JP6033004B2 - Cylindrical fuel cell with inert support - Google Patents

Description

  The present invention relates to a method for manufacturing a cylindrical fuel cell.

  Furthermore, the present invention relates to a cylindrical fuel cell manufactured by the above method.

  Furthermore, the present invention relates to a fuel cell system and a vehicle equipped with a fuel cell system and a cogeneration (combined heat and power) facility equipped with the fuel cell system.

  Solid oxide fuel cells (SOFCs) work to generate electrical current and, in some cases, heat, and are often used as auxiliary equipment or cords for home energy supply or industrial energy supply. It is used for generation facilities (KWK) and for on-board power generation of power plants and vehicles. Since the solid oxide fuel cell is usually operated at a temperature of 600 ° C. to 1000 ° C., it is also called a high temperature fuel cell.

  The solid oxide fuel cell may have a tubular or flat support. Since the fuel cell related to the present application has a tubular support, it can be distinguished from a fuel cell formed in a flat plate shape based on its geometric shape. A fuel cell provided with a tubular support is also called a tube-type or cylindrical fuel cell. This cylindrical fuel cell may be formed open on both sides, thereby not only guiding the combustion gas or air through the cylindrical fuel cell, but also being closed on one end side. May be. In that case, combustion gas or air can be guided inside the fuel cell via a lance.

  Cylindrical fuel cells can be distinguished especially with respect to the form of the support.

  In an electrolyte-supported fuel cell having a tubular support, the electrolyte also functions as a support and is formed to be significantly thicker than the electrode. In such a fuel cell, the electrodes are usually attached to the inner and outer surfaces of the support. In order to ensure the support function, the electrolyte has a layer thickness of at least 200 μm. However, the large layer thickness of the electrolyte has a negative effect on the ohmic resistance of the fuel cell. Therefore, such fuel cells are operated at higher temperatures, in particular up to 950 ° C., in order to obtain sufficient conductivity of the electrolyte and good output performance.

  WO 2010/037670 and DE 10219096 describe a cylindrical fuel cell having a tubular support made of a porous metal material.

  U.S. Pat. No. 6,379,485 describes a method for manufacturing a cylindrical fuel cell closed on one side.

International Publication No. 2010/037670 German Patent Application Publication No. 10219096 US Pat. No. 6,379,485

  Accordingly, an object of the present invention is to provide a method for manufacturing a cylindrical fuel cell in which an electrolyte is formed into a thinner film.

  To solve this problem, the method according to the present invention comprises the following method steps: a) an injection mold with a cavity and an injection mold core insertable into the cavity. And by inserting the injection mold core into the cavity, a substantially tubular hollow chamber can be formed between the injection mold core and the injection mold core. Alternatively, a sandwich-like functional layer sequence having a cathode layer, an electrolyte layer, and an anode layer for forming at least one electrode / electrolyte assembly is disposed on the cavity forming surface of the injection mold, b) inserting an injection mold core into the cavity, c) at least one of the tubular hollow chambers so that gas permeable pores and / or openings can be formed, especially in the section adjacent to the functional layer sequence. Part Injecting at least one component for forming a ceramic support material and / or a glassy support material, d) solidifying the component, in particular an object formed in a tubular hollow chamber, and a functional layer sequence For example, simultaneous sintering at a temperature of 1200 ° C. or lower.

  According to an advantageous embodiment of the method according to the invention, the electrolyte layer contains a nanoscale electrolyte material, in particular nanoscale zirconium dioxide, such as nanoscale yttria stabilized zirconia (YSZ).

  According to an advantageous embodiment of the method according to the invention, the at least one component for forming the ceramic support material and / or the glassy support material is an electrically insulating and / or ionic insulating ceramic support. Defined to form body material and / or glassy support material.

  According to an advantageous embodiment of the method according to the invention, the cathode layer is on the side of the functional layer sequence opposite the injection mold core or on the side of the functional layer sequence opposite the cavity forming surface of the injection mold. The functional layer sequence is disposed on the injection mold core or on the cavity forming surface of the injection mold.

  According to an advantageous embodiment of the method according to the invention, the injection mold core is partly or completely formed as a disappearing core.

  According to an advantageous aspect of the method according to the invention, the injection mold core comprises an injection mold core base body and a removable support sleeve or support sheet that covers the injection mold core base body. In this way, the injection mold core is partly formed as a disappearing core, and the functional layer sequence is covered on a removable support sleeve or support sheet, for example by screen printing, in particular rotary screen printing. Worn or injection mold core is formed as a completely disappearing core, in particular in the form of a removable injection mold core or a removable injection mold core sleeve; The functional layer sequence is applied to the removable injection mold core or the removable injection mold core sleeve, for example by curved screen printing. There.

  According to an advantageous embodiment of the method according to the invention, the removal of the removable support sleeve, the removable support sheet, the removable injection mold core sleeve or the removable injection mold core is at least partly performed. Mechanically, at least partly by dissolution in a solvent and / or at least partly by decomposition, evaporation and / or melting.

  According to an advantageous embodiment of the method according to the invention, in method step c), the ceramic support material is placed in a tubular hollow chamber so that the sections not adjacent to the functional layer sequence can be formed gastight. And / or injecting at least two components to form a glassy support material.

