an air electrode layer 12 located, each extending over the entire inner and outer straight surface (tube surface). The cap-shaped end section (dome) 113 however, it is not coated.

The storage electrode layer 13 is located on the electrolyte surface 111 on the inside or inside the tubular carrier (tube) 11 , The storage electrode layer 13 In particular, it comprises a reversibly oxidizable and reducible material between a metallic form and an oxidic form 131 , The air electrode layer 12 is located on the electrolyte surface 111 on the outer side or the outer surface of the tubular carrier body (tube) 11 and may comprise, for example, an oxygen-ion-conducting or mixed-conducting ceramic as the electrochemically active material. Alternatively, the electrode layers 12 . 13 also be reversed from their position.

Optionally, the storage electrode layer 13 and / or the air electrode layer 12 one or more ceramic interconnects (not shown), can be realized either over the entire surface or web-shaped. In this case, the interconnector material may be dense or porous.

The 2 and 3 show that the metal-air cell 10 via the gas connection flange-shaped end section 112 with a carrier plate 20 can be connected, which in the region of the interior of the cell 10 has a continuous opening through which a gas lance 30 in the interior of the cell 10 is guided. The double arrows illustrate that by the gas lance 30 surrounding area of the continuous recess in the support plate 20 and the gas lance 30 a gas through, the interior of the cell 10 can be performed. About the outside of the cell 10 surrounding space can be another gas supplied or removed. The hollow cylindrical intermediate section 111 can do this - exclusive of the two electrode layers 12 . 13 - For example, a wall thickness d of ≥ 15 microns to ≤ 300 microns, auweisen. As part of the 16a to 16f explained in more detail, can be a tubular metal-air cell 10 with such a small wall thickness by (ceramic) injection molding, optionally be achieved in combination with a grinding process. In particular, therefore, the hollow cylindrical intermediate portion may have a ground off outside, on which in turn the outer electrode layer 12 is applied.

As part of the in 1 . 2 and 4 Shown embodiment, the gasanschlussflanschförmige end portion (not shown in FIG 1 ) and the cap-shaped end portion 113 from the same, gas-tight, oxygen-ion-conductive material as the hollow-cylindrical intermediate section 111 educated. The visible edges between the sections 111 . 112 ; 111 . 113 serve therefore essentially to illustrate the hollow cylindrical 111 , gas connection flange shaped 112 and cap-shaped 113 Section.

The as part of 3 The embodiment shown differs essentially from that in FIG 2 shown embodiment, that the gland flange end portion 112 is formed of a different material than the hollow cylindrical intermediate section 111 , In addition, if appropriate, the cap-shaped end portion 113 from the material of the gas connection flange-shaped end section 113 be educated. In particular, the gas connection flange-shaped end section is in this case 112 and optionally the cap-shaped end portion 113 from a gas-tight, non-oxygen conductive or electrochemically inactive material, in particular with a particularly high mechanical stability formed. Characterized in that the material of the gas connection flange end portion 112 can not be selected from the group of oxygen ion conductive materials, the material can be advantageously selected from a wider range of materials.

In the 2 and 3 With the reference numerals A and B marked sections can - as in the context of 13 and 14 explained in more detail - have a toothing in the context of a specific embodiment.

4 indicates that the storage electrode layer 13 inside the tubular carrier (tube) 11 a rib structure 132 of a ceramic, electrically conductive and redox-stable material, for example, an interconnect material may have, between which the reversibly oxidizable and reducible material 131 the storage electrode layer 13 is trained. From the electron-conducting and redox-stable material or interconnector material 132 can, for example, on the inside or the inner side of the tubular support body 11 Longitudinal ribs or grid-shaped ribs 132 be carried out in their sinks the reversibly oxidizable and reducible material 131 the storage electrode layer 13 (Anode material / cathode material depending on the mode of operation) is introduced. Advantageous electrically conductive and redox-stable materials or interconnector materials 132 are for example from LaCrO ₃ or scandium-doped lanthanum-strontium-manganese oxide. Ribs 132 may for example have a height or thickness of 20 to 200 microns or even up to 1000 microns. 4 illustrates that the height or thickness of the ribs 132 greater than the thickness of the reversibly oxidizable and reducible material 131 the storage electrode layer 13 , especially in oxidized form.

