JP6198854B2 - Cylindrical solid oxide battery - Google Patents

Description

  The present invention relates to a method of manufacturing a cylindrical solid oxide battery, a solid oxide battery, the use of a solid oxide battery, and an energy system equipped with the solid oxide battery.

  A solid oxide fuel cell (SOFC) including a ceramic battery is one of high temperature fuel cells. Solid oxide fuel cells operate between 600 ° C. and 1000 ° C. and provide a very high electrical efficiency of about 50%.

  Solid oxide fuel cells have evolved mainly in two forms: one developed as a tube (cylindrical) and one developed as a flat membrane (planar).

  German patent application DE 1 801 440 describes a method for producing electrodes, electrolytes and units for high temperature fuel cells.

  Japanese Laid-Open Patent Publication No. 9-199138 describes a method of manufacturing an electrode for a fuel cell.

  EP 1237065 describes a method for producing a solid oxide fuel cell.

  The object of the present invention is a method of manufacturing a cylindrical solid oxide battery.

  In step a) of the method, in particular a substrate formed from components forming a porous ceramic material with gas permeability or a substrate formed from an ashless, completely combustible material is provided. .

  In step b) of the method, in particular, an electrode assembly is applied to the substrate.

  For example, a tubular (support) body is injection-molded on a substrate provided with an electrode assembly by film decorative molding, in particular by ceramic injection molding.

  This is the case, for example, by inserting the substrate with the electrode assembly into the cavity of the injection mold in step c) of the method, so that the hollow of the injection mold with the electrode assembly of the substrate with the electrode assembly. This is done by defining a chamber or cavity. Then, in step d) of the method, in particular the injection molding component is injection molded into the hollow chamber or cavity.

  In step c) of the method, a hollow cylindrical hollow chamber can be defined in the electrode assembly, in particular by inserting a substrate comprising the electrode assembly into the cavity of the injection mold. Thereafter, in step d) of the method, the injection molding component can be injected into a hollow cylindrical hollow chamber.

  In step e) of the method, in particular, the component that forms, for example, the gas-permeable porous ceramic material is sintered, so that the injection-molded body formed in step d) of the method is porous. The ashless and completely combustible material is completely burned.

  The solid oxide battery can be, for example, a solid oxide fuel battery, a solid oxide electrolyte battery, and / or a solid oxide metal-air battery. In particular, a method for producing a solid oxide fuel cell, a solid oxide electrolyte cell and / or a solid oxide metal-air cell is, for example, a solid oxide fuel cell or a solid oxide electrolyte cell such as a solid oxide. Type fuel cell.

  The method advantageously provides a cylindrical solid oxide battery, in particular a cylindrical solid oxide battery with an electrode assembly on the inside, for example between a negative electrode layer, a positive electrode layer, a negative electrode layer and a positive electrode layer. It is possible to manufacture a cylindrical solid oxide battery having a functional layer system assembly including an electrolyte layer disposed therein. Whether it is a substrate made of a component that forms a porous ceramic material with gas permeability or an ashless, completely combustible material, it is advantageously manufactured It is possible to reduce the number of processes, avoid damage to the electrode assembly, in particular damage to the functional layer system assembly, and / or reduce the defective product rate.

  In particular, it is advantageous both when a base material made of a component that forms a porous ceramic material having gas permeability is used and when a base material made of an ashless and completely combustible material is used. Can simplify or omit the mold release step. It is thus possible advantageously to avoid damage to the electrode assembly, in particular to the functional layer system assembly, and / or to reduce the defective rate.

  In the case of film decorative molding, the electrode assembly, in particular the functional layer system assembly, can be secured directly to the injection molded body or green body consisting of the injection molding components directly during the injection molding process, which is preferably a further manufacturing process. Can be omitted.

  When the substrate is formed from a component that forms a porous ceramic material having gas permeability, a porous ceramic material having gas permeability is formed during the sintering process. The porous ceramic material having is connected in material connection to the electrode assembly or functional layer system, for example to the negative electrode layer or the positive electrode layer of the functional layer system, and passes a gas such as hydrogen / combustion gas or air, for example. It remains as a gas permeable porous wall that can then be diffused into the electrode assembly or functional layer system, for example, into the negative electrode layer or positive electrode layer of the functional layer system. Since the substrate remains on the electrode assembly, particularly on the functional layer system assembly, as a wall with sufficient gas permeability, additional steps for demolding are omitted, leaving no undesirable residue.

  If the substrate is formed from a material that is ashless and completely combustible, the substrate material is completely ashless and residue free during the sintering process. In this case, the electrode assembly or functional layer system, eg, the negative electrode layer or positive electrode layer of the functional layer system is exposed, so that gas such as hydrogen / combustion gas or air is not hindered. It is possible to diffuse into the layer system, for example into the negative or positive electrode layer of the functional layer system. Since the substrate burns completely ashless during sintering, additional steps for demolding are omitted, leaving no undesirable residue.

  In this embodiment, the electrode assembly is printed on the substrate, particularly in step b) of the method. This printing can be carried out in particular by screen printing. Screen printing has proven particularly advantageous. In particular, the electrode assembly can be a functional layer system assembly formed from a negative electrode layer, a positive electrode layer, and an electrolyte layer formed between the negative electrode layer and the positive electrode layer. Thus, in step c) of the method, it is possible to insert a particularly printed substrate into the cavity of the injection mold.

The negative electrode material can include, for example, nickel. The positive electrode material can include, for example, a conductive oxide. The negative electrode material and / or the positive electrode material can be, for example, a material that is sintered porously. The electrolyte material can be, for example, a ceramic solid electrolyte, in particular a material that conducts oxygen ions, such as zirconium dioxide (ZrO ₂ ) doped with rare earths, in particular scandium, yttrium and / or cerium. be able to. The electrolyte material can be sintered particularly tightly.

