CN104995775A - Solid tubular oxide cell - Google Patents

Solid tubular oxide cell Download PDF

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Publication number
CN104995775A
CN104995775A CN201480010164.0A CN201480010164A CN104995775A CN 104995775 A CN104995775 A CN 104995775A CN 201480010164 A CN201480010164 A CN 201480010164A CN 104995775 A CN104995775 A CN 104995775A
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CN
China
Prior art keywords
substrate
monocell
electrode group
ceramic material
porous ceramic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201480010164.0A
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Chinese (zh)
Inventor
H.格鲁恩
U.格兰茨
G.厄勒
N.莫赖拉
M.西贝尔特
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Robert Bosch GmbH
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Robert Bosch GmbH
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Publication of CN104995775A publication Critical patent/CN104995775A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/002—Shape, form of a fuel cell
    • H01M8/004—Cylindrical, tubular or wound
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0247—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the form
    • H01M8/0252—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the form tubular
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/1213—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M2008/1293—Fuel cells with solid oxide electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

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

Description

Tubular solid-oxide monocell
The present invention relates to the energy system of a kind of method for the manufacture of tubular solid-oxide monocell, soild oxide monocell and application and respective design.
Background technology
Solid oxide fuel monocell (solid oxide fuel monocell, SOFC) with ceramic monocell is one of high temperature modification of individual fuel cell.They, 600 DEG C to 1000 DEG C work, provide the highest electrical efficiency of about 50% in this case.
Solid oxide fuel monocell main development goes out two kinds of main variant: (tube type design) of tubular type and (the plate design) of planar film formula.
Document DE 198 01 440 A1 describes a kind of method of the electrode-electric solution matter-unit for the manufacture of high-temperature fuel monocell.
Document JP 09199138 A describes a kind of method of the electrode for the manufacture of individual fuel cell.
Document EP 1 237 065 B1 describes a kind of manufacture method for solid oxide fuel monocell.
Summary of the invention
Theme of the present invention is a kind of method for the manufacture of tubular solid-oxide monocell.
In method step (a), especially provide a kind of substrate at this, it is made up of the assembly for the formation of ventilative porous ceramic film material, or is made up of the material can burnt without lacquer putty.
In method step (b), especially electrode group is applied on substrate at this.
By spraying after film, on the substrate being provided with electrode group, particularly can be sprayed (carrying) body of such as tubulose by ceramic injection moulding.
The implementation of this point can be such as, in method step (c), the substrate being provided with electrode group is encased in the cave, chamber of injection mold, especially, the electrode group being provided with the substrate of electrode group is defined as a cavity or is defined as cave, described chamber, in method step (d), by injection moulded components particularly spray in cavity or cave, chamber.
Especially in method step (c), the substrate being provided with electrode group can be encased in the cave, chamber of injection mold, thus electrode group is defined as the cavity of hollow pillar.Then can in method step (d) by injection moulded components spray in the cavity of hollow pillar.
In method step (e), particularly sinter the injection molding body from method step (d), wherein, the assembly for the formation of ventilative porous ceramic film material changes ventilating porous ceramic material into, or the material can burnt without lacquer putty is burnt.
Soild oxide monocell can be such as solid oxide fuel monocell and/or solid oxide electrolyte monocell and/or soild oxide-metal-air-monocell.Described method especially can be designed to manufacture solid oxide fuel monocell and/or solid oxide electrolyte monocell and/or soild oxide-metal-air-monocell, such as manufacture solid oxide fuel monocell or solid oxide electrolyte monocell, such as solid oxide fuel monocell.
The method advantageously can realize the soild oxide monocell manufacturing tubulose in a straightforward manner, particularly with the electrode group in inside, such as with in inside by anode layer, cathode layer and the soild oxide monocell of tubulose being arranged at the functional layer system group that the dielectric substrate between them is formed.Here, no matter when using the substrate be made up of the assembly for the formation of ventilating porous ceramic material, or when using the substrate be made up of the material can burnt without lacquer putty, advantageously can save processing step, avoid injuring electrode group particularly functional layer system group, and/or rate of reducing the number of rejects and seconds.
Especially, no matter when using the substrate be made up of the assembly for the formation of ventilating porous ceramic material, or when using the substrate be made up of the material can burnt without lacquer putty, can be advantageously less or avoid knockout course.Can advantageously avoid thus injuring electrode group particularly functional layer system group, and/or rate of reducing the number of rejects and seconds.
After film in spraying situation, electrode group particularly functional layer system group can directly be fixed on injection molding body during spraying process, or is fixed on by the matrix that injection moulded components is formed, thus can advantageously save other manufacturing step.
If substrate is made up of the assembly for the formation of ventilating porous ceramic material, then during sintering process, form ventilating porous ceramic material, and be connected with electrode group or functional layer group to material fit in this case, or be connected with the anode layer of functional layer system or cathode layer, and stay as ventilating porous wall, gas such as hydrogen/burning gases or air can diffuse to electrode group or functional layer group through described wall, such as, diffuse to anode layer or the cathode layer of functional layer system.Because substrate stays electrode group particularly in functional layer system group as fully ventilative wall, eliminate the additional process steps for the demoulding, and can not remain and the residue of undesirable.
If substrate is made up of the material can burnt without lacquer putty, then backing material is burnt without lacquer putty or without residue during sintering process.Electrode group or functional layer system, the anode layer of such as functional layer system or cathode layer, out exposed in this case, thus gas such as hydrogen/burning gases or air can diffuse to electrode group or functional layer system without hindrance, such as, extend to anode layer or the cathode layer of functional layer system.Because substrate is burnt without lacquer putty during sintering, so eliminate the additional process steps for the demoulding, and can not remain and the residue of undesirable.
