CN114976102A - Preparation method of integrated connector supported electricity symbiotic solid oxide fuel cell/cell stack reactor - Google Patents
Preparation method of integrated connector supported electricity symbiotic solid oxide fuel cell/cell stack reactor Download PDFInfo
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- CN114976102A CN114976102A CN202210581376.0A CN202210581376A CN114976102A CN 114976102 A CN114976102 A CN 114976102A CN 202210581376 A CN202210581376 A CN 202210581376A CN 114976102 A CN114976102 A CN 114976102A
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Images
Classifications
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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
-
- 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
- H01M8/0273—Sealing or supporting means around electrodes, matrices or membranes with sealing or supporting means in the form of a frame
-
- 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
- H01M8/0276—Sealing means characterised by their form
-
- 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
- H01M8/028—Sealing means characterised by their material
- H01M8/0282—Inorganic 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
- H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
- H01M8/0286—Processes for forming seals
-
- 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 provides a preparation method of an integrated connector supported electric symbiotic solid oxide fuel cell/cell stack reactor, which comprises the following steps: the self-sealing integrated connector body structure is manufactured by designing and preparing pore-forming agents with different flow passage shapes, then spreading powder layer by layer and pressing by a compression molding method. And sequentially printing anode slurry, electrolyte slurry and cathode slurry on the porous area on the upper surface of the connecting body blank by utilizing a screen printing mode, so that the anode covers the porous area on the upper surface of the connecting body, the electrolyte covers the anode functional layer, and then pre-burning, glue removing, roasting, shrinking and forming are carried out to prepare the self-sealing battery reactor. The preparation method effectively simplifies the manufacturing process of the battery reactor, reduces the sealing workload of the battery reactor, is beneficial to reducing the manufacturing cost of the battery, and promotes the commercial popularization of the solid oxide battery.
Description
Technical Field
The invention relates to the technical field of solid oxide fuel cells, in particular to a preparation method of an integrated connector supported electricity symbiotic solid oxide fuel cell/cell stack reactor.
Background
An electric energy-value added chemical symbiotic solid oxide fuel cell (electric energy-value added chemical symbiotic SOFC) is a reaction device which converts chemical energy stored in fuel into electric energy through electrochemical reaction and simultaneously generates high-value chemicals, and various physical and chemical changes can be generated simultaneously in the conversion process. Unlike the traditional Solid Oxide Fuel Cell (SOFC) which only generates electricity and supplies energy, the electric energy-value added chemical symbiosis SOFC is a special fuel cell reactor and can obtain valuable chemicals while generating electricity. Compared with other reactors, the symbiotic SOFC reactor provides an internal reforming condition, has small polarization resistance and higher utilization rate of fuel gas, and has a series of characteristics of stable electric energy output and the like. Therefore, in recent years, research on the cell structure and composition of the symbiotic SOFC is increasingly active, and fuel gas selection is more abundant, so that research on the symbiotic SOFC has practical value.
By constructing a symbiotic proton conductor SOFC, selective oxidative conversion of ethane on the anode side, rather than complete oxidation, can be achieved not only in the absence of CO 2 And generating power under the discharge condition, and obtaining the value-added chemical ethylene. In addition, the proton conductor electrolyte has higher ion conductivity than the oxygen ion conductor electrolyte, and can operate at medium and low temperature. Further, since no water is generated in the fuel electrode, it is not necessary to circulate the fuel.
However, most of the research on the proton conductor SOFC symbiotic reactor at present focuses on the development and design of functional layer materials, particularly anode materials, and the research on the structure and the preparation method of the proton conductor SOFC symbiotic reactor is very little. Therefore, it is urgently required for researchers to develop a production method for a reactor for cogeneration.
Disclosure of Invention
In order to solve the problems in the related art, the application provides a preparation method of an intergrowth solid oxide fuel cell/cell stack reactor supported by an integrated connector, which can effectively simplify the preparation process of the reactor and improve the preparation efficiency of the reactor, and the specific content is as follows:
in a first aspect, the present invention provides a method of making an integrally connected supported symbiotic solid oxide fuel cell reactor, said method of making comprising:
placing an oxidation gas flow channel filling body in the middle area of the bottom of a mold, laying first precursor powder in a hole of the oxidation gas flow channel filling body, and laying second precursor powder between the edge of the bottom of the mold and the oxidation gas flow channel filling body to form a first ceramic powder layer; wherein the laying height of the first precursor powder and the second precursor powder is the same as the height of the oxidizing gas flow channel filler;
further, laying a second precursor powder on the first ceramic powder layer to form a second ceramic powder layer;
further, a reducing gas flow channel filling body is placed in the middle area above the second ceramic powder layer, first precursor powder is laid in a hole of the reducing gas flow channel filling body, and second precursor powder is laid between the edge of the die and the reducing gas flow channel filling body; wherein the laying heights of the first precursor powder and the second precursor powder are the same and are greater than the height of the reducing gas flow channel filling body; the first precursor powder has a laydown area that is greater than 90% of the laydown area of the first precursor powder and the second precursor powder;
further, pressing the connector composite powder body to obtain a connector green body;
further, anode slurry and electrolyte slurry are respectively printed on the upper surface of the connecting body blank, and are dried and cured to form a first semi-finished product of the solid oxide fuel cell reactor supported by the connecting body;
further, pre-burning and first roasting the first semi-finished product of the solid oxide fuel cell reactor supported by the connector to obtain a second semi-finished product of the solid oxide fuel cell reactor supported by the connector;
further, printing cathode slurry on the electrolyte layer of the second semi-finished solid oxide fuel cell reactor supported by the connector to form a third semi-finished solid oxide fuel cell reactor supported by the connector;
further, carrying out second roasting on a third semi-finished product of the solid oxide fuel cell reactor supported by the connector to obtain an integrated connector-supported electric symbiotic solid oxide fuel cell reactor;
the first precursor powder is obtained by mixing ceramic powder, a pore-forming agent and a binder, and the second precursor powder is obtained by mixing ceramic powder and the binder;
the anode slurry comprises anode powder which is a catalytic material capable of catalyzing dehydrogenation and oxidation of hydrocarbon fuel;
the electrolyte slurry contains an electrolyte powder, which is a proton conductor material.
Optionally, the method according to claim 1, wherein the first precursor powder has a particle size of 50-300 μ ι η and the second precursor powder has a particle size of 50-300 μ ι η;
in the first precursor powder, the mass ratio of the ceramic powder to the binder to the pore-forming agent is 65-90: 5-15: 5-20, the particle size of the ceramic powder is 0.5-10 μm, and the particle size of the pore-forming agent is 1-5 μm;
in the second precursor powder, the mass ratio of the ceramic powder to the binder is 95-85: 5-10, and the particle size of the ceramic powder is 0.5-5 μm.
