EP2959525A1

EP2959525A1 - Solid tubular oxide cell

Info

Publication number: EP2959525A1
Application number: EP14705792.1A
Authority: EP
Inventors: Herbert Gruhn; Uwe Glanz; Gudrun Oehler; Ney MOREIRA; Markus Siebert
Original assignee: Robert Bosch GmbH
Current assignee: Robert Bosch GmbH
Priority date: 2013-02-25
Filing date: 2014-02-24
Publication date: 2015-12-30
Also published as: WO2014128292A1; JP6198854B2; JP2016507880A; CN104995775A; DE102013203039A1; KR20150122144A

Abstract

The invention relates to a method for producing a solid tubular oxide cell (10), in particular a fuel cell. The aim of the invention is to produce a solid tubular oxide cell, for example a solid oxide fuel cell with an inner electrode package, using few process steps and with a low reject rate in particular. This is achieved in that in a method step a) a substrate (1) is provided which (1) is made of a component for forming a gas-permeable porous ceramic material, which is inert in particular, or is made of a material which can be burned out in an ash-free manner. In a method step b) an electrode package (11) is applied onto the substrate. In a method step c) the substrate (1) provided with the electrode package (11) is introduced into a cavity of an injection molding tool such that the electrode package (11) delimits a hollow cylindrical cavity. In a method step d) an injection molding component (12) is injected into the hollow cylindrical cavity. In a method step e) the injection molded body (11, 12) is then sintered, wherein the component for forming a gas-permeable porous ceramic material is converted into a gas-permeable porous ceramic material, or the material which can be burned out in an ash-free manner is burned out. The invention further relates to a solid tubular oxide cell, in particular a solid oxide fuel cell, to the use thereof, and to a correspondingly equipped energy system.

Description

Description title

Tubular solid oxide cell

The present invention relates to a process for the preparation of a tubular solid oxide cell, solid oxide cells and their use and a correspondingly equipped energy system.

State of the art

Solid oxide fuel cells (Solid Oxide Fuel Cells, SOFC) with ceramic cells are one of the high-temperature variants of the fuel cell. They will join

600 ° C to 1000 ° C operated and deliver the highest electrical

Efficiencies of about 50%.

The solid oxide fuel cells are mainly developed in two main variants: as a tube (tubular concept) and as a flat membrane (planar concept).

Document DE 198 01 440 A1 describes a method for producing an electrode-electrolyte unit for a high-temperature fuel cell. The document JP 09199138 A describes a method for producing a

Electrode for a fuel cell.

The document EP 1 237 065 Bl describes a Herstellungsverfah

Solid oxide fuel cells. Disclosure of the invention

The present invention is a process for producing a tubular solid oxide cell.

In a method step (a), in particular a substrate is used

provided, which consists of a component for forming a

gas-permeable porous, ceramic material or is formed from an ashless ausbrennbaren material.

In a method step (b), in particular an electrode package is applied to the substrate.

By means of film injection molding can, for example, to the provided with the electrode package substrate, in particular by ceramic injection molding

tubular, (carrier) body are molded.

This can be done, for example, by virtue of the fact that, in a method step (c), the substrate provided with the electrode packet enters a cavity of a

Injection molding tool is introduced, in particular wherein the electrode package of the substrate provided with the electrode package has a cavity

or the cavity is limited, and in a method step (d) an injection molding component, in particular in the cavity or the cavity, is injected.

In particular, in a method step (c), the substrate provided with the electrode package can be introduced into a cavity of an injection molding tool such that the electrode package delimits a hollow cylindrical cavity. In a method step (d), an injection-molded component can then be injected into the hollow-cylindrical cavity.

In a process step (e), in particular the injection-molded body, for example from process step d), sintered, wherein the component for forming a gas-permeable porous, ceramic material in a gas permeable porous, ceramic material is transferred or wherein the ashless ausbrennbare material is burned out.

A solid oxide cell may be, for example, a solid oxide fuel cell and / or solid oxide electrolysis cell and / or solid oxide metal-air cell. In particular, the method can be designed for producing a solid oxide fuel cell and / or solid oxide electrolysis cell and / or solid oxide metal-air cell, for example a solid oxide fuel cell or solid oxide electrolysis cell, for example a solid oxide fuel cell.

The method advantageously makes possible a tubular solid oxide cell, in particular a tubular solid oxide cell with an internal one

Electrode package, for example with an internal

Functional layer system package of an anode layer, a cathode layer and an electrolyte layer disposed therebetween, in a simple manner. It can be both when using a substrate from a

Component for forming a gas-permeable porous, ceramic material as well as when using a substrate of an ashless

ausbrennbaren material advantageously saved process steps,

Damage to the electrode package, in particular the

Function layer system package, avoided and / or lowered the reject rate.

In particular, both when using a substrate from a

ausbrennbaren material advantageously demolding processes are reduced or avoided. So can advantageously damage the

Electrode package, in particular the functional layer system package, avoided and / or the rejection rate can be lowered.

In the film backing, the electrode package, in particular the functional layer system package, can be produced directly from the injection-molded component during the injection process on the injection-molded body or green body be fixed so that advantageously further manufacturing steps can be saved.

Insofar as the substrate consists of a component for forming a

porous, gas-permeable, ceramic material is formed, formed during the sintering process, the gas-permeable porous, ceramic material and connects cohesively with the electrode package

or functional layer system, for example an anode layer or cathode layer of the functional layer system, and remains as a gas-permeable porous wall, through which gas, for example

Hydrogen / fuel gas or air, to the electrode package

or functional layer system, for example, to the anode layer or cathode layer of the functional layer system, can diffuse through. Since the substrate remains as a sufficiently gas-permeable wall on the electrode package, in particular functional layer system package, eliminates additional process steps for demolding and there can be no unwanted residues remain.

