CN114914507A - Conductive flat tube support type solid oxide fuel cell/electrolytic cell, preparation method thereof and cell stack structure - Google Patents
Conductive flat tube support type solid oxide fuel cell/electrolytic cell, preparation method thereof and cell stack structure Download PDFInfo
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- CN114914507A CN114914507A CN202210581334.7A CN202210581334A CN114914507A CN 114914507 A CN114914507 A CN 114914507A CN 202210581334 A CN202210581334 A CN 202210581334A CN 114914507 A CN114914507 A CN 114914507A
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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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/1286—Fuel cells applied on a support, e.g. miniature fuel cells deposited on silica supports
-
- 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
- H01M8/023—Porous and characterised by the material
- H01M8/0241—Composites
- H01M8/0245—Composites in the form of layered or coated products
-
- 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
- H01M8/0256—Vias, i.e. connectors passing through the separator 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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0258—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
-
- 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
- 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
- H01M8/1226—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 characterised by the supporting layer
-
- 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
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
-
- 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
- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Fuel Cell (AREA)
Abstract
The invention provides a conductive flat tube supported solid oxide fuel cell/electrolytic cell structure, a preparation method thereof and a cell stack structure. Realize establishing ties or parallelly connected through the supporter between the group battery, make the electrically conductive flat tube supporter have supporting role and current transmission effect concurrently, realize collecting the cathode current in the group battery under reducing atmosphere to at the low temperature open end drainage, solve the difficulty that the electric current was collected, reduce the ohmic loss of electric current conduction. In addition, the arrangement mode that a plurality of monocells are connected in series can achieve the purposes of outputting high voltage and low current and improving the volumetric power density of the battery/electrolytic cell.
Description
Technical Field
The invention relates to the field of energy structure optimization and solid oxide fuel cells, in particular to a conductive flat tube support type solid oxide fuel cell/electrolytic cell structure, a preparation method thereof and a cell stack structure.
Background
A Solid Oxide Fuel Cell (SOFC) is a device that directly converts chemical energy into electrical energy, and has the advantages of high power generation efficiency, wide fuel application range, all-solid-state structure, and the like. From the structural point of view, the solid oxide fuel cell can be classified into a flat plate type and a tube type.
In a planar SOFC, the current flows perpendicular to the cell, so the ohmic polarization of the cell is lower than that of a tubular SOFC. And the flat SOFC has simple structure, and the preparation technology of the electrode functional layer is simple and easy to control. Furthermore, the flat SOFC has a shorter current flow, is uniform in collection, and has a higher battery power density than a tubular SOFC. However, the battery has strict requirements on performance, and the sealing technology is a technical problem which restricts the development of the battery.
Depending on the support structure, the solid oxide fuel cell can be divided into a functional layer self-supporting structure and a support body supporting structure. The self-supporting type, i.e. the support is provided by thickening one of the components (about 1mm), because expensive electrode and electrolyte materials are widely used as the support, the cost of the self-supporting structure solid oxide fuel cell is very high, and the anode support design is widely adopted at present, wherein the most commonly adopted nickel-based porous anode support is adopted.
However, in the related art, the self-supporting SOFC is generally a tubular SOFC structure, and only one cell is disposed on a single tube surface, the power density of the cell/electrolytic cell is low, and the voltage is low. There is therefore a need to develop a self-supporting SOFC structure with high power density, high voltage and self-sealing in high temperature environments.
Disclosure of Invention
In order to solve the technical problems in the related art, the application provides a conductive flat tube supported solid oxide fuel cell/electrolytic cell structure, a preparation method thereof and a cell stack structure, so as to solve the problems that a self-supported SOFC structure is difficult to seal at high temperature and the self-supported SOFC does not have high voltage and high power density.
The specific invention content is as follows:
in a first aspect, the present invention provides a conductive flat tube supported solid oxide fuel cell/electrolyser structure, comprising: the battery pack comprises a conductive flat tube support body, an insulating layer and a battery pack;
the conductive flat tube supporting body consists of an opening area, a main power generation area and a closed area, wherein the opening area corresponds to openings at two ends of the conductive flat tube supporting body, the closed area corresponds to circular arc parts at two sides of the conductive flat tube supporting body, and the main power generation area is a main area of the conductive flat tube supporting body;
the battery pack is formed by connecting a plurality of single batteries in series through a connector, and the battery packs are distributed on a first plane and a second plane which are parallel to each other in the main body area to form a first plane battery pack and a second plane battery pack; the first planar battery pack and the second planar battery pack are arranged in an axisymmetrical manner by the axis of the conductive flat tube support body, or the first planar battery pack and the second planar battery pack are arranged in a centrosymmetric manner by the axis of the conductive flat tube support body;
the conductive flat tube support body is used for transmitting current generated in the conductive flat tube support type solid oxide fuel cell/electrolytic cell;
the insulating layer is located between the conductive flat tube supporting body and the battery pack.
Optionally, when the first planar battery pack and the second planar battery pack are arranged in axial symmetry with respect to the axis of the conductive flat tube support, the first planar battery pack is connected in parallel with the second planar battery pack, the cathode layer of the last single cell in the first planar battery pack is connected to the conductive flat tube support through the connector, and the cathode layer of the last single cell in the second planar battery pack is connected to the conductive flat tube support through the connector;
when the first planar battery pack and the second planar battery pack are arranged in a central symmetry manner by taking the axis of the conductive flat tube support body as a center, the first planar battery pack is connected with the second planar battery pack in series, the cathode layer of the last single cell in the first planar battery pack is connected with the conductive flat tube support body through the connector, and the anode layer of the last cell in the second planar battery pack is connected with the conductive flat tube support body through the connector.
Optionally, the outer surface of the closed region is covered with a dense functional layer, and the dense functional layer is an electrolyte layer or a connector.
Optionally, a fuel gas channel is arranged inside the conductive flat tube support body, and the fuel gas channel is used for flowing in and flowing out of fuel gas;
the conductive flat tube support body is provided with through air holes, and the through air hole rate is 10% -40%;
the thickness of the conductive flat tube support body is 0.5 mm-3 mm;
the distance between the first plane and the second plane is 3mm-15 mm.
In a second aspect, the present invention provides a conductive flat tube supported solid oxide fuel cell stack structure, including: a stack structure comprising two or more conductive flat tube-supported solid oxide fuel cells/electrolyzers according to the first aspect.
In a third aspect, the present invention provides a method for preparing a conductive flat tube supported solid oxide fuel cell/electrolytic cell structure, wherein the method comprises the following steps:
s1, preparing the support body powder into a conductive flat tube support body blank body with an internal flow channel by using an extrusion molding device; the conductive flat tube support body blank body consists of an opening area, a main power generation area and a closed area, wherein the opening area corresponds to openings at two ends of the conductive flat tube support body blank body, the closed area corresponds to circular arc parts at two sides of the conductive flat tube support body blank body, and the main power generation area is a main area of the conductive flat tube support body blank body; the support body powder consists of ceramic powder which can not be reduced by hydrogen, ceramic powder which can be reduced by hydrogen, a bonding agent and a pore-forming agent;
s2, spraying insulating layer slurry on a first plane and a second plane which are parallel to each other in the main power generation area by adopting a wet spraying mode, and drying and curing to form an insulating layer;
s3, printing anode bus layer slurry on the surface of the insulating layer at intervals, drying and curing to form a plurality of anode bus layers;
s4, printing anode slurry on the surface of each anode confluence layer, drying and curing to form a plurality of anode layers;
s5, printing electrolyte slurry on the surface of each anode layer, drying and curing to form a plurality of electrolyte layers; wherein one end of each electrolyte layer partially covers an adjacent one of the anode layers, and the other end of each electrolyte layer is in contact with a part of the insulating layer; each of the anode bus layers forms a plurality of single cell intermediates with a corresponding one of the anode layers and a corresponding one of the electrolyte layers;
s6, printing connector slurry at intervals of the single cell intermediates, printing connector slurry or electrolyte slurry in the closed area, drying and curing to form a first battery blank intermediate body with a plurality of connectors; wherein one end of the connector is in contact with the anode layer and the electrolyte of one adjacent cell intermediate, and the other end thereof is covered with the electrolyte layer of the other adjacent cell intermediate;
s7, pre-burning and roasting the first battery blank intermediate for one time to obtain a second battery blank intermediate;
s8, printing cathode slurry on the surface of each electrolyte layer of the second battery blank intermediate, drying and curing to form a plurality of cathode layers; wherein each of said cathode layers partially covers a corresponding one of said electrolyte layers and a corresponding one of said connectors;
s9, printing cathode confluence layer slurry on the surface of each cathode layer, drying and curing to obtain a conductive flat tube support type solid oxide fuel cell/electrolytic cell blank;
and S10, performing secondary pre-sintering and secondary roasting on the conductive flat tube supported solid oxide fuel cell/electrolytic cell blank to obtain the conductive flat tube supported solid oxide fuel cell/electrolytic cell.