Optionally, the ceramic powder is at least one component of doped lanthanum titanate and doped lanthanum chromate;
the binder is at least one component of polyvinyl butyral (PVB), ethyl cellulose, polyvinylpyrrolidone (K60-K90) and polyvinyl alcohol (PVA);
the pore-forming agent is any one of graphite, starch, polymethyl methacrylate, ammonium bicarbonate and sucrose.
Optionally, the catalytic material is at least one component of doped strontium titanate and doped strontium chromate;
the proton conductor material is: BaCe 1-x Y x O 3-δ 、BaZr 1-x Y x O 3-δ And Ba (Ce, Zr) 1-y Y y O 3-δ And any one of the above, wherein x is more than or equal to 0.1 and less than or equal to 0.9, and y is more than or equal to 0.1 and less than or equal to 0.9.
Optionally, the catalytic material comprises SrTiO 3 、La 0.7 Sr 0.3 TiO and La 0.7 Sr 0.3 CrO 3 At least one component of (a);
the proton conductor material comprises BaZr 0.8 Y 0.2 O 3–δ 、BaZr 0.1 Ce 0.7 Y 0.2 O 3–δ And BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3–δ Any one of the components (a) to (b);
the cathode slurry contains cathode powder, and the cathode powder is prepared from the following components in a mass ratio of 1:1 with La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ Or the cathode powder consists of the following components in a mass ratio of 1:1 with Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ And (4) forming.
Optionally, the oxidizing gas flow channel filler and the reducing gas flow channel filler are formed by powder press forming or die pressing and laser processing from flow channel filler powder, wherein the flow channel filler powder is at least one of PMMA, ammonium bicarbonate, starch, sucrose and carbon powder.
Optionally, the pressure for pressing the connected composite powder body ranges from 50MPa to 200 MPa.
Optionally, the catalytic material is one or more of doped strontium titanate and doped strontium chromate;
the quality isThe sub-conductor material includes: BaCe 1-x Y x O 3-δ 、BaZr 1-x Y x O 3-δ And Ba (Ce, Zr) 1-y Y y O 3-δ And any one of the above, wherein x is more than or equal to 0.1 and less than or equal to 0.9, and y is more than or equal to 0.1 and less than or equal to 0.9.
Optionally, the anode paste, the electrolyte paste and the cathode paste are prepared on the connector green body by screen printing, the mesh number of the screen printing is 180-350 meshes, the scraper speed of the screen printing is 5cm/s, and the scraper angle of the screen printing is 55-85 ℃.
Optionally, the pre-sintering temperature range is 100-600 ℃, and the time is 1-10 h;
the temperature range of the first roasting is 1350-1600 ℃, and the time is 4-6 h;
the temperature range of the second roasting is 600-1200 ℃, and the time is 4-6 h.
In a second aspect, the present invention provides a method for preparing an integrally connected supported symbiotic solid oxide fuel cell reactor, wherein the reactor comprises two or more than two reactors prepared by the method of the second aspect, and the preparation method of the reactor comprises:
and contacting and sealing the cathode of one cell reactor with the integrated connector of the next cell reactor to form the connector supported electricity symbiotic solid oxide fuel cell stack reactor.
Compared with the related art, the preparation method of the integrated connector supported electrical symbiotic solid oxide fuel cell/cell stack reactor provided by the application has at least the following advantages:
1. in the electric symbiotic solid oxide fuel cell reactor supported by the integrated connector prepared by the preparation method, the connector with the function of the support body is of a full-ceramic integrated structure, and the structural design can solve the problem that the ceramic connector is difficult to seal, simplify the sealing process of the solid oxide fuel cell stack reactor and improve the long-term operation stability. In addition, the invention adopts ceramic anode material with good catalytic performance and excellent carbon deposition resistance to prepare the connector with the supporting function, so that a heterogeneous interface does not exist between the connector and the anode layer, and the connector has good thermal matching and structure matching performance, and can obviously improve the high-efficiency output and stability of the reactor in the long-term service process; the connector can play its own role and simultaneously can make the fuel gas fully catalyze and dehydrogenate, can make ethane efficiently and selectively converted into ethylene at low temperature, and simultaneously can generate electric energy.
2. The invention presses an integrated connector body blank structure with the characteristic of self-sealing structure by optimizing the particle size ratio of connector powder, regulating and controlling the content of pore-forming agent and designing the powder spreading sequence and combining with a mould. And sequentially printing anode slurry, electrolyte slurry and cathode slurry on the upper surface of the connecting body blank by using a screen printing mode, and roasting to obtain the battery reactor with the self-sealing effect. The preparation method provided by the invention can be used for preparing the battery reactor with the self-sealing function, effectively simplifies the manufacturing process of the symbiotic battery reactor of electric appliances, reduces the sealing workload of the battery reactor, is beneficial to reducing the manufacturing cost of the battery, and promotes the commercial popularization of the solid oxide battery.
3. The all-ceramic solid oxide fuel cell/cell stack reactor prepared by the preparation method has good structural chemical stability and thermal corrosion resistance, can operate at a high temperature of more than 800 ℃, and has excellent output performance.
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 description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present application, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 shows a flow diagram of a method of making an integrated interconnector-supported, intergrowth solid oxide fuel cell reactor made in accordance with an embodiment of the present invention;
FIG. 2 is a schematic structural diagram of an oxidizing gas flow path filler prepared according to an embodiment of the present invention;
FIG. 3 is a schematic structural diagram of a reducing gas flow channel packing body prepared by an embodiment of the present invention;
FIG. 4 shows a schematic structural view of a linker prepared by an embodiment of the present invention;
FIG. 5 shows a schematic diagram of an integrally connected supported CoMP reactor configuration made in accordance with an embodiment of the present invention;
figure 6 shows a schematic diagram of an integrated cogeneration solid oxide fuel cell stack reactor supported by an interconnector made 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 indicated in the examples and can be performed according to the procedures or conditions of the conventional experimental procedures described in the prior art in this field. The reagents and other instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Ethylene, the most produced organic compound in the world, is generally obtained by thermally cracking hydrocarbons in high-temperature steam with high energy consumption. Catalytic dehydrogenation of ethane into an endothermic process, which requires combustion of a large amount of hydrocarbon fuel to supplement heat, and which in turn produces CO 2 Greenhouse gases, therefore, have prompted researchers to seek more efficient, safe and environmentally friendly methods to increase ethane conversion efficiency due to their limitations on high endotherms, carbon deposition and thermodynamic equilibrium. The partial oxidative dehydrogenation of ethane converts the endothermic process of catalytic dehydrogenation of ethane into an exothermic oxidative reaction, thereby having a greater thermodynamic driving force for the reaction, which can be carried out at lower temperaturesWork at moderate temperature. The exothermic nature of the ethane partial oxydehydrogenation process, combined with the lower operating temperature requirements, can save over 30% of energy compared to conventional steam cracking catalysts, but under oxygen-containing conditions ethane is readily oxidized to carbon dioxide.