Insofar as the substrate is formed from an ashless burn-out material, the substrate material burns ashless or residue-free during the sintering process. The electrode packet or functional layer system, for example an anode layer or

Cathode layer of the functional layer system is thereby exposed, so that gas, for example hydrogen / fuel gas or air, unhindered to the electrode package or functional layer system, for example, the anode layer or cathode layer of the

Functional layer system, can diffuse. Since the substrate burns out ashless during sintering, additional process steps for

Removal and no unwanted residues can remain.

In one embodiment, in particular in method step b), the substrate is printed with the electrode packet. The printing can be done in particular by means of screen printing. Screen printing has proven to be particularly advantageous. In particular, the electrode package may be a functional layer system package comprising an anode layer, a cathode layer and an electrolyte layer formed between the anode layer and the cathode layer. In method step c), therefore, in particular a printed substrate can be introduced into the cavity of the injection molding tool. The anode material may include, for example, nickel. The

For example, cathode material may include electrically conductive oxides. The anode material and / or the cathode material may, for example, be a porous sintered material. The electrolyte material can be, for example, a ceramic solid electrolyte, in particular an oxygen-ion-conducting material, for example with rare earths, in particular scandium, yttrium and / or

Cerium, doped zirconia (Zr0 ₂ ). The electrolyte material may in particular be gas-tight sintering.

The substrate may in particular be a sleeve, for example in the form of a tube, or a foil, for example in the form of a band or a so-called tape. In particular, the substrate may be a

Be green body sleeve or a green sheet.

A sleeve can be printed in particular by screen printing. A sleeve can advantageously be used without an additional shaping machining and / or directly on an injection mold core or a

Inner wall of the cavity can be positioned. In addition, when using a

Sleeve may be waived form-stabilizing measures.

Optionally, when using a sleeve even on a

Omitted injection molding tool or the injection mold and / or the

Injection molding tool core or their handling can be simplified.

In particular, the substrate may be an extruded or injection molded sleeve.

A film, in particular a planar film, can advantageously be printed very well by planar screen printing. In this way, the method can advantageously be simplified. In addition, a film can be transferred from planar to one, for example round, injection mold core, or one For example, round, carrier sleeve are handled well. A transfer, for example to an injection molding tool core or an inner wall of the cavity of the injection molding tool and / or a carrier sleeve, and / or a positioning, for example on the injection mold core or the inner wall of the cavity of the injection molding tool and / or the carrier sleeve, and / or a shaping processing advantageously be realized very easily by the use of a vacuum, for example by means of a vacuum technology.

In particular, the substrate may be a cast film.

In the context of a further embodiment, in particular in

Process step e), the injection molding component and the electrode package, in particular functional layer system package, and optionally the

Component of the substrate, in particular together, sintered. Thus, advantageously, further process steps can be avoided. In particular, the sintering, in particular in method step e), can take place in a single sintering step. During sintering, the electrode package, in particular

Function layer system package, in particular cohesively with the

Injection molding component and optionally connect the component of the substrate. The sintering, in particular in process step e), can

for example, at a temperature in a range of> 1000 ° C or> 1 100 ° C to <1300 C or <1200 C.

In another embodiment, in particular

Process step c), the substrate provided with the electrode package, in particular printed, a hollow cylindrical shape or is in a

hollow cylindrical shape brought. This can be done in the case of a film by vacuum, such as a vacuum technology, and / or applying the film to a support sleeve. In particular, an outer lateral surface or an inner lateral surface of the hollow cylindrical substrate provided with the electrode package, in particular a printed substrate, can be formed by the electrode package, in particular functional layer package. The formed by the electrode package, in particular functional layer package, outer or inner The lateral surface may in particular limit the hollow cylindrical cavity.

In the context of a further embodiment, the component for forming a gas-permeable, porous, ceramic material is a component for forming an inert, gas-permeable, porous, ceramic material.

By inert, it can be understood in particular that the material does not serve as an electrode or electrolyte. In this case, the solid oxide cell can be referred to, for example, as an inertly supported solid oxide cell.

As a component for forming a gas-permeable porous ceramic material, in particular in process step a), in principle all, in particular inert, ceramic materials are suitable from which a substrate, in particular a sleeve or film, can be produced and from the means

Pore formers and by sintering a highly porous material can be displayed. For example, the component for forming a, in particular inert, gas-permeable porous, ceramic material, in particular in

Process step a) comprise at least one material which is selected from the group consisting of magnesium silicates, in particular forsterite (Mg ₂ Si0 ₄ ), spinels, for example aluminum magnesium spinels such as MgAI ₂ 0 ₄ , doped zirconium dioxides, for example less than 3 wt % doped zirconia, undoped zirconia, alumina, alumina-zirconia mixtures, zirconia-glass mixtures, zinc oxide, and mixtures thereof.

Within the scope of a further embodiment, the component comprises for forming a, in particular inert, gas-permeable porous ceramic material, in particular in method step a), forsterite, aluminum magnesium spinel (AlMg spinel) and / or doped zirconium dioxide. In particular, the component for forming a gas-permeable porous, ceramic

Materials, in particular in process step a) include forsterite.