Optionally, the ceramic powder that is not reducible by hydrogen comprises one or a combination of alumina, mullite, panzelite, titania, calcia and doped zirconia;
the ceramic powder capable of being reduced by hydrogen comprises one or a combination of nickel oxide, iron oxide, cobalt oxide and copper oxide;
the mass ratio of the ceramic powder which cannot be reduced by hydrogen gas to the ceramic powder which can be reduced by hydrogen gas is 4: 6-6: 4;
the mass ratio of the sum mass of the ceramic powder which can not be reduced by hydrogen and the ceramic powder which can be reduced by hydrogen to the pore-forming agent is less than or equal to 7: 3;
the mass ratio of the binder to the sum of the ceramic powder and the pore-forming agent is 1: 9-3: 7;
the binder comprises one or a combination of polyvinyl butyral, ethyl cellulose, polyvinylpyrrolidone and polyvinyl alcohol;
the pore-forming agent comprises one or a combination of more of ammonium bicarbonate, soluble starch, sucrose, polymethyl methacrylate and carbon powder.
Optionally, the insulating layer slurry includes insulating powder, and the insulating powder is: the mass ratio is 2:326:5 MgAl 2 O 4 With MgO, doped zirconia, SrTiO 3 And SrZrO 3 One or more components of (a);
the anode confluence layer slurry comprises anode confluence powder, wherein the anode confluence powder is as follows: the mass ratio is 6:4 NiO/5YSZ, doped strontium titanate and doped lanthanum chromate;
the electrolyte slurry comprises electrolyte powder, wherein the electrolyte powder is one or more of doped zirconia, doped ceria, doped lanthanum gallate and doped barium cerate;
the anode layer slurry comprises anode powder, and the anode powder is prepared from the following components in a mass ratio of 6:4 with the electrolyte powder;
the connector slurry comprises connector powder, wherein the connector powder is one or more of doped strontium titanate, doped lanthanum chromate and doped lanthanum manganate;
the cathode slurry comprises cathode powder, wherein the cathode powder is one or more of doped lanthanum manganate and doped lanthanum cobaltate;
the cathode confluence layer slurry comprises cathode confluence powder, wherein the cathode confluence powder is (Mn, Co) 3 O 4 One or more of lanthanum cobaltate and lanthanum manganate.
Optionally, the insulating layer has a thickness of 20 μm to 100 μm;
the thickness of the anode bus layer is 100-200 μm;
the thickness of the anode layer is 10-30 μm;
the thickness of the electrolyte layer is 10-30 μm;
the thickness of the connector layer is 100-200 μm;
the thickness of the cathode layer is 10-20 μm;
the thickness of the cathode bus layer is 100-200 μm.
Optionally, the temperature ranges of the primary pre-sintering and the secondary pre-sintering are both 100 ℃ to 600 ℃; the time of the primary pre-sintering and the time of the secondary pre-sintering are both 1h to 10 h;
the temperature range of the primary roasting is 1250-1500 ℃, and the time of the primary roasting is 4-6 h;
the temperature range of the secondary roasting is 1100-1400 ℃, and the time of the secondary roasting is 2-4 h.
Compared with the related art, the conductive flat tube supported solid oxide fuel cell/electrolytic cell structure, the preparation method thereof and the cell stack structure provided by the invention have the following advantages:
the invention provides a novel flat tube type self-supporting SOFC structure, which is characterized in that a conductive material is used as a support body to improve the temperature tolerance of a solid oxide fuel cell and further improve the output power of the solid oxide fuel cell, and a battery pack formed by connecting a plurality of single cells in series is further distributed on two mutually parallel surfaces of the conductive flat tube support body, so that the conductive flat tube support body has the supporting function and the current transmission function, and the ohmic loss of current conduction is reduced. The arrangement mode of a plurality of monocells in series can realize the output of high voltage and low current and improve the volume power density of the battery.
In addition, the battery functional layer is prepared by adopting a wet spraying and screen printing method, so that the film forming speed can be increased, the preparation efficiency can be effectively increased, the preparation method can be simplified, the preparation cost can be saved, and the commercial popularization of the solid oxide fuel battery can be facilitated;
furthermore, in the preparation method provided by the invention, the support body and the single cell group on the support body are subjected to twice pre-sintering and twice roasting, so that the conductive flat tube support body blank, the connector, the electrolyte layer and the like are fully shrunk simultaneously in the pre-sintering and roasting processes, and the connector and the electrolyte layer are fully densified to realize a self-sealing effect. And reduces the cost and time for manufacturing the whole battery to a certain extent.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings used in the embodiments or the prior art descriptions will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is a schematic top view of a conductive flat tube supported solid oxide fuel cell/electrolyzer structure provided in an embodiment of the present invention;
fig. 2 is a schematic side view of a structure of an electric conduction flat tube-supported solid oxide fuel cell/electrolyzer provided in an embodiment of the present invention;
fig. 3 is a schematic side view of another conductive flat tube supported solid oxide fuel cell/electrolyzer structure provided in an embodiment of the invention;
fig. 4 is a schematic cross-sectional view illustrating a structure of a conductive flat tube supported solid oxide fuel cell/electrolytic cell according to an embodiment of the present invention;
fig. 5 is a schematic cross-sectional view illustrating another structure of a conductive flat tube supported solid oxide fuel cell/electrolyzer according to an embodiment of the present invention;
fig. 6 is a schematic cross-sectional view illustrating a support body of a conductive flat tube according to an embodiment of the present invention;
fig. 7 shows a flowchart of a method for manufacturing a conductive flat tube supported solid oxide fuel cell/electrolytic cell structure according to an embodiment of the present invention.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and can be performed according to the procedures or conditions of the conventional experimental procedures described in the prior art in the field. The reagents and other instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
To further understand the present invention, the present invention will be further illustrated with reference to specific examples, and the structure of the present invention is also applicable to a solid oxide electrolytic cell structure, since the electrolytic cell and the fuel cell are a pair of energy conversion devices with the same structure and the reverse operation.
In view of the problems of difficult high-temperature sealing of the solid oxide fuel cell/electrolytic cell with the self-supporting structure of the functional layer and the fact that only one single cell can be arranged on the surface of the existing single round tubular supporting body, the self-supporting SOFC does not have high voltage and high power density, the technical concept of the invention is as follows: the utility model provides a conductive flat tube supports type solid oxide fuel cell/electrolytic cell and battery pile structure, wherein, flat tub of supporter is the cermet structure, possesses electrically conductive function, and two sets of series connection group distributions are on two planes that conductive flat tub of supporter is parallel to each other, and realize establishing ties or parallelly connected through the supporter that possesses electrically conductive function between the group. According to the invention, the series battery packs are arranged on two planes of the flat tube support body parallel to each other to increase the arrangement amount of the batteries, so that the power density of the batteries/electrolytic cells is improved, and high voltage is obtained. In addition, for realizing the structural self sealss effect of electrically conductive flat tube support type solid oxide fuel cell/electrolysis cell, isolated gaseous revealing avoids extra sealing work, when electrically conductive flat tube support body surface preparation electrode layer, in the lump at the surface preparation fine and close functional layer (fine and close functional layer can be electrolyte layer or connector material) of electrically conductive flat tube support body closed region (both sides circular arc structure) for electrically conductive flat tube support body surface is covered by group battery and fine and close functional layer, thereby realizes the self sealss. Based on the technical concept, the invention provides a conductive flat tube supported solid oxide fuel cell/electrolytic cell, a cell stack structure and a preparation method thereof, and the specific implementation contents are as follows:
in a first aspect, the present invention provides a conductive flat tube supported solid oxide fuel cell/electrolysis cell structure, and fig. 1 shows a schematic plan view of the conductive flat tube supported solid oxide fuel cell/electrolysis cell structure provided in an embodiment of the present invention, and as shown in fig. 1, the cell/electrolysis cell structure includes: the battery pack comprises a conductive flat tube support body, an insulating layer and a battery pack consisting of a plurality of monocells. Wherein, the battery cell includes: an anode bus layer, an anode layer (not shown), an electrolyte layer, a cathode layer, and a cathode bus layer, and the single cells are connected in series by a connector. The conductive flat tube supporting body consists of an opening area (area A), a main power generation area (area B) and a closed area (area C), wherein the opening area (area A) corresponds to openings at two ends of the conductive flat tube supporting body, the closed area (area C) corresponds to circular arc parts at two sides of the conductive flat tube supporting body, and the main power generation area (area B) is a main area of the conductive flat tube supporting body; the battery packs are distributed on a first plane and a second plane which are parallel to each other in the main body area to form a first plane battery pack and a second plane battery pack.