  The substrate can be a sleeve, for example in the form of a tube, or it can be a sheet, for example in the form of a ribbon or so-called tape. The substrate can in particular be a green body sleeve or a green sheet.

  The sleeve can be printed in particular by curved screen printing. The sleeve can advantageously be used without additional molding processing and / or can be positioned directly on the injection mold core or on the inner wall of the cavity. In the case of using a sleeve, the shape stabilization process may be omitted depending on circumstances.

  If a sleeve is used, it is possible in some cases even to omit the injection mold core, or to simplify the injection mold and / or the injection mold core or its handling. is there.

  The substrate can in particular be an extruded sleeve or an injection-molded sleeve.

  Sheets, in particular flat sheets, can be printed very well, preferably by flat screen printing. In this way, the method can be advantageously simplified. In addition, the sheet can be carried well when moving from a flat surface, for example, to a curved injection mold core, or to a curved support sleeve, for example. Eg movement to the injection mold core or to the inner wall of the injection mold cavity, movement to the support sleeve, eg positioning at the injection mold core or the inner wall of the injection mold cavity, support sleeve The positioning and / or the molding process in can advantageously be realized very simply, for example by using a vacuum technique, by utilizing a vacuum.

  The substrate can be a particularly cast sheet.

  In another embodiment, in particular in step e) of the method, the injection molding component, the electrode assembly, in particular the functional layer system assembly and optionally the component of the substrate are sintered, in particular sintered together. The Thus, further steps can advantageously be avoided. In particular, this sintering in step e) of the method can be carried out in only one sintering step. During sintering, the electrode assembly, in particular the functional layer system assembly, can be followed, particularly in material connection, to the injection molding component and possibly to the component of the substrate. In particular, this sintering in step e) of the process can be carried out at a temperature in the range, for example, higher than 1000 ° C. or 1100 ° C. and lower than 1300 ° C. or 1200 ° C.

  In another embodiment, in particular in step c) of the method, the substrate comprising the electrode assembly, in particular the substrate on which the electrode assembly is printed, has a hollow cylindrical shape or is made into a hollow cylindrical shape. This can be done by a vacuum in the case of a sheet, in particular by a vacuum technique, and / or by applying the sheet to a support sleeve. The outer circumferential surface or the inner circumferential surface of a particularly printed hollow cylindrical substrate comprising an electrode assembly can be constituted by an electrode assembly, in particular a functional layer assembly. A hollow chamber, in particular a hollow cylindrical shape, can be defined by an outer peripheral surface or an inner peripheral surface constituted by an electrode assembly, in particular a functional layer assembly.

  In another embodiment, the component that forms a porous ceramic material having gas permeability is a component that forms a porous ceramic material having inert gas permeability.

  The term inert can be understood in particular as that the material is not used as an electrode or electrolyte. The solid oxide battery can be referred to as, for example, a solid oxide battery provided with an inert support.

In principle, all ceramic materials, in particular inert ceramic materials, are suitable as components for forming a gas-permeable porous ceramic material, particularly in step a) of the method. In particular, substrates such as sleeves or sheets can be produced and can be made into a highly porous material by sintering with a pore-forming agent. The components that form a particularly inert, gas-permeable porous ceramic material, particularly in step a) of the process, are magnesium silicate, in particular forsterite (Mg ₂ SiO ₄ ), and spinel, for example MgAl ₂ O _4. Aluminum magnesium spinel, such as doped zirconium dioxide, eg, less than 3 wt% doped zirconium dioxide, undoped zirconium dioxide, aluminum oxide, aluminum oxide / zirconium oxide mixture, and zirconium oxide -It may comprise at least one material selected from the group consisting of glass-mixtures, zinc oxide, and mixtures thereof.

  In another embodiment, the components that form a particularly inert, gas-permeable porous ceramic material, particularly in step a) of the method, include forsterite, aluminum magnesium spinel (AlMg spinel) and And / or doped zirconium dioxide. In particular, the component forming the gas-permeable porous ceramic material in step a) of the process may comprise forsterite in particular.

Forsterite is substantially based on the general molecular formula Mg ₂ SiO ₄ . Forsterite is advantageously highly insulating both electrically and ionically, for example having an electrical resistivity of 10 ¹¹ Ω · m at 20 ° C. and an electrical resistivity of 10 ⁵ Ω · m at 600 ° C. Can do. Thus, advantageously, electrical and ionic shorts can be avoided and one or more additional insulating layers can be omitted. A further advantage of forsterite is the sintering behavior and thermal expansion coefficient of forsterite. That is, forsterite can have advantageous shrinkage properties and advantageous shrinkage kinetics. Furthermore, the thermal expansion coefficient of forsterite can substantially match the thermal expansion coefficient of the material of the functional layer system, and can be about 10-11 · 10 ⁻⁶ K ⁻¹ . This is advantageous for simultaneously sintering (co-sintering) the cylindrical (support) body and the electrode assembly, in particular the functional layer system assembly. Furthermore, forsterite can be obtained by reactive sintering from inexpensive raw materials such as talc and magnesium oxide, which further helps to reduce manufacturing costs.

  Furthermore, the component forming the porous ceramic material having gas permeability may comprise at least one pore former. For example, a compound that decomposes, evaporates and / or dissolves during heat treatment, for example during sintering, can be used as a pore former. For example, an organic pore forming agent is suitable as the pore forming agent. The organic pore former can be completely burned during the heat treatment, for example after molding by injection molding, for example leaving permeable cavities.