Forsterite is based essentially on the general empirical formula Mg ₂ Si0 ₄ . Forsterite may advantageously be highly electrically and ionically highly insulating and for example, at 20 ° C, a specific electrical resistance of 10 Dm and 600 ° C have a resistivity of 10 ⁵ Dm. 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 is advantageous to a simultaneous sintering (co-sintering) of the tubular (carrier) body and the electrode package, in particular the functional layer system package. 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.

Furthermore, the component for forming a gas-permeable porous, ceramic material may comprise at least one pore-forming agent. When

Pore formers can be used, for example, compounds which decompose, evaporate and / or melt out during a thermal treatment, for example during sintering. Suitable pore formers are, for example, organic pore formers. These can during a thermal process, for example, after the shaping by the

Injection molding, are burned out and leave behind percolating cavities, for example.

The ashless ausbrennbare material, in particular in process step a), for example, be selected from the group consisting of elementary carbon forms such as carbon black, polymers, in particular native polymers such as cellulose and / or starch, and combinations thereof. In particular, the ashless burn-out material may include or be carbon black and / or cellulose and / or starch. In the context of a further embodiment, in particular in

Process step d), an injection molding component for forming a gas-permeable porous, ceramic material used. In particular, the injection-molded component for forming a gas-permeable porous, ceramic material may be an injection-molded component for forming an inert, gas-permeable, porous, ceramic material.

During sintering, in particular in method step e), in particular also the injection molding component for forming a, in particular inert,

permeable to gas, porous ceramic material in a, in particular inert, gas permeable porous, ceramic material are transferred.

As injection molding component for forming a gas-permeable porous, ceramic material, in particular in process step d), in principle all, in particular inert, ceramic materials are suitable from which a substrate, in particular a sleeve or film, can be produced and from the means of pore formers and by sintering highly porous material can be displayed. For example, the injection molding component, in particular in

Process step d), for forming a gas-permeable porous, ceramic material comprise at least one material which is selected from the group consisting of magnesium silicates, especially forsterite (Mg ₂ Si0 ₄ ), spinels, for example, aluminum magnesium spinels, such as MgAI ₂ 0 ₄ , doped Zirconia dioxides, for example, with less than 3 wt.% Doped zirconia, undoped zirconia, alumina, alumina-zirconia mixtures, zirconia-glass mixtures, zinc oxide, and mixtures thereof

Within the scope of a further embodiment, the injection-molding component comprises, for the formation of a gas-permeable, porous, ceramic material, in particular in process step d), forsterite, aluminum magnesium spinel

(AlMg spinel) and / or doped zirconia. In particular, the injection molding component may comprise forsterite to form a gas-permeable porous ceramic material. Furthermore, the injection-molded component for forming a gas-permeable porous, ceramic material may comprise at least one pore-forming agent.

In a further embodiment, the component is for

Formation of a gas-permeable porous, ceramic material also used as injection molding component. For example, the component for forming a gas-permeable porous, ceramic material, in particular in process step a), the same component as the injection molding to form a gas-permeable porous ceramic material, in particular in process step d), be.

In particular, the injection molding tool can have an injection mold core insertable into the cavity. By introducing the

Injection mold core into the cavity can between the

Injection mold core and the inner wall of the cavity a, in particular substantially, tubular cavity can be formed. In this case, it can be understood, in particular, in particular that the tubular cavity comprises a hollow-cylindrical cavity (section), the tube-shaped cavity also still having cavity sections of a different shape,

in particular cavity end portions, for example for forming a mounting portion and a cap portion or for forming two mounting portions having.

The substrate provided with the electrode package, in particular the functional layer system package, can be applied to the injection mold core or the inner wall of the cavity.

Because that with the electrode package, in particular

Functional layer system package, provided substrate on the

Injection molding tool core is applied, a cell can be produced, which has a tubular support body on the inside of the electrode package, in particular functional layer system package, is applied.

Because that with the electrode package, in particular

Functional layer system package, provided substrate on the inner wall of the Cavity is applied, a cell can be produced, which has a tubular carrier body on the outside of the electrode package, in particular functional layer system package, is applied. If a substrate provided with a functional layer system package is used in which an anode layer is applied to the substrate, wherein an electrolyte layer is again applied to the anode layer, wherein a cathode layer is applied to the electrolyte layer, in particular the cathode layer can be the hollow cylindrical cavity, for example , in particular in process step c) and / or d) limit.

Insofar as such provided with the functional layer system package

Substrate is applied to the injection mold core, a cell can be produced, which has a tubular support body on the inside of the functional layer system package is applied, wherein the

Anode layer is an inner layer and the cathode layer is an outer layer. In this case, in particular the cathode layer, in particular cohesively, at the tubular support body and the anode layer at least temporarily, in particular cohesively connect to the substrate. When the substrate is burned out ashless, the anode layer can be exposed thereby.

Insofar as such provided with the functional layer system package

Substrate is applied to the inner wall of the cavity, a cell can be produced, which has a tubular support body on the outside of the functional layer system package is applied, wherein the

Cathode layer is an inner layer and the anode layer is an outer layer. In this case, in particular the cathode layer, in particular cohesively, at the tubular support body and the anode layer at least temporarily, in particular cohesively connect to the substrate. When the substrate is burned out ashless, the anode layer can be exposed thereby.

If a substrate provided with a functional layer system package is used in which a cathode layer is applied to the substrate, wherein an electrolyte layer is again applied to the cathode layer, an anode layer being applied to the electrolyte layer in particular, the anode layer, for example, the tubular, cavity, in particular in process step c) and / or d) limit.