  According to an advantageous embodiment of the method according to the invention, the tubular hollow chamber corresponds at least approximately to the shape of the tubular support to be formed, in particular a cylindrical mold in which the tubular hollow chamber is formed at one end. Is formed to form an open base section for securing the fuel cell to the support substrate, and at the other end is formed to form a closed cap section, or a tubular hollow chamber , At both ends, formed to form one open base section each for fixing the formed cylindrical fuel cell to the support substrate.

  Furthermore, in order to solve the above-described problems, according to the cylindrical fuel cell according to the present invention, the cylindrical fuel cell includes a tubular support and at least one electrode / electrolyte assembly. The electrode / electrolyte assembly comprises a cathode, an anode, and a particularly gas-tight electrolyte disposed between the cathode and anode, wherein at least one electrode / electrolyte assembly is tubular An inner or outer surface, in particular an inner surface, of the support, the tubular support being formed from one or more types of ceramic and / or glassy materials, the tubular support being One or more sections adjacent to the electrode / electrolyte assembly have gas permeable pores and / or openings.

  According to an advantageous embodiment of the cylindrical fuel cell according to the invention, the material of the tubular support is ion-insulating and / or electrically insulating.

  According to an advantageous embodiment of the cylindrical fuel cell according to the invention, the tubular support is closed by a cap section at one end of the tube, the cap section being gastight.

  According to an advantageous embodiment of the cylindrical fuel cell according to the invention, the cathode of at least one electrode-electrolyte assembly is adjacent to the support, in particular the anode is exposed in the inner chamber of the tubular support. Has been.

  According to an advantageous embodiment of the cylindrical fuel cell according to the invention, the cathode of the at least one electrode-electrolyte assembly is formed from a conductive and gas-permeable cathode material, The electrolyte of the electrolyte assembly is formed from an ion conductive, gas tight and electrically insulating electrolyte material, and the anode of at least one electrode / electrolyte assembly is formed from a conductive and gas permeable anode material. Has been.

  According to an advantageous embodiment of the cylindrical fuel cell according to the invention, the tubular support has open pores with a porosity of 20% or more in one or more porous sections.

The subject of the invention is in particular a method for producing a cylindrical fuel cell, which will be described later. This method consists of the following method steps:
a) An injection mold having a cavity and an injection mold core that can be inserted into the cavity are prepared, and the injection mold core and the injection mold are inserted by inserting the injection mold core into the cavity. A generally tubular hollow chamber can be formed between the mold and the mold, and at least one, particularly a large number of electrode / electrolyte assemblies are formed on the injection mold core or on the cavity forming surface of the injection mold. A functional layer array in the form of a sandwich having a cathode layer, an electrolyte layer, and an anode layer is disposed,
b) Insert an injection mold core into the cavity,
c) a ceramic support material in the tubular hollow chamber or in at least part of the tubular hollow chamber, such that gas-permeable pores and / or openings can be formed, particularly in the section adjacent to the functional layer sequence; Injecting at least one component to form a glassy support material;
d) solidify this component:
have.

  In method step d), an object formed from a tubular hollow chamber (from one or more types of components) and a sandwich-like functional layer sequence are bonded together, in particular physically and / or chemically. can do. In particular, in step d), the object formed in the tubular hollow chamber (from one or more components) and the functional layer sequence can be (simultaneously) sintered or co-sintered. be able to. One or more types of components can form in particular a ceramic support material and / or a glassy support material. Therefore, an object formed in a tubular hollow chamber can also be called a support, in particular after solidification or sintering.

  The object (support) advantageously makes it possible to form the electrode / electrolyte assembly as a very thin functional layer set. The electrolyte can be formed into a thin film even so that it no longer has a layer thickness of about 15 μm. This advantageously reduces the operating temperature to at least 750 ° C. and improves the output performance of the fuel cell. Furthermore, material costs can be saved by the configuration of the thin film. Furthermore, the reduction in operating temperature has the advantage that more advantageous materials with less temperature stability can also be used. Thereby, the material cost can be further reduced.

  By means of the method according to the invention, ceramic and / or glass-like objects (supports) can advantageously be produced particularly simply and inexpensively.

  Furthermore, in the method according to the invention, it is possible advantageously to omit the multiple sintering steps, the object formed in the tubular hollow chamber and the functional layer sequence from one common sintering. The steps (co-sintering, co-firing steps) can be converted into one tubular support and one or more electrode-electrolyte assemblies. Since the sintering step is costly, manufacturing costs can be significantly reduced by such simultaneous sintering.

  A further advantage is that the functional layer sequence and thus the entire electrode set can be arranged in the combustion gas chamber, for example on the inner surface of a tubular object (support). This has the advantage that the current lead-out line and / or the anode can be realized more easily by a metal conductor. For example, base metals and their alloys, such as nickel and nickel alloys, can be used as anode materials and / or materials used in electrical lines, particularly for electrically connecting the anode and cathode. The base metal and its alloy can have high chemical stability even at a high temperature in a reducing atmosphere, for example, a combustion gas atmosphere. Otherwise, this can only be achieved with expensive noble metals such as platinum, particularly in an oxidizing atmosphere. In this way, material and manufacturing costs can be advantageously reduced.