According to a kind of execution mode, particularly at method step b) in, to substrate printing top electrode group.Describedly be printed on this and can be particularly undertaken by silk screen printing.Silk screen printing has shown advantageous particularly.Electrode group especially can be the functional layer system group be made up of anode layer, cathode layer and the dielectric substrate that constructs between anode layer and cathode layer at this.Therefore can at method step c) in particularly the substrate printed is encased in the cave, chamber of injection mold.
Anode material such as can comprise nickel.Cathode material such as can comprise the oxide of conduction.Anode material and/or cathode material can be such as the sintered materials of porous.Electrolyte can be such as the solid electrolyte of pottery, particularly conducts cationic material, and it is such as with the zirconium dioxide (ZrO of rare earth, particularly scandium, yttrium and/or cerium, doping 2).Electrolyte can sinter especially airtightly.
Substrate especially can be the sleeve of such as form of tubes, or the film of such as belt or so-called band forms.Substrate especially can be blank body sleeve or blank film.
Sleeve especially can be undertaken the printing of by circular wire reticulated printing.Sleeve advantageously can use when processing without the need to additional moulding, and/or is directly positioned on injection mold core, or is positioned on the inwall in cave, chamber.In addition, sometimes dimensionally stable measure can be saved when using sleeve.If desired, injection mold core be can even save when using sleeve, or injection mold and/or injection mold core or its operation simplified.
Substrate especially can be the sleeve of extruding or injection moulding.
Can advantageous by flat screen printing well to film particularly flat film undertaken the printing of.Can advantageously simplify described method in this way.In addition, film can be operated well when being transferred to such as circular injection mold from plane injection mold or being transferred to such as circular carrying sleeve.Vacuum technique advantageously can be such as adopted to realize very simply such as transferring on injection mold core by utilizing vacuum, or transfer on cave, the chamber inwall of injection mold, and/or transfer on carrying sleeve, and/or realize such as being positioned on injection mold core, or be positioned on cave, the chamber inwall of injection mold, and/or be positioned on carrying sleeve, and/or realize moulding processing.
Substrate especially can be the film of cast.
According to another execution mode, particularly at method step e) in, injection moulded components and electrode group particularly functional layer system group and if desired substrate assembly be particularly jointly sintered.So just can advantageously avoid other process steps.Particularly can make to sinter especially at method step e) in carry out in a unique sintering step.In sintering situation, electrode group particularly functional layer system group can especially be connected with injection moulded components to material fit, is connected if desired with substrate assembly.Sintering is particularly at method step e) in can such as being in >=1000 DEG C or >=1100 DEG C ~≤1300C or≤1200C within the scope of temperature conditions under carry out.
According to another execution mode, particularly at method step c) in, that be provided with electrode group, that particularly be there is by the substrate of undertaking the printing of hollow pillar shape, or be processed to the shape of hollow pillar.This such as can be undertaken by vacuum technique by vacuum in film situation, and/or is undertaken by film being applied on carrying sleeve.Especially, hollow pillar, be provided with electrode group particularly by the outer surface of substrate of undertaking the printing of or inner surface, can by electrode group particularly functional layer group form.By electrode group, particularly the outer surface that forms of functional layer group or inner surface especially can be defined as the cavity of hollow pillar at this.
According to another execution mode, the assembly for the formation of ventilative porous ceramic film material is the assembly of the ventilative porous ceramic film material for the formation of inertia.
At this, 'inertia' especially can mean, material is not used as electrode or electrolyte.Here, soild oxide monocell such as can be called the soild oxide monocell that inertia carries.
As the assembly for the formation of ventilating porous ceramic material, particularly method step a) in, the ceramic material of substantially whole particularly inertia is all applicable, substrate particularly sleeve or film can be obtained, by this substrate by pore formation and by sintering the material that can produce very porous by these materials.Such as, the assembly for the formation of the particularly ventilating porous ceramic material of inertia such as particularly a) can comprise at least one material at method step, and described material is selected from by the following group formed: magnesium silicate, particularly forsterite (Mg 2siO 4), spinelle such as magnalium-spinelle such as MgAl 2o 4, doping zirconium dioxide such as adulterate less than 3%(weight) zirconium dioxide, unadulterated zirconium dioxide, aluminium oxide, aluminium oxide-zirconium oxide-mixture, zirconia-glass-mixture, zinc oxide and composition thereof.
According to another execution mode, the assembly for the formation of the particularly ventilating porous ceramic material of inertia particularly a) comprises the zirconium dioxide of forsterite, magnalium-spinelle (AlMg-spinelle) and/or doping at method step.Assembly for the formation of ventilating porous ceramic material particularly especially a) can comprise forsterite at method step.
Forsterite is mainly based on common total chemical formula Mg 2siO 4.Forsterite advantageously can in electric and ions insulate very much, and such as 20 DEG C time, have 10 11the ratio resistance of _ m, and 10 are had 600 DEG C time 5the ratio resistance of _ m.So just advantageously can avoid electrical short and ion short circuit, and save one or more additional insulating barrier.Other advantage of forsterite is its sintering characteristic and thermal coefficient of expansion thereof.Thus forsterite can have favourable shrinkage character and favourable contraction dynamic property.The thermal coefficient of expansion of forsterite can also be substantially equal to the thermal coefficient of expansion of the material of functional layer system at this, can be roughly 10 ~ 1110 -6k -1, this to sinter simultaneously (jointly sinter) tubulose (carrying) body and electrode group particularly functional layer system group have Beneficial Effect.In addition, forsterite can be obtained by original material with low cost such as talcum and magnesium oxide by reduction sintering, and this contributes to saving manufacturing cost further.