By constructing a symbiotic proton conductor Solid Oxide Fuel Cell (SOFC), ethane is subjected to selective oxidation conversion at an anode instead of complete oxidation, and efficient clean ethane utilization power generation (without CO) can be realized 2 Discharge) to obtain the value-added chemical ethylene with increased yield. In addition, the proton conductor electrolyte has higher ion conductivity than the oxygen ion conductor electrolyte, and thus can be operated at a medium-low temperature, and the fuel electrode is free from water generation without performing fuel circulation.
In addition, the inventor of the present invention has conducted extensive studies to find that when a metal material is used as a connecting body of an intergrowth solid oxide fuel cell reactor, the oxidation resistance, vulcanization resistance and carbon deposition resistance of the metal material to the environment are insufficient, and the thermal expansion coefficient of the metal material is too large compared with that of a component in contact with the metal material, and the mechanical properties of the metal material are also sharply reduced with the increase of temperature.
Therefore, in order to simplify the preparation process and obtain the electric symbiotic solid oxide fuel cell/cell stack reactor with simple structure and self-sealing property, the application provides the following preparation method:
in a first aspect, the present invention provides a method for preparing an integrally connected supported symbiotic solid oxide fuel cell reactor, and fig. 1 shows a flow chart of a method for preparing an integrally connected supported symbiotic solid oxide fuel cell reactor prepared according to an embodiment of the present invention, as shown in fig. 1, the method comprises the following steps:
s1, placing the oxidizing gas flow channel filling body in the middle area of the bottom of the mold, laying first precursor powder in holes of the oxidizing gas flow channel filling body, and laying second precursor powder between the edge of the bottom of the mold and the oxidizing gas flow channel filling body to form a first ceramic powder layer; wherein the laying height of the first precursor powder and the second precursor powder is the same as the height of the oxidizing gas flow channel filler.
In specific implementation, in step S1 of this embodiment, the oxidizing gas flow channel filling body correspondingly prepares the oxidizing gas flow channel, the first precursor powder correspondingly prepares the middle porous connector region of the connector blank, the second precursor powder correspondingly prepares the edge dense connector region of the connector blank, and the hole between the oxidizing gas flow channel and the flow channel is filled with the first precursor powder, so as to implement diffusion of the oxidizing gas through the porous connector region in the cell stack reactor, increase the contact area between the oxidizing gas and the cathode, and improve the reaction efficiency.
And S2, laying a second precursor powder on the first ceramic powder layer to form a second ceramic powder layer.
In step S2 of this embodiment, the second ceramic powder layer is located between the reducing gas channel and the oxidizing gas channel, and the second precursor powder is used to fill the second ceramic powder layer to prepare a dense connecting body region, so that independent spaces that do not interfere with each other are formed between the reducing gas channel and the oxidizing gas channel.
S3, placing a reducing gas flow channel filling body in the middle area above the second ceramic powder layer, laying first precursor powder into a hole of the reducing gas flow channel filling body, and laying second precursor powder between the edge of the die and the reducing gas flow channel filling body to form a connector composite powder body; wherein the laying heights of the first precursor powder and the second precursor powder are the same and are greater than the height of the reducing gas flow channel filling body; the first precursor powder has a laydown area greater than 90% of the laydown area of the first and second precursor powders.
In step S3, a reducing gas flow channel is prepared by a reducing gas flow channel filling body, in order to ensure that the reducing gas smoothly diffuses to the upper surface of a connecting body to contact with an anode layer and perform catalytic dehydrogenation reaction, thereby improving the catalytic dehydrogenation reaction efficiency of the hydrocarbon fuel, and achieving self-sealing of the connecting body structure, the invention fills a first precursor powder in a hole between the flow channel and the flow channel of the reducing gas flow channel filling body to prepare a porous connecting body region, and fills a second precursor powder in an edge region of a mold to prepare a dense connecting body region, so that the peripheral edge of the connecting body forms a dense connecting body region, the upper surface of the connecting body forms a connecting body region with a dense edge and a porous middle, and the porous connecting body region in the middle of the upper surface occupies 90% of the total area of the upper surface.
Fig. 2 shows a schematic structural diagram of an oxidizing gas flow channel filler prepared according to an embodiment of the present invention, and fig. 3 shows a schematic structural diagram of a reducing gas flow channel filler prepared according to an embodiment of the present invention, as shown in fig. 2, the flow channel filler is formed by pressing a formed mold, the length, width, thickness, and flow channel shape of a pore-forming agent block obtained can be adjusted according to actual requirements, a mold corresponding to the pore-forming agent block having a desired flow channel shape is prepared in advance, and then a pore-forming agent having a desired flow channel shape is prepared by a pressing method. And, as shown in fig. 2, the diagonal sides of the channel-shaped pore-forming agent block are designed with gas channels, so that the cathode oxidizing gas and the anode fuel gas can be introduced through the channels after the entire integrated seal-support structure is successfully prepared.
And S4, pressing the connector composite powder body to obtain a connector blank.
In step S4 of this embodiment, the connected composite powder body is pressed with a certain pressure to form a compact, on one hand, the compact is convenient to take out of the mold, and on the other hand, the compact is used to improve the sintering formability of the integrated structure of the support.
And S5, respectively printing anode slurry and electrolyte slurry on the upper surface of the connector blank, and drying and curing to form a first semi-finished product of the solid oxide fuel cell reactor supported by the connector.
In step S5, an anode slurry is printed on the top surface of the green connector having the porous connector region, and is dried and cured to form an anode layer, and an electrolyte slurry is printed on the surface of the anode layer, and is dried and cured to form an electrolyte layer.
And S6, pre-burning and first roasting the first semi-finished product of the solid oxide fuel cell reactor supported by the connector to obtain a second semi-finished product of the solid oxide fuel cell reactor supported by the connector.
In step S6 of this embodiment, first, the first semi-finished product is pre-baked to remove the oxide gas flow channel filling body and the reducing gas flow channel filling body in the first semi-finished product, and also to remove a portion of organic components in the anode layer and the electrolyte layer, so as to prevent the organic components in the electrode layer from generating large impact on the functional layer at high temperature and causing deformation and cracking during the subsequent baking process.
And secondly, carrying out first roasting on the pre-sintered green body to ensure that the green body of the connecting body and the electrolyte layer are sufficiently shrunk to achieve a self-sealing effect, and controlling the shrinkage rates of the connecting body and the electrolyte layer to be within the range of 12-20% in the firing process, and more preferably 15-17% (if the shrinkage rate of the connecting body is too small, the shrinkage rate of the electrolyte membrane is too large, and the shrinkage rates of the connecting body and the electrolyte membrane are not matched to crack the electrolyte layer).