Furthermore, the insulating layer is located two surfaces that are parallel to each other of electrically conductive flat pipe support body main part region, and first plane group battery and second plane group battery further cover the surface of insulating layer. The first planar battery pack and the second planar battery pack can be arranged in an axial symmetry manner or a central symmetry manner by using the shafts of the conductive flat pipe supporting bodies, so that the first planar battery pack and the second planar battery pack are connected in parallel or in series. The battery pack formed by arranging the single battery units can effectively reduce the gaps among the batteries, increase the contact area between the batteries and the supporting body and achieve the purpose of increasing the power density of the batteries. The functional layers constituting the single cell include an anode layer, an electrolyte layer, and a cathode layer, and may further include an anode bus layer, an anode layer, an electrolyte layer, a cathode layer, and a cathode bus layer.
In the conductive flat tube supported solid oxide fuel cell/electrolytic cell structure provided by the invention, the plurality of single cells are arranged on the two parallel surfaces of the flat tube support body with the conductive function, so that the volume power density of the cell is increased, the ohmic loss is reduced, the current output in a low-current and high-voltage mode is realized, and the problems of large polarization loss, difficult current collection, low cell output performance, poor stability in long-term operation, low mechanical strength and the like in the solid oxide fuel cell/electrolytic cell are effectively solved.
In some embodiments, when the first planar battery pack and the second planar battery pack are arranged in axial symmetry with respect to the axis of the conductive flat tube support, the first planar battery pack is connected in parallel with the second planar battery pack, the cathode layer of the last single cell in the first planar battery pack is connected to the conductive flat tube support through the connector, and the cathode layer of the last single cell in the second planar battery pack is connected to the conductive flat tube support through the connector.
In specific implementation, when a first planar battery pack and a second planar battery pack can work in parallel, fig. 2 shows a schematic side view structure of a conductive flat tube supported solid oxide fuel cell/electrolytic cell structure provided in an embodiment of the present invention, as shown in fig. 2, the arrangement of the first planar battery pack and the arrangement of the second planar battery pack are in an axisymmetric structure with an axis of the conductive flat tube support, a cathode layer of a last single cell in the first planar battery pack contacts with the connector, a cathode current in the first planar battery pack is conducted to the conductive flat tube support, then the conductive flat tube support conducts the cathode current to an opening end, and the cathode current is collected by an anode current collecting layer extending from the first single cell in the first planar battery pack. Similarly, the cathode layer of the last single cell in the second planar battery pack is in contact with the connector, the cathode current in the second planar battery pack is conducted to the conductive flat tube support body, then conducted to the opening end through the conductive flat tube support body, and collected by the anode collector layer extending from the first single cell in the second planar battery pack. The support body is used as a common current transmission electrode, and the parallel connection of the first planar battery pack and the second planar battery pack can be realized.
In some embodiments, when the first planar battery pack and the second planar battery pack are arranged in a central symmetry manner with respect to the axis of the conductive flat tube support, the first planar battery pack and the second planar battery pack are connected in series, the cathode layer of the last single cell in the first planar battery pack is connected to the conductive flat tube support through the connector, and the anode layer of the last single cell in the second planar battery pack is connected to the conductive flat tube support through the connector.
In specific implementation, the first planar battery pack may also work in tandem with the second planar battery pack, fig. 3 shows a schematic side view of another structure of the conductive flat tube supported solid oxide fuel cell/electrolysis cell provided in an embodiment of the present invention, as shown in fig. 3, the first planar battery pack and the second planar battery pack are arranged to have a central symmetry with respect to the support axis, the cathode layer of the last single cell in the first planar battery pack is connected and contacted with the conductive flat tube support through the connector, the anode layer of the last single cell in the second planar battery pack is also connected and contacted with the conductive flat tube support through the connector, so that the sealed region of the conductive flat tube support serves as the connector to connect the cathode current of the last single cell in the first planar battery pack to the anode of the last single cell in the second planar battery pack through the closed end of the conductive flat tube support, the series connection of the first planar battery and the second planar battery is realized, and the current generated by the battery/electrolytic cell is conducted to the opening end for collection through the series connection of the first planar battery and the second planar battery, so that the flat tube battery has the characteristics of low current and high voltage output, the current transmission polarization loss is reduced, and the output power density and the output power of a single tube are easily improved.
In some embodiments, in order to achieve the self-sealing effect of the conductive flat tube supported solid oxide fuel cell/electrolytic cell in the structure, isolate the leakage of gas, and avoid additional sealing work, when the electrode functional layer is prepared on the surface of the conductive flat tube support, a compact functional layer is prepared on the outer surface of the closed area of the conductive flat tube support (the circular arc structures on both sides of the conductive flat tube support), and the compact functional layer may be an electrolyte layer or a connector material.
In specific implementation, fig. 4 shows a schematic cross-sectional view of a conductive flat tube supported solid oxide fuel cell/electrolytic cell structure provided in an embodiment of the present invention, and as shown in fig. 4, an enclosed region (outer surfaces of circular arc structures on both sides of a conductive flat tube) of the cell/electrolytic cell structure is covered with an electrolyte layer.
In specific implementation, fig. 5 shows a schematic cross-sectional view of another conductive flat tube supported solid oxide fuel cell/electrolytic cell structure provided in an embodiment of the present invention, and as shown in fig. 5, a closed region (outer surfaces of circular arc structures on both sides of a conductive flat tube) of the cell/electrolytic cell structure is covered with a connector material.
In some embodiments, a fuel gas channel is provided inside the conductive flat tube support body, and the fuel gas channel is used for the inflow and outflow of fuel gas. The conductive flat tube support body is prepared by extrusion molding, and in order to ensure that gas in a fuel gas flow channel can be smoothly transmitted to an electrode layer through the conductive flat tube support body to carry out electrochemical reaction, the conductive flat tube support body is provided with through air holes, the through air hole rate of the conductive flat tube support body needs to be controlled, and when the porosity is too low, the gas cannot normally flow, so that the performance of a battery is influenced; when the porosity is too large, the strength and the surface roughness of the support body of the conductive flat tube cannot be guaranteed, the service life and the performance of the battery cannot be better, and the through porosity of the support body of the conductive flat tube in the embodiment of the application is 10% -40%. In addition, the thickness of the support body of the conductive flat tube can be 0.5 mm-3 mm; the distance between the first plane and the second plane can be 3mm-15mm, so that the obtained conductive flat tube support type solid oxide fuel cell/electrolytic cell structure has excellent mechanical property and comprehensive power generation performance, and has volume advantage when a cell stack is integrated.
In specific implementation, fig. 6 shows a schematic cross-sectional view of the conductive flat tube support body provided in the embodiment of the present invention, and as shown in fig. 6, a fuel gas flow channel is provided inside the conductive flat tube support body.
In a second aspect, the present invention provides a conductive flat tube supported solid oxide fuel cell stack structure, including: a stack structure comprising two or more conductive flat tube-supported solid oxide fuel cells/electrolyzers according to the first aspect.
In a third aspect, the present invention provides a method for manufacturing a conductive flat tube supported solid oxide fuel cell/electrolytic cell structure, and fig. 7 shows a flowchart of a method for manufacturing a conductive flat tube supported solid oxide fuel cell/electrolytic cell structure according to an embodiment of the present invention, where the method includes the following steps:
s1, preparing the support body powder into a conductive flat tube support body blank body with an internal flow channel by using an extrusion molding device; the conductive flat tube support body blank body consists of an opening area, a main power generation area and a closed area, wherein the opening area corresponds to openings at two ends of the conductive flat tube support body blank body, the closed area corresponds to circular arc parts at two sides of the conductive flat tube support body blank body, and the main power generation area is a main area of the conductive flat tube support body blank body; the support body powder consists of ceramic powder which can not be reduced by hydrogen, ceramic powder which can be reduced by hydrogen, a binder and a pore-forming agent.
In specific implementation, in the method for manufacturing the conductive flat tube supported solid oxide fuel cell/electrolytic cell structure, the support body needs to perform a function of guiding out/in current generated by the series battery pack on the surface of the support body during the operation of the cell/electrolytic cell, so in step S1 of this embodiment, the support body powder used is composed of ceramic powder that is not reducible by hydrogen and ceramic powder that is reducible by hydrogen, wherein the ceramic powder that is reducible by hydrogen can reduce a simple metal substance under the action of hydrogen, thereby achieving the function of guiding out/in current.