In addition, the assembly for the formation of ventilating porous ceramic material can comprise at least one pore formation.As pore formation, such as, can use compound, it during heating treatment such as decomposes during sintering, evaporate and/or fusing.As pore formation, such as organically pore formation is applicable.These pore formations such as can be burnt during thermal process after the moulding of employing injection moulding process, and such as leave the cavity of diafiltration (perkolierend).
The material can burnt without lacquer putty particularly method step a) in such as can be selected from by the following group formed: basic (elementar) carbon formation such as carbon black, polymer particularly originally (nativ) polymer such as cellulose and/or starch and combination thereof.The material can burnt without lacquer putty especially can comprise or be exactly carbon black and/or cellulose and/or starch.
According to another execution mode, particularly at method step d) in, in order to form ventilating porous ceramic material, use injection moulded components.Injection moulded components for the formation of ventilating porous ceramic material especially can be the injection moulded components of the ventilating porous ceramic material for the formation of inertia.
In sintering situation, particularly at method step e) in, especially also the injection moulded components for the formation of the particularly ventilating porous ceramic material of inertia can be changed into the ventilating porous ceramic material of particularly inertia.
As the injection moulded components for the formation of ventilating porous ceramic material, particularly at method step d) in, the ceramic material of substantially whole particularly inertia is all applicable, substrate particularly sleeve or film can be obtained, by this substrate by pore formation and by sintering the material that can produce very porous by these materials.Such as, particularly at method step d) in can comprise at least one material for the formation of the injection moulded components of ventilating porous ceramic material, described material is selected from by the following group formed: magnesium silicate, particularly forsterite (Mg 2siO 4), spinelle such as magnalium-spinelle such as MgAl 2o 4, doping zirconium dioxide such as adulterate less than 3%(weight) zirconium dioxide, unadulterated zirconium dioxide, aluminium oxide, aluminium oxide-zirconium oxide-mixture, zirconia-glass-mixture, zinc oxide and composition thereof.
According to another execution mode, for the formation of the injection moulded components of ventilating porous ceramic material particularly at method step d) comprise the zirconium dioxide of forsterite, magnalium-spinelle (AlMg-spinelle) and/or doping.Injection moulded components for the formation of ventilating porous ceramic material particularly can comprise forsterite.
In addition, the injection moulded components for the formation of ventilating porous ceramic material can comprise at least one pore formation.
According to another execution mode, the assembly for the formation of ventilating porous ceramic material is also used as injection moulded components.Such as, for the formation of ventilating porous ceramic material assembly particularly method step a) in can be with particularly at method step d) in for the formation of the identical assembly of the injection moulded components of ventilating porous ceramic material.
Injection mold especially can have the injection mold core that can be encased in cave, chamber.At this, injection mold core is encased in cave, chamber, so just can forms particularly the cavity of tubulose substantially between injection mold core and cave, chamber inwall.At this, " substantially " especially mean, the cavity of tubulose comprises the cavity (section) of hollow pillar, wherein, the cavity of tubulose also has the cavity section adopting alternate manner to be formed, particularly cavity end section, such as, install section and a housing section for the formation of one, or install section for the formation of two.
The substrate being provided with electrode group particularly functional layer system group can be applied on injection mold core at this, or is applied on the inwall of cave, chamber.
The substrate being provided with electrode group particularly functional layer system group is applied on injection mold core, and can obtain a kind of monocell thus, this monocell has the supporting body of tubulose, and electrode group particularly functional layer system group is applied on the medial surface of described supporting body.
The substrate being provided with electrode group particularly functional layer system group is applied on the inwall of cave, chamber, and can obtain a kind of monocell thus, this monocell has the supporting body of tubulose, and electrode group particularly functional layer system group is applied on the lateral surface of described supporting body.
If use the substrate being provided with functional layer system group, be laid with anode layer over the substrate, this anode layer has laid again dielectric substrate, lay cathode layer on the electrolyte layer, so, particularly cathode layer especially at method step c) and/or d) in be defined as the cavity of such as hollow pillar.
If this substrate being provided with functional layer system group is laid on injection mold core, then can obtain a kind of monocell with tubulose supporting body, functional layer system group is laid on the medial surface of this supporting body, wherein, anode layer is exactly internal layer, and cathode layer is exactly outer.At this, especially cathode layer can particularly be connected with tubulose supporting body to material fit, and anode layer is at least temporarily particularly connected with substrate to material fit.If substrate is burnt without lacquer putty, then anode layer can be made thus out exposed.
If this substrate being provided with functional layer system group is applied on the inwall of cave, chamber, then can obtain a kind of monocell with tubulose supporting body, functional layer system group is laid on the lateral surface of this supporting body, wherein, cathode layer is exactly internal layer, and anode layer is exactly outer.At this, especially cathode layer can particularly be connected with tubulose supporting body to material fit, and anode layer is at least temporarily particularly connected with substrate to material fit.If substrate is burnt without lacquer putty, then anode layer can be made thus out exposed.
If use the substrate being provided with functional layer system group, be laid with cathode layer over the substrate, this cathode layer has laid again dielectric substrate, lay anode layer on the electrolyte layer, so, particularly anode layer especially at method step c) and/or d) in be defined as the cavity of such as tubulose.
If this substrate being provided with functional layer system group is laid on injection mold core, then can obtain a kind of monocell with tubulose supporting body, functional layer system group is laid on the medial surface of this supporting body, wherein, cathode layer is exactly internal layer, and anode layer is exactly outer.At this, especially anode layer can particularly be connected with tubulose supporting body to material fit, and cathode layer is at least temporarily particularly connected with substrate to material fit.If substrate is burnt without lacquer putty, then cathode layer can be made thus out exposed.