Insofar as such a substrate provided with the functional layer system package is applied to the injection mold core, a cell can be produced which has a tubular carrier body on the inside of which the functional layer system package is applied, in which the cathode layer is an inner layer and the anode layer is an outer layer. In this case, in particular the anode layer, in particular cohesively, at the tubular carrier body and the cathode layer at least temporarily, in particular materially, connect to the substrate. When the substrate is burned out ashless, the cathode layer can be exposed thereby.

Insofar as such a substrate provided with the functional layer system package is applied to the inner wall of the cavity, a cell can be produced which has a tubular carrier body on the outside of which the functional layer system package is applied, in which the anode layer is an inner layer and the cathode layer is an outer layer, wherein the anode layer, in particular cohesively, is connected to the tubular carrier body. In this case, in particular, the anode layer, in particular cohesively, on the tubular support body and the

Cathode layer at least temporarily, in particular cohesively connect to the substrate. When the substrate is burned out ashless, the cathode layer can be exposed thereby.

Furthermore, the method can have at least one further method step (d1): injection of a further injection-molded component. The further injection-molded component can be designed in particular for forming a, in particular inert, gas-tight, ceramic material.

During sintering, in particular in method step e), the further

Injection molding component for forming a, in particular inert, gas-tight, ceramic material, in particular from process step dl), into a, in particular inert, gas-tight, ceramic material are transferred. As injection molding component for forming a gas-tight ceramic material, in particular in process step d1), basically all, in particular inert, ceramic materials are suitable, from which a substrate, in particular a sleeve or foil, can be produced and from which a gas-tight material is represented by sintering can. For example, the further injection molding component, in particular in method step d1), for forming a gas-tight, ceramic material may likewise comprise at least one material which is selected from the group consisting of

Magnesium silicates, in particular forsterite (Mg ₂ Si0 ₄ ), spinels, for example aluminum magnesium spinels, such as MgAl ₂ 0 ₄ , doped zirconium dioxides, for example with less than 3 wt% doped zirconia, undoped zirconia, alumina, alumina-zirconia mixtures, Zirconia-glass mixtures, zinc oxide and mixtures thereof

For example, the further injection molding component for forming a gas-tight, ceramic material, in particular in process step dl), forsterite, aluminum magnesium spinel (AlMg spinel) and / or doped

Include zirconia. In particular, the other

Injection molding component for forming a gas-tight, ceramic material forsterite include.

In particular, the further injection molding component, in particular in

Process step d1) thereby differ from the component, in particular in process step a), and / or the injection-molding component, in particular in process step d), in that it is pore-forming free.

The injection molding tool can in particular be designed such that a tubular cavity can be formed therein, which has a hollow cylindrical cavity and two cavity end sections for forming a

Mounting portion and a cap portion or for forming two mounting portions. The further injection-molding component for forming a gas-tight, ceramic material can, in particular in process step d1), in this case be injected into one or both cavity end sections.

Overall, it is thus advantageously possible to produce tubular solid oxide cells, for example tubular high-temperature fuel cells (tubular SOFC), which have a tubular support body (tube) with a gas-permeable porous, in particular hollow-cylindrical, region, with functional layers on its inside or optionally outside at the level of the porous region can be placed. The tubular support body (tube) acts as an electrochemically inert support for the functional layers. Such a structure has the advantage that very thin layer packages can be realized thereby, which is not limited to one

Saving of material of the functional layers (cost, availability lanthanum compounds) but in particular associated with a high electrical power.

Insofar as a substrate is used in the form of a film, this can be applied to a carrier sleeve with the electrode package, in particular functional layer package, which in turn can be applied to an injection molding tool core.

With regard to further advantages and technical features is hereby explicitly to the explanations in connection with the inventive

Solid oxide cells, the use according to the invention and the

Energy system according to the invention and to the figures and the

Figure description referenced.

Another object of the invention is a tubular solid oxide cell, which is produced by a method according to the invention. In particular, the solid oxide cell may be a solid oxide fuel cell and / or

Solid oxide electrolysis cell and / or solid oxide metal-air cell. With regard to further advantages and technical features is hereby explicitly to the explanations in connection with the inventive method, the solid oxide cell according to the invention, the inventive use and the energy system according to the invention and to the figures and the

Figure description referenced.

Another object of the invention is a tubular solid oxide cell.

In particular, the solid oxide cell may be a solid oxide fuel cell and / or solid oxide electrolysis cell and / or solid oxide metal-air cell.

In particular, the tubular solid oxide cell may comprise an electrode packet, wherein the electrode packet is arranged between a first wall of a,

in particular inert, gas-permeable porous, ceramic material and a second wall of a, in particular inert, gas-permeable porous, ceramic material is arranged. In particular, the

Connect the electrode package to the first and second wall with a material fit.

In one embodiment, the electrode package is a

A functional layer system package comprising an anode layer, a cathode layer and an electrolyte layer formed between the anode layer and the cathode layer. As part of an embodiment closes the

Cathode layer, in particular cohesively, to the first wall and the anode layer, in particular cohesively, to the second wall. In another embodiment, the anode layer, in particular cohesively, to the first wall and the cathode layer, in particular cohesively, connects to the second wall. For example, the electrode package can connect to the first and second walls over the whole area. For example, the cathode layer over the entire surface, in particular cohesively, on the first wall and the anode layer over the entire surface, in particular cohesively, on the second wall, or vice versa, the anode layer over the entire surface, in particular cohesively, on the first wall and the cathode layer over the entire surface, in particular cohesively, on the second Connect wall. In the context of a further embodiment, the first wall is a section of a tubular carrier body. The tubular carrier body may in particular have a hollow-cylindrical intermediate section and two end sections, wherein one of the end sections is a mounting section

or foot section, in particular for mounting the cell, and wherein the other end portion, a cap portion which closes one of the ends of the hollow cylindrical intermediate portion, or another

Mounting section or foot section, in particular for mounting the cell is. In particular, the hollow-cylindrical intermediate section may comprise or form the first wall.