In some embodiments, the ceramic powder that is not reducible by hydrogen comprises one or a combination of alumina, mullite, panzelite, titania, calcium oxide, and doped zirconia, and the ceramic powder that is reducible by hydrogen comprises one or a combination of nickel oxide, iron oxide, cobalt oxide, and copper oxide, wherein the mass ratio of the ceramic powder that is not reducible by hydrogen to the ceramic powder that is reducible by hydrogen is 4: 6-6: 4.
in some embodiments, the binder comprises one or a combination of polyvinyl butyral, ethyl cellulose, polyvinyl pyrrolidone, and polyvinyl alcohol; the pore-forming agent comprises one or a combination of more of ammonium bicarbonate, soluble starch, sucrose, polymethyl methacrylate and carbon powder, wherein the mass ratio of the sum of the ceramic powder which can not be reduced by hydrogen and the ceramic powder which can be reduced by hydrogen to the pore-forming agent is less than or equal to 7: 3; the mass ratio of the binder to the sum of the ceramic powder and the pore-forming agent is 1: 9-3: 7.
and S2, spraying insulating layer slurry on the two parallel first planes and second planes of the main power generation region by adopting a wet spraying mode, and drying and curing to form an insulating layer.
In step S2 of this embodiment, insulating layer slurry is wet-sprayed on two mutually parallel first and second planes of a main power generation region of a green body of a support body of a conductive flat tube to obtain an insulating layer with a thickness of 20 μm to 100 μm, which is used as a basic support for further preparing a plurality of single cell series structures. Wherein the spraying distance is 50-100mm, and the sedimentation rate of the slurry is at least 60 mu m/s.
In specific implementation, the insulating layer slurry contains an electronic insulating porous ceramic material which is MgAl 2 O 4 MgO, doped zirconia, SrTiO 3 And SrZrO 3 One or more components of (a). The electronic conductivity of the formed insulating layer is lower than 1 percent so as to ensure the insulation among the support body, the anode bus layer and the connecting body which are separated by the insulating layer in the battery pack; the through porosity of the porous insulating layer is 10-40% so as to ensure that the reducing atmosphere gas can be fully diffused to the anode layer.
And S3, printing anode bus layer slurry on the surface of the insulating layer at intervals, drying and curing to form a plurality of anode bus layers.
In some embodiments, the anode bus layer slurry includes anode bus powder formed from a mass ratio of 6:4 NiO/5YSZ, doped strontium titanate (e.g. Sr) 0.9 La 0.1 TiO 3 ) And doped lanthanum chromate (e.g. La) 0.8 Sr 0.2 CrO 3 ) One or more components in the composition; in step S3, the thickness of the anode bus layer is 100 μm-200 μm.
And S4, printing anode slurry on the surface of each anode confluence layer, drying and curing to form a plurality of anode layers.
In some embodiments, the anode layer slurry includes an anode powder composed of nickel oxide and an electrolyte powder, and the mass ratio of the nickel oxide to the electrolyte powder is 6: 4; in step S4, the anode layer has a thickness of 10 μm to 30 μm.
S5, printing electrolyte slurry on the surface of each anode layer, drying and curing to form a plurality of electrolyte layers; wherein one end of each electrolyte layer partially covers an adjacent one of the anode layers, and the other end of each electrolyte layer is in contact with a part of the insulating layer; each of the anode bus layers forms a plurality of single cell intermediates with a corresponding one of the anode layers and a corresponding one of the electrolyte layers.
In some embodiments, the electrolyte slurry includes an electrolyte powder that is doped zirconia (e.g., 8YSZ, ScSZ), doped ceria (e.g., GDC), doped lanthanum gallate (e.g., La) 0.9 Sr 0.1 Ga 0.8 Mg 0.2 O 3 ) And doped barium cerate (e.g. BaZr) 0.1 Ce 0.7 Y 0.2 O 3 ) One or more components of (a); in step S5, the thickness of the electrolyte layer is 10 μm to 30 μm.
S6, printing connector slurry at intervals of the single cell intermediates, printing connector slurry or electrolyte slurry in the closed area, drying and curing to form a first battery blank intermediate body with a plurality of connectors; wherein one end of the connector is in contact with the anode layer and the electrolyte of one adjacent cell intermediate, and the other end portion covers the electrolyte layer of the other adjacent cell intermediate.
In some embodiments, the linker slurry includes a linker powder that is doped strontium titanate (e.g., La) 0.7 Sr 0.3 TiO 3 ) Doped lanthanum chromate (e.g. La) 0.8 Sr 0.2 CrO 3 ) And doped lanthanum manganate (e.g., La) 0.8 Sr 0.2 MnO 3 ) One or more components of (a); in step S6, the thickness of the connecting body layer is 100 μm to 200 μm.
And S7, pre-burning and roasting the first battery blank intermediate for one time to obtain a second battery blank intermediate.
In step S7 of this embodiment, because the tolerance temperature of the cathode layer and the cathode bus layer is lower than that of the anode layer, the anode bus layer, the electrolyte layer, and the connector, after the anode bus layer, the anode layer, the electrolyte layer, and the connector are prepared, a semi-finished product of the battery needs to be pre-baked for one time and baked for one time, where the pre-baking temperature is 100 ℃ to 600 ℃, the pre-baking time is 1h to 10h, the primary baking temperature is 1250 ℃ to 1500 ℃, and the baking time is 4h to 6h, so as to obtain a semi-finished product in which the support body and the electrolyte layer are fully shrunk; and then continuously preparing a cathode layer and a cathode confluence layer on the upper surface and the lower surface of the fully shrunk semi-finished product.
S8, printing cathode slurry on the surface of each electrolyte layer of the second battery blank intermediate, drying and curing to form a plurality of cathode layers; wherein each of the cathode layers partially covers a corresponding one of the electrolyte layers and a corresponding one of the connectors.
In some embodiments, a cathode powder is included in the cathode slurry, the cathode powder being doped lanthanum manganate (e.g., La) 0.8 Sr 0.2 MnO 3 ) And lanthanum cobaltate (e.g., La) 0.6 Sr 0.4 Co 0.8 Fe 0.2 O 3 ) One or more components of (a); in step S7 of this embodiment, the thickness of the cathode layer is 10 μm to 20 μm.
And S9, printing cathode confluence layer slurry on the surface of each cathode layer, drying and curing to obtain the conductive flat tube supported solid oxide fuel cell/electrolytic cell blank.
In some embodiments, the cathodic disbursement slurry comprises a cathodic disbursement powder that is (Mn, Co) 3 O 4 (e.g., Mn) 1.5 Co 1.5 O 4 ) Doped lanthanum cobaltate (e.g., La) 0.6 Sr 0.4 Co 0.8 Fe 0.2 O 3 ) And doped lanthanum manganate (e.g. La) 0.8 Sr 0.2 MnO 3 ) One or more components of (a); in step S9, the thickness of the cathode bus layer is 100 μm to 200 μm.
In specific implementation, the invention sequentially prints an anode bus layer, an anode layer, an electrolyte layer, a connector, a cathode layer and a cathode bus layer of a plurality of single cells by a screen printing technology. Wherein, the mesh number of the silk screen printing technology is 80-350 meshes, the rotating speed of the tubular support body blank is 5.0rad/s, and the scraper angle is 45-75 degrees. In addition, when the single cell is prepared, the preparation of the anode bus layer and the cathode bus layer with better mechanical property and higher conductivity is added, and the current collecting effect of the cell/the electrolytic cell on current is effectively improved.
And S10, carrying out secondary pre-sintering and secondary roasting on the conductive flat tube supported solid oxide fuel cell blank to obtain the conductive flat tube supported solid oxide fuel cell/electrolytic cell.
In specific implementation, the prepared conductive flat tube supported solid oxide fuel cell blank is subjected to secondary forming firing (the support body and the single cell group on the support body are subjected to secondary sintering forming), so that the support body blank, the connector and the electrolyte layer are fully shrunk in the two pre-sintering and two roasting processes, the structure of the connector and the electrolyte layer is fully densified to realize a self-sealing effect, and meanwhile, the manufacturing process of the metal ceramic flat tube supported solid oxide fuel cell/electrolytic cell is simplified. The pre-sintering process is a binder removal process, which is to remove substances such as pore-forming agents, binders, organic matters and the like used in the preparation process of the conductive flat tube supported solid oxide fuel cell blank at a certain temperature, so as to further obtain a tubular supported solid oxide fuel cell blank with a more stable structure, and prevent the tubular supported solid oxide fuel cell blank from being broken due to high temperature caused by direct roasting without pre-sintering.
In some embodiments, the temperature of the secondary pre-sintering ranges from 100 ℃ to 600 ℃; the pre-sintering time is 1-10 h; the temperature range of the secondary roasting is 1100-1400 ℃, and the time of the secondary roasting is 2-4 h.