S7, printing cathode slurry on the electrolyte layer of the second semi-finished product of the solid oxide fuel cell reactor supported by the connector to form a third semi-finished product of the solid oxide fuel cell reactor supported by the connector;
s8, carrying out second roasting on the third semi-finished product of the solid oxide fuel cell reactor supported by the connector to obtain an integrated connector-supported electric symbiotic solid oxide fuel cell reactor;
in step S8, since the tolerance temperature of the cathode layer is lower than that of the electrolyte layer, in order to ensure the self-sealing effect of the connector due to sufficient shrinkage of the electrolyte layer, the present invention uses secondary calcination to obtain a formed intergrowth solid oxide fuel cell reactor supported by the integrated connector, wherein the primary calcination obtains a semi-finished product in which the connector and the electrolyte layer are sufficiently shrunk, and the secondary calcination tightly combines the cathode layer and the electrolyte layer, so as to finally obtain a finished product of the intergrowth solid oxide fuel cell reactor supported by the integrated connector with the self-sealing effect.
The first precursor powder is obtained by mixing ceramic powder, a pore-forming agent and a binder, and the second precursor powder is obtained by mixing ceramic powder and the binder; the anode slurry contains anode powder, and the anode powder is a catalytic material capable of catalyzing the dehydrogenation and oxidation of the hydrocarbon fuel; the electrolyte slurry contains electrolyte powder, and the electrolyte powder is a proton conductor material.
In specific implementation, fig. 4 shows a schematic structural diagram of a connector prepared in the embodiment of the present invention, fig. 5 shows a schematic structural diagram of an intergrowth solid oxide fuel cell stack reactor supported by an integrated connector prepared in the embodiment of the present invention, and as shown in fig. 4 and fig. 5, the connector structure prepared by the preparation method of the present invention includes a reducing gas flow channel and an oxidizing gas flow channel. The connector is an integral body of all-ceramic material and has no heterogeneous interface structure; a compact connector area is arranged between the oxidizing gas flow passage and the reducing gas flow passage so as to ensure that the gas flowing in the oxidizing gas flow passage and the gas flowing in the reducing gas flow passage cannot influence each other; the porous connector area is arranged above the reducing gas flow channel, so that the reducing gas (hydrocarbon fuel gas) can permeate into the anode functional layer above the porous connector area and can generate catalytic dehydrogenation reaction with catalytic substances in the anode functional layer, hydrogen protons generated by the reaction are transferred to one side of the cathode functional layer through the electrolyte layer consisting of proton conductors and are combined with oxygen to generate water, and then the reactor has the functions of synthesizing high value-added chemicals and generating electric energy.
In addition, the side surface of the connector provided by the invention is a compact connector area, an electrode layer is prepared in a porous connector area on the upper surface of the connector, and the electrode layer is in contact with and partially covers the compact connector area on the side surface of the connector, so that the self-sealing effect of the reactor of the electric symbiotic solid oxide fuel cell on the structure is realized.
In specific implementation, in order to ensure that the reducing gas in the reducing gas channel can be smoothly diffused and transmitted to the surface of the anode functional layer to perform catalytic dehydrogenation, the porosity of the porous connector region is designed to be 15% -60%, in order to ensure mutual independence of the reducing gas channel and the oxidizing gas channel, the porosity of the compact connector region is less than 7%, and when the porosity is less than 7%, the porosity can be considered to be closed pores. Therefore, the particle size of the first precursor powder provided by the invention is 50-300 μm, and the particle size of the second precursor powder is 50-300 μm; in the first precursor powder, the mass ratio of the ceramic powder to the binder to the pore-forming agent is 65-90: 5-15: 5-20, the particle size of the ceramic powder is 0.5-10 μm, and the particle size of the pore-forming agent is 1-5 μm; in the second precursor powder, the mass ratio of the ceramic powder to the binder is 95-85: 5-10, and the particle size of the ceramic powder is 0.5-5 μm, so that the porosity of a porous connector area prepared from the second precursor powder is ensured to be between 15% and 60%.
In some embodiments, the ceramic powder is at least one of doped lanthanum titanate, doped lanthanum chromate;
the binder is at least one component of polyvinyl butyral (PVB), ethyl cellulose, polyvinylpyrrolidone (K60-K90) and polyvinyl alcohol (PVA);
the pore-forming agent is any one of graphite, starch, polymethyl methacrylate, ammonium bicarbonate and sucrose.
In the specific implementation, in order to prepare the electric symbiotic solid oxide fuel cell reactor supported by the integrated connector, the invention adopts ceramic powder with good catalysis and excellent carbon deposition resistance to prepare the connector with the supporting function (the anode layer preparation material is the same as the preparation material of the connector in the invention), so that a heterogeneous interface does not exist between the connector and the anode layer, and the connector and the anode layer have good thermal matching and structural matching properties, and the high-efficiency output and the stability of the reactor in the long-term service process can be obviously improved; the anode functional layer can play a role of itself and simultaneously can enable fuel gas to be fully catalyzed and dehydrogenated, hydrocarbon fuel ethane can be efficiently and selectively converted into ethylene at low temperature, and electric energy is generated at the same time.
In some embodiments, the method of preparing the ceramic powder comprises: any one of a solid phase method, a sol-gel method, a citric acid-nitrate combustion method, and a coprecipitation method.
In some embodiments, the oxidizing gas flow channel filler and the reducing gas flow channel filler are formed by powder press forming or die pressing and laser machining from a flow channel filler powder that is at least one of PMMA, ammonium bicarbonate, starch, sucrose, and carbon powder.
In the specific implementation, the oxidizing gas flow passage filler and the reducing gas flow passage filler which are composed of the pore-forming agent are removed at high temperature in the pre-sintering process to form a hollow oxidizing gas flow passage and a hollow reducing gas flow passage.
In some embodiments, the pressure at which the connected composite powder body is compacted ranges from 50MPa to 200 MPa.
In some embodiments, the catalytic material is one or more of doped strontium titanate and doped strontium chromate;
the proton conductor material is: BaCe 1-x Y x O 3-δ 、BaZr 1-x Y x O 3-δ And Ba (Ce, Zr) 1-y Y y O 3-δ And any one of the above, wherein x is more than or equal to 0.1 and less than or equal to 0.9, and y is more than or equal to 0.1 and less than or equal to 0.9.