  The ashless, completely combustible material, in particular in step a) of the process, consists of the elemental carbon form, in particular carbon black, and polymers, in particular natural polymers such as cellulose and / or starch, and combinations thereof. You can select from a group. In particular, the ashless, fully combustible material can be or can include carbon black and / or cellulose and / or starch.

  In another embodiment, in particular in step d) of the method, an injection molding component is used which forms a gas permeable porous ceramic material. In particular, the injection molding component that forms a porous ceramic material having gas permeability can be an injection molding component that forms a porous ceramic material having inert gas permeability.

  In particular, the injection-molding component which forms a particularly inert, gas-permeable porous ceramic material during sintering in step e) of the process is also converted into a particularly inert, gas-permeable porous ceramic material. Can be converted.

In principle, all ceramic materials, in particular inert ceramic materials, are suitable as injection-moulding components for forming gas-permeable porous ceramic materials, particularly in step d) of the method. In particular, a substrate such as a sleeve or a sheet can be produced, and a highly porous material can be obtained by sintering using a pore-forming agent. In particular, in step d) of the method, the injection-moulding components that form a gas-permeable porous ceramic material are magnesium silicates, in particular forsterite (Mg ₂ SiO ₄ ) and spinels such as MgAl ₂ O ₄ . Aluminum magnesium spinel, doped zirconium dioxide, eg less than 3 wt.% Doped zirconium dioxide, undoped zirconium dioxide, aluminum oxide, aluminum oxide / zirconium oxide / mixture, zirconium oxide / glass / It may include at least one material selected from the group consisting of a mixture, zinc oxide, and a mixture thereof.

  In another embodiment, in particular in step d) of the method, the injection-molding component forming the gas-permeable porous ceramic material is forsterite, aluminum magnesium spinel (AlMg spinel) and / or doping. Containing oxidized zirconium dioxide. The injection-molding component that forms a porous ceramic material with gas permeability can in particular comprise forsterite.

  Further, the injection molding component that forms the porous ceramic material having gas permeability may include at least one pore former.

  In another embodiment, the components that form a gas permeable porous ceramic material are also used as injection molding components. For example, the component that forms the gas permeable porous ceramic material, particularly in step a) of the method, in particular the injection molding component that forms the gas permeable porous ceramic material, in step d) of the method. Can be the same component.

  The injection mold may in particular have an injection mold core that can be inserted into the cavity. By inserting the injection mold core into the cavity, a particularly substantially tubular hollow chamber can be formed between the injection mold core and the inner wall of the cavity. Substantially, this tubular hollow chamber comprises a hollow cylindrical hollow chamber (part) and in addition to form one attachment part and one cap part, or 2 It can be understood that it has a hollow chamber part of another shape, in particular a hollow chamber end part, to form one attachment part.

  A substrate comprising an electrode assembly, particularly a functional layer system assembly, can be applied to an injection mold core or to the inner wall of a cavity.

  Manufacturing a battery having a tubular support with an electrode assembly, in particular a functional layer system assembly, on the inside, by depositing an electrode assembly, in particular a substrate comprising a functional layer system assembly, on an injection mold core can do.

  Manufacturing a battery having a tubular support with an electrode assembly, in particular a functional layer system assembly, on the outside, by depositing an electrode assembly, in particular a substrate comprising a functional layer system assembly, on the inner wall of the cavity Can do.

  In the case of using a base material provided with a functional layer system assembly, the negative electrode layer is applied to the base material, the electrolyte layer is applied to the negative electrode layer, and the positive electrode layer is applied to the electrolyte layer. If applied, in particular the positive electrode layer can define, for example, a hollow cylindrical hollow chamber, in particular in step c) and / or d) of the method.

  When such a substrate comprising a functional layer system assembly is applied to an injection mold core, a battery having a tubular support having a functional layer system assembly attached thereto can be produced. In this functional layer system assembly, the negative electrode layer becomes the inner layer and the positive electrode layer becomes the outer layer. In particular, the tubular support can be followed by a positive electrode layer, particularly in material connection, and the substrate can be followed at least temporarily by a negative electrode layer, particularly in material connection. When the base material burns completely without ash, this allows the negative electrode layer to be exposed.

  When such a substrate with a functional layer system assembly is deposited on the inner wall of the cavity, a battery having a tubular support with the functional layer system assembly deposited on the outside can be produced; In this functional layer system assembly, the positive electrode layer is the inner layer and the negative electrode layer is the outer layer. In particular, the tubular support can be followed by a positive electrode layer, particularly in material connection, and the substrate can be followed at least temporarily by a negative electrode layer, particularly in material connection. When the base material burns completely without ash, this allows the negative electrode layer to be exposed.

  In the case of using a base material provided with a functional layer system assembly, the positive electrode layer is applied to the base material, the electrolyte layer is applied to the positive electrode layer, and the negative electrode layer is applied to the electrolyte layer. If applied, it is possible to define, for example, a tubular hollow chamber, in particular by means of the negative electrode layer, in particular in step c) and / or d) of the method.

  When such a substrate comprising a functional layer system assembly is applied to an injection mold core, a battery having a tubular support having a functional layer system assembly attached thereto can be produced. In this functional layer system assembly, the positive electrode layer becomes the inner layer and the negative electrode layer becomes the outer layer. In particular, the tubular support can be followed by a negative electrode layer, particularly in material connection, and the substrate can be followed at least temporarily by a positive electrode layer, particularly in material connection. In the case where the base material is completely burned ashless, this allows the positive electrode layer to be exposed.