The 5 to 12 show embodiments of inert, inert, tubular metal-air cell according to the invention 10 , As part of the in the 5 to 12 shown embodiments is the hollow cylindrical intermediate section 111 of the tubular carrier body 11 , not as part of the in the 1 to 4 shown electrolyte-supported embodiments of a gas-tight, oxygen-ion conductive material, but from gas-permeable porous, inert ceramic support material formed. As part of the in the 5 to 12 The embodiments shown serve the tubular carrier body 11 consequently not as an electrolyte, but only as a carrier. Therefore, an additional electrolyte layer 14 provided, which between the air electrode layer 12 and the storage electrode layer 13 is arranged. Overall, the air electrode layer form 12 , the electrolyte layer 14 and the Storage electrode layer 13 a functional layer system package.

This functional layer system 12 . 14 . 13 is part of the in the 5 . 7 . 9 and 11 shown embodiments on the outside and in the frame in the 6 . 8th . 10 and 12 shown embodiments on the inside of the tubular support body 11 , in particular of its hollow cylindrical intermediate section 111 arranged. As part of the in the 9 to 12 shown embodiments, the storage electrode layer 13 a rib structure 132 of an electrically conductive and redox-stable material, between the ribs 132 the reversibly oxidizable and reducible material 131 the storage electrode layer is formed, wherein the height or thickness of the ribs 132 greater than the thickness of the reversibly oxidizable and reducible material 131 the storage electrode layer 13 , especially in oxidized form.

As part of the in 5 and 8th The embodiments shown adjacent borders the reversibly oxidizable material 132 the storage electrode layer 13 on the one hand (directly) to the gas-permeable porous intermediate section 111 of the tubular carrier body 11 and on the other hand to the electrolyte layer 14 of the functional layer system 12 . 14 . 13 at. The air electrode layer 12 on the one hand adjoins that of the storage electrode layer 13 opposite side of the electrolyte layer 14 of the functional layer system 12 . 14 . 13 on the other hand is open.

As part of the in the 6 . 7 . 10 and 11 the embodiments shown adjacent the air electrode layer 12 on the one hand to the gas-permeable porous intermediate section 111 of the tubular carrier body 11 and on the other hand to the electrolyte layer 14 of the functional layer system 12 . 14 . 13 at. The reversibly oxidizable material 132 the storage electrode layer 13 on the one hand adjoins that of the air electrode layer 12 opposite side of the electrolyte layer 14 of the functional layer system 12 . 14 . 13 on the other hand is open.

As part of the in the 9 and 12 Embodiments shown is at least in one form of reversibly oxidizable and reducible material 131 the storage electrode layer 13 , in which its layer thickness is less than its maximum layer thickness, in particular in oxidized form, is, for example in an at least partially reduced form, due to the rib structure 132 the storage electrode layer 13 a cavity 133 between the porous intermediate section 111 of the tubular carrier body 11 and the reversibly oxidizable and reducible material 131 the storage electrode layer 13 in front. This is bordered by the reversibly oxidizable and reducible material 131 the storage electrode layer 13 therefore not as in the 5 and 8th embodiments shown directly to the gas-permeable porous intermediate section 111 of the tubular carrier body 11 at. The cavity 133 can in particular laterally through the ribs of the rib structure 132 the storage electrode layer 13 be limited.