In the case of a design with a closed end, the unused gas, for example fuel gas, can advantageously be returned to the gas cycle, for example the fuel gas cycle, which advantageously allows a higher electrical efficiency

The first wall or the hollow cylindrical intermediate section can in particular be made of the injection-molded component to form a,

in particular inert, gas-permeable porous, ceramic material, in particular from process step d) of the process according to the invention, be formed or gas-permeable porous.

The end sections may in particular be made of a gas-tight, ceramic material, in particular from method step d1) of the method according to the invention, or be gas-tight.

The second wall may have a hollow cylindrical shape. The second wall may in particular be formed by the substrate used in the method according to the invention or may be porous to gas.

In the context of a further embodiment, the second wall has a smaller wall thickness than the first wall. In particular, the wall thickness of the second wall may be less than 75%, for example less than 50%, for example less than 25%, of the wall thickness of the first wall. With regard to further advantages and technical features is hereby explicitly to the explanations in connection with the inventive method, the solid oxide cell according to the invention, the inventive use and the energy system according to the invention and to the figures and the

Figure description referenced.

Furthermore, the invention relates to the use of a tubular solid oxide cell, in particular a tubular solid oxide cell according to the invention, for example as a fuel cell and / or as an electrolytic cell and / or as a metal-air cell, for example in a (micro) cogeneration plant, for industrial power Heat-coupling (CHP), for domestic energy supply, in a power plant for power generation and / or power generation on board a vehicle. In particular, the tubular solid oxide cell may have a tubular carrier body with a hollow cylindrical section of a, in particular inert, gas-permeable porous ceramic material, for example forsterite, on the inside or outside, in particular inside, an electrode package, in particular functional layer system package of one

Anode layer, a cathode layer and a formed between the anode layer and the cathode layer electrolyte layer is applied. For example, the hollow cylindrical portion may be a hollow cylindrical

Be intermediate portion of the tubular support body. The tubular support body may in particular have the hollow cylindrical intermediate section and two end sections. Here, for example, one of

End sections a mounting section or foot section,

in particular for mounting the cell, and wherein the other end portion of a cap portion, which is one of the ends of the hollow cylindrical

Intermediate section closes, or another mounting section

or foot section, in particular for mounting the cell may be.

The end sections may be, for example, one, in particular inert, gas-tight ceramic material, for example forsterite. In this case, the cathode layer, in particular cohesively, on the

connect hollow cylindrical (intermediate) section of the tubular support body. The anode layer may be exposed or to a substrate or a wall of a gas-permeable porous material, for example, materially connect. Or the anode layer may, in particular cohesively, connect to the hollow cylindrical (intermediate) portion of the tubular carrier body, in particular wherein the

Cathode layer are exposed or to a substrate or a wall of a gas-permeable porous material, for example, cohesively connect.

With regard to further advantages and technical features is hereby explicitly to the explanations in connection with the inventive method, the solid oxide cells according to the invention and the inventive

Energy system and to the figures and the description of the figures referenced.

Furthermore, the present invention relates to an energy system, for example a

Energy storage and / or converter plant or a (micro) combined heat and power plant or a kraftwärmegekoppelte energy storage and / or - converter system, 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 which / s comprises at least one cell according to the invention or produced or used according to the invention. Under a (micro-) cogeneration plant can be understood in particular a system for the simultaneous generation of electricity and heat from an energy source.

Use and reference is made to the figures and the description of the figures.

drawings 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 have only descriptive character and are not intended to limit the invention in any way. Show it

Figure 1 is a schematic cross-section through an embodiment of a tubular solid oxide cell according to the invention, which was prepared by means of a substrate made of a component for forming a gas-permeable porous ceramic material. and

2 shows a schematic cross-section through an embodiment of a tubular solid oxide cell according to the invention, which is produced by means of a substrate made of an ashless burn-out material, prior to burning out of the ashless burn-out material during a sintering process.

Figures 1 and 2 show tubular solid oxide cell 10, for example

Solid oxide fuel cells (SOFC), which has an electrode packet 11 in the form of a functional layer system package lla.lla ', IIb, IIb', llc.llc ', which an anode layer IIa, IIa', a cathode layer IIb, IIb 'and a between the anode layer IIa 'IIa' and the cathode layer IIb, IIb 'formed electrolyte layer llc.llc' includes. Here, the anode layer IIa, IIa 'anode regions IIa, which are separated by electrically and ionically insulating regions IIa'. The cathode layer IIb, IIb 'includes

Cathode areas IIb, which are also separated by electrically and ionically insulating areas IIb '. The electrolyte layer IIc.IIc 'comprises electrolyte regions 11c, which are separated from one another by electrically conductive and ionically insulating regions 11c' (interconnector regions).

FIGS. 1 and 2 furthermore show that the anode regions IIa,

Cathode regions IIb and electrolyte regions 11c are formed offset from each other, wherein in each case an anode region IIa of an anode electrolyte cathode unit lla, llc, llb via an electrically conductive and ionically insulating interconnector region 11c 'of the electrolyte layer llc.llc' electrically conductive with a cathode region IIb a neighboring anode electrolyte Cathode unit lla, llc, llb is connected. In this way, strands of serially interconnected anode-electrolyte-cathode units lla, llc, llb formed (see left and right sides). Outside the illustrated

At the cross-sectional level, the strands (left and right) may be separated by one or more electrically and ionically insulating regions.