In the specific implementation, the closed area of the support body blank of the conductive flat tube is covered by the connector or the electrolyte layer, on one hand, because the support body powder for preparing the support body blank of the conductive flat tube contains a pore-forming agent (removed by high temperature in the pre-sintering process to form a porous ceramic support body structure), the connector or the electrolyte layer prepared in the closed area and the battery pack which is positioned in the main power generation area and is connected in series by the connector are in overall synergistic action, and the self-sealing effect of the battery/electrolytic cell structure prepared by the method is realized. On the other hand, the cathode current generated by the first plane battery set or the second plane battery set can also be introduced into the support body structure through the connecting body, and is led out through the support body; or the cathode current generated by the first planar battery pack is conducted to the anode of the second planar battery pack through the connector and the support structure, and the current is led out through the series connection of the battery packs (the first planar battery pack and the second planar battery pack), so that the power density of the battery/battery pack is improved, the output of high voltage and low current of the battery/battery pack is realized, and the volume power density of the battery/battery pack is improved.
In the technical scheme, YSZ represents yttria-stabilized zirconia, nYSZ represents yttria-stabilized zirconia with the molar ratio of yttria being n%; GDC represents gadolinium doped ceria; ScSZ represents scandia stabilized zirconia; CSZ stands for calcia stabilized zirconia.
In order to make the present invention more comprehensible to those skilled in the art, a structure of a conductive flat tube supported solid oxide fuel cell/electrolyzer, a method for manufacturing the same, and a stack structure according to the present invention will be described below with reference to a plurality of specific examples.
Example 1
The following description is not intended to limit the invention. The schematic diagrams of the solid oxide fuel cell/electrolyser prepared in this example are shown in fig. 3 and 4. The material constituting the tube comprises, by mass, 1:1 of 3YSZ and NiO mixed powder and 10 wt% of starch as pore-forming agents, wherein the particle diameters of the mixed powder and the NiO mixed powder are respectively 3-5 microns, 0.5-1 micron and 10-30 microns, the mixed powder and the pore-forming agents are mixed in a ball mill for 6 hours, the rotating speed is 360r/min, the mixture is dried and ground at 140 ℃, the mixture is sieved for later use, 4 wt% of methyl cellulose, 5 wt% of glycerol, 14 wt% of water and the like are added as extrusion forming solvents, the mixture is placed in a kneader and mixed for 3 hours to obtain pug, the pug is kept stand for 2-3 days at 4-15 ℃, and the conductive flat tube support body with the length of 500mm, the width of 80mm and the height of 6mm is prepared through extrusion forming. The particle sizes of 3YSZ and NiO can be in the above ranges, and the degree of shrinkage of the powder particles varies depending on the particle size ratio, and the porosity of the support after firing varies, and the particle size is selected to obtain the desired porosity. The additive components used for extrusion molding are not limitative of the present invention, and molding may be performed using other component systems. Then, the porous support is prepared by a method of extrusion molding, but the molding method is not limited thereto.
In this case, the insulating layer is formed on the surface of the support by a wet spraying method, and the anode bus layer, the anode, the electrolyte, and the connecting body are formed on the surface of the insulating layer by a screen printing method, and then fired together with the support. The length of the support may vary after firing, and therefore the shrinkage of the porous support during firing is preferably in the range of 12-20%, more preferably 15-17%. The porous support has too small a shrinkage rate, the electrolyte membrane has too large a shrinkage rate, and the two shrinkage rates are not matched to cause the electrolyte layer to crack.
Next, after the porous support to be extruded was dried at 80 ℃, an insulating layer was prepared on the support using a wet spraying method, and the coating range was as shown in fig. 3 and 4. The main components of the insulating layer are 35 wt% of CSZ, 5 wt% of PMMA as pore-forming agent, 10 wt% of binder, 2 wt% of dispersant and 48 wt% of organic solvent, the particle diameter of the CSZ is 500nm (D50), and the particle diameter of the pore-forming agent is 1 μm (D50). The insulating layer slurry is ball-milled for 4h to prepare the insulating layer, the spraying speed is 70 mu m/s, the spraying distance is 75cm, the thickness of the insulating layer is 20 +/-3 mu m, and the insulating layer is dried at 80 ℃ after the preparation.
And respectively preparing 30 single cells on the first plane insulating layer and the second plane insulating layer through screen printing.
An anode bus layer was prepared on the insulating layer using a screen printing method, and the coating range was as shown in fig. 3 and 4. The anode bus layer mainly comprises 60 wt% of NiO and 5YSZ (mass ratio of 6:4), 2 wt% of binder, 0.5 wt% of dispersant and 37.5 wt% of organic solvent, wherein the NiO and the 5YSZ have the particle size of D50-200 nm. And performing ball milling on the anode confluence layer slurry for 4h, performing screen printing to prepare an anode confluence layer, wherein the mesh number of the used screen is preferably 100 meshes, the rotation speed of a support body is preferably 5.0cm/s, the thickness of the anode confluence layer is 150 +/-3 mu m, and drying at 80 ℃ after printing. The length of each section of anode is 10mm, and the interval between two adjacent sections of anodes is 2 mm.
The anode functional layer was prepared on the insulating layer using a screen printing method, and the coating range was as shown in fig. 3 and 4. The main components of the anode functional layer are 50 wt% of NiO and 8YSZ (mass ratio of 6:4), 2.5 wt% of binder, 0.5 wt% of dispersant and 47 wt% of organic solvent, and the particle diameters of the NiO and the 8YSZ are both D50-200 nm. And performing ball milling on the anode functional layer slurry for 4 hours to prepare an anode functional layer by screen printing, wherein the mesh number of the used screen is preferably 180 meshes, the rotating speed of a support body is preferably 5.0cm/s, the thickness of the anode functional layer is 30 +/-3 mu m, and drying at 80 ℃ after printing. The length of each section of anode is 10mm, and the interval between two adjacent sections of anodes is 2 mm.
The electrolyte layer was prepared on the anode functional layer using a screen printing method, and the coating range was as shown in fig. 3 and 4. The electrolyte layer comprises 50 wt% of 8YSZ and 2.5 wt% of a binder, 0.5 wt% of a dispersant and 47 wt% of an organic solvent, wherein the particle size of the 8YSZ is D50-100 nm. The electrolyte layer slurry can be subjected to screen printing to prepare an electrolyte layer after ball milling for 4h, the mesh number of the used screen is preferably 250 meshes, the rotating speed of the support is preferably 5.0cm/s, the thickness of the electrolyte layer is 25 +/-3 mu m, and the electrolyte layer is dried at 80 ℃ after printing. The length of each section of electrolyte is 10mm, the interval between two adjacent sections of electrolyte is 2mm, and the anode which is not covered by the electrolyte along the axial direction of the support body is 1 mm.
The connector layer was prepared on the electrolyte layer using a screen printing method, and the coating range was as shown in fig. 3 and 4. The main component of the connector layer was 50 wt% of La 0.7 Sr 0.3 TiO 3 And 2.5 wt% of a binder, 0.5 wt% of a dispersant and 47 wt% of an organic solvent, and La 0.7 Sr 0.3 TiO 3 The particle diameter of (D50) was 100 nm. The connecting body layer slurry can be subjected to silk screen printing to prepare the connecting body layer after ball milling for 4h, the mesh number of the used silk screen is preferably 100 meshes, the rotating speed of the support body is preferably 5.0cm/s, the thickness of the connecting body layer is 150 +/-3 mu m, and the connecting body layer is dried at 80 ℃ after printing. The length of each connector is 3 mm.
After drying, heating to 300 ℃ at the heating rate of 1 ℃/min, discharging rubber in the air for 4h, then discharging rubber from 300 ℃ at the heating rate of 1 ℃/min to 600 ℃ for 8h, and then preserving heat in the air at 1450 ℃ at the heating rate of 2 ℃/min for 4h, and sintering and forming.
The coating range was as shown in fig. 3 and 4 by the same operation as the above-described printing method of the anode functional layer, and the main component of the cathode slurry was La in a mass ratio of 1:1 0.8 Sr 0.2 MnO 3 And 8YSZ, printing cathode slurry on the connector and the electrolyte, wherein the thickness of the cathode functional layer is 10 +/-3 mu m, and drying at 80 ℃. The length of each section of cathode is 10.5mm, and the interval between two adjacent sections of cathodes is 1.5 mm.