  Furthermore, the functional layer sequence can be formed in a particularly wide variety, preferably by printing methods, for example in addition to the cathode layer, the electrolyte layer and the anode layer, further functional ranges such as a current deriving device. A range for forming, an electrical interconnector for interconnecting two or more electrode-electrolyte assemblies and / or a range for electrically and / or ionic isolation of individual ranges. You may have.

  Cylindrical fuel cells have the advantage that gas chambers can advantageously be separated from one another, in an extremely simple manner, compared to flat plate fuel cells. This is because the seal member can be omitted within the high temperature range.

  Tubular objects (supports) or chambers are in particular essentially round, for example substantially hollow, which may have not only a circular or oval-shaped (elliptical) bottom but also a polygonal bottom. Means a cylindrical object or chamber. In particular, a tubular object or chamber can have a circular bottom.

  Ceramic material means in particular non-metallic inorganic materials. The ceramic material is at least partially crystalline.

  “Nonmetallic” means that the material does not have metallic properties, especially based on metallic bonds. Thus, the concept of “non-metallic” excludes that the material may contain metal compounds such as metal oxides and / or metal silicates such as magnesium silicate, zirconium oxide and / or aluminum oxide. is not.

  By vitreous material is meant an amorphous or non-crystalline non-metallic inorganic material.

  The concept of “ceramic (material) and / or glassy (material)” is in particular partly crystalline and partly amorphous or glassy, for example having a so-called “glass phase”. It means that a mixed form such as a non-metallic inorganic material may be included.

  The support material may be particularly inert. Here, “inert” means that the material does not act as an electrode or electrolyte. In this case, the fuel cell can be called an inert support type fuel cell.

  In method step c), the formation of gas permeable pores and / or openings in the tubular body to be formed can be achieved, for example, by adding at least one pore former to at least one component, twinning to the starting powder. This can be done by the use of a ridge distribution or a multimodal distribution of particle sizes or by an overhanging structured part provided in the injection mold. Advantageously, in method step c), the pore former-containing component is injected so as to cover the functional layer sequence.

  As pore former, compounds that decompose, evaporate and / or elute during heat treatment, eg sintering, can be used. As the pore-forming agent, for example, an organic pore-forming agent is suitable. This organic pore-forming agent is completely burned during heat treatment, for example after shaping by injection molding, and can leave behind, for example, a permeation hollow chamber.

  Within the scope of one embodiment of the method according to the invention, the electrolyte layer contains a nanoscale electrolyte material, in particular nanoscale zirconium dioxide, such as nanoscale yttria stabilized zirconia (YSZ).

  “Nanoscale material” means a material having an average particle size of less than 1 μm, for example less than 100 nm, in particular in at least one spatial direction.

  Furthermore, the use of a nanoscale electrolyte material can form a gas tight electrolyte layer, advantageously at temperatures below 1200 ° C.

  Within the scope of one further embodiment of the method according to the invention, the at least one component for forming the ceramic support material and / or the glassy support material is in particular electrically insulating and / or ionic insulating. For forming an electrically conductive ceramic support material and / or a glassy support material, for example an electrically insulating and ionic insulating ceramic support material and / or a glassy support material.

  Within the scope of one further aspect of the method according to the invention, the cathode layer is a cavity-forming surface of the injection mold, on the side of the functional layer sequence opposite to the injection mold core or of the functional layer sequence. As arranged on the opposite side, the functional layer sequence is arranged on the injection mold core or on the cavity forming surface of the injection mold.

  The injection mold core can be formed substantially rotationally symmetric, for example substantially cylindrical or possibly hollow cylindrical.

  Within one further aspect of the method according to the invention, the injection mold core is partly or completely formed as a disappearing core.

  “Disappearing core” or “disappearing mold” means an injection mold core or mold that cannot be used again, especially because it is removed by destruction during the manufacturing process.

  Within the scope of one further aspect of the method according to the invention, an injection mold core core is provided with an injection mold core base body and a removable support sleeve which can be placed over the injection mold core base body. Alternatively, by having a support sheet, the injection mold core is partially formed as a disappearing core, and the functional layer sequence can be removed by, for example, screen printing, in particular curved screen printing. Or it is attached to the support sheet.

  Alternatively, the injection mold core is formed as a completely extinguished core, especially in the form of a removable injection mold core or a removable injection mold core sleeve. The functional layer sequence is applied to the removable injection mold core or the removable injection mold core sleeve by, for example, curved screen printing.

  Analogously to this, the injection mold may be formed at least partly as a disappearing mold, for example by applying a removable support sheet or support sleeve to the cavity forming surface of the injection mold.

  The injection mold core may be formed as a completely disappearing core, in particular in the form of a removable injection mold core or a removable injection mold core sleeve. The functional layer sequence is attached to the removable injection mold core or the removable injection mold core sleeve by, for example, curved screen printing.

  Within one alternative aspect of the method according to the invention, removal of the removable support sleeve, the removable support sheet, the removable injection mold core sleeve or the removable injection mold core, It is carried out at least partly mechanically, at least partly by dissolution in a solvent and / or at least partly by decomposition, evaporation and / or melting.