FIGS. 1 and 2 further illustrate that the strands (left and right) are electrically conductively connected to one another by two anode regions IIa of anode-electrolyte-cathode units 11a, 11c, 11b of different strands being interconnected by an annular conductor 11a "of anode material are connected.

The arrows 0 ₂ in FIGS. 1 and 2 illustrate that oxygen ions can pass via the electrolyte regions 11c from one of the cathode regions IIb to one of the anode regions IIa, respectively. The arrows e ^" in FIGS. 1 and 2 illustrate that the interconnector regions 11c 'and the ring conductor 11c" serially interconnect the anode-electrolyte-cathode units 11a, 11c, 11b in such a way that the current flows through the one strand towards the ring conductor IIa "and on the ring conductor IIa" and the other strand can be led back. Thus, advantageously, the electrical interconnection on one side of the

Cell. FIGS. 1 and 2 illustrate that the current through the anode material IIa and / or cathode material IIb and / or

Interconnector material 11c 'can be removed. FIGS. 1 and 2 further show that the functional layer system 11a, 11a ', 11b, 11b', 11c, 1cc 'on the inside of a hollow cylindrical

Section 12 of a tubular carrier body is applied. In this case, the cathode layer IIb, IIb 'on the hollow cylindrical portion 12 which is formed of an inert, gas-permeable porous material.

Figures 1 and 2 sketch that an end portion of the tubular

Carrier body is formed as a mounting portion or foot portion 13, wherein the other end portion is formed as a cap portion 14 which closes the hollow cylindrical intermediate portion 12. The two end sections 13, 14 are formed from one, optionally inert, gas-tight, ceramic material.

Figure 1 illustrates that by an embodiment of the

according to the invention, in the context of which the cell by applying an electrode assembly 11 to a substrate 1 of a component for forming an inert, gas-permeable porous ceramic material, and by film injection molding with an injection molding component 12 for forming an inert, gas-permeable porous ceramic material and Conversion of the components 1.12 into inert, gas-permeable porous, ceramic materials is formed by means of sintering, the resulting inert, gas-permeable porous, ceramic substrate 1 remains on the electrode package 11. FIG. 1 shows that the electrode package 11 is arranged between a first wall 12 made of the injection-molded component 12 made of an inert, gas-permeable porous ceramic material and a second wall 1 formed of the substrate 1 made of inert, gas-permeable, porous ceramic material. In this case, the electrode package 11 connects to the first 12 and second 1 wall materially. In particular, the cathode layer IIb, IIb 'adjoins the first wall 12 and the anode layer 11a.lla' adjoins the second wall 1, or vice versa. FIG. 1 shows that the second wall 1 can have a significantly smaller wall thickness than the first wall 12.

In the following, the embodiment by means of an inert porous

Support material 1 explained in more detail. In the context of this embodiment, in particular an electrode package 11 is printed on a substrate 1, which can remain in the tube 12 as a sufficiently porous layer, for example as an inner wall 1. This can be done in particular by technical screen printing on an inert porous carrier material 1 in tape or tube form. In this way, advantageously in particular a tubular

Solid oxide fuel cell (SOFC) with internal electrodes.

In the context of this embodiment, in particular from the provided for the tube 12 wall material, for example, forsterite, AlMg spinel or doped Zr0 ₂ , a cast film, in particular green film, for example in tape form, or an extruded sleeve or an extruded tube 1 are produced. On the film (green sheet, tape) or the sleeve (tube) 1 can functional layers lla, lla ', llb, llb', llc, llc 'means

Screen printing technology are printed. The functional layer package 11a, 11a ', 11b, 11b', 11c, 11c 'can be fixed directly to the green body 12, for example from forsterite, via film back-injection during the injection process, so that advantageously manufacturing steps can be saved. During the sintering process, the porous inert material of the film (tape) or the sleeve (tube) 1 connects cohesively with the

Functional layer package lla, lla ', llb, llb', llc, llc ', in particular the anode IIa, and remains as inner wall 1, through which, for example

Hydrogen, can diffuse to the anode IIa. In general, this process can be applied to all inert materials, for example AlMg-

Spinel, doped Zr0 ₂ , etc.) are transferred from which a film (tape) or a sleeve (extrusion tube) 1 can be produced, which can be represented with pore formers after sintering as highly porous material. The advantage of using a green sheet 1 of inert material as

Substrate material for the functional layer package 11 is that it can be printed very well in planar printing and, for example, can also be handled well in the transfer from planar to a round injection mold core, for example a CIM core (CIM, English: Ceramic Injection Molding). A

Positioning on the injection mold core, for example CIM core, can be done very easily by vacuum. Since the film 1 (tape) remains as a highly porous inner layer in the tube 12, additional

Process steps for demoulding are eliminated and the risk of damage to the functional layer package by the demolding processes are significantly reduced. In addition, so unwanted residues can be avoided.

In addition to the use of a film (tape) 1, it is also possible to extrude a sleeve 1 (tube) made of an inert ceramic, for example forsterite, AlMg spinel or doped ZrO 2. This 1 can be printed directly in round printing and has the advantage, among other things, that it 1 directly on the Injection molding tool core, for example CIM core, is positionable. Again, the sleeve 1 would remain as an inner wall 1 in the tube 12. Gas, for example hydrogen, would then diffuse through the porous inner wall 1, for example to the anode IIb.