In the specific implementation, the ceramic material for preparing the connector is the same as the catalytic material for forming the anode layer, so that the catalytic dehydrogenation reaction can be carried out under the action of the catalytic material in the process of diffusing and transferring a reducing gas (such as ethane) to the anode layer to generate hydrogen protons, and the proton conductor can transfer the hydrogen protons to the side of the cathode layer to react with an oxidizing gas (such as oxygen) to generate water, so that the sufficient catalytic dehydrogenation of the reducing gas is realized, the ethane serving as a hydrocarbon fuel is efficiently and selectively converted into ethylene at low temperature, and electric energy is generated at the same time.
In some embodiments, the catalytic material comprises SrTiO 3 、La 0.7 Sr 0.3 TiO and La 0.7 Sr 0.3 CrO 3 At least one component of (a);
the proton conductor material comprises BaZr 0.8 Y 0.2 O 3–δ 、BaZr 0.1 Ce 0.7 Y 0.2 O 3–δ And BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3–δ Any one of the components of (a);
the cathode slurry contains cathode powder, and the cathode powder is prepared from the following components in a mass ratio of 1:1 with La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ Or the cathode powder consists of the following components in a mass ratio of 1:1 with Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ And (4) forming.
In some embodiments, the anode paste, the electrolyte paste and the cathode paste are prepared on the green interconnector body by screen printing, the screen mesh number of the screen printing is 180-350 mesh, the squeegee speed of the screen printing is 5cm/s, and the squeegee angle of the screen printing is 55-85 ℃.
In some embodiments, the pre-sintering temperature ranges from 100 ℃ to 600 ℃ and the time ranges from 1h to 10 h;
the temperature range of the first roasting is 1350-1600 ℃, and the time is 4-6 h;
the temperature range of the second roasting is 600-1200 ℃, and the time is 4-6 h.
In a second aspect, the present invention provides a method for preparing an integrally connected body supported co-electrical solid oxide fuel cell reactor, wherein the reactor is composed of two or more than two cell reactors prepared by the method of the first aspect, and the preparation method of the reactor comprises:
and contacting and sealing the cathode of one reactor with the integrated connector of the next reactor to form the connector supported electricity symbiotic solid oxide fuel cell reactor.
When the method is specifically implemented, two or more than two prepared electric symbiotic solid oxide fuel cell stack reactors supported by the integrated connector are accumulated, then a cell stack is formed, all cells are connected through Manganese Cobalt Oxide (MCO), namely, the manganese cobalt oxide can be prepared into slurry at normal temperature, then the slurry is coated on the surface of a cathode, and then the cells are bonded layer by layer and sintered and cured to obtain the electric symbiotic solid oxide fuel cell stack reactor supported by the integrated connector.
Fig. 6 shows a schematic structural diagram of an integrated connector-supported symbiotic solid oxide fuel cell stack reactor prepared by the embodiment of the invention, and fig. 6 shows a stack reactor obtained by adding 5 single cells.
The invention adopts the electric symbiotic solid oxide fuel cell reactor supported by the integrated connector to prepare the corresponding cell stack reactor, the integrated connector prepared by the all-ceramic material can ensure that the cell stack reactor can stably run at high temperature, and meanwhile, the self-sealing characteristic of the structure can solve the sealing problem of the ceramic-supported SOFC.
In order to make the present invention more comprehensible to those skilled in the art, the following will illustrate a method for manufacturing a ceramic flat tube supported solid oxide fuel cell/electrolyzer having a self-sealing end according to the present invention by using a plurality of specific examples.
Example 1
An ammonium bicarbonate block having both flow channel shapes as shown in fig. 2 and 3 was prepared by a pressing method through a mold prepared in advance corresponding to the flow channel shape of the ammonium bicarbonate block as shown in fig. 2 and 3, and the ammonium bicarbonate block was 8cm × 8 cm. Mixing strontium titanate ceramic powder with ammonium bicarbonate and polyvinyl butyral (PVB) to obtain porous ceramic precursor powder, wherein the content of ammonium bicarbonate is 20 wt.%, and the content of PVB is 5 wt.%. Strontium titanate ceramic powder was mixed with polyvinyl butyral (PVB) to obtain a dense ceramic precursor powder with a PVB content of 5 wt.%.
Placing an ammonium bicarbonate block in a flow channel shape as shown in fig. 2 at the bottom of a 10cm × 10cm mould, laying porous ceramic precursor powder with the particle size of about 20 μm in a hole of the ammonium bicarbonate block in the flow channel shape as shown in fig. 2, and laying dense ceramic precursor powder in a region between the mould and the ammonium bicarbonate block to form a first ceramic powder layer, wherein the laying height of the porous ceramic precursor powder and the dense ceramic precursor powder is the same as the height of the ammonium bicarbonate block; further laying a layer of compact ceramic precursor powder on the first ceramic powder layer to form a second ceramic powder layer; and then placing the ammonium bicarbonate with the shape of the flow channel shown in the figure 3 on a second ceramic powder layer, continuously filling porous ceramic precursor powder into a plurality of flow channel holes of the ammonium bicarbonate with the shape of the flow channel shown in the figure 3, and filling the space between the ammonium bicarbonate block and the mold with dense ceramic precursor powder to obtain a composite powder layer filling structure system with the dense ceramic precursor powder surrounding the porous ceramic precursor powder. And pressing the structural system by using the pressure of 500MPa to form a blank body, thereby obtaining the connector blank body.
At this time, an anode functional layer and an electrolyte were formed on the surface of the green interconnector body by a screen printing method, and the green interconnector body was fired together with a support. The length of the green interconnector body may vary after firing, and therefore, the shrinkage of the green interconnector body during firing is preferably in the range of 12 to 20%, more preferably 15 to 17%. The shrinkage rate of the connector blank is too small, the shrinkage rate of the electrolyte membrane is too large, and the shrinkage rates of the electrolyte membrane and the electrolyte membrane are not matched to crack the electrolyte layer.
Specifically, the anode layer was prepared on the porous regions of the interconnect green body using a screen printing method, and the coating range was as shown in fig. 5. The main component of the anode functional layer is 50 wt% SrTiO 3 2.5 wt% of binder, 0.5 wt% of dispersant and 47 wt% of organic solvent, and SrTiO 3 Particle diameter D 50 200 nm. And (3) carrying out ball milling on the anode functional layer slurry for 24h, then carrying out screen printing to prepare the anode functional layer, wherein the mesh number of the used screen is preferably 180 meshes, the scraper speed is 5.0cm/s, the scraper angle is preferably 70 ℃, the thickness of the anode functional layer is 30 mu m, and drying at 80 ℃ after printing. The area of the anode collector layer is 8cm multiplied by 8 cm.