Preparing a cathode bus layer on the surface of the dried cathode through screen printing, wherein the cathode bus layer slurry is prepared from 50 wt% of a slurry with a volume ratio of 1:1 La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ With Mn 1.5 Co 1.5 O 4 And 2.5 wt% of a binder, 0.5 wt% of a dispersant and 47 wt% of an organic solvent, and La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ With Mn 1.5 Co 1.5 O 4 The particle size of (A) is 300 to 500 nm. And uniformly mixing the confluence layer slurry, then carrying out screen printing to prepare the confluence layer, wherein the mesh number of a used screen is preferably 80 meshes, the rotating speed of a support is preferably 5.0cm/s, the thickness of the confluence layer is 200 +/-3 mu m, and drying at 80 ℃ after printing.
After drying, heating to 300 ℃ at the heating rate of 1 ℃/min, discharging the glue in the air for 4h, then discharging the glue from 300 ℃ at the heating rate of 1 ℃/min to 600 ℃ for 8h, and then preserving the heat in the air at 1200 ℃ at the heating rate of 2 ℃/min for 4h, and sintering and forming.
Example 2
Examples of the present invention will be described in more detail by examples as follows. The following description is not intended to limit the invention. The structure schematic diagram of the solid oxide fuel cell/electrolytic cell of the invention is shown in fig. 2 and fig. 4. The material constituting the tube comprises, by mass, 6:4, mixing the mixed powder of CSZ and NiO and 15 wt% of ammonium bicarbonate serving as pore-forming agents, wherein the particle diameters of the mixed powder and the pore-forming agents are respectively 3-5 microns, 0.5-1 micron and 10-30 microns, mixing the mixed powder and the pore-forming agents in a ball mill for 6 hours, the rotating speed is 360r/min, drying and grinding at 140 ℃, sieving for later use, adding 4 wt% of methyl cellulose, 5 wt% of glycerol, 14 wt% of water and the like serving as extrusion forming solvents, placing the mixture in a kneader for mixing for 3 hours to obtain pug, standing the pug for 2-3 days at 4-15 ℃, and preparing the conductive flat tube support body with the length of 300mm, the width of 50mm and the height of 8mm through extrusion forming. The particle sizes of CSZ and NiO can be in the above ranges, and the particle sizes can be selected to obtain a desired porosity by varying the degree of shrinkage between particles depending on the particle size ratio of the powder particles and changing the porosity of the support after firing. The additive components used for extrusion molding are not limitative of the present invention, and molding may be performed using other component systems. Then, the porous support is prepared by a method of extrusion molding, but the molding method is not limited thereto. Preferably, the porosity is in the range of 25-35%, more preferably 30-35%.
At this time, an insulating layer, an anode manifold layer, an anode, an electrolyte, and a connecting body were formed on the surface of the support by a screen printing method, and fired together with the support. The length of the support may vary after firing, and therefore, the shrinkage of the porous support during firing is preferably in the range of 12 to 20%, more preferably 15 to 17%. The porous support has too small a shrinkage rate, the electrolyte membrane has too large a shrinkage rate, and the two shrinkage rates are not matched to cause the electrolyte layer to crack.
Next, after the porous support to be extruded was dried at 80 ℃, an insulating layer was prepared on the support using a screen printing method, and the coating range was as shown in fig. 2 and 4. The main component of the insulating layer was SrZrO 35 wt% 3 +Al 2 O 3 (Al 2 O 3 In an amount of SrZrO 3 3 mol%) of 5 wt% of PMMA as pore-forming agent, 10 wt% of binder, 2 wt% of dispersant and 48 wt% of organic solvent, and SrZrO is used 3 Has a particle diameter of D 50 500nm, Al used 2 O 3 Has a particle diameter of D 50 200nm, pore former particle diameter D 50 1 μm. The insulating layer slurry can be subjected to silk-screen printing to prepare the insulating layer after ball milling for 4h, the mesh number of the used silk screen is preferably 200 meshes, and the rotating speed of the support bodyThe degree is preferably 5.0cm/s, the thickness of the insulating layer is 20 + -3 μm, and the printing is completed and then the drying is carried out at 80 ℃.
The first planar battery pack and the second planar battery pack are respectively formed by connecting 15 single cells in series.
An anode bus layer was prepared on the insulating layer using a screen printing method, and the coating range was as shown in fig. 2 and 4. The main components of the anode confluence layer are 60 wt% of NiO and La 0.7 Sr 0.3 CrO 3 (mass ratio of 7:3), 2 wt% of binder, 0.5 wt% of dispersant, 37.5 wt% of organic solvent, NiO and La 0.7 Sr 0.3 CrO 3 All particle diameters of (A) are D 50 200 nm. And performing ball milling on the anode confluence layer slurry for 4h, performing screen printing to prepare an anode confluence layer, wherein the mesh number of the used screen is preferably 100 meshes, the rotation speed of a support body is preferably 5.0cm/s, the thickness of the anode confluence layer is 150 +/-3 mu m, and drying at 80 ℃ after printing. The length of each section of anode is 10mm, and the interval between two adjacent sections of anodes is 2 mm.
The anode functional layer was prepared on the insulating layer using a screen printing method, and the coating range was as shown in fig. 2 and 4. The main components of the anode functional layer are 50 wt% of NiO and ScSZ (mass ratio is 6:4), 2.5 wt% of binder, 0.5 wt% of dispersant and 47 wt% of organic solvent, and the particle diameters of the NiO and the ScSZ are D 50 200 nm. And performing ball milling on the anode functional layer slurry for 4 hours to prepare an anode functional layer by screen printing, wherein the mesh number of the used screen is preferably 180 meshes, the rotating speed of a support body is preferably 5.0cm/s, the thickness of the anode functional layer is 30 +/-3 mu m, and drying at 80 ℃ after printing. The length of each section of anode is 10mm, and the interval between two adjacent sections of anodes is 2 mm.
The electrolyte layer was prepared on the anode functional layer using a screen printing method, and the coating range was as shown in fig. 2 and 4. The electrolyte layer comprises 50 wt% of ScSZ, 2.5 wt% of binder, 0.5 wt% of dispersant and 47 wt% of organic solvent, wherein the particle diameter of ScSZ is D 50 100 nm. The electrolyte layer slurry can be subjected to screen printing to prepare an electrolyte layer after ball milling for 4h, the mesh number of the used screen is preferably 250 meshes, the rotating speed of the support is preferably 5.0cm/s, the thickness of the electrolyte layer is 25 +/-3 mu m, and the electrolyte layer is dried at 80 ℃ after printing. Each section of electrolyte is longThe degree is 10mm, the interval between two adjacent sections of electrolyte is 2mm, and the anode which is not covered by the electrolyte along the axial direction of the support body is 1 mm.
The connector layer was prepared on the electrolyte layer using a screen printing method, and the coating range was as shown in fig. 2 and 4. The main component of the connector layer was 50 wt% of La 0.9 Sr 0.1 TiO 3 And 2.5 wt% of a binder, 0.5 wt% of a dispersant and 47 wt% of an organic solvent, and La 0.9 Sr 0.1 TiO 3 Has a particle diameter of D 50 100 nm. The connecting body layer slurry can be subjected to silk screen printing to prepare the connecting body layer after ball milling for 4h, the mesh number of the used silk screen is preferably 100 meshes, the rotating speed of the support body is preferably 5.0cm/s, the thickness of the connecting body layer is 150 +/-3 mu m, and the connecting body layer is dried at 80 ℃ after printing. The length of each connector is 3 mm.
After drying, heating to 300 ℃ at the heating rate of 1 ℃/min for glue discharging for 4h in the air, then heating to 600 ℃ at the heating rate of 1 ℃/min for glue discharging for 8h from 300 ℃, and then preserving heat at 1450 ℃ for 4h in the air at the heating rate of 2 ℃/min for sintering and molding.
By the same operation as the above-described printing method of the anode functional layer, the coating range is as shown in fig. 2 and 4, and the cathode slurry contains La as a main component in a mass ratio of 8:2 0.8 Sr 0.2 MnO 3 And 8YSZ, printing cathode slurry on the connector and the electrolyte, wherein the thickness of the cathode functional layer is 10 +/-3 mu m, and drying at 80 ℃. The length of each section of cathode is 10.5mm, and the interval between two adjacent sections of cathodes is 1.5 mm.
Preparing a cathode bus layer on the surface of the dried cathode through screen printing, wherein the cathode bus layer slurry is prepared from 50 wt% of a slurry with a volume ratio of 1:1 La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ With Mn 1.5 Co 1.5 O 4 And 2.5 wt% of a binder, 0.5 wt% of a dispersant and 47 wt% of an organic solvent, and La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ With Mn 1.5 Co 1.5 O 4 The particle size of (A) is 300 to 500 nm. The confluence layer slurry can be subjected to screen printing to prepare a confluence layer after being uniformly mixed, the mesh number of the used screen is preferably 80 meshes, and the rotating speed of the support is preferably 5.0 cm-s, the thickness of the confluence layer is 200 +/-3 mu m, and the confluence layer is dried at 80 ℃ after printing.