13 exemplified by an enlarged view of the in 2 or 3 designated by the reference A region of an electrolyte-supported metal-air cell 10 in that in the context of a special embodiment between the hollow cylindrical intermediate section 111 and the gland flange end portion 112 a tongue and groove type toothing 15 can be trained. An analogous, tongue and groove type of toothing 15 can also be in an inert-supported metal-air cell between the hollow cylindrical intermediate section 111 and the gland flange end portion 112 be formed.

14 exemplified by an enlarged view of the in 3 designated by the reference B region of an electrolyte-supported metal-air cell 10 in that in the context of another special embodiment between the hollow cylindrical intermediate section 111 and the cap-shaped end portion 113 a tongue and groove type toothing 16 can be trained. An analogous, tongue and groove type of toothing 16 can also be in an inert-supported metal-air cell between the hollow cylindrical intermediate section 111 and the cap-shaped end portion 113 be formed.

These tongue and groove type gears 15 . 16 may have an at least partial or possibly complete circumferential extent. Preferably, the teeth are 15 . 16 thereby formed such that thereby the electrochemically active surface of the cell 10 not or at least possible little reduced. This can be done, for example, by the fact that - as in 13 and 14 shown - in the gearing area 15 . 16 the hollow cylindrical intermediate section 111 substantially convex and the gland flange end portion 112 or the cap-shaped end portion 113 is substantially concave. In 13 and 14 is just a simple gearing 15 . 16 shown. To the mechanical stability of the connection area between the hollow cylindrical intermediate section 111 and the gland flange end portion 112 or the cap-shaped end portion 113 However, to increase further, can be a multiple gearing 15 . 16 , for example in shape a double or triple tongue and groove profile or wave profile, be useful.

The 15a to 15c illustrate exemplified by an electrolyte-supported metal-air cell 10 a special embodiments of the cap-shaped end portion 113 in which the cap-shaped end portion 113 three circumferentially distributed trained, in particular to each other rotationally symmetrical inner struts 17 ( 15a ) or indents 17 ( 15b ) having. An analogous, training the cap-shaped end portion 113 can also be formed in an inert-supported metal-air cell. The 15a and 15b show in particular schematic cross-sectional detail, in a relative to the in the 1 to 12 shown about the cell longitudinal axis rotated cross-sectional plane. 15c shows a schematic cross sections of the in the 15a and 16b shown cap portion configurations, in a direction perpendicular to the cell longitudinal axis cross-sectional plane. The 15a to 15c illustrate that the inner struts 17 or indents 17 delimiting a free space extending therebetween such that its diameter extends along the axis of symmetry of the hollow cylindrical intermediate section 111 toward the center of the cap-shaped end portion 113 reduced. By such trained inner struts 17 or indents 17 can advantageously centering and stabilizing the gas lance 30 be achieved.

The 16a to 16f illustrate embodiments of methods of making electrolyte-supported metal-air cells according to the present invention 10 ,

16a shows that initially in a method step a) an injection molding tool 40 which has a cylindrical cavity and an injection mold core positioned in the longitudinal center axis of the cavity, wherein a tubular cavity is formed by inserting the injection mold core into the cavity 41 with a hollow cylindrical intermediate section 411 , an end section designed to form a gas connection flange 412 and an end portion designed to form a cap 413 can be trained.

16b illustrates that in the context of a variant b1) of a process step b) an electrode layer 13 , For example, a storage electrode layer or an air electrode layer is applied to the tool core in a position in which the electrode layer 13 in the introduced into the cavity state of the tool core, the hollow cylindrical intermediate section 411 of the tubular cavity 41 limited. The dashed rectangles illustrate that alternatively, in the context of an inverted variant b1), the electrode layer (FIG. 12 . 13 ) on the opposite, the hollow cylindrical intermediate section 411 of the tubular cavity 41 limiting inner wall of the cavity can be applied. Or in the context of a variant b2) can both on the tool core 13 ( 12 ) as well as on the inner wall of the cavity ( 12 . 13 ) in each case an electrode layer can be applied. Or in the context of a variant b3), a functional layer system package can be applied to the tool core 13 ( 12 ) or the inner wall of the cavity ( 12 . 13 ) can be applied.