  The support sleeve or injection mold core sleeve and optionally the injection mold core are particularly advantageously removed mechanically during removal, for example by being crushed during withdrawal. be able to. For this purpose, the support sleeve or the injection mold core sleeve or the injection mold core is advantageously formed from a plastic material. Such shaped bodies can advantageously be produced particularly inexpensively, for example as injection-molded parts and are therefore particularly suitable for use as a vanishing core.

  The support sheet can advantageously be easily removed mechanically by peeling.

  To remove the removable support sleeve, the removable support sheet, the removable injection mold core sleeve or the removable injection mold core at least in part, and even completely, by dissolution in a solvent For example, the removable element may be formed, for example, from a soluble, in particular water-soluble polymer, such as cellulose or methylcellulose, and based on acrylic acid, maleic acid, vinyl pyrrolidone, vinyl imidazole or polyvinyl alcohol It may be formed from a polymer. For example, the assembly can be placed in a solvent, such as water, prior to mechanical removal of the injection mold core to dissolve the polymer between the injection mold core and the functional layer sequence.

  In order to remove the removable support sleeve, the removable support sheet, the removable injection mold core sleeve or the removable injection mold core by disassembly, the removable element can be used at elevated temperatures, for example It may be formed from a material that can be removed by decomposition, evaporation and / or melting during sintering, advantageously without residue.

  Advantageously, a removable sheet-like support sleeve or a removable support sheet is used. Advantageously, the functional layer sequence can be applied, in particular printed, on a sheet in a particularly simple manner. Furthermore, the material cost for the sheet material is small compared to a solid disappearance injection mold core. The functional layer can be applied not only to a sheet-like support sleeve that can be removed by, for example, curved screen printing, but also to a flat support sheet that can be removed by, for example, planar printing. In some cases, a removable sheet-like support sleeve can then be formed from this removable flat support sheet. On the side facing the injection mold core or the injection mold, the support sleeve or the support sheet has a particularly low static friction, whereby mechanical removal can be easily performed.

  Within the scope of one further aspect of the method according to the invention, in method step c), one or more sections that are not adjacent to the functional layer sequence can be formed gastight. At least two components for forming a ceramic support material and / or a glassy support material are injected into the hollow chamber. In particular, gas-permeable pores and / or openings can be formed in the section adjacent to the functional layer sequence.

Method step d) may in particular have one or more sub-method steps. For example, method step d)
-Cooling to form a green compact by temperature-induced solidification of at least one charged component, for example one or more cooling steps,
One or more heat treatments at different temperatures, for example in particular for partial or complete degreasing and / or calcination and / or sintering or ceramization and / or annealing of the green compact,
-For example one or more treatments with a solvent for partial or complete degreasing and / or -1 or more process treatment steps, eg formed from injection molds Removal of the tubular object and / or removal of the injection mold core from the formed tubular object;
There may be one or more sub-method steps selected from

  In particular, method step d) may comprise the sintering or co-sintering of an object formed in a tubular hollow chamber (from one or more types of components) and a functional layer sequence. This sintering or simultaneous sintering can be performed at a temperature of 1200 ° C. or less.

  In the meaning of the present application, the concept of “degreasing” includes the removal of other organic compounds such as pore formers, softeners, etc., in addition to the removal of the organic binder.

  For example, first, one or more kinds of components can be partially degreased by a dissolution method, and then degreased by a heat treatment at a low temperature within a range of, for example, 100 ° C. or more and 300 ° C. or less. Thereafter, at least one type of pore-forming agent and / or support sleeve, support sheet, molded core sleeve or molded core, in particular, decomposes and evaporates, for example, by heat treatment at a moderate temperature in the range of 250 ° C. to 600 ° C. And / or can be removed by melting. Finally, the tubular object formed with the functional layer sequence can be sintered, for example, at a temperature in the range of 1000 ° C. to 1200 ° C.

  Advantageously, the sintering is performed after releasing the tubular object formed with the functional layer sequence from the injection mold.

  Within the scope of one further aspect of the invention, the tubular hollow chamber corresponds at least approximately to the shape of the tubular support to be formed, in particular a cylinder in which the tubular hollow chamber is formed at one end. It has been proposed to form an open base section for securing a fuel cell of the type to a support substrate and at the other end to form a closed cap section (One side closed cylinder).

  As an alternative to this, a tubular hollow chamber is formed at each end to form one open base section for fixing the formed cylindrical fuel cell to the support substrate. Yes (both sides open cylinder).

  For further advantages and features, the fuel cell according to the present invention, the fuel cell system according to the present invention, the cogeneration facility according to the present invention or the detailed description related to the vehicle according to the present invention, the drawings and the description of the drawings. Are described in detail.

  A further subject matter of the invention is a fuel cell produced according to the invention.

  A further subject matter of the invention is, for example, a cylindrical fuel cell manufactured by the method according to the invention. The fuel cell on the cylinder side has a tubular support and at least one electrode / electrolyte assembly, and the electrode / electrolyte assembly is interposed between the cathode, the anode, and the cathode and anode. And at least one electrode / electrolyte assembly is applied to the inner or outer surface of the tubular support, in particular the inner surface. According to the present invention, the tubular support is formed from one or more types of ceramic materials and / or glassy materials and is divided into one or more sections adjacent to the electrode-electrolyte assembly. , Gas permeable pores and / or openings.