After drying, heating to 300 ℃ at the heating rate of 1 ℃/min, discharging the glue in the air for 4h, then discharging the glue from 300 ℃ at the heating rate of 1 ℃/min to 600 ℃ for 8h, and then preserving the heat in the air at 1200 ℃ at the heating rate of 2 ℃/min for 4h, and sintering and forming.
Example 3
The structure of the solid oxide fuel cell/electrolyzer provided in this example is schematically shown in fig. 3 and 5. The material constituting the tube comprises, by mass, 1:1 MgAl 2 O 4 And NiO mixed powder and 15 wt% of PMMA (polymethyl methacrylate) are used as pore forming agents, the particle sizes are respectively 3-5 microns, 0.5-1 micron and 10-30 microns, the mixed powder and the pore forming agents are mixed in a ball mill for 6 hours at the rotating speed of 360r/min, the mixture is dried and ground at the temperature of 140 ℃ and is sieved for later use, 4 wt% of methyl cellulose, 5 wt% of glycerol, 14 wt% of water and the like are added as solvents for extrusion molding, the mixture is placed in a kneader and is mixed for 3 hours to obtain pug, the pug is placed still for 2-3 days at the temperature of 4-15 ℃, and the conductive flat tube support body with the length of 1000mm, the width of 100mm and the height of 15mm is prepared through extrusion molding. For MgAl 2 O 4 And NiO, the particle size can be within the above range, and the degree of shrinkage of the powder particles is different depending on the size and the particle size ratio of the powder particles, and the porosity of the support after firing is changed by selecting the particle size in order to obtain a desired porosity. The additive components used for extrusion molding are not limitative of the present invention, and molding may be performed using other component systems. Then, the porous support is prepared by a method of extrusion molding, but the molding method is not limited thereto. Preferably, the porosity is in the range of 25-35%, more preferably 30-35%.
At this time, an insulating layer, an anode manifold layer, an anode, an electrolyte, and a connecting body were formed on the surface of the support by a screen printing method, and fired together with the support. The length of the support may vary after firing, and therefore, the shrinkage of the porous support during firing is preferably in the range of 12 to 20%, more preferably 15 to 17%. The porous support has too small a shrinkage rate, the electrolyte membrane has too large a shrinkage rate, and the two shrinkage rates are not matched to cause the electrolyte layer to crack.
Next, after the porous support to be extruded was dried at 80 ℃, an insulating layer was prepared on the support using a screen printing method, and the coating range was as shown in fig. 3 and 5. The insulating layer mainly comprises 35 wt% of CSZ, 5 wt% of PMMA as a pore-forming agent, 10 wt% of a binder, 2 wt% of a dispersant and 48 wt% of an organic solvent, wherein the particle size of the CSZ is D50-500 nm, and the particle size of the pore-forming agent is D50-1 μm. The insulating layer slurry can be subjected to silk screen printing to prepare an insulating layer after ball milling for 4h, the mesh number of the used silk screen is preferably 200 meshes, the rotating speed of a support body is preferably 5.0rad/s, the thickness of the insulating layer is 20 +/-3 mu m, and the insulating layer is dried at 80 ℃ after printing.
And respectively preparing 30 single cells on the first plane insulating layer and the second plane insulating layer through screen printing.
An anode bus layer was prepared on the insulating layer using a screen printing method, and the coating range was as shown in fig. 3 and 5. The main components of the anode confluence layer are 60wt percent of NiO and Sr 0.7 La 0.3 TiO 3 (mass ratio of 7:3), 2 wt% of binder, 0.5 wt% of dispersant, 37.5 wt% of organic solvent, NiO and Sr 0.7 La 0.3 TiO 3 All the particle diameters of (A) were D50-200 nm. And performing ball milling on the anode confluence layer slurry for 4h, performing screen printing to prepare an anode confluence layer, wherein the mesh number of the used screen is preferably 100 meshes, the rotating speed of a support body is preferably 5.0rad/s, the thickness of the anode confluence layer is 150 +/-3 mu m, and drying at 80 ℃ after printing. The length of each section of anode is 10mm, and the interval between two adjacent sections of anodes is 2 mm.
The anode functional layer was prepared on the insulating layer using a screen printing method, and the coating range was as shown in fig. 3 and 5. The main components of the anode functional layer are 50 wt% of NiO and GDC (mass ratio is 6:4), 2.5 wt% of a binder, 0.5 wt% of a dispersant and 47 wt% of an organic solvent, wherein the NiO and the GDC have the particle size of D50-200 nm. And performing ball milling on the slurry of the anode functional layer for 4h to prepare the anode functional layer by screen printing, wherein the mesh number of the used screen is preferably 180 meshes, the rotating speed of a support body is preferably 5.0rad/s, the thickness of the anode functional layer is 30 +/-3 mu m, and drying at 80 ℃ after printing. The length of each section of anode is 10mm, and the interval between two adjacent sections of anodes is 2 mm.
The electrolyte layer was prepared on the anode functional layer using a screen printing method, and the coating range was as shown in fig. 3 and 5. The electrolyte layer was composed mainly of 50 wt% GDC, 2.5 wt% binder, 0.5 wt% dispersant, and 47 wt% organic solvent, and the particle size of GDC used was D50 ═ 100 nm. The electrolyte layer slurry can be subjected to screen printing to prepare an electrolyte layer after ball milling for 4h, the mesh number of the used screen is preferably 250 meshes, the rotating speed of the support is preferably 5.0rad/s, the thickness of the electrolyte layer is 25 +/-3 mu m, and the electrolyte layer is dried at 80 ℃ after printing. The length of each section of electrolyte is 10mm, the interval between two adjacent sections of electrolyte is 2mm, and the anode which is not covered by the electrolyte along the axial direction of the support body is 1 mm.
The connector layer was prepared on the electrolyte layer using a screen printing method, and the coating range was as shown in fig. 3 and 5. The main component of the connector layer was 50 wt% of La 0.7 Sr 0.3 TiO 3 And 2.5 wt% of a binder, 0.5 wt% of a dispersant and 47 wt% of an organic solvent, and La 0.7 Sr 0.3 TiO 3 The particle diameter of (D50) was 100 nm. The connector layer slurry can be subjected to silk screen printing to prepare the connector layer after ball milling for 4h, the mesh number of the used silk screen is preferably 100 meshes, the rotating speed of the support body is preferably 5.0rad/s, the thickness of the connector layer is 150 +/-3 mu m, and the connector layer is dried at 80 ℃ after printing. The length of each connector is 3 mm.
After drying, heating to 300 ℃ at the heating rate of 1 ℃/min, discharging rubber in the air for 4h, then discharging rubber from 300 ℃ at the heating rate of 1 ℃/min to 600 ℃ for 8h, and then preserving heat in the air at 1450 ℃ at the heating rate of 2 ℃/min for 4h, and sintering and forming.
The coating range was as shown in fig. 3 and 5 by the same operation as the above-described printing method of the anode functional layer, and the main component of the cathode slurry was La in a mass ratio of 1:1 0.8 Sr 0.2 MnO 3 And 8YSZ, printing cathode slurry on the connector and the electrolyte, wherein the thickness of the cathode functional layer is 10 +/-3 mu m, and drying at 80 ℃. The length of each section of cathode is 10.5mm, and the interval between two adjacent sections of cathodes is 1.5 mm.
Preparing a cathode bus layer on the surface of the dried cathode through screen printing, wherein the cathode bus layer slurry is prepared from 50 wt% of a slurry with a volume ratio of 1:1 La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ With Mn 1.5 Co 1.5 O 4 And 2.5 wt% of a binder, 0.5 wt% of a dispersant and 47 wt% of an organic solvent, and La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ With Mn 1.5 Co 1.5 O 4 The particle size of (A) is 300 to 500 nm. The confluence layer slurry can be subjected to screen printing to prepare the confluence layer after being uniformly mixed, the mesh number of the used silk screen is preferably 80 meshes, the rotating speed of the support is preferably 5.0rad/s, the thickness of the confluence layer is 200 +/-3 mu m, and the confluence layer is dried at 80 ℃ after printing.
After drying, heating to 300 ℃ at the heating rate of 1 ℃/min, discharging rubber in the air for 4h, then heating to 600 ℃ from 300 ℃ at the heating rate of 1 ℃/min, discharging rubber for 8h, and then preserving heat in the air at 1250 ℃ at the heating rate of 2 ℃/min for 4h, and sintering and forming.