If this substrate being provided with functional layer system group is applied on the inwall of cave, chamber, then can obtain a kind of monocell with tubulose supporting body, functional layer system group is laid on the lateral surface of this supporting body, wherein, anode layer is exactly internal layer, cathode layer is exactly outer, and wherein, anode layer is particularly connected with tubulose supporting body to material fit.At this, especially anode layer can particularly be connected with tubulose supporting body to material fit, and cathode layer is at least temporarily particularly connected with substrate to material fit.If substrate is burnt without lacquer putty, then cathode layer can be made thus out exposed.
In addition, the method can have at least one other method step (d1): spray another injection moulded components.This another injection moulded components is at this can especially be designed to be formed particularly inertia, airtight ceramic material.
In sintering situation, particularly at method step e) in, can the airtight ceramic material for the formation of particularly inertia particularly from method step d1) this another injection moulded components change the airtight ceramic material of particularly inertia into.
As the injection moulded components for the formation of airtight ceramic material, particularly at method step d1) in, the ceramic material of substantially whole particularly inertia is all applicable, can obtain substrate particularly sleeve or film by these materials, can produce airtight material by this substrate by sintering.Such as, particularly at method step d1) in also can comprise at least one material for the formation of this another injection moulded components of airtight ceramic material, described material is selected from by the following group formed: magnesium silicate, particularly forsterite (Mg 2siO 4), spinelle such as magnalium-spinelle such as MgAl 2o 4, doping zirconium dioxide such as adulterate less than 3%(weight) zirconium dioxide, unadulterated zirconium dioxide, aluminium oxide, aluminium oxide-zirconium oxide-mixture, zirconia-glass-mixture, zinc oxide and composition thereof.
Such as, for the formation of this another injection moulded components of airtight ceramic material particularly at method step d1) in can comprise the zirconium dioxide of forsterite, magnalium-spinelle (AlMg-spinelle) and/or doping.This another injection moulded components for the formation of airtight ceramic material particularly can comprise forsterite.
Particularly at method step d1) in this another injection moulded components with particularly method step a) in assembly and/or with particularly at method step d) in the difference of injection moulded components especially can be, it does not have pore formation.
Injection mold especially can suitably design, make the cavity that can form tubulose wherein, this cavity has cavity and two cavity end sections of a hollow pillar, installs section and a housing section for the formation of one, or installs section for the formation of two.
At this, for the formation of this another injection moulded components of airtight ceramic material particularly at method step d1) in can be injected in one or two cavity end section.
In a word, so just advantageously can obtain tubular solid-oxide monocell, such as tubular high temperature individual fuel cell (tubular SOFC), it has tubulose supporting body (socket), this supporting body is with the region of ventilating porous particularly hollow pillar, wherein, on the medial surface of described supporting body or sometimes on its outer lateral surface, the height in porous zone can place some functional layers.Tubulose supporting body (socket) is used as the supporting body of inertia in electrochemistry of functional layer at this.The advantage that this structure has is, can realize very thin layer group thus, and this not only saves the material (availability of cost, lanthanum compound) of functional layer, and particularly creates large electrical power.
If use the substrate of form of film, then it can be laid in together with electrode group particularly functional layer group and carry on sleeve, this carrying sleeve can be applied to again on injection mold.
As for other advantage and technical characteristic, at this specifically see the explanation done in conjunction with soild oxide monocell of the present invention, application of the present invention and energy system of the present invention and see accompanying drawing and accompanying drawing explanation.
Another theme of the present invention is tubular solid-oxide monocell, and it adopts method of the present invention to obtain.Described soild oxide monocell especially can be solid oxide fuel monocell and/or solid oxide electrolyte monocell and/or soild oxide-metal-air-monocell at this.
As for other advantage and technical characteristic, at this specifically see the explanation done in conjunction with method of the present invention, soild oxide monocell of the present invention, application of the present invention and energy system of the present invention and see accompanying drawing and accompanying drawing explanation.
Another theme of the present invention is tubular solid-oxide monocell.Described soild oxide monocell especially can be solid oxide fuel monocell and/or solid oxide electrolyte monocell and/or soild oxide-metal-air-monocell at this.
Tubular solid-oxide monocell especially can comprise electrode group, and wherein, this electrode group is arranged in the first wall of being made up of the ventilating porous ceramic material of particularly inertia and between the second wall be made up of the ventilating porous ceramic material of particularly inertia.Electrode group especially can be connected with the first wall and the second wall to material fit at this.
According to a kind of execution mode, electrode group is by anode layer, cathode layer and is configured in the functional layer system group that the dielectric substrate between anode layer and cathode layer forms.Design according to one at this, cathode layer is particularly connected with the first wall to material fit, and anode layer is particularly connected with the second wall to material fit.According to another design, anode layer is particularly connected with the first wall to material fit, and cathode layer is particularly connected with the second wall to material fit.Such as electrode group can be connected with the first wall and the second wall all sidedly.Such as, cathode layer can particularly be connected with the first wall to material fit all sidedly, anode layer is particularly connected with the second wall to material fit all sidedly, or it is contrary, anode layer is particularly connected with the first wall to material fit all sidedly, and cathode layer is particularly connected with the second wall to material fit all sidedly.
According to another execution mode, the first wall is a section of tubulose supporting body.Tubulose supporting body particularly can have centre portion and two end section of a hollow pillar at this, wherein, one of end section is the installation section or the footing section that are particularly useful for installing monocell, the other end section is the housing section or another installation section or the footing section that are particularly useful for installing monocell, and one of end of the centre portion of hollow pillar is closed by described housing section.The centre portion of hollow pillar especially can comprise or be formed the first wall at this.
Under the design conditions of an end-enclosed, can advantageously unworn gas such as burning gases be fed back in gas return path such as burning gases loop, this advantageously can realize higher electrical efficiency.
The centre portion of the first wall or hollow pillar especially can by the method step d from method of the present invention) the injection moulded components for the formation of the particularly ventilating porous ceramic material of inertia form, or ventilative ground porous.