  When such a substrate with a functional layer system assembly is deposited on the inner wall of the cavity, a battery having a tubular support with the functional layer system assembly deposited on the outside can be produced; In this functional layer system assembly, the negative electrode layer becomes the inner layer and the positive electrode layer becomes the outer layer, in which case the negative electrode layer follows the tubular support, in particular in material connection. In particular, the tubular support can be followed by a negative electrode layer, particularly in material connection, and the substrate can be followed at least temporarily by a positive electrode layer, particularly in material connection. In the case where the base material is completely burned ashless, this allows the positive electrode layer to be exposed.

  The method can further comprise step d1) of at least one other method, ie injecting another injection molding component d1). This further injection molding component can be configured to form a particularly inert, gas-tight ceramic material.

  In particular during sintering in method step e), another injection-molding component which forms a particularly inert, gas-tight ceramic material, in particular in method step d1), is also converted into a particularly inert, gas-tight ceramic material. be able to.

In principle, all ceramic materials, in particular inert ceramic materials, are suitable as another injection-molding component for forming an airtight ceramic material, particularly in step d1) of the method, from such ceramic materials, In particular, substrates such as sleeves or sheets can be produced and can be made airtight by sintering. Another injection-molding component that forms an airtight ceramic material, particularly in step d1) of the process, is also magnesium silicate, in particular forsterite (Mg ₂ SiO ₄ ), and spinel, eg aluminum magnesium spinel such as MgAl ₂ O _4. And doped zirconium dioxide, eg, less than 3% by weight doped zirconium dioxide, undoped zirconium dioxide, aluminum oxide, aluminum oxide / zirconium oxide mixture, zirconium oxide / glass / mixture, and oxidation. It may comprise at least one material selected from the group consisting of zinc and mixtures thereof.

  In another embodiment, in particular in step d1) of the method, another injection-molding component forming the hermetic ceramic material is forsterite, aluminum magnesium spinel (AlMg spinel) and / or doped zirconium dioxide. including. Another injection-moulding component that forms an airtight ceramic material can include forsterite, among others.

  In particular, the other injection-molding component in step d1) of the method, in particular the component in step a) of the method and / or the injection-molding component in particular of step d) of the method, is that no pore former is used. Is different.

  The injection mold can in particular be configured such that a tubular hollow chamber can be formed inside the injection mold, the tubular hollow chamber comprising one mounting part and one cap part. Or two hollow chamber end portions and one hollow cylindrical hollow chamber for forming two attachment portions.

  Another injection-molding component forming an airtight ceramic material can be injected into one or two hollow chamber end portions, in particular in step d1) of the method.

  In this way as a whole, in particular a cylindrical solid oxide cell, for example a cylindrical high temperature, having a tubular support (cylinder) with a hollow cylindrical gas-permeable porous region Type fuel cell (cylindrical SOFC) can be manufactured, and the functional layer can be arranged up to the height of the porous region inside or in some cases outside this tubular support. In this case, the tubular support (cylinder) functions as an electrochemically inert support for the functional layer. The advantage of such a structure is that this allows a very thin layer assembly to be realized, which not only saves the material of the functional layer (cost, lanthanum compounds can be used), but also in particular the electrical output. To increase.

  When using a substrate in the form of a sheet, the substrate can be applied to a support sleeve together with an electrode assembly, in particular a functional layer assembly, and the support sleeve itself can be applied to an injection mold core. .

  Here, for further advantages and technical features, reference is made to the description of the solid oxide cell of the invention, the use of the invention, the energy system of the invention and the drawings and the description associated with the drawings.

  Another object of the present invention is a cylindrical solid oxide battery produced by the method of the present invention. The solid oxide cell can be a solid oxide fuel cell, a solid oxide electrolyte cell and / or a solid oxide metal-air cell, in particular.

  Here, with regard to further advantages and technical features, the description of the method of the invention, the solid oxide battery of the invention, the use of the invention, the energy system of the invention and the description relating to the drawings and drawings are clearly shown. Please refer to it.

  Another object of the present invention is a cylindrical solid oxide battery.

  The solid oxide cell can be a solid oxide fuel cell, a solid oxide electrolyte cell and / or a solid oxide metal-air cell, in particular.

  The cylindrical solid oxide cell may in particular comprise an electrode assembly, the electrode assembly being in particular inert and having a first wall of porous ceramic material with gas permeability and in particular inert. And a second wall made of a porous ceramic material having gas permeability. In particular, the electrode assembly can be connected in material connection to the first wall and the second wall.

  In one embodiment, the electrode assembly is a functional layer system assembly consisting of a negative electrode layer, a positive electrode layer, and an electrolyte layer formed between the negative electrode layer and the positive electrode layer. In one embodiment, the first wall is followed by a positive electrode layer, particularly in material connection, and the second wall is followed by a negative electrode layer, particularly in material connection. In another embodiment, the first wall is followed by a negative electrode layer, particularly in material connection, and the second wall is followed by a positive electrode layer, particularly in material connection. For example, the electrode assembly can be fully extended to the first wall and the second wall. For example, the first wall can be followed entirely by a positive electrode layer, particularly material-connected, and the second wall can be entirely followed by a material-connected material, or vice versa. In addition, the negative electrode layer can be continued over the first wall, particularly in terms of material connection, and the positive electrode layer can be continued over the second wall, particularly in terms of material connection.

  In another embodiment, the first wall is part of a tubular support. The tubular support can in particular have one hollow cylindrical middle part and two end parts, one of the two end parts being a mounting part or a bottom part, in particular for mounting a battery. And the other end part is a cap part that closes one end of the hollow cylindrical intermediate part, or another mounting part or bottom part, in particular for mounting a battery . In particular, the hollow cylindrical intermediate part may comprise or constitute the first wall.