Regardless of the specific variant, the electrode layer 13 or the electrode layers 12 . 13 or the functional layer system package 12 . 14 . 13 in particular by a plastic film (not shown) are worn. The injection molding tool core is preferably shaped so that the plastic film can be applied to it (not shown). This can be achieved, for example, by the foot of the tool core having a larger outer diameter around the film thickness, so that the film can be pushed over the tip of the tool core onto the tool core and the side surface of the film can be applied to the side surface of the tool core foot (not shown).

16c illustrates that in a process step c) an injection molding component 11 in the tubular cavity 41 was injected. 16c illustrates that while the injection molding component 11 the electrode layer 13 flowed over - without this move or aufwellen - and thereby intimately with the material of the electrode layer 13 combines.

16c illustrates that - because the electrode layer 13 projects beyond the outer diameter of the tool core in this embodiment - the injection-molded component is molded not only on the outer surface, but also on the side surfaces, so that in the gasanschlussflanschbildenden 412 and the cap-forming 413 End section injected material laterally to the electrode layer 13 borders. To train in the 2 . 3 . 13 and 14 In embodiments shown, in method step c), two or more injection molding components different from one another can also be used. If appropriate, method step c) can have two or more process steps. In particular, an injection molding tool with two or more tool units can be used. For example, in a first tool unit from a first injection-molded component, an injection-molded body, a so-called pre-molded part, can be formed, which is then in a second tool unit transferred and molded there with a second injection molding component.

16d illustrates that after removal from the mold, the injection-molded body produced in process step c) 11 . 13 the shape of a one-sided closed tube 111 . 113 with a gas connection flange 112 and with an electrode layer applied to the inside 13 , which up to the gas connection flange 112 enough. In the context of the reverse variant b1), the electrode layer can be on the outside, in variants b2) in each case an electrode layer on the inside and an electrode layer on the outside, and in variant b3) a complete functional layer system 12 . 14 . 13 be applied to the inside or outside (not shown). Optionally, after a thermal debindering the injection molded body produced in process step c) 11 . 13 be sintered in a process step d).

16e shows that in the case of the variant b1) in a process step e0) the outside of the hollow cylindrical intermediate section 411 of the injection mold 40 formed hollow cylindrical intermediate section 111 of the injection-molded body 11 . 13 can be ground down. As part of the in 16e The embodiment shown here was only the outside of the hollow cylindrical intermediate section 111 sanded, wherein the outside of the gasanschlussflanschförmigen end portion 112 and the cap-shaped end portion were not abraded. 16f shows that then in a method step e) on the ground outside (ground surface) of the hollow cylindrical intermediate portion 111 of the injection-molded body 11 . 13 another electrode layer 12 was applied. Subsequently, the injection-molded body produced in process step e) 11 . 12 . 13 in a process step f) are still sintered (Postfiring).

17 illustrates the operation of a metal-air cell, which is an air electrode layer 12 , a metal-metal oxide storage electrode layer, and an oxygen-ion conductive electrolyte layer formed therebetween 111 . 14 having. 17 illustrates that when the cell is supplied with electrical energy and charged 51 , Oxygen ions (O ^2- ) from the storage electrode layer 13 (Metal-metal oxide electrode) through the electrolyte layer 111 . 14 to the air electrode layer 12 hike. If, however, to the cell, a load or a consumer 52 and the cell is discharged, the oxygen ions (O ^2- ) migrate from the air electrode layer 12 through the electrolyte layer 111 . 14 to the storage electrode layer 13 (Metal-metal oxide electrode).