Thus, advantageously, a tubular SOFC cell containing an internal electrode package 11 can be produced. This electrode package 11 can be printed in particular by screen printing on a green sheet 1 made of an above-mentioned inert material or an extruded sleeve 1 made of the same material. The sleeve 1 and the injection core with the

applied electrode package 11 may be in an injection mold,

In particular, a CIM tool, inserted and overmoulded. The film (tape) or sleeve (tube) 1 can remain in the tube 12 after the injection process. During the sintering process, the pore former present in the film (tape) or sleeve (pipe) can burn out and leave behind a porous inert layer in the interior of the tube 12, through which, for example, hydrogen can reach the anode IIb.

In particular, this concept can provide a single sintering step, in which the electrode package 11 and the porous tube 12 join together

Temperatures, for example between 1100 ° C and 1300 ° C, are sintered.

In this case, the cathode IIb can in particular be connected to the ceramic tube 12 with a material fit and still be sufficiently porous after the sintering process. In this case, the anode IIa can in particular connect in a materially bonded manner to the inner inert porous layer 1 or the inert inner ceramic tube.

In particular, an inert, for example, forsterite-based, porous green sheet or extruded sleeve can serve as the substrate 1 for the functional layer package 11, onto which the electrode package 11 is printed by means of rotary screen printing. In this case, the tube 12 can be a so-called cermet (derived from CIM) produced by film injection molding, a tube made of an inert porous material, for example forsterite. FIG. 2 illustrates that, by means of an embodiment of the method according to the invention, in which the cell is rendered ash-free by applying an electrode packet 11 to a substrate 1 made of an ashless material

ausbrennbaren material and by film injection with a

Injection molding component 12 for forming an inert, gas-permeable porous, ceramic material and by converting the components 1.12 in inert, gas-permeable porous, ceramic materials is formed by sintering, the substrate 1 may still cover the electrode package 11 before sintering. By sintering, however, the substrate can be completely removed in the context of this embodiment, so that the inside of the

Electrode packet 11, in particular the anode layer 11a "is then open (not shown in Figure 2) .In the following, the embodiment by means of an ashless ausbrennbaren

Support material 1 explained in more detail. In the context of this embodiment, in particular, an electrode package 11 is printed on a substrate 1, which burns out ashes and residue-free during the sintering process. This can be done in particular by technical screen printing on an ashless ausbrennbares carrier material 1 in tape or tube form. In this way, it is advantageously possible in particular to produce a tubular solid oxide fuel cell (SOFC) with an internally internal electrode package IIa.

In the context of this embodiment, in particular, a carrier film or an extruded tube 1 can be produced from an ashless-burnable material, for example carbon black and / or cellulose and / or starch. On this film or this tube 1 can functional layers

lla, lla ', llb, llb', llc, llc 'are printed by screen printing technology. The functional layer package lla, lla ', llb, llb', llc, llc 'can over

Film back injection directly during the injection process on the green body 12, for example, forsterite, to be fixed, so that advantageously

Manufacturing steps can be saved. During the sintering process, the substrate material 1 can burn off without residue. So can

be effected advantageously that the porous anode layer IIa is exposed or as the first functional layer in the interior of the Tubuses, in which, for example, a fuel gas atmosphere can be generated may be located.

The advantage of using an ashless burn-out carrier film 1 for the functional layer package 11 is that it can be printed very well in planar printing and, for example, can also be handled well in the transfer from planar to a round injection mold core, for example a CIM core. A positioning on the injection mold core, for example CIM core, can be done in a very simple way by vacuum. Since the film 1 can burn out ashes during sintering, no residues can remain on the electrode package 11.

In addition to using a film 1, it is also possible to extrude a sleeve 1 of ashless burn-out material (e.g., carbon black, cellulose, starch). This 1 can be printed directly in round printing and has the advantage, among other things, that it can be positioned directly on the injection mold core, for example the CIM core. The sleeve 1 would serve as inner wall 1 for the functional layer package 11 and burn out without residue during the sintering process.

Thus, advantageously, a tubular SOFC cell containing an internal electrode package 11 can be produced. This electrode package 11 can in particular by means of screen printing on a green sheet 1 of ashless

burnable material, for example carbon black and / or cellulose and / or starch, or an extruded sleeve 1 are printed from the same material. The sleeve 1 or the injection-molded core with the applied

Electrode packet 11 can be inserted into an injection molding tool, in particular a CIM tool, and injection-molded around. During the sintering process, the film (tape) or the sleeve can burn out without residue, so that, for example, the anode IIa can be free or open inside the tube 12.

Temperatures, for example between 1100 ° C and 1300 ° C, are sintered. In this case, the cathode IIb can in particular be connected to the ceramic tube 12 with a material fit and still be sufficiently porous after the sintering process. The substrate 1 of the electrode assembly 11 can burn off without residue.

In particular, serve as substrate 1 for the functional layer package 11 is an ashless ausbrennbare planar carrier film or an extruded sleeve, for example made of carbon black and / or cellulose and / or starch serve on the 1 in the screen printing the electrode package 11 is printed and which remains residue-free during the sintering process burns out. The tube 12 can be a by

Foil injection molded, so-called cimter (derived from CIM), tube of an inert porous material, for example, forsterite be.