Specifically, an electrolyte layer was prepared on the anode functional layer using a screen printing method, and the coating range was as shown in fig. 5. The main component of the electrolyte layer was 50 wt% BaZr 0.8 Y 0.2 O 3–δ (BZY20) and 2.5% by weight of a binder, 0.5% by weight of a dispersant and 47% by weight of an organic solvent, BaZr used 0.8 Y 0.2 O 3–δ Has a particle diameter of D 50 100 nm. And performing ball milling on the electrolyte layer slurry for 24h, performing screen printing to prepare the electrolyte layer, wherein the mesh number of a screen is preferably 250 meshes, the scraper speed is 5.0cm/s, the scraper angle is preferably 70 ℃, the thickness of the electrolyte layer is 25 +/-3 mu m, and drying at 80 ℃ after printing. The electrolyte area was 8.2cm x 8.2cm and the electrolyte layer was in contact with the dense region of the interconnect edge (as shown by the positional relationship of 2-4 to 2-1 in fig. 2).
Further, the reactor intermediate is heated to 300 ℃ at the speed of 1 ℃/min by adopting a step-by-step heating method for discharging glue for 4h in the air, so as to remove the pore-forming agent ammonium bicarbonate in the reactor intermediate, and the reducing gas flow channel filling body and the oxidizing gas flow channel filling body, the glue is discharged from 300 ℃ to 600 ℃ at the heating rate of 1 ℃/min for 8h, and then the temperature is kept at 1550 ℃ for 4h in the air at the heating rate of 2 ℃/min for sintering and forming.
The main component of the cathode slurry was 60 wt% of La by the same operation as the above-described printing method of the anode functional layer 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ /BaZr 0.8 Y 0.2 O 3–δ (mass ratio 1:1), 2 wt% of binder, 0.5 wt% of dispersant and 37.5 wt% of organic solvent, printing the cathode slurry on the electrolyte, wherein the mesh number of the used silk screen is preferably 180 meshes, the scraper speed is 5.0cm/s, the scraper angle is preferably 70 ℃, the thickness of the cathode functional layer is 10 +/-3 mu m, and drying at 80 ℃. The area of the cathode is 8cm x 8 cm.
Further adopting a step-by-step heating method to heat the reactor intermediate to 300 ℃ at the temperature of 1 ℃/min for glue removal for 4h in the air, heating the reactor intermediate to 600 ℃ at the temperature of 1 ℃/min for glue removal for 8h from 300 ℃, and then keeping the temperature at 1200 ℃ at the temperature of 2 ℃/min in the air for 4h for sintering and molding.
The cathode, anode and electrolyte materials used in the present invention may be commonly used materials, but are not limited in the present invention.
Example 2
Preparing soluble starch blocks with the shape of runner as shown in figure 2 and figure 3 by pressing with a mold corresponding to the soluble starch blocks2 and 3, the soluble starch blocks in the flow passage shapes are 9cm multiplied by 18 cm. La 0.7 Sr 0.3 TiO 3 Mixing the ceramic powder with soluble starch and polyvinylpyrrolidone (K60-K90) to obtain porous ceramic precursor powder, wherein the content of soluble starch is 9 wt.% and the content of polyvinylpyrrolidone (K60-K90) is 6 wt.%. La having a particle size of about 30 μm 0.7 Sr 0.3 TiO 3 The ceramic powder was mixed with polyvinylpyrrolidone (K60-K90) to obtain a dense ceramic precursor powder with a polyvinylpyrrolidone (K60-K90) content of 6 wt.%.
Placing a soluble starch block in a flow channel shape shown in figure 2 at the bottom of a 10cm x 20cm mould, laying porous ceramic precursor powder in a hole of the soluble starch block in the flow channel shape shown in figure 2, and laying dense ceramic precursor powder in an area between the mould and the soluble starch block to form a first ceramic powder layer; wherein the laying height of the porous ceramic precursor powder and the compact ceramic precursor powder is the same as the height of the soluble starch block; further laying a layer of compact ceramic precursor powder on the first ceramic powder layer to form a second ceramic powder layer; then placing the soluble starch with the shape of the runner as shown in the figure 3 on a second ceramic powder layer, continuously filling porous ceramic precursor powder into a plurality of runner holes of a soluble starch block with the shape of the runner as shown in the figure 3, and filling compact ceramic precursor powder into a space between the soluble starch block and a mold to obtain a composite powder layer filling structure system of the compact ceramic precursor powder surrounding the porous ceramic precursor powder; and pressing the structural system by using the pressure of 300MPa to form a blank body, thereby obtaining the connector blank body.
Further, an anode layer and an electrolyte layer were formed on the surface of the green body by a screen printing method, and fired together with the support. The length of the green interconnector body may vary after firing, and therefore, the shrinkage of the green interconnector body during firing is preferably in the range of 12 to 20%, more preferably 15 to 17%. The shrinkage rate of the connector blank is too small, the shrinkage rate of the electrolyte membrane is too large, and the shrinkage rates of the two are not matched to crack the electrolyte layer.
Specifically, the anode functional layer was prepared on the porous region of the interconnect green body using a screen printing method, and the coating range was as shown in fig. 5. The main component of the anode functional layer is 50 wt% of La 0.7 Sr 0.3 TiO 3 2.5 wt% of a binder, 0.5 wt% of a dispersant and 47 wt% of an organic solvent, La used 0.7 Sr 0.3 TiO 3 Particle diameter D 50 200 nm. And (3) carrying out ball milling on the slurry of the anode functional layer for 24h, then carrying out screen printing to prepare the anode functional layer, wherein the mesh number of the used screen is preferably 180 meshes, the scraper speed is 5.0cm/s, the scraper angle is preferably 70 ℃, the thickness of the anode functional layer is 30 mu m, and drying at 80 ℃ after printing. The area of the anode functional layer is 9cm multiplied by 18 cm.
Specifically, an electrolyte layer was prepared on the anode functional layer using a screen printing method, and the coating range was as shown in fig. 5. The main component of the electrolyte layer was 50 wt% BaZr 0.1 Ce 0.7 Y 0.2 O 3–δ (BZCY) and 2.5 wt% of binder, 0.5 wt% of dispersant and 47 wt% of organic solvent, and BaZr 0.1 Ce 0.7 Y 0.2 O 3–δ Has a particle diameter of D 50 100 nm. And performing ball milling on the electrolyte layer slurry for 24 hours, performing screen printing to prepare the electrolyte layer, wherein the mesh number of a used screen is preferably 300, the speed of a scraper is 5.0cm/s, the angle of the scraper is preferably 70 ℃, the thickness of the electrolyte layer is 15 +/-3 mu m, and drying at 80 ℃ after printing. The electrolyte area was 9.2cm x 18.2cm and the electrolyte layer was in contact with the dense region of the interconnect edge (as shown by the positional relationship of 2-4 to 2-1 in fig. 2).