18 shows that the cell 10 can be operated exclusively as a metal-air cell in one embodiment. In this case, the cell a the interior of the tubular carrier body 11 facing storage electrode layer 13 , one for mounting the cell 10 on a support element 20 designed end section 112 and an end portion configured as a closed cap 113 and on a closed carrier element 30 be mounted. About the outside of the tubular carrier body 11 surrounding space can be passed air or oxygen. In the interior of the tubular carrier body 11 If appropriate, an inert gas atmosphere can be provided. 18 also illustrates a cell whose end section designed for mounting 112 is formed from another, in particular gas-tight, electrically insulating, ceramic material as the hollow cylindrical intermediate section 111 and cap-shaped end portion 113 , which are formed in particular of a gas-tight electrolyte material.

19 shows a schematic cross section illustrating an embodiment of an energy system according to the invention, which is a gas line system 55a . 55b . 56a . 56b and several via electrical lines 31 . 32 in series, combined metal-air electrolysis fuel cells 10 includes. About electrical circuits 53 . 54 can be the metal-air electrolysis fuel cells 10 with a power supply 51 , in particular a DC power supply, for example a photovoltaic system, (charging) or a load 52 (Discharge) are electrically connected.

The arrows 55a and 55b illustrate that the outer sides of the tubular support body 11 of the tubular metal-air electrolysis fuel cells 10 surrounding space a gas, such as air in the metal-air cell discharge operation and / or fuel cell operation, led out and, for example, oxygen in metal-air-cell charging operation and / or electrolysis operation, can be dissipated. The arrows 56a and 56b illustrate that another gas, for example hydrogen and / or carbon monoxide in fuel cell operation, or water and / or carbon monoxide in the electrolysis operation, the interior of the tubular support body 11 to led and, for example, water and / or carbon dioxide in fuel cell operation, or hydrogen and / or carbon monoxide in the electrolysis operation, can be dissipated.

19 illustrates that while doing the cells 10 gas connection flange-shaped end sections 112 and a support element 20 are mounted, which continuous openings 200 as well as the openings 200 bounding clamps 202 having. 19 shows that while the terminals 202 of the carrier element 20 the gas-terminal end portions 112 pinch and thereby on the support element 20 fix. On the support element 20 are also contact elements 33 attached, which are designed on the one hand electrically insulating with respect to the support element and on the other hand, the cells 10 in series switching, electrical lines 31 . 32 are electrically connected to each other. 10 further illustrates that in the on the support element 20 attached state the external environment around the cells 10 gas-tight from the interior of the cell 10 is disconnected.

19 further shows that the gas pipeline system 55a . 55b . 56a . 56b gas lances 30 has, which in each case on the one hand in a first gas line 20A flow through the continuous openings 200 in the carrier element 20 extend and on the other hand, respectively in the interiors of the cells 10 lead. The interiors of the cells 10 in turn lead respectively via the respective gas lance 30 surrounding, and in turn itself from the gas connection flange-shaped end portion 112 surrounded, opening areas 110 the tubular carrier body 11 the cells 10 in a second gas line 20B , The second gas line 20B is between the first gas line 20A and the carrier element 20 and in particular parallel thereto, formed and has one with the first gas line 20A common wall 21 on. The common wall 21 the first 20A and second 20B Gas line has push-through openings 210 on, through which the gas lances 30 from the first gas line 20A through the second gas line 20B through into the interiors of the cells 10 extend. At the same time the gas lances open 30 on the one hand via an opening 300 in the first gas line 20A and then another opening 310 into the interiors of the tubular cells 10 , The first gas line 20A delimiting, dashed line indicates that the gas line 20A may either have another wall at this point, or that the complete gas line cell system can be mirrored or doubled on this side.