  The tubular support may be open at one tube end and closed at the other tube end, or may be formed open at both tube ends. In particular, the tubular support may be formed open at one tube end and closed at the other tube end, in particular by a cap section.

  Within one further aspect, the support material is ionic insulating and / or electrically insulating, for example ionic insulating and electrically insulating.

  In one or more sections that do not include an electrode-electrolyte assembly, the tubular support can be formed in a particularly gastight manner.

  The tubular support may have a base section for fixing the cylindrical fuel cell to the support substrate at at least one open tube end. This base section may in particular be formed gas tight.

  In the embodiment of a tubular support open at both tube ends, the tubular support can have a base section at each of both tube ends. In this way, the fuel cell can be fixed, for example, to one support substrate, in particular to two support substrates, via both base sections.

  In the case of a tubular support that is open at one tube end and closed at the other tube end, the tubular support fixes the cylindrical fuel cell to the support substrate at the open tube end. Can have a base section for closing and can be closed by a cap section at the closed tube end.

  Within one further aspect, the tubular support is closed by a cap section at one tube end. This cap section can be formed particularly gas tight.

  Within one further aspect, the cathode of at least one electrode-electrolyte assembly is adjacent to the support. The anode may in particular be exposed in the inner chamber of the tubular support. In particular, the cathode of all electrode / electrolyte assemblies can be adjacent to the support.

  In this embodiment, air is supplied to the outside of a cylindrical fuel cell, in particular a tubular support, and combustion gas, for example hydrogen or natural gas, for example underground natural, is provided inside the cylindrical fuel cell, in particular a tubular support. Suitable for operation in which gas, biogas, methane gas, ethane gas, propane gas, butane gas or a gas mixture containing at least one of these gases is supplied.

  Basically, however, it is also possible that the anode of at least one electrode-electrolyte assembly is adjacent to the support, in particular the cathode is exposed in the inner chamber of the tubular support. This aspect is particularly suitable for an operation in which combustion gas is supplied to the outside of a cylindrical fuel cell, particularly a tubular support, and air is supplied to the inside of a cylindrical fuel cell, particularly a tubular support.

  The former embodiment has the advantage that a base metal, such as nickel, can be used as the anode material and / or the material used for the electrical lines. This is because the anode material or electrical line is used in a reducing atmosphere, such as a combustion gas atmosphere, and can have high chemical stability even at high temperatures. Otherwise, this stability can only be achieved with expensive noble metals such as platinum, particularly in an oxidizing atmosphere.

  Within one alternative embodiment, the cathode of at least one electrode-electrolyte assembly is formed from a conductive and gas permeable cathode material, and the electrolyte of at least one electrode-electrolyte assembly comprises: The anode of the at least one electrode / electrolyte assembly is formed from a conductive and gas permeable anode material, which is formed from an ion conductive, gas tight and electrically insulating electrolyte material.

  The cathode of at least one electrode / electrolyte assembly may contain, for example, at least one kind of cathode material, or may be formed from at least one kind of cathode material. This cathode material is lanthanum, strontium, manganese oxide (LSM), scandium doped lanthanum, strontium, manganese oxide (LSSM), lanthanum, strontium, cobalt, ferrite (LSCF), lanthanum, nickel, ferrite (LNF) And a group consisting of combinations thereof. In particular, the cathode of at least one electrode-electrolyte assembly can be formed from a conductive and gas permeable or porous cathode material. In addition, the cathode material may be ionically conductive, thereby increasing the reaction zone. In particular, all electrode / electrolyte assemblies of the fuel cell may contain such a cathode material, or may be formed from such a cathode material.

  The cathode of the at least one electrode / electrolyte assembly may have a cathode layer thickness of, for example, 150 μm or less, for example 120 μm or less. In particular, the cathodes of all electrode / electrolyte assemblies of the fuel cell may have such a cathode layer thickness.

The anode of at least one electrode / electrolyte assembly may contain, for example, at least one kind of anode material, or may be formed from at least one kind of anode material. The anode material is a cermet containing nickel and yttria stabilized zirconia (Ni / YSZ), titanate, for example manganese doped titanate, such as lanthanum strontium titanate (Sr _1-X La _X TiO ₃ ), aluminates such as manganese and / or lanthanum and / or strontium-containing aluminates ((La, Sr) (Al, Mn) O ₃ ) and combinations thereof Yes. In particular, the anode of at least one electrode-electrolyte assembly can be formed from a conductive and gas permeable or porous anode material. In some cases, the anode material may be further ionically conductive, thereby increasing the reaction zone. In particular, all electrode / electrolyte assemblies of the fuel cell may contain such an anode material or may be formed from such an anode material.

  The anode of the at least one electrode-electrolyte assembly may have an anode layer thickness of, for example, 100 μm or less, for example 50 μm or less. In particular, the anodes of all electrode / electrolyte assemblies of the fuel cell may have such an anode layer thickness.