Those end section can particularly by the method step d1 especially from method of the present invention) airtight ceramic material form, or airtight.
Second wall can have the shape of hollow pillar.Second wall especially can be made up of the substrate used in the method for the invention, or ventilative ground porous.
According to another execution mode, the wall thickness of the second wall is less than the first wall.At this, the wall thickness of the second wall especially can be less than the wall thickness of the first wall 75%, be such as less than 50%, be such as less than its 25%.
As for other advantage and technical characteristic, at this specifically see the explanation done in conjunction with method of the present invention, soild oxide monocell of the present invention, application of the present invention and energy system of the present invention and see accompanying drawing and accompanying drawing explanation.
The invention still further relates to the application of tubular solid-oxide monocell, particularly tubular solid-oxide monocell of the present invention, it is such as individual fuel cell and/or as electrolyte monocell and/or as metal-air-monocell, such as in (miniature) electric power-thermal coupling equipment for industrial electric power-heat-coupling (BHKW), for the supply of house energy, for generating and/or for generating electricity on carried on vehicle electrical network in power plant.
Tubular solid-oxide monocell especially can comprise the tubulose supporting body with hollow pillar section, this section is made up of the ventilating porous ceramic material such as forsterite of particularly inertia, the medial surface of supporting body or lateral surface particularly medial surface lays electrode group, particularly forms functional layer system group by anode layer, cathode layer and the dielectric substrate that constructs between anode layer and cathode layer.Hollow pillar section can be such as the centre portion of the hollow pillar of tubulose supporting body.Tubulose supporting body especially can have centre portion and two end section of described hollow pillar at this.At this, one of described end section can be such as the installation section or the footing section that are particularly useful for installing monocell, the other end section is the housing section closed one of end of the centre portion of hollow pillar, or is particularly useful for another installation section or footing section of installing monocell.These end section such as can be made up of the airtight ceramic material such as forsterite of particularly inertia at this.At this, cathode layer can particularly be connected with (centre) section of the hollow pillar of tubulose supporting body to material fit.At this, anode layer can be out exposed, or the substrate such as formed with by ventilating porous material to material fit or wall are connected.Or anode layer can particularly be connected with (centre) section of the hollow pillar of tubulose supporting body to material fit, and especially, cathode layer is out exposed, or the substrate that can such as form with by ventilating porous material to material fit or wall are connected.
As for other advantage and technical characteristic, at this specifically see the explanation done in conjunction with method of the present invention, soild oxide monocell of the present invention, energy system of the present invention and see accompanying drawing and accompanying drawing explanation.
The invention still further relates to such as photovoltaic apparatus, wind energy plant, biogas facility, room or shop, industrial equipment, power plant or energy system such as the energy reservoir and/or energy conversion devices of motor vehicle or the energy reservoir of (miniature) electric power-heat-Coupling device or electric power thermal coupling and/or energy conversion devices, it comprises at least one according to monocell of the present invention or constructed in accordance or used according to the invention.(miniature) electric power-heat-Coupling device especially can be a kind of for the equipment by generation current while of energy carrier and heat.
As for other advantage and technical characteristic, at this specifically see the explanation done in conjunction with method of the present invention, soild oxide monocell of the present invention, application of the present invention and see accompanying drawing and accompanying drawing explanation.
Accompanying drawing
Other advantage of theme of the present invention and expedients are illustrated by accompanying drawing, and are introduced in follow-up explanation.Here it should be noted that accompanying drawing only has introductory feature, and should not be considered as limiting the present invention in any form.Wherein:
Fig. 1 is the schematic sectional elevation of an execution mode of tubular solid-oxide monocell of the present invention, and it is obtained by a kind of assembly for the formation of ventilative porous ceramic film material by substrate; With
Fig. 2 is the schematic sectional elevation before a kind of material combustion that can fall without lacquer putty combustion during sintering process of an execution mode of tubular solid-oxide monocell of the present invention, and this soild oxide monocell is obtained by the described material that can fall without lacquer putty combustion by substrate.
Fig. 1 and 2 illustrates tubular solid-oxide monocell 10 such as solid oxide fuel monocell (SOFC), it has the electrode group 11 of functional layer system group 11a, 11a', 11b, 11b', 11c, 11c' form, and this electrode group comprises anode layer 11a, 11a', cathode layer 11b, 11b' and at anode layer 11a, 11a' and dielectric substrate 11c, 11c' of constructing between cathode layer 11b, 11b'.Here, anode layer 11a, 11a' comprise anode region 11a, these anode regions by electric and the region 11a' of ions insulation be separated from each other.Cathode layer 11b, 11b' comprise cathode zone 11b, these cathode zones also by electric and the region 11b' of ions insulation be separated from each other.Dielectric substrate 11c, 11c' comprise electrolyte area 11c, these electrolyte area by conduct electricity but ions insulation 11c'(internal connector region, region) be separated from each other.
Fig. 1 and 2 also illustrates, anode region 11a, cathode zone 11b and electrolyte area 11c construct with offseting one from another, wherein, the anode region 11a of anode-electrolyte-cathode-unit 11a, 11c, 11b is respectively by being but connected with the cathode zone 11b of adjacent anode-electrolyte-cathode-unit 11a, 11c, 11b conductively at the internal connector region 11c' of ions insulation of conduction of dielectric substrate 11c, 11c'.Form the bar bundle (see left side and right side) be made up of the anode-electrolyte-cathode be connected in series-unit 11a, 11c, 11b in this way.Outside shown cross section, these bundles (left side and right side) can by one or more in electric and the region of ions insulation be separated from each other.
Fig. 1 and 2 also illustrates, these bundles (left side and right side) are connected to each other conductively, its mode is, two anode region 11a of the anode-electrolyte-cathode of different bar bundle-unit 11a, 11c, 11b are interconnected by the ring shaped conductor 11a'' be made up of anode material.