QUOTES INCLUDE IN THE DESCRIPTION

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Cited patent literature

• WO 01/80335 A3 [0011]

Claims (15)

Tubular metal-air cell ( 10 ), in particular high-temperature metal-air cell, comprising - a tubular carrier body ( 11 ), and - a functional layer system ( 12 . 13 . 111 ; 12 . 13 . 14 ) from an air electrode layer ( 12 ), a storage electrode layer ( 13 ) and one between the air electrode layer ( 12 ) and the storage electrode layer ( 13 ) formed electrolyte layer ( 111 . 14 ), wherein the storage electrode layer ( 13 ) a reversibly oxidizable and reducible material between a metallic form and an oxidic form ( 131 ), wherein the tubular carrier body ( 11 ) a section ( 111 ) comprises a gas-tight, oxygen-ion-conductive material, which as the electrolyte layer ( 111 ) of the functional layer system ( 12 . 13 . 11 ) or wherein the tubular carrier body ( 11 ) a section ( 111 ) of a gas-permeable porous, ceramic material, on whose ( 111 ) Outside or inside the functional layer system ( 12 . 13 . 14 ) is applied. Tubular metal-air cell ( 10 ) according to claim 1, wherein the reversibly oxidizable and reducible material of the storage electrode layer ( 13 ) in oxidized form has a maximum layer thickness in oxidic form in a range of ≥ 300 μm to ≤ 2500 μm. Tubular metal-air cell ( 10 ) according to claim 1 or 2, wherein the electrolyte layer ( 111 . 14 ) has a layer thickness in a range of ≥ 15 microns to ≤ 300 microns. Tubular metal-air cell ( 10 ) according to one of claims 1 to 3, wherein the storage electrode layer ( 13 ) formed from an electrically conductive and redox-stable material rib structure ( 132 ), wherein the reversibly oxidizable and reducible material ( 131 ) of the storage electrode layer ( 13 ) between the ribs of the rib structure ( 132 ) is trained. Tubular metal-air cell ( 10 ) according to claim 4, wherein the ribs of the rib structure ( 132 ) of the storage electrode layer ( 13 ) have a height which is greater than or equal to the maximum layer thickness of the reversibly oxidizable and reducible material ( 131 ) in oxidic form. Tubular metal-air cell ( 10 ) according to one of claims 1 to 5, wherein the tubular carrier body ( 11 ) a hollow cylindrical intermediate section ( 111 ) and two end sections ( 112 . 113 ), wherein the hollow cylindrical intermediate section ( 111 ) the section formed of the gas-tight, oxygen-ion-conductive material ( 111 ) or the portion formed from the gas-permeable porous ceramic material ( 111 ), wherein at least one of the end sections ( 112 . 113 ) of the tubular carrier body ( 11 ) for mounting the cell ( 10 ), in particular on a carrier element ( 20 ), in particular wherein the at least one end section ( 112 ) is designed as a gas connection flange. Tubular metal-air cell ( 10 ) according to claim 6, wherein the other end portion ( 113 ) of the tubular carrier body ( 11 ) is designed as a closed cap. Tubular metal-air cell ( 10 ) according to claim 6 or 7, wherein the at least one designed for mounting, in particular gasanschlussflanschförmige, end portion ( 112 ) and / or the cap-shaped end portion ( 113 ) of a different material than the hollow cylindrical intermediate section ( 111 ), in particular wherein the at least one, designed for mounting, in particular gasanschlussflanschförmige, end portion ( 112 ) and / or the cap-shaped end portion ( 113 ) is formed of a gas-tight, inert, in particular electrically insulating, ceramic material. Tubular metal-air cell ( 10 ) according to one of claims 6 to 8, wherein between the designed for mounting, in particular gasanschlussflanschförmigen, end portion ( 112 ) and the hollow cylindrical intermediate section ( 111 ), in particular tongue and groove-like, toothing ( 15 ), and / or wherein between the cap-shaped end portion ( 113 ) and the hollow cylindrical intermediate section ( 111 ), in particular tongue and groove-like, toothing ( 16 ), is trained. Tubular metal-air cell ( 10 ) according to one of claims 6 to 9, wherein the cap-shaped end portion ( 113 ) at least three, in particular circumferentially distributed, indents