The electrolyte of at least one electrode / electrolyte assembly may contain at least one kind of material or may be formed from at least one kind of material. This material is selected from the group consisting of yttria stabilized zirconia (YSZ), cerium oxide (CeO ₂ ), and combinations thereof. The electrolyte of the at least one electrode-electrolyte assembly can be formed in particular from an ion-conductive, gas-tight and electrically insulating electrode material. In particular, the electrolyte of all electrode / electrolyte assemblies of the fuel cell may contain such an electrolyte material, or may be formed from such an electrolyte material.

  The electrolyte of the at least one electrode-electrolyte assembly can have a layer thickness of, for example, 50 μm or less, such as 45 μm or less, or 40 μm or less, or 35 μm or less, or 30 μm or less, or 25 μm or less, or 20 μm or less, such as about 15 μm. In particular, the electrolyte of all electrode / electrolyte assemblies of the fuel cell may have such an electrolyte layer thickness.

  The cathode, electrolyte and anode of the at least one electrode-electrolyte assembly form a layer sequence having a layer sequence thickness, in particular (total) of 500 μm or less or 300 μm or less, for example 250 μm or less, for example 200 μm or less or 150 μm or less. be able to. In particular, all electrode / electrolyte assemblies of the fuel cell may form one layer sequence and have such a layer sequence thickness.

  The base section may have a protrusion for fixing the cylindrical fuel cell to the support substrate, extending over the entire circumference, in particular on the outer surface of the tubular support.

  Within one alternative embodiment, the support has a porosity of 20% or more, such as 25% or 30% or 40% or more, such as about 40%, in one or more porous sections. Has open pores. The porosity can be measured by, for example, a photoelectron microscope or a scanning electron microscope and / or flow measurement.

  The tubular support may have a thickness of, for example, 5000 μm or less or 2000 μm or less, for example, a thickness in the range of 250 μm to 2000 μm, or 500 μm to 2000 μm, for example, a thickness of about 1000 μm.

  The pores may have an average pore size of, for example, 300 μm or less, such as 200 μm or less, or 100 μm or less, or 50 μm or less. In particular, the pores can have a generally elongated shape. For example, the pores have an average length in the range of 100 μm to 300 μm, particularly 150 μm to 250 μm, for example, an average length of about 200 μm, and 1 μm to 70 μm, particularly 5 μm to 30 μm, for example, about 5 μm or more. It may have an average diameter in the range of 10 μm or less or an average diameter of about 20 μm.

  The pores can form an osmotic pore network having a passage distribution in the range of 1 μm to 20 μm, particularly 1 μm to 10 μm, for example, a passage distribution of about 5 μm. Such a pore passage distribution advantageously allows free gas diffusion, especially without the occurrence of the so-called “Knusen effect”.

The tubular support may contain, for example, at least one kind of material, or may be formed from at least one kind of material. This material comprises magnesium silicate, in particular forsterite, zirconium dioxide, in particular doped zirconium dioxide, for example zirconium dioxide doped with 6.5% by weight of yttrium oxide (Y ₂ O ₃ ), aluminum oxide, aluminum oxide. And a mixture of zirconium oxide, spinel such as magnesium aluminate, a mixture of zirconium oxide and glass, zirconia and combinations thereof. Forsterite is mainly based on the general chemical formula Mg ₂ SiO ₄ .

  The tubular support may be formed by injection methods and / or molding methods, in particular injection molding methods. In particular, the tubular support can be formed by a multi-component injection molding method.

  A cylindrical fuel cell can have a large number of electrode / electrolyte assemblies.

  For further advantages and features, the method according to the present invention, the fuel cell system according to the present invention, the cogeneration facility according to the present invention or the detailed description related to the vehicle according to the present invention, the drawings and the description of the drawings. It is described in detail.

  Furthermore, the invention relates to a fuel cell system comprising at least one, in particular a large number of fuel cells according to the invention or fuel cells produced according to the invention.

  For further advantages and features, the method according to the present invention, the fuel cell according to the present invention, the cogeneration facility according to the present invention or the detailed description relating to the vehicle according to the present invention, the drawings and the description of the drawings are detailed. It is described.

  Furthermore, the present invention relates to a cogeneration facility having a fuel cell system according to the present invention, or a vehicle having a fuel cell system according to the present invention, which is used in, for example, a house, commercial facility, industrial facility or power plant.

  Further advantages and features are described in detail in the method according to the invention, the detailed description relating to the fuel cell according to the invention or the fuel cell system according to the invention, the drawings and the description of the drawings.

  Further advantages and advantageous aspects of the subject matter according to the invention are shown in the drawings and will be explained below. It should be noted that the drawings only show the features to be described below, and the drawings are not intended to limit the present invention in any way.

  According to the present invention, the electrolyte can be formed in a thinner film.

1 is a schematic cross-sectional view of a fuel cell according to an embodiment of the present invention. It is a schematic cross-sectional view for showing the 1st method step of the manufacturing method concerning an embodiment of the invention. It is a schematic cross-sectional view for showing the 2nd method step of the manufacturing method concerning an embodiment of the invention.

  In the following, embodiments for carrying out the present invention will be described in detail with reference to the drawings.