  In the case of embodiments with closed ends, it is possible advantageously to recycle unused gas, in particular unused combustion gas, into the gas circuit, in particular to the combustion gas circuit. The electrical efficiency can be improved.

  The intermediate part of the first wall or hollow cylinder can be composed of an injection-molding component that forms a particularly inert, gas-permeable porous ceramic material, particularly in step d) of the method of the invention. Or it can be made into gas-permeable porous.

  The end portion can be composed of an airtight ceramic material, particularly in step d1) of the method of the invention, or can be airtight.

  The second wall can have a hollow cylindrical shape. The second wall can be constituted in particular by the substrate used in the method of the invention or can be gas permeable porous.

  In another embodiment, the wall thickness of the second wall has a thinner wall thickness than the first wall. The wall thickness of the second wall can in particular be less than 75% of the wall thickness of the first wall, for example less than 50%, for example less than 25%.

  Here, with regard to further advantages and technical features, the description of the method of the invention, the solid oxide battery of the invention, the use of the invention, the energy system of the invention and the description relating to the drawings and drawings are clearly shown. Please refer to it.

  The invention further provides a cylindrical solid oxide cell, in particular a cylindrical solid oxide cell according to the invention, for example as a fuel cell in a (micro) cogeneration facility, as an electrolyte cell and / or as a metal-air cell. To use for industrial combined heat and power (CHP), for household energy supply, for generating current in power plants and / or for generating current in vehicles.

  In particular, a cylindrical solid oxide battery has a tubular support with a hollow cylindrical part made of a porous ceramic material with a particularly inert gas permeability, for example forsterite. An electrode assembly is applied to the inner surface or outer surface, particularly the inner surface of the support, and particularly from the negative electrode layer, the positive electrode layer, and the electrolyte layer formed between the negative electrode layer and the positive electrode layer. A functional layer system assembly is applied. For example, the hollow cylindrical portion can be a hollow cylindrical intermediate portion of a tubular support. The tubular support can in particular have one hollow cylindrical intermediate part and two end parts. One of the two end portions can be a mounting portion or a bottom portion, in particular for mounting the battery, and the other end portion is a cap portion that closes one end of the hollow cylindrical intermediate portion. Or it can be another mounting part or bottom part, in particular for mounting the battery.

  The end portion can be formed from a particularly inert, gas-tight ceramic material, such as forsterite. Here, the hollow cylindrical (intermediate) part of the tubular support can be followed by a positive electrode layer, particularly in material connection. In this case, the negative electrode layer can be exposed or can be connected in material connection to a substrate or wall made of a gas permeable porous material. Alternatively, the negative electrode layer can be connected to the hollow cylindrical (intermediate) part of the tubular support, in particular in material connection, in which case the positive electrode layer can in particular be exposed or the gas It can be connected in material connection to a substrate or wall of a permeable porous material.

  Here, for further advantages and technical features, explicitly refer to the description of the method of the invention, the solid oxide battery of the invention, the energy system of the invention and the drawings and the description associated with the drawings. .

  The invention further comprises wind power generation for energy systems, for example solar power installations comprising at least one battery according to the invention, at least one battery produced according to the invention or at least one battery used according to the invention. Energy storage and / or conversion equipment for equipment, for biogas equipment, for residential or commercial facilities, for industrial equipment, for power plants or for vehicles, (micro) It relates to an energy system such as a combined heat and power facility or a combined heat and power energy storage and / or conversion facility. A (micro) cogeneration facility can be understood as a facility that simultaneously forms current and heat from an energy carrier.

  Here, for further advantages and technical features, reference should be made explicitly to the method of the invention, the solid oxide cell of the invention, the description of the use of the invention and the drawings and the description associated with the drawings.

  Further advantages and advantageous embodiments of the object of the invention are shown in the drawings and explained in the following description. However, it should be noted that these drawings are merely illustrative and are not intended to limit the present invention in any way.

1 is a schematic cross-sectional view of one embodiment of a cylindrical solid oxide battery of the present invention manufactured with a substrate composed of components that form a porous ceramic material with gas permeability. FIG. One of the cylindrical solid oxide batteries of the present invention produced by a substrate made of an ashless and completely combustible material before the ashless and completely combustible material is completely burned during the sintering process. 1 is a schematic cross-sectional view of one embodiment.

  1 and 2 illustrate a cylindrical solid oxide cell 10, for example, a solid oxide fuel cell (SOFC). The solid oxide cell 10 has an electrode assembly 11 in the form of functional layer system assemblies 11a, 11a ', 11b, 11b', 11c, 11c '. The electrode assembly 11 includes negative electrode layers 11a and 11a ′, positive electrode layers 11b and 11b ′, and electrolyte layers 11c and 11c ′ formed between the negative electrode layers 11a and 11a ′ and the positive electrode layers 11b and 11b ′. . The negative electrode layers 11a and 11a 'include a plurality of negative electrode regions 11a, and these negative electrode regions 11a are separated from each other via an electrically insulating and ion insulating region 11a'. The positive electrode layers 11b and 11b 'include a plurality of positive electrode regions 11b, and these positive electrode regions 11b are also separated from each other via electrically insulating and ion insulating regions 11b'. The electrolyte layers 11c and 11c 'include a plurality of electrolyte regions 11c, and these electrolyte regions 11c are separated from each other via a conductive and ion insulating region 11c' (interconnector region).