and / or inner struts ( 16 ), wherein the indents and / or struts ( 16 ) of a clearance extending therebetween whose diameter is along the axis of symmetry of the hollow cylindrical intermediate section ( 111 ) in the direction of the center of the cap-shaped end portion ( 113 ) decreased. Tubular metal-air cell ( 10 ) according to one of claims 1 to 10, wherein the storage electrode layer ( 13 ) the interior of the tubular carrier body ( 11 ) and the air electrode layer ( 12 ) of the external environment around the tubular carrier body ( 11 ) is facing. Tubular metal-air cell ( 10 ) according to any one of claims 1 to 11, wherein the cell is a combined metal-air electrolysis fuel cell. Method for producing a tubular metal-air cell ( 10 ), in particular according to one of claims 1 to 12, comprising the method steps: a) providing an injection molding tool ( 40 ) with a cavity and an injection mold core insertable into the cavity, wherein by inserting the injection mold core into the cavity a tubular cavity ( 41 ) can be formed; and b1) applying a storage electrode layer ( 13 ) or an air electrode layer ( 12 ) on the tool core or on an inner wall of the cavity; or b2) applying a storage electrode layer ( 13 ) on the tool core and an air electrode layer ( 12 ) on an inner wall of the cavity opposite the tool core, or vice versa; or b3) applying a storage electrode layer ( 13 ) functional layer system ( 12 . 13 . 13 ) from an air electrode layer ( 12 ), the storage electrode layer ( 13 ) and one between the air electrode layer ( 12 ) and the storage electrode layer ( 13 ) formed electrolyte layer ( 111 . 14 ) on the tool core or an inner wall of the cavity; and c) injecting at least one injection molding component ( 11 ) in the tubular cavity ( 41 ), and d) thermal treatment, in particular sintering, of the injection-molded body ( 11 . 13 ; 11 . 12 . 13 . 14 ) from process step c), wherein the process in the case of process variant b1) furthermore after process step d) process step e). Application of an air electrode layer ( 12 ) or a storage electrode layer ( 13 ) on the side of the injection-molded body which is opposite the electrode layer applied in method step b1) ( 11 . 13 ; 11 . 12 . 13 . 14 ), wherein the storage electrode layer ( 13 ) a reversibly oxidizable and reducible material between a metallic form and an oxidic form ( 131 ) or a material precursor which, in process step d), is converted into a material which is reversibly oxidizable and reducible between a metallic form and an oxidic form (US Pat. 131 ) is convertible. Use of a cell according to one of claims 1 to 11 or a cell produced by a method according to claim 13, as a metal-air cell or as an electrolysis cell or as a fuel cell, in particular as a combined metal-air electrolysis fuel cell, in particular for a Photovoltaic system or a wind turbine. Energy system, in particular for a photovoltaic system, a wind turbine, a biogas plant, a residential or commercial building, an industrial plant, a power plant or a vehicle which / s at least one cell according to one of claims 1 to 14 and / or used, in particular wherein the Energy system continues to use a gas pipeline system ( 55a . 55b . 56a . 56b ), wherein the at least one cell ( 10 ) on a carrier element ( 20 ) of the gas pipeline system ( 55a . 55b . 56a . 56b ) is fastened or fastened, wherein in one of the support element ( 20 ) attached state the external environment around the cell ( 10 ) gas-tight from the interior of the cell ( 10 ), the gas line system ( 55a . 55b . 56a . 56b ) at least one gas lance ( 30 ), which on the one hand into a first gas line ( 56a ), through a continuous opening ( 200 ) in the carrier element ( 20 ) and on the other hand into the interior of the at least one cell ( 10 ), wherein the interior of the at least one cell ( 10 ) over one, the gas lance ( 30 ), and in turn itself from one, in particular gasanschlussflanschförmigen, end portion ( 112 ) of the tubular carrier body ( 11 ) of the cell ( 10 ), opening area ( 110 ) in a second gas line ( 56b ) opens.

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