Further, the reactor intermediate is heated to 300 ℃ at the speed of 1 ℃/min by adopting a step-by-step heating method for discharging glue for 4h in the air, pore-forming agent soluble starch in the reactor blank body, including fuel gas and oxidizing gas runner filling bodies, is removed from 300 ℃ at the heating speed of 1 ℃/min to 600 ℃ for discharging glue for 8h, and then is subjected to heat preservation in the air at the temperature of 1500 ℃ at the heating speed of 2 ℃/min for 4h, and then is sintered and molded.
The main component of the cathode slurry was 60 wt% of La by the same operation as the above-described printing method of the anode functional layer 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ /BaZr 0.1 Ce 0.7 Y 0.2 O 3–δ (mass ratio 1:1), 2 wt% of binder, 0.5 wt% of dispersant and 37.5 wt% of organic solvent, printing the cathode slurry on the electrolyte, wherein the mesh number of the used silk screen is preferably 180 meshes, the scraper speed is 5.0cm/s, the scraper angle is preferably 70 ℃, the thickness of the cathode functional layer is 30 +/-3 mu m, and drying at 80 ℃. The area of the cathode is 9cm x 18 cm.
Further, a step-by-step heating method is adopted, the reactor intermediate is heated to 300 ℃ at the speed of 1 ℃/min for 4h, the temperature is raised to 600 ℃ at the speed of 1 ℃/min from 300 ℃ for 8h, and then the reactor intermediate is subjected to heat preservation at the temperature of 1200 ℃ for 4h in the air and is sintered and molded.
The cathode, anode and electrolyte materials used in the present invention may be any commonly used materials, but are not limited thereto.
Example 3
Two kinds of polymethyl methacrylate (PMMA) blocks of flow channel shapes as shown in fig. 2 and 3 were prepared in advance by molding and laser processing, and the PMMA block was 12cm × 12 cm. La 0.7 Sr 0.3 CrO 3 Mixing the ceramic powder with PMMA and polyvinyl alcohol (PVA) to obtain porous ceramic precursor powder, wherein the content of PMMA is 9 wt%, and the content of PVA is 4 wt%. La having a particle size of about 30 μm 0.7 Sr 0.3 CrO 3 The ceramic powder was mixed with polyvinyl alcohol (PVA) to give a dense ceramic precursor powder with a PVB content of 4 wt.%.
Placing a PMMA block in the shape of a flow channel in the figure 2 at the bottom of a mould of 15cm multiplied by 15cm, paving porous ceramic precursor powder with the particle size of about 20 mu m in a hole of the PMMA block in the shape of the flow channel in the figure 2, and paving compact ceramic precursor powder in a region between the mould and the PMMA block to form a first ceramic powder layer; wherein the laying height of the porous ceramic precursor powder and the compact ceramic precursor powder is the same as the height of the PMMA block; further laying a layer of compact ceramic precursor powder on the first ceramic powder layer to form a second ceramic powder layer; and then placing the PMMA with the shape of the flow channel shown in the figure 3 on a second ceramic powder layer, continuously filling porous ceramic precursor powder into a plurality of flow channel holes of the PMMA with the shape of the flow channel shown in the figure 3, and filling the space between the PMMA block body and the mold with compact ceramic precursor powder to obtain a composite powder layer filling structure system with the compact ceramic precursor powder surrounding the porous ceramic precursor powder. And pressing the structural system by using the pressure of 200MPa to form a blank body, thereby obtaining the connector blank body.
At this time, an anode functional layer and an electrolyte were formed on the surface of the green interconnector body by a screen printing method, and the green interconnector body was fired together with a support. The length of the green interconnector body may vary after firing, and therefore, the shrinkage of the green interconnector body during firing is preferably in the range of 12 to 20%, more preferably 15 to 17%. The shrinkage rate of the connector blank is too small, the shrinkage rate of the electrolyte membrane is too large, and the shrinkage rates of the electrolyte membrane and the electrolyte membrane are not matched to crack the electrolyte layer.
Specifically, the anode functional layer was prepared on the porous region of the interconnect green body using a screen printing method, and the coating range was as shown in fig. 5. The main component of the anode functional layer is 50 wt% of La 0.7 Sr 0.3 CrO 3 2.5 wt% of a binder, 0.5 wt% of a dispersant and 47 wt% of an organic solvent, La used 0.7 Sr 0.3 CrO 3 Particle diameter D 50 200 nm. And (3) carrying out ball milling on the anode functional layer slurry for 24h, then carrying out screen printing to prepare the anode functional layer, wherein the mesh number of the used screen is preferably 180 meshes, the scraper speed is 5.0cm/s, the scraper angle is preferably 70 ℃, the thickness of the anode functional layer is 30 mu m, and drying at 80 ℃ after printing. The area of the anode collector layer is 12cm multiplied by 12 cm.
Specifically, an electrolyte layer was prepared on the anode functional layer using a screen printing method, and the coating range was as shown in fig. 5. The main component of the electrolyte layer was 50 wt% BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3–δ (BZCYb) 2.5 wt% binder, 0.5 wt% dispersant and 47 wt% organic solvent, BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3–δ Has a particle diameter of D 50 100 nm. The electrolyte layer slurry can be subjected to silk-screen printing to prepare an electrolyte layer after ball milling for 24 hours, and the used silkThe mesh number is preferably 350 mesh, the doctor blade speed is 5.0cm/s, the doctor blade angle is preferably 70 ℃, the electrolyte layer thickness is 15 +/-3 μm, and drying is carried out at 80 ℃ after printing is finished. The electrolyte area was 12.2cm by 12.2cm and the electrolyte layer was in contact with the dense region of the interconnect edge (as shown by the positional relationship of 2-4 to 2-1 in fig. 2).
Further, a step-by-step heating method is adopted, the reactor intermediate is heated to 300 ℃ at the speed of 1 ℃/min for rubber removal for 4h in the air, the pore-forming agent PMMA in the reactor blank is removed, the filler comprises a fuel gas and oxidizing gas flow channel filler, the temperature is raised to 600 ℃ from 300 ℃ at the speed of 1 ℃/min for rubber removal for 8h, and then the temperature is maintained at 1600 ℃ at the speed of 2 ℃/min in the air for 4h for sintering and forming.
The main component of the cathode slurry was 60 wt% of La by the same operation as the above-described printing method of the anode functional layer 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ /BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3–δ (mass ratio 1:1), 2 wt% of binder, 0.5 wt% of dispersant and 37.5 wt% of organic solvent, printing the cathode slurry on the electrolyte, wherein the mesh number of the used silk screen is preferably 180 meshes, the scraper speed is 5.0cm/s, the scraper angle is preferably 70 ℃, the thickness of the cathode functional layer is 30 +/-3 mu m, and drying at 80 ℃. The cathode area was 12cm by 12 cm.