  1 and 2 further illustrate a state in which the negative electrode region 11a, the positive electrode region 11b, and the electrolyte region 11c are configured to be shifted from each other. Here, the negative electrode region 11a of a certain negative electrode / electrolyte / positive electrode / unit 11a, 11c, 11b is adjacent to each other via the conductive and ion insulating region 11c ′ of the electrolyte layers 11c, 11c ′. Are electrically connected to the positive electrode region 11b of each of the negative electrode, electrolyte, positive electrode, and units 11a, 11c, and 11b. In this way, each strand composed of a plurality of negative electrodes, electrolytes, positive electrodes, and units 11a, 11c, and 11b connected in a direct system is formed (see the left and right sides). Outside the cross-sectional plane shown, these strands (left and right) can be separated from each other via one or more regions that are electrically and ionically insulating.

  1 and 2 further show that each negative electrode, electrolyte, positive electrode, and each negative electrode region 11a of the units 11a, 11c, and 11b of two different strands are connected to each other via a single ring conductor 11a "made of a negative electrode material. As a result, the strands (the left side and the right side) are illustrated as being electrically connected to each other.

The arrows O _{2 in} FIGS. 1 and 2 illustrate how oxygen ions can each reach one of the negative electrode regions 11a from one of the positive electrode regions 11b through the electrolyte region 11c. The arrows e ^{− in} FIGS. 1 and 2 allow current to flow through one strand to the ring conductor 11a ″ and return through this ring conductor 11a ″ and the other strand. A state in which a plurality of negative electrodes / electrolytes / positive electrodes / units 11a, 11c, and 11b can be directly connected to each other by a plurality of interconnector regions 11c ′ and one ring conductor 11a ″ is illustrated. Advantageously, electrical wiring can be performed on one side of the battery, and Figures 1 and 2 show that current is conducted through the negative electrode material 11a and / or the positive electrode material 11b and / or the interconnector material 11c '. It shows how it can be done.

  1 and 2 further show that the functional layer systems 11a, 11a ′, 11b, 11b ′, 11c, 11c ′ are deposited inside the hollow cylindrical portion 12 of the tubular support. Show. The positive cylindrical layers 11b and 11b 'are in contact with the hollow cylindrical portion 12, and the hollow cylindrical portion 12 is formed of an inert gas-permeable porous material.

  FIGS. 1 and 2 show a cap in which one end part of a tubular support is configured as an attachment part or bottom part 13 and the other end part closes a hollow cylindrical intermediate part 12. A state of being configured as the portion 14 is illustrated.

  These two end portions 13, 14 are formed from an optionally inert, airtight ceramic material.

  FIG. 1 illustrates one embodiment of the method of the present invention, in which an electrode assembly is applied to a substrate 1 comprising components that form a porous ceramic material having an inert gas permeability. 11 is applied and film back molding is performed by injection molding component 12 which forms a porous ceramic material having inert gas permeability, and both components 1 and 12 are inert by sintering. A battery is formed by converting into a porous ceramic material having a gas permeability of the following. As a result, the formed inert gas permeable porous ceramic substrate 1 remains on the electrode assembly 11. FIG. 1 shows a first wall 12 formed from an injection molding component 12 made of a porous ceramic material having inert gas permeability, and a substrate made of a porous ceramic material having inert gas permeability. 1 illustrates a state in which the electrode assembly 11 is disposed between the second wall 1 and the second wall 1. The electrode assembly 11 follows the first wall 12 and the second wall 1 in material connection. In particular, the positive electrode layers 11 b and 11 b ′ are in contact with the first wall 12, and the negative electrode layers 11 a and 11 a ′ are in contact with the second wall 1, or vice versa. FIG. 1 illustrates a state in which the wall thickness of the second wall 1 can be made much thinner than the wall thickness of the first wall 12.

  Hereinafter, the embodiment using the inert porous support material 1 will be described in more detail. In this embodiment, in particular, the electrode assembly 11 is printed on the substrate 1 that can remain in the tube 12 as the inner wall 1 as a layer having sufficient porosity. This can in particular be carried out by subjecting the inert porous support material 1 in the form of a tape or tube to screen printing techniques. In this way, in particular, a cylindrical solid oxide fuel cell (SOFC) with electrodes on the inside can be produced in particular.

In this example in particular, a cast sheet, for example in the form of a tape, in particular a green sheet, can be produced from a wall material for the tube 12, such as forsterite, AlMg spinel or doped ZrO _2. Alternatively, an extruded sleeve or tube 1 can be produced. Functional layers 11a, 11a ′, 11b, 11b ′, 11c, and 11c ′ can be printed on the sheet (green sheet, tape) or sleeve (tube) 1 by screen printing technology. The functional layer assemblies 11a, 11a ′, 11b, 11b ′, 11c, 11c ′ can be fixed directly to the green body 12 made of forsterite, for example, directly during the injection process by means of film decoration, thereby advantageously The number of manufacturing processes can be reduced. During the sintering process, the inert porous material of the sheet (tape) or sleeve (tube) 1 is the material in the functional layer assemblies 11a, 11a ′, 11b, 11b ′, 11c, 11c ′, in particular the negative electrode 11a. It remains connected as an inner wall 1 that is connected in a connected manner and can be diffused, for example, through hydrogen into the negative electrode 11a.

The above method can generally be applied to all inert materials such as AlMg spinel, doped ZrO _{2 and} the like. From these materials, a sheet (tape) or a sleeve (extruded tube) 1 can be produced, which can be made into a highly porous material after sintering with a pore-forming agent.