Arrow O in Fig. 1 and 2 2show, oxonium ion can arrive one of anode region 11a from one of cathode zone 11b respectively by electrolyte area 11c.Arrow e in Fig. 1 and 2 -show, internal connector region 11c' and ring shaped conductor 11c'' makes anode-electrolyte-cathode-unit 11a, 11c, 11b be connected in series, thus electric current can be guided by a bar Shu Chaoxiang ring shaped conductor 11a'', and back guided again by ring shaped conductor 11a'' and another bundle.So just can advantageously be electrically connected in the side of monocell.Fig. 1 and 2 illustrates, electric current guides via anode material 11a and/or cathode material 11b and/or internal connector material 11c'.
Fig. 1 and 2 also illustrates, functional layer system 11a, 11a', 11b, 11b', 11c, 11c' are placed in the inner side of the section of the hollow pillar of tubulose supporting body.At this, negative electrode section 11b, 11b' abut on the section 12 of hollow pillar, and this section is made up of the breathable porous material of inertia.
Fig. 1 and 2 illustrates, an end section of tubulose supporting body is configured to install section or footing section 13, and wherein, another end section is configured to housing section 14, and the centre portion 12 of hollow pillar is closed by this housing section.Two end section 13,14 are formed at this airtight ceramic material by inertia if desired.
Fig. 1 illustrates, according to an execution mode of method of the present invention, electrode group 11 is applied on substrate 1, this substrate is made up of a kind of assembly of the ventilative porous ceramic film material for the formation of inertia, and utilize the injection moulded components 12 for the formation of the ventilative porous ceramic film material of inertia to carry out spraying (Folienhinterspritzung) after film, and by sintering by described assembly 1, the 12 ventilative porous ceramic film materials changing inertia into, form monocell thus, by this execution mode, the ventilating porous ceramic substrate 1 of the inertia produced is retained in electrode group 11.Fig. 1 illustrates, electrode group 11 is arranged between the first wall 12 be made up of injection moulded components 12 and the second wall 1 formed by substrate 1, and the first wall is made up of the ventilative porous ceramic film material of inertia, and the second wall is made up of the ventilative porous ceramic film material of inertia.At this, be connected with the first wall 12 and the second wall 1 to electrode group 11 material fit.Especially, here, cathode layer 11b, 11b' and the first wall 12 adjoin, and anode layer 11a, 11a' and the second wall 1 adjoin, or on the contrary.Fig. 1 illustrates, at this, the second wall 1 can have obviously less wall thickness compared to the first wall 12.
The execution mode of the loading material 1 by inertia porous is described in detail in detail below.According to this execution mode, particularly electrode group 11 is printed onto on substrate 1, this electrode group such as can be retained in socket (Tubus) 12 as inwall 1 as the layer of sufficiently porous.This especially can adopt band shape or tubulose to carry out by engineering silk screen printing on the loading material 11 of inertia porous.Which is adopted advantageously can particularly to obtain the solid oxide fuel monocell (SOFC) with the tubulose of internal electrode.
According to this execution mode, especially can by the ZrO of the wall material arranged for socket 12 such as forsterite, AlMg-spinelle or doping 2the such as banded film particularly blank film of obtained cast, or obtain the sleeve pipe of extruding or the pipe 1 of extruding.Silk-screen process can be adopted functional layer 11a, 11a', 11b, 11b', 11c, 11c' to be printed onto on film (blank film, band) or sleeve pipe (pipe) 1.Functional layer group 11a, 11a', 11b, 11b', 11c, 11c' directly can be fixed to by spraying after film on the matrix 12 that is such as made up of forsterite at this, thus advantageously can save manufacturing step during spraying process.During sintering process, the inert material of the porous of film (band) or sleeve pipe (pipe) 1 is particularly connected to anode 11a material fit with functional layer group 11a, 11a', 11b, 11b', 11c, 11c', and remain as inwall 1, such as hydrogen can diffuse to anode 11a through this inwall.
Generally, the method can be converted to the ZrO of all inert materials such as AlMg-spinelle or doping 2deng, can obtain film (band) or sleeve (extruded tube) 1 by described material, described material can be formed as the material of very porous after the sintering in company with pore formation (Porenbildner).
The blank film 1 that use is made up of inert material is as the advantage of the backing material for functional layer group 11, this blank film can adopt planographic to undertake the printing of well, and such as also can be transferred to circular injection molding mould such as CIM core (CIM from plane injection mold, English is: Ceramic Injection Moulding, ceramic injection forming) time operated well.Very simple mode can be adopted to be positioned on injection mold such as CIM core by vacuum.Because film 1(is with) be retained in socket 12 as the internal layer of unusual porous, so the additional processing step for the demoulding can be saved, and obviously can reduce risk functional layer group being caused to damage because knockout course causes.Can also avoid like this and the residue of undesirable.
Except using film (band) 1, can also by the ZrO of inactive ceramic such as forsterite, AlMg-spinelle or doping 2be squeezed into sleeve 1.This sleeve 1 can directly be undertaken the printing of in circle printing (Runddruck), and especially tool has the following advantages: this sleeve 1 can directly be positioned on injection mold such as CIM core.Here, sleeve 1 also can be retained in socket 12 as inwall 1.So gas such as hydrogen can such as diffuse to anode 11b through the inwall 1 of porous.
So just advantageously can obtain the tubular SOFC-monocell containing being positioned at inner electrode group 11.On the blank film 1 that this electrode group 11 particularly can adopt silk screen printing to be printed to be made up of above-mentioned inert material, or be printed onto on the sleeve 1 of the extruding be made up of commaterial.With being encased in injection mold by the sleeve 1 of electrode group 11 that lays or injection moulding core particularly in CIM mould, and injection encapsulated.Film (band) or sleeve (pipe) 1 can be retained in socket 12 after injection moulding process.During sintering process, the pore formation be positioned on film (band) or sleeve (pipe) can be burnt, and leave the inert layer of porous in socket 12 inside, such as hydrogen can arrive anode 11b through described inert layer.