  FIG. 1 shows one embodiment of a fuel cell according to the present invention. This fuel cell includes a ceramic and / or glass-like tubular support 1. An electrode / electrolyte assembly 2 is attached to the inner surface of the support 1. Although not shown in the drawings, the electrode / electrolyte assembly 2 may be disposed on the outer surface of the tubular support 1 within the scope of another alternative embodiment.

As shown in FIG. 1, the tubular support 1 has a plurality of gas permeable pores in a section 1 a adjacent to the electrode / electrolyte assembly 2. In other words, the electrode / electrolyte assembly 2 is arranged on the inner surface of the tubular support 1 at the exact height of the porous section 1a. Further, as shown in FIG. 1, the tubular support body 1 is continuously closed at one tube end by a cap section 1b, and the base section 1c and the fuel cell are supported at the open tube end section. It has a so-called “assembly flange” for fixing to the plate . Advantageously, base section 1c is a fuel cell in the support base plate without additional sealing by the glass-like material are formed in order to fix the gas-tight. The cap section 1b and the base section 1c are formed in a gas tight manner. As shown in FIG. 1, the cap section 1 b has a concave lead-in and / or stay for centering and / or stabilizing a gas supply lance 5 that can be introduced into the tubular support 1. Yes.

  As shown in FIG. 1, the intermediate hollow cylindrical gas-permeable porous section 1a supporting the electrode / electrolyte assembly 2 is adjacent to the cap section 1b on the one hand in the coupling range 3, respectively. On the other hand, it is adjacent to the base section 1c. The sections 1a, 1b, 1c are connected to each other in a material connection.

  As shown in FIG. 1, the electrode / electrolyte assembly 2 includes a cathode 2a, an anode 2c, and an electrolyte 2b disposed between the cathode 2a and the anode 2c. The cathode 2a, the electrolyte 2b, and the anode 2c form a functional layer sequence. This functional layer sequence is arranged on the tubular support 1 such that the cathode 2 a is adjacent to the tubular support 1 and the anode 2 c is exposed in the inner chamber of the tubular support 1.

  The tubular support 1 is formed in particular from an ion-insulating and / or electrically insulating ceramic material and / or glassy material.

  2a and 2b show one embodiment of the manufacturing method according to the invention based on ceramic injection molding.

  For this purpose, as shown in FIGS. 2a and 2b, injection molds 10 and 11 having a cavity and a cylindrical injection mold core 12 which can be inserted into the cavity are prepared. The injection molds 10 and 11 and the injection mold core 12 are inserted between the injection mold core 12 and the injection molds 10 and 11 by inserting the injection mold core 12 into the cavity. It is formed so that a substantially tubular hollow chamber can be formed. This hollow chamber substantially corresponds to the shape of the tubular support 1 to be formed of the fuel cell to be formed.

  As shown in FIGS. 2 a and 2 b, the injection mold core 12 has a sandwich-like functional layer sequence for forming at least one, particularly a large number of electrode / electrolyte assemblies 2, 2 a, 2 b, 2 c. 2, 2a, 2b, 2c are arranged. Thus, a fuel cell in which the electrode / electrolyte assembly is disposed on the inner surface of the tubular support 1 can be manufactured.

  In order to produce a fuel cell in which the electrode / electrolyte assembly is arranged on the outer surface of the tubular support 1, functional layer sequences 2, 2a, 2b, 2c (as shown in FIGS. 2a and 2b) Instead of the injection mold core 12, it may be attached to the surface of the injection mold 10, 11 that forms the cavity (not shown).

  As shown in FIGS. 2a and 2b, the sandwich-shaped functional layer sequence 2, 2a, 2b, 2c has a cathode layer 2a, an electrolyte layer 2b, and an anode layer 2c. The electrolyte layer 2b is disposed between the cathode layer 2a and the anode layer 2c.

  2a and 2b, the injection mold core 12 is inserted into the cavity of the injection mold 10, 11, and then the injection mold core 12 and the injection mold 10, 11 are connected. At least one kind of component 1 is injected into at least a part of the hollow chamber in between. Advantageously, this at least one component 1 is for forming a plurality of pores in the ceramic material and / or glassy material to be formed, in addition to the component for forming the ceramic material and / or glassy material. It contains at least one type of pore-forming agent.

  As shown in FIG. 2b, the injection mold core 12 can be removed after the injection of component 1, for example before the degreasing step and / or the sintering step. At this time, the formed tubular body 1 and the sandwich-like functional layer sequence 2, 2a, 2b, 2c remain physically and / or chemically bonded to each other. For example, the pore-forming agent is removed by heat treatment during the degreasing step and / or the sintering step to form pores.