  The advantage of using a green sheet 1 made of an inert material as a substrate material for the functional layer assembly 11 is that the green sheet 1 can be printed very well by flat printing and, for example, from a flat surface Also when moving to a curved injection mold core, for example, a CIM core (CIM, Ceramic Injection Molding), it can be handled well. Positioning on an injection mold core, for example a CIM core, can be performed very simply by vacuum. Since the sheet (tape) 1 remains in the tube 12 as a highly porous inner layer, an additional step for release can be omitted, and the risk of damage to the functional layer assembly due to the release step is reduced. It can be remarkably reduced. Furthermore, undesirable residues can be avoided.

In addition to using the sheet (tape) 1, it is also possible to extrude the sleeve (tube) 1 from an inert ceramic such as forsterite or AlMg spinel or doped ZrO ₂ . The sleeve (tube) 1 can be directly printed by curved printing, and in particular, the sleeve (tube) 1 has the advantage that it can be directly positioned on an injection mold core such as a CIM core. In this case as well, the sleeve 1 can remain in the tube 12 as the inner wall 1. Thus, a gas such as hydrogen can diffuse through the porous inner wall 1 to the negative electrode 11a, for example.

  In this way, advantageously, a cylindrical SOFC battery with the electrode assembly 11 inside can be produced. This electrode assembly 11 can be printed, in particular by screen printing, on a green sheet 1 made of the inert material listed above or on an extruded sleeve 1 made of the inert material listed above. Insert molding can be performed by inserting the sleeve 1 or the injection-molded core to which the electrode assembly 11 is attached into an injection mold, particularly a CIM mold. The sheet (tape) or sleeve (tube) 1 can remain in the tube 12 after the injection molding process. During the sintering process, the pore former present in the sheet (tape) or sleeve (tube) can be completely burned, for example, hydrogen can be passed through to reach the negative electrode 11a. An active porous layer can remain inside the tube 12.

  In particular, according to this idea, only one sintering step can be performed in which the electrode assembly 11 and the porous tube 12 are sintered together at a temperature of 1100 ° C. to 1300 ° C., for example.

  The ceramic tube 12 can be followed by a positive electrode 11b, particularly in material connection, and can maintain sufficient porosity after the sintering process. The negative electrode 11a can be connected in particular to the inert porous layer 1 or tube provided on the inside in a material connection.

  In particular, it is possible to use, for example, an inert porous green sheet or an extruded sleeve based on forsterite as the substrate 1 for the functional layer assembly 11, this green sheet or extruded An electrode assembly 11 is printed on the sleeve 1 by curved screen printing. The tube 12 may be a so-called CIM (ceramic injection molded) tube made of an inert porous material such as forsterite and manufactured by film decorative molding.

  FIG. 2 illustrates one embodiment of the method of the present invention, in which an electrode assembly 11 is deposited on a substrate 1 made of an ashless, fully combustible material and is inert. Film decoration molding by injection molding component 12 forming a porous ceramic material having gas permeability, and converting the component 12 into a porous ceramic material having inert gas permeability by sintering. To form a battery. The substrate 1 can cover the electrode assembly 11 before sintering. However, in this embodiment, since the substrate is completely removed by sintering, the inside of the electrode assembly 11, particularly the negative electrode layers 11a and 11a ″, is exposed (not shown in FIG. 2).

  Hereinafter, the embodiment using the support material 1 capable of burning completely without ash is described in more detail. In this embodiment, in particular, the electrode assembly 11 is printed on the base material 1 that burns completely in an ashless and residue-free manner during the sintering process. This can in particular be carried out by applying a screen printing technique to the tape- or tube-shaped ashless, fully combustible support material 1. In this way, it is possible in particular to produce a cylindrical solid oxide fuel cell (SOFC) with an electrode assembly 11a on the inside.

  In this embodiment, in particular, the support sheet or the extruded tube 1 can be produced from an ashless, completely combustible material such as carbon black and / or cellulose and / or starch. The functional layer 11a, 11a ', 11b, 11b', 11c, 11c 'can be printed on the sheet or tube 1 by, for example, a screen printing technique. The functional layer assemblies 11a, 11a ′, 11b, 11b ′, 11c, 11c ′ can be fixed directly to the green body 12 made of forsterite, for example, directly during the injection process by means of film decoration, thereby advantageously The number of manufacturing processes can be reduced. The base material 1 can be burned off in a residue-free manner during the sintering process. Therefore, advantageously, the porous negative electrode layer 11a can be exposed, or the porous negative electrode layer 11a can be present in the tube as the first functional layer. In this tube, for example, a combustion gas atmosphere can be generated.

  The advantages of using an ashless and completely combustible support sheet 1 for the functional layer assembly 11 are that the support sheet 1 can be printed very well by flat printing and, for example, from a flat surface Also when moving to a curved injection mold core, for example, to a CIM core, it can be handled well. Positioning on an injection mold core, for example a CIM core, can be performed very simply by vacuum. Since the sheet 1 can be completely burned ashless during sintering, no residue can remain on the electrode assembly 11.

  In addition to using the sheet 1, it is also possible to extrude the sleeve 1 from an ashless and completely combustible material (for example, carbon black, cellulose, starch). The sleeve 1 can be directly printed by curved printing, and in particular the sleeve 1 has the advantage that it can be positioned directly on an injection mold core such as a CIM core. The sleeve 1 is used as the inner wall 1 for the functional layer assembly 11 and can burn completely without residue during the sintering process.

  In this way, advantageously, a cylindrical SOFC battery with the electrode assembly 11 inside can be produced. This electrode assembly 11 can be applied, in particular by screen printing, to a green sheet 1 made of an ashless and completely combustible material such as carbon black and / or cellulose and / or starch or to an ashless and completely combustible material. It is possible to print on an extruded sleeve 1 made of active material. The sleeve 1 or injection-molded core with the electrode assembly 11 applied can be surrounded by injection molding by inserting it into an injection mold, in particular a CIM mold. Since the sheet (tape) or sleeve completely burns without residue during the sintering process, the negative electrode 11a can be exposed or exposed inside the tube 12, for example.