The conductive flat tube supported solid oxide fuel cell/electrolytic cell structure, the preparation method thereof and the cell stack structure provided by the invention are described in detail, specific examples are applied in the description to explain the principle and the implementation mode of the invention, and the description of the examples is only used for helping to understand the method and the core idea of the invention; meanwhile, for a person skilled in the art, according to the idea of the present invention, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present invention.
Claims (10)
1. An electrically conductive flat tube supported solid oxide fuel cell/electrolyser structure, characterized in that it comprises: the conductive flat tube support body, the insulating layer and the battery pack;
the conductive flat tube supporting body consists of an opening area, a main power generation area and a closed area, wherein the opening area corresponds to openings at two ends of the conductive flat tube supporting body, the closed area corresponds to circular arc parts at two sides of the conductive flat tube supporting body, and the main power generation area is a main area of the conductive flat tube supporting body;
the battery pack is formed by connecting a plurality of single batteries in series through a connecting body, and the battery pack is distributed on a first plane and a second plane which are parallel to each other in the main body area to form a first plane battery pack and a second plane battery pack; the first planar battery pack and the second planar battery pack are arranged in an axisymmetrical manner by the axis of the conductive flat tube support body, or the first planar battery pack and the second planar battery pack are arranged in a centrosymmetric manner by the axis of the conductive flat tube support body;
the conductive flat tube support body is used for transmitting current generated in the conductive flat tube support type solid oxide fuel cell/electrolytic cell;
the insulating layer is located between the conductive flat tube supporting body and the battery pack.
2. The structure according to claim 1, wherein when the first planar battery pack and the second planar battery pack are arranged in axial symmetry about the axis of the flat conductive pipe support, the first planar battery pack and the second planar battery pack are connected in parallel, the cathode layer of the last single cell in the first planar battery pack is connected to the flat conductive pipe support through the connector, and the cathode layer of the last single cell in the second planar battery pack is connected to the flat conductive pipe support through the connector;
when the first planar battery pack and the second planar battery pack are arranged in a central symmetry manner by taking the axis of the conductive flat tube support body as a center, the first planar battery pack is connected with the second planar battery pack in series, the cathode layer of the last single cell in the first planar battery pack is connected with the conductive flat tube support body through the connector, and the anode layer of the last cell in the second planar battery pack is connected with the conductive flat tube support body through the connector.
3. The structure according to claim 1, characterized in that the outer surface of the enclosed area is covered with a dense functional layer, which is an electrolyte layer or a tie.
4. The structure according to claim 1, characterized in that a fuel gas flow passage for inflow and outflow of fuel gas is provided inside the conductive flat tube support body;
the conductive flat tube support body is provided with through air holes, and the through air hole rate is 10-40%;
the thickness of the conductive flat tube support body is 0.5 mm-3 mm;
the distance between the first plane and the second plane is 3mm-15 mm.
5. An electrically conductive flat tube supported solid oxide fuel cell stack structure, comprising: a stack of two or more electrically conductive flat tube supported solid oxide fuel cells/electrolysers as claimed in any of claims 1 to 4.
6. A preparation method of a conductive flat tube supported solid oxide fuel cell/electrolytic cell structure is characterized by comprising the following steps:
s1, preparing the support body powder into a conductive flat tube support body blank body with an internal flow channel by using an extrusion molding device; the conductive flat tube support body blank body consists of an opening area, a main power generation area and a closed area, wherein the opening area corresponds to openings at two ends of the conductive flat tube support body blank body, the closed area corresponds to circular arc parts at two sides of the conductive flat tube support body blank body, and the main power generation area is a main area of the conductive flat tube support body blank body; the support body powder consists of ceramic powder which can not be reduced by hydrogen, ceramic powder which can be reduced by hydrogen, a binder and a pore-forming agent;
s2, spraying insulating layer slurry on a first plane and a second plane which are parallel to each other in the main power generation area by adopting a wet spraying mode, and drying and curing to form an insulating layer;
s3, printing anode bus layer slurry on the surface of the insulating layer at intervals, drying and curing to form a plurality of anode bus layers;
s4, printing anode slurry on the surface of each anode confluence layer, drying and curing to form a plurality of anode layers;
s5, printing electrolyte slurry on the surface of each anode layer, drying and curing to form a plurality of electrolyte layers; wherein one end of each electrolyte layer partially covers an adjacent one of the anode layers, and the other end of each electrolyte layer is in contact with a part of the insulating layer; each of the anode bus layers forms a plurality of single cell intermediates with a corresponding one of the anode layers and a corresponding one of the electrolyte layers;
s6, printing connector slurry at intervals of the single cell intermediates, printing connector slurry or electrolyte slurry in the closed area, drying and curing to form a first battery blank intermediate body with a plurality of connectors; wherein one end of the connector is in contact with the anode layer and the electrolyte of an adjacent one of the cell intermediates, and the other end portion covers the electrolyte layer of another adjacent one of the cell intermediates;
s7, pre-burning and roasting the first battery blank intermediate for one time to obtain a second battery blank intermediate;
s8, printing cathode slurry on the surface of each electrolyte layer of the second battery blank intermediate, drying and curing to form a plurality of cathode layers; wherein each of said cathode layers partially covers a corresponding one of said electrolyte layers and a corresponding one of said connectors;
s9, printing cathode confluence layer slurry on the surface of each cathode layer, drying and curing to obtain a conductive flat tube supported solid oxide fuel cell/electrolytic cell blank;
and S10, performing secondary pre-sintering and secondary roasting on the conductive flat tube supported solid oxide fuel cell/electrolytic cell blank to obtain the conductive flat tube supported solid oxide fuel cell/electrolytic cell.
7. The preparation method according to claim 6, wherein the ceramic powder that is not reducible by hydrogen comprises one or a combination of alumina, mullite, panlite, titania, calcium oxide, and doped zirconia;
the ceramic powder capable of being reduced by hydrogen comprises one or a combination of nickel oxide, iron oxide, cobalt oxide and copper oxide;
the mass ratio of the ceramic powder which cannot be reduced by hydrogen gas to the ceramic powder which can be reduced by hydrogen gas is 4: 6-6: 4;
the mass ratio of the sum mass of the ceramic powder which can not be reduced by hydrogen and the ceramic powder which can be reduced by hydrogen to the pore-forming agent is less than or equal to 7: 3;
the mass ratio of the binder to the sum of the ceramic powder and the pore-forming agent is 1: 9-3: 7;
the binder comprises one or a combination of polyvinyl butyral, ethyl cellulose, polyvinylpyrrolidone and polyvinyl alcohol;
the pore-forming agent comprises one or a combination of more of ammonium bicarbonate, soluble starch, sucrose, polymethyl methacrylate and carbon powder.
8. The production method according to claim 6, wherein an insulating powder is included in the insulating layer slurry, and the insulating powder is: MgAl with the mass ratio of 2: 3-26: 5 2 O 4 With MgO, doped zirconia, SrTiO 3 And SrZrO 3 One or more components of (a);
the anode confluence layer slurry comprises anode confluence powder, wherein the anode confluence powder is as follows: the mass ratio is 6:4 NiO/5YSZ, doped strontium titanate and doped lanthanum chromate;
the electrolyte slurry comprises electrolyte powder, wherein the electrolyte powder is one or more of doped zirconia, doped ceria, doped lanthanum gallate and doped barium cerate;
the anode layer slurry comprises anode powder, and the anode powder is prepared from the following components in a mass ratio of 6:4 with the electrolyte powder;
the connector slurry comprises connector powder, wherein the connector powder is one or more of doped strontium titanate, doped lanthanum chromate and doped lanthanum manganate;
the cathode slurry comprises cathode powder, wherein the cathode powder is one or more of doped lanthanum manganate and doped lanthanum cobaltate;
the cathode confluence layer slurry comprises cathode confluence powder, wherein the cathode confluence powder is (Mn, Co) 3 O 4 One or more of lanthanum cobaltate and lanthanum manganate.
9. The production method according to claim 6, wherein the insulating layer has a thickness of 20 μm to 100 μm;
the thickness of the anode bus layer is 100-200 μm;
the thickness of the anode layer is 10-30 μm;
the thickness of the electrolyte layer is 10-30 μm;
the thickness of the connector layer is 100-200 μm;
the thickness of the cathode layer is 10-20 μm;
the thickness of the cathode bus layer is 100-200 μm.
10. The preparation method according to claim 6, wherein the temperature ranges of the primary pre-sintering and the secondary pre-sintering are both 100 ℃ to 600 ℃; the time of the primary pre-sintering and the time of the secondary pre-sintering are both 1h to 10 h;
the temperature range of the primary roasting is 1250-1500 ℃, and the time of the primary roasting is 4-6 h;
the temperature range of the secondary roasting is 1100-1400 ℃, and the time of the secondary roasting is 2-4 h.
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