Claims

claims

1. A process for producing a tubular solid oxide cell (10), in particular a fuel cell, comprising the method steps

a) providing a substrate (1), wherein the substrate (1) is formed of a component for forming a, in particular inert, gas-permeable porous, ceramic material or of an ashless ausbrennbaren material;

b) applying an electrode packet (11) to the substrate (1);

c) introducing the substrate (11) provided with the electrode package (11) into a cavity of an injection molding tool so that the electrode package (11) delimits a hollow cylindrical cavity;

d) injecting an injection molding component (12) into the tubular cavity; and

e) sintering of the injection-molded body (11,12), wherein the component (1) for forming a, in particular inert, gas-permeable porous ceramic material (1) is converted into a, in particular inert, gas-permeable porous, ceramic material or wherein the ashless ausbrennbare Material is burned out.

2. The method of claim 1, wherein in step e) the

Injection molding component (12) and the electrode package (11) and

optionally the component of the substrate (1) are sintered together.

3. The method according to claim 1 or 2, wherein in process step b) the

Substrate with the electrode package is printed by screen printing, in particular wherein the electrode package is a functional layer system package of an anode layer (IIa, IIa '), a cathode layer (IIb, IIb') and between the anode layer (lla.lla ') and the cathode layer (llb. llb ') formed electrolyte layer (llc.llc') is. Method according to one of claims 1 to 3, wherein in process step c) provided with the electrode package substrate (1, 1 1) a

hollow cylindrical shape or is brought into a hollow cylindrical shape, in particular wherein an outer surface or an inner circumferential surface of the hollow cylindrical printed substrate (1, 1 1) by the electrode package, in particular functional layer package, (1 1) is formed and wherein the through the electrode package (1 1) formed outer or inner circumferential surface bounded the tubular cavity

Method according to one of claims 1 to 4, wherein the substrate (1) is a cast film or an extruded or injection-molded sleeve.

Method according to one of claims 1 to 5, wherein the component (1) for forming a gas-permeable porous, ceramic material is a component for forming an inert, gas-permeable porous, ceramic material.

Method according to one of claims 1 to 6,

wherein component (1) comprises a forsterite, aluminum magnesium spinel and / or doped zirconium dioxide, in particular forsterite, for forming a gas-permeable porous ceramic material, in particular from process step a), or

wherein the ashless ausbrennbare material (1) is selected from the group consisting of elemental carbon forms, in particular carbon black, native polymers, in particular cellulose and / or starch, and

Combinations thereof, in particular wherein the ashless burn-out material (1) is carbon black and / or starch and / or cellulose.

Method according to one of claims 1 to 7, wherein in step d) an injection molding component (12) for forming a, in particular inert, gas-permeable porous, ceramic material is used.

Method according to one of claims 1 to 8, wherein the

Injection molding component (12) in process step d) forsterite, Aluminum magnesium spinel and / or doped zirconia, especially forsterite.

Method according to one of claims 1 to 9, wherein the component (1) for forming a gas-permeable porous, ceramic material is also used as injection molding component (12).

Tubular solid oxide cell (10), in particular fuel cell cell, produced by a method according to one of claims 1 to 10.

Tubular solid oxide cell (10), in particular fuel cell, comprising an electrode packet (11), the electrode packet (11) being connected between a first wall (12) of a, in particular inert, gas-permeable porous ceramic material and a second wall (1) of a In particular, inert, gas-permeable porous, ceramic material is arranged, in particular wherein the electrode package (11) on the first

(12) and second (1) wall materially connected.

Tubular solid oxide cell (10) according to claim 12, wherein the electrode package (11) comprises a functional layer system package comprising an anode layer (11a, 11a '), a cathode layer (11b, 11b') and an intermediate between the anode layer (11a, 11a ') and the cathode layer (11). IIb, IIb ') trained

Electrolyte layer (llc.llc '), wherein the cathode layer (IIb, IIb') or the anode layer (lla.lla ') adjacent to the first wall (12), wherein the anode layer (lla.lla') and the cathode layer (IIb IIb ') abuts the second wall (1), in particular wherein the first wall (12) is a section of a tubular support body, in particular wherein the tubular support body has a hollow cylindrical intermediate section (12) and two end sections (13, 14) one of the end sections

(13) is a mounting portion, and wherein the other end portion (14) has a cap portion which is one of the ends of the hollow cylindrical

Closing intermediate portion (12), or is another mounting portion, wherein the hollow cylindrical intermediate portion (12) comprises the first wall (12) or is, and wherein the second wall (1) has a hollow cylindrical shape. Tubular solid oxide cell (10) according to claim 12 or 13, wherein the second wall (1) has a smaller wall thickness than the first wall (12).

Use of a tubular solid oxide cell (10), which has a tubular carrier body (12, 13, 14) with a hollow-cylindrical section (12) made of a, in particular inert, gas-permeable, porous, ceramic material, on its inside or outside, in particular inside Electrode package (11), in particular

Functional layer system package (lla.lla ', IIb, IIb', llc.llc ') of an anode layer (IIa, IIa', IIa "), a cathode layer (IIb, IIb ') and one between the anode layer (IIa, IIa') and the cathode layer

(IIb, IIb ') formed, wherein the hollow cylindrical portion (12) is a hollow cylindrical intermediate portion of the tubular support body (12,13,14), wherein the tubular support body (12,13,14 ) further comprises two end portions (13, 14), one (13) of which is a mounting portion, and the other

End portion (14) has a cap portion, which closes one of the ends of the hollow cylindrical intermediate portion (12), or another mounting portion, in particular wherein the end portions (13,14) of a, in particular inert, gas-tight ceramic material, are formed, in particular a tubular Solid oxide cell according to one of

Claims 11 to 14, as a fuel cell and / or as an electrolytic cell and / or as a metal-air cell, in particular in a combined heat and power plant, for industrial cogeneration, for domestic energy supply, in a power plant for power generation and / or power generation on board a vehicle.