This design particularly can specify a unique sintering step, and in this sintering step, the socket 12 of electrode group 11 and porous is jointly sintered under the temperature conditions such as between 1100 DEG C and 1300 DEG C.
Negative electrode 11b particularly can be connected with the pipe 12 of pottery to material fit at this, and still porous fully after the firing process.Anode 11a especially can be connected with the porous layer 1 being positioned at inner inertia to material fit at this, or is connected with the inner earthenware that is positioned at of inertia.
Here, as the substrate 1 for functional layer group 11, especially can use inertia such as based on the blank film of the porous of forsterite or the sleeve of extruding, electrode group 11 adopts circular wire reticulated printing to be printed on described substrate 1.Socket 12 can be (the coming from CIM) socket by the obtained so-called CIMization be made up of inert porous material such as forsterite of spraying after film at this.
Fig. 2 illustrates, according to an execution mode of method of the present invention, electrode group 11 is applied on substrate 1, this substrate is made up of a kind of material that can fall without lacquer putty combustion, and utilize the injection moulded components 12 of the ventilative porous ceramic film material for the formation of inertia to carry out spraying after film, and by sintering by described assembly 1, the 12 ventilative porous ceramic film materials changing inertia into, form monocell thus, by this execution mode, although substrate 1 before sintering also can coated electrode group 11, but according to this execution mode, substrate can be removed completely by sintering, so electrode group 11 is anode layer 11a particularly, the medial surface of 11a'' is exposed out (not shown in Fig. 2).
Execution mode by the loading material 1 that can fall without lacquer putty combustion is described in detail in detail below.According to this execution mode, particularly electrode group 11 is printed onto on substrate 1, this substrate is burnt without residue without lacquer putty during sintering process.This especially can adopt band shape or tubulose to carry out by engineering silk screen printing on the loading material 11 that can fall without lacquer putty combustion.Which is adopted advantageously can particularly to obtain the solid oxide fuel monocell (SOFC) with the tubulose of internal electrode group 11a.
According to this execution mode, the pipe 1 of bearing film or extruding especially can be obtained by the material such as carbon black and/or cellulose that can fall without lacquer putty combustion and/or starch.Silk-screen process can be adopted functional layer 11a, 11a', 11b, 11b', 11c, 11c' to be printed onto on described film or described pipe 1.Functional layer group 11a, 11a', 11b, 11b', 11c, 11c' directly can be fixed to by spraying after film on the matrix 12 that is such as made up of forsterite at this, thus advantageously can save manufacturing step during spraying process.During sintering process, backing material 1 can be burnt without residue.So just advantageously can realize making the anode layer 11a of porous out exposed, or make it can be positioned at the inside of socket 12 as the first functional layer, in this socket, such as can produce burning gases atmosphere.
Use the advantage of the bearing film 1 that can fall without lacquer putty combustion to be for functional layer group 11, this bearing film can adopt planographic to undertake the printing of well, and such as also can be operated well when being transferred to circular injection molding mould such as CIM core from plane injection mold.Very simple mode can be adopted to be positioned on injection mold such as CIM core by vacuum.Because film 1 can be burnt without lacquer putty during sintering, so residue can not be left in electrode group 11.
Except using film 1, sleeve 1 can also be squeezed into by firing without lacquer putty the material (such as carbon black, cellulose, starch) fallen.This sleeve 1 can directly be undertaken the printing of in circle printing, and especially tool has the following advantages: this sleeve 1 can directly be positioned on injection mold such as CIM core.Here, sleeve 1 can be used as the inwall 1 of functional layer group 11, and fires without residue during sintering process.
So just advantageously can obtain the tubular SOFC-monocell containing being positioned at inner electrode group 11.This electrode group 11 particularly can adopt silk screen printing to be printed to by firing on the material such as carbon black and/or cellulose that fall and/or the blank film 1 that forms of starch without lacquer putty, or is printed onto on the sleeve 1 of the extruding be made up of commaterial.With being encased in injection mold by the sleeve 1 of electrode group 11 that lays or injection moulding core particularly in CIM mould, and injection encapsulated.Film (band) or sleeve can be burnt without residue during sintering process, thus such as anode 11a can be inner out exposed or expose at socket 12.
This design particularly can specify a unique sintering step, and in this sintering step, the socket 12 of electrode group 11 and porous is jointly sintered under the temperature conditions such as between 1100 DEG C and 1300 DEG C.
Negative electrode 11b particularly can be connected with the pipe 12 of pottery to material fit at this, and still porous fully after the firing process.The substrate 1 of electrode group 11 can be burnt without residue.
Here, as the substrate 1 for functional layer group 11, especially can use can without lacquer putty combustion fall the bearing film of plane or the sleeve of extruding, it is such as made up of carbon black and/or cellulose and/or starch, electrode group 11 adopts silk screen printing to be printed on described substrate 1, and this substrate is burnt without residue during sintering process.Socket 12 can be (the coming from CIM) socket by the obtained so-called CIMization be made up of inert porous material such as forsterite of spraying after film at this.