1 support 1a segment 1b cap segment 1c base section 2 electrode-electrolyte assemblies 2a cathode layer 2b electrolyte layer 2c anode layer 3 bonds the range 5 gas supply run scan
1 0 Injection Mold 11 Injection Mold 12 Injection Mold Core

Claims (15)

In a method for manufacturing a cylindrical fuel cell, the method comprises the following method steps:
a) an injection mold having a cavity and (10, 11), to prepare the insertable injection mold core into the cavity (12), the molding die core (12 out the injection) or injection molding A cathode layer (2a), an electrolyte layer (2b), and an anode layer (2c) for forming at least one electrode / electrolyte assembly (2) on the cavity forming surface of the mold (10, 11); Sandwiched functional layer sequence (2, 2a, 2b, 2c) having
b) Inserting an injection mold core (12) into the cavity, thereby forming a tubular hollow chamber between the injection mold core (12) and the injection mold (10, 11). ,
c) Ceramic at least in part of the tubular hollow chamber so that gas permeable pores and / or openings are formed in the section (1a) adjacent to the functional layer sequence (2, 2a, 2b, 2c). Injecting at least one component (1) for forming the material and / or glassy material,
d) Simultaneously sintering the tubular body formed in the tubular hollow chamber and the functional layer sequence (2, 2a, 2b, 2c) at a temperature of 1200 ° C. or less :
A method for producing a cylindrical fuel cell, comprising: The method according to claim 1 , wherein the electrolyte layer (2 b) contains an electrolyte material having a particle size of less than 1 μm . The method of claim 2 , wherein the electrolyte material is zirconium dioxide having a particle size of less than 1 μm . The method of claim 3 , wherein the zirconium dioxide is yttria stabilized zirconia (YSZ) having a particle size of less than 1 μm . At least one of the components for forming the ceramic material and / or glass-like material (1) is a ceramic material and / or glass-like material of electrically insulating and / or ion-insulating, of claims 1-4 The method according to any one of the above. In method step a), the cathode layer (2a) is placed on the side of the functional layer sequence (2, 2a, 2b, 2c) opposite to the injection mold core (12) or the functional layer sequence (2, 2a, 2b, of 2c), arranged on the opposite side of the cavity-forming surface of the injection mold (10, 11), any one process of claim 1 to 5. Injection mold core (12), the injection mold core base body has a removable support sleeve or support sheet is placed over the forming mold core base body out the injection, functional layer sequence (2 , 2a, 2b, 2c) is, by the scan screen printing, whether it is applied to a removable support sleeve or support sheet, or injection mold core (12), dividing removed by possible injection mold core or Removable injection mold core sleeve, which is formed in the form of a removable sleeve, and the functional layer sequence (2, 2a, 2b, 2c) can be removed by curved screen printing or removable injection mold core. The method of claim 6 , wherein the method is applied to a mold core sleeve. Removal of the removable support sleeve or removable support sheet, or the removal of removable injection mold core sleeve or removable injection mold core, and / or degraded by dissolution in a solvent, evaporation and The method according to claim 7 , wherein the method is carried out by melting. In method step c), the ceramic material and / or the tubular hollow chamber is formed such that sections (1b, 1c) that are not adjacent to the functional layer sequence (2, 2a, 2b, 2c) are gastight. or injecting the Ingredients to form a glassy material, any one process of claim 1 to 8. The tubular hollow chamber corresponds to the shape of the tubular support (1) to be formed, and the tubular hollow chamber is open at one end for fixing the formed cylindrical fuel cell to the support substrate. Formed to form a base section (1c) and at the other end is formed to form a closed cap section (1c), or a tubular hollow chamber is formed at both ends cylindrical and the fuel cell are formed to form a respective one of the open base section for fixing to the supporting substrate (1c), any one process of claim 1 to 9. In the fuel cell of the circle tubular fuel cell of the cylindrical type, tubular support (1) has at least one electrode-electrolyte assembly (2),
The electrode / electrolyte assembly (2) has a cathode (2a), an anode (2c), and a gas-tight electrolyte (2b) disposed between the cathode (2a) and the anode (2c). And at least one electrode / electrolyte assembly (2) is applied to the inner or outer surface of the tubular support (1), and the tubular support (1) is of one or more types. Formed of a ceramic material and / or a glassy material,
The tubular support (1) has gas permeable pores and / or openings in one or more sections (1a) adjacent to the electrode-electrolyte assembly (2) ;
The cap section (1b) and the base section (1c) that are not adjacent to the electrode / electrolyte assembly (2) are formed gas tight,
The tubular support (1) is closed at one tube end by a cap section (1b);
The electrolyte (2b) of at least one electrode / electrolyte assembly (2) is formed of an ion-conductive, gas-tight and electrically insulating electrolyte material, and has a layer thickness of 20 μm or less,
A cylindrical fuel cell , wherein the cathode (2a), the electrolyte (2b) and the anode (2c) of at least one electrode / electrolyte assembly (2) have a thickness of 150 μm or less . The cylindrical fuel cell according to claim 11 , wherein the material of the tubular support (1) is ionic insulating and / or electrically insulating. The cathode (2a) of at least one electrode / electrolyte assembly (2) is adjacent to the support (1), and the anode (2c) is exposed in the inner chamber of the tubular support (1). The cylindrical fuel cell according to claim 11 or 12 . At least one electrode-electrolyte assembly (2) a cathode (2a) is electrically conductive and gas permeable and formed from a cathode material, even without least one electrode-electrolyte assembly (2) an anode ( The cylindrical fuel cell according to any one of claims 11 to 13 , wherein 2c) is formed from a conductive and gas permeable anode material. The tubular support (1) according to any one of claims 11 to 14 , wherein the one or more porous sections (1a) have open pores with a porosity of 20% or more. Cylindrical fuel cell.