  In particular, according to this idea, only one sintering step can be performed in which the electrode assembly 11 and the porous tube 12 are sintered together at a temperature of 1100 ° C. to 1300 ° C., for example.

  The ceramic tube 12 can be followed by a positive electrode 11b, particularly in material connection, and can maintain sufficient porosity after the sintering process. The substrate 1 of the electrode assembly 11 can be burned away without residue.

  In particular, as a substrate 1 for the functional layer assembly 11, it is possible to use a flat support sheet or an extruded sleeve, for example ashless, completely combustible, consisting of carbon black and / or cellulose and / or starch. The electrode sheet 11 can be printed on the support sheet or the extruded sleeve 1 by screen printing, and the support sheet or the extruded sleeve 1 burns completely without residue during the sintering process. The tube 12 may be a so-called CIM (ceramic injection molded) tube made of an inert porous material such as forsterite and manufactured by film decorative molding.

Claims (15)

A method for producing a cylindrical solid oxide battery (10), comprising:
a) providing a substrate (1) formed from a component that forms a porous ceramic material having gas permeability or a substrate (1) formed from an ashless and completely combustible material; ,
b) attaching an electrode assembly (11) to the substrate (1);
c) defining a hollow cylindrical hollow chamber in the electrode assembly (11) by inserting the substrate (1) comprising the electrode assembly (11) into a cavity of an injection mold; ,
d) injecting an injection molding component (12) into the tubular hollow chamber;
e) Sintering the injection-molded body (12) to convert the component (1) forming the gas permeable porous ceramic material (1) into a gas permeable porous ceramic material. Or completely burning the ashless, completely combustible material;
Have
The electrode assembly (11) includes a negative electrode layer (11a, 11a ′), a positive electrode layer (11b, 11b ′), a negative electrode layer (11a, 11a ′), and a positive electrode layer (11b, 11b ′). Between the adjacent negative electrode / electrolyte / positive electrode / unit (11a, 11c, 11b), only the electrolyte layer (11c, 11c ′) is an interconnector region (11c, 11c ′). 11c ′),
A method for producing a cylindrical solid oxide battery. The negative electrode layer (11a, 11a ′) includes a plurality of negative electrode regions (11a) separated from each other via an electrically insulating and ion insulating region (11a ′),
The positive electrode layer (11b, 11b ′) includes a plurality of positive electrode regions (11b) separated from each other via an electrically insulating and ion insulating region (11b ′),
The electrolyte layer (11c, 11c ′) includes a plurality of electrolyte regions (11c) separated from each other via a conductive and ion insulating region (11c ′) as the interconnector region (11c ′). ,
An electrically insulating and ionic insulating region (11a ′) of the negative electrode layer (11a, 11a ′), an electrically insulating and ionic insulating region (11b ′) of the positive electrode layer (11b, 11b ′), and At least partially overlaps the conductive and ion insulating region (11c ′) of the electrolyte layer (11c, 11c ′),
The method according to claim 1, wherein: In step e),
3. A method according to claim 1 or 2, characterized in that at least the injection molding component (12) and the electrode assembly (11) are sintered together. In step b)
Printing the electrode assembly (11) on the substrate by screen printing;
The method according to claim 1, characterized in that: In step c)
The substrate (1) comprising the electrode assembly (11) has a hollow cylindrical shape or is formed into a hollow cylindrical shape,
The outer peripheral surface or the inner peripheral surface of the hollow cylindrical base material (1) on which the electrode assembly (11) is printed is constituted by the electrode assembly (11),
The tube-shaped hollow chamber is defined by the outer peripheral surface or the inner peripheral surface constituted by the electrode assembly (11).
5. A method according to any one of claims 1 to 4, characterized in that 6. A method according to any one of the preceding claims, characterized in that the substrate (1) is a cast sheet or an extruded sleeve or an injection-molded sleeve. The component (1) for forming a porous ceramic material having gas permeability is a component for forming a porous ceramic material having gas permeability that is not used as an electrode or an electrolyte. Item 7. The method according to any one of Items 1 to 6. Said component (1) forming a porous ceramic material with gas permeability according to said step a) comprises forsterite, aluminum magnesium spinel and / or doped zirconium dioxide,
Or
The ashless and completely combustible material (1) is selected from the group consisting of elemental carbon, natural polymers, and combinations thereof,
8. A method according to any one of the preceding claims, characterized in that the ashless and completely combustible material (1) is carbon black and / or starch and / or cellulose. The method of claim 8, wherein the elemental carbon is carbon black. 10. The method according to claim 8 or 9, characterized in that the natural polymer is cellulose and / or starch. In step d)
11. Method according to any one of the preceding claims, characterized in that an injection molding component (12) is used which forms a porous ceramic material with gas permeability. 12. Method according to any one of the preceding claims, characterized in that the injection molding component (12) in step d) comprises forsterite, aluminum magnesium spinel and / or doped zirconium dioxide. . 13. Method according to any one of the preceding claims, characterized in that said component (1) forming a porous ceramic material with gas permeability is also used as said injection molding component (12). . The cylindrical solid oxide cell (10) is a fuel cell.
14. A method according to any one of the preceding claims, characterized in that The component (1) forming the porous ceramic material having gas permeability used also as the injection molding component (12) is a material that is not used as an electrode or an electrolyte. 13. The method according to 13.

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