Claims (15)

1., for the manufacture of a method for tubular solid-oxide monocell (10) particularly individual fuel cell, comprise following method step:
A) provide a kind of substrate (1), wherein, substrate (1) is made up of the assembly for the formation of the particularly ventilating porous ceramic material of inertia, or is made up of the material can burnt without lacquer putty;
B) electrode group (11) is applied on substrate (1);
C) substrate (11) being provided with electrode group (11) is encased in the cave, chamber of injection mold, thus electrode group (11) is defined as the cavity of hollow pillar;
D) by injection moulded components (12) spray in the cavity of tubulose; With
E) injection molding body (11,12) is sintered, wherein, make the assembly (1) for the formation of the particularly ventilating porous ceramic material (1) of inertia change the ventilating porous ceramic material of particularly inertia into, or wherein, the material can burnt without lacquer putty is burnt.
2. the method for claim 1, wherein at method step e) in, the assembly of injection moulded components (12) and electrode group (11) and substrate (1) if desired is jointly sintered.
3. method as claimed in claim 1 or 2, wherein, at method step b) in, to be printed electrode group to substrate by silk screen printing, especially, electrode group is the functional layer system group be made up of anode layer (11a, 11a'), cathode layer (11b, 11b') and the dielectric substrate (11c, 11c') that constructs between anode layer (11a, 11a') and cathode layer (11b, 11b').
4. the method according to any one of claim 1 ~ 3, wherein, at method step c) in, the substrate (1,11) being provided with electrode group has the shape of hollow pillar, or be processed to the shape of hollow pillar, especially, the outer surface of the printed substrate (1,11) of hollow pillar or inner surface by electrode group particularly functional layer group (11) form, wherein, the outer surface be made up of electrode group (11) or inner surface are defined as the cavity of tubulose.
5. the method according to any one of claim 1 ~ 4, wherein, substrate (1) is the film of cast, or extruding or the sleeve of injection moulding.
6. the method according to any one of claim 1 ~ 5, wherein, the assembly (1) for the formation of ventilating porous ceramic material is the assembly of the ventilating porous ceramic material for the formation of inertia.
7. the method according to any one of claim 1 ~ 6,
Wherein, particularly comprise the zirconium dioxide particularly forsterite of forsterite, magnalium-spinelle and/or doping from the method step assembly for the formation of ventilating porous ceramic material a) (1), or,
Wherein, the material (1) can burnt without lacquer putty is selected from by the following group formed: basic carbon formation such as carbon black, originally polymer be cellulose and/or starch and combination thereof particularly, especially, the material (1) can burnt without lacquer putty is carbon black and/or starch and/or cellulose.
8. the method according to any one of claim 1 ~ 7, wherein, at method step d) in use injection moulded components (12) for the formation of the particularly ventilating porous ceramic material of inertia.
9. the method according to any one of claim 1 ~ 8, wherein, at method step d) in injection moulded components (12) comprise the zirconium dioxide particularly forsterite of forsterite, magnalium-spinelle and/or doping.
10. the method according to any one of claim 1 ~ 9, wherein, the assembly (1) for the formation of ventilating porous ceramic material is also used as injection moulded components (12).
Soild oxide monocell (10) the particularly individual fuel cell of 11. tubuloses adopting the method any one of claim 1 ~ 10 to obtain.
Soild oxide monocell (10) the particularly individual fuel cell of 12. tubuloses, comprise electrode group (11), wherein, electrode group (11) is arranged in the first wall (12) of being made up of the ventilating porous ceramic material of particularly inertia and between the second wall (1) be made up of the ventilating porous ceramic material of particularly inertia, especially, be connected with the first wall (12) and the second wall (1) to electrode group (11) material fit.
The soild oxide monocell (10) of 13. tubuloses as claimed in claim 12, wherein, electrode group (11) is by anode layer (11a, 11a'), cathode layer (11b, 11b') with at anode layer (11a, 11a') with cathode layer (11b, dielectric substrate (the 11c of structure 11b'), functional layer system group 11c') formed, wherein, cathode layer (11b, 11b') or anode layer (11a, 11a') adjoin with the first wall (12), wherein, anode layer (11a, 11a') or cathode layer (11b, 11b') adjoin with the second wall (1), especially, first wall (12) is a section of tubulose supporting body, especially, tubulose supporting body has centre portion (12) and two end section (13 of a hollow pillar, 14), wherein, one of end section (13) installs section, the other end section (14) is housing section or another installation section, one of end of the centre portion (12) of hollow pillar is closed by described housing section, wherein, the centre portion (12) of hollow pillar comprises or is exactly the first wall (12), wherein, second wall (1) has the shape of hollow pillar.
The soild oxide monocell (10) of 14. tubuloses as described in claim 12 or 13, wherein, the wall thickness of the second wall (1) is less than the first wall (12).
The application of the soild oxide monocell of soild oxide monocell (10) tubulose particularly any one of claim 11 ~ 14 of 15. tubuloses, described soild oxide monocell is as individual fuel cell and/or as electrolyte monocell and/or as metal-air-monocell, particularly in electric power-thermal coupling equipment for industrial electric power-heat-coupling, supply for house energy, for generating and/or for generating electricity on carried on vehicle electrical network in power plant, described soild oxide monocell has the tubulose supporting body (12 being with hollow pillar section (12), 13, 14), this section is made up of the ventilating porous ceramic material of particularly inertia, and the medial surface of supporting body or lateral surface particularly medial surface lay electrode group (11), particularly by anode layer (11a, 11a', 11a''), cathode layer (11b, 11b') with at anode layer (11a, 11a') with cathode layer (11b, dielectric substrate (the 11c of structure 11b'), 11c') form functional layer system group (11a, 11a', 11b, 11b', 11c, 11c'), wherein, hollow pillar section (12) is tubulose supporting body (12, 13, 14) centre portion of hollow pillar, wherein, tubulose supporting body (12, 13, 14) also there are two end section (13, 14), one of them end section (13) installs section, and the other end section (14) is the housing section closed one of end of the centre portion of hollow pillar (12), or another installs section, especially, and described end section (13, 14) be made up of the airtight ceramic material of particularly inertia.
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