Further, a step-by-step heating method is adopted, the reactor intermediate is heated to 300 ℃ at the speed of 1 ℃/min for 4h, the temperature is raised to 600 ℃ at the speed of 1 ℃/min from 300 ℃ for 8h, and then the reactor intermediate is subjected to heat preservation at the temperature of 1200 ℃ for 4h in the air and is sintered and molded.
The cathode, anode and electrolyte materials used in the present invention may be any commonly used materials, but are not limited thereto.
Example 4
The carbon powder blocks with two runner shapes as shown in fig. 2 and fig. 3 are prepared in advance by adopting a die pressing sintering mode, and the ammonium bicarbonate blocks are 18cm x 18cm ammonium bicarbonate blocks. La with the particle size of 80 mu m 0.75 Sr 0.25 Cr 0.5 Mn 0.5 O 3 (LSCM) ceramic powder was mixed with carbon powder, polyvinyl alcohol (PVA) to obtain porous ceramic precursor powder, wherein the carbon powder content was 20 wt.%, and the PVB content was 2 wt.%. La having a particle size of about 10 μm 0.75 Sr 0.25 Cr 0.5 Mn 0.5 O 3 The ceramic powder was mixed with polyvinyl alcohol (PVA) to obtain a dense ceramic precursor powder with a PVB content of 2 wt.%.
Placing the carbon powder block with the shape of the flow channel shown in the figure 2 at the bottom of a 20cm multiplied by 20cm mould, laying porous ceramic precursor powder with the particle size of about 20 mu m in the hole of the carbon powder block with the shape of the flow channel shown in the figure 2, and laying dense ceramic precursor powder in the area between the mould and the carbon powder block to form a first ceramic powder layer, wherein the laying heights of the porous ceramic precursor powder and the dense ceramic precursor powder are the same as the height of the carbon powder block; further laying a layer of compact ceramic precursor powder on the first ceramic powder layer to form a second ceramic powder layer; and continuously filling porous ceramic precursor powder into a plurality of flow channel holes of the carbon powder block body with the flow channel shape as shown in figure 3, and filling the space between the carbon powder block body and the mould with compact ceramic precursor powder to obtain a composite powder layer filling structure system with the compact ceramic precursor powder surrounding the porous ceramic precursor powder. And pressing the structural system by using the pressure of 100MPa to form a blank body, thereby obtaining the integrated connector blank body.
At this time, an anode functional layer, an anode, and an electrolyte were formed on the surface of the green interconnector by a screen printing method, and the green interconnector was fired together with a support. The length of the green interconnector body may vary after firing, and therefore, the shrinkage of the green interconnector body during firing is preferably in the range of 12 to 20%, more preferably 15 to 17%. The shrinkage rate of the connector blank is too small, the shrinkage rate of the electrolyte membrane is too large, and the shrinkage rates of the electrolyte membrane and the electrolyte membrane are not matched to crack the electrolyte layer.
Specifically, the method of screen printing was used to prepare the anode functional layer on the porous regions of the green interconnector body, and the application range is shown in fig. 5. The main component of the anode functional layer is 50 wt% of La 0.75 Sr 0.25 Cr 0.5 Mn 0.5 O 3 2.5 wt% of binder, 0.5 wt%Dispersant and 47 wt% organic solvent, La used 0.75 Sr 0.25 Cr 0.5 Mn 0.5 O 3 Particle diameter D 50 200 nm. And (3) carrying out ball milling on the anode functional layer slurry for 24h, then carrying out screen printing to prepare the anode functional layer, wherein the mesh number of the used screen is preferably 180 meshes, the scraper speed is 5.0cm/s, the scraper angle is preferably 70 ℃, the thickness of the anode functional layer is 30 mu m, and drying at 80 ℃ after printing. The area of the anode collector layer is 18cm multiplied by 18 cm.
Specifically, an electrolyte layer was prepared on the anode functional layer using a screen printing method, and the coating range was as shown in fig. 5. The main component of the electrolyte layer was 50 wt% BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3–δ (BZCYb) 2.5 wt% binder, 0.5 wt% dispersant and 47 wt% organic solvent, BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3–δ Has a particle diameter of D 50 100 nm. And performing ball milling on the electrolyte layer slurry for 24h, performing screen printing to prepare the electrolyte layer, wherein the mesh number of a screen is 350 meshes, the scraper speed is 5.0cm/s, the scraper angle is 70 ℃, the thickness of the electrolyte layer is 15 +/-3 mu m, and drying at 80 ℃ after printing. The electrolyte area was 18.2cm x 18.2cm and the electrolyte layer was in contact with the dense region of the interconnect edge (as shown by the positional relationship of 2-4 to 2-1 in fig. 2).
Further, the reactor intermediate is heated to 300 ℃ at the speed of 1 ℃/min by adopting a step-by-step heating method for rubber removal for 4h in air, pore-forming agent carbon powder in a reactor blank is removed, the pore-forming agent carbon powder comprises fuel gas and oxidizing gas flow passage filling bodies, the rubber removal is carried out for 8h from 300 ℃ at the heating speed of 1 ℃/min to 600 ℃, and then the temperature is kept at 1550 ℃ for 4h in air at the heating speed of 2 ℃/min for sintering and forming.
The main component of the cathode paste was 60 wt% of Ba by the same operation as the printing method of the anode functional layer described above 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ /BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3–δ (mass ratio 1:1), 2 wt% of a binder, 0.5 wt% of a dispersant and 37.5 wt% of an organic solvent, and printing a cathode over the electrolyteThe slurry, the mesh number of the used silk screen is preferably 180 meshes, the speed of the scraper is 5.0cm/s, the angle of the scraper is preferably 70 ℃, the thickness of the cathode functional layer is 30 +/-3 mu m, and the slurry is dried at 80 ℃. The area of the cathode is 18cm x 18 cm.
Further, the reactor intermediate is heated to 300 ℃ at the speed of 1 ℃/min for glue removal for 4h by adopting a step-by-step heating method, the temperature is raised to 600 ℃ at the speed of 1 ℃/min from 300 ℃ for glue removal for 8h, and then the reactor intermediate is subjected to heat preservation at 1200 ℃ for 4h in the air at the speed of 2 ℃/min for sintering and forming.
The above detailed description of the method for manufacturing an integrally connected supported co-existing sofc/cell stack reactor according to the present invention is provided, and the specific examples are used herein to illustrate the principles and embodiments of the present invention, and the above description of the examples is only used to help understanding the method of the present invention and its core concept; 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. A method of making an integrally connected supported symbiotic solid oxide fuel cell reactor, said method comprising:
placing an oxidation gas flow channel filling body in the middle area of the bottom of a mold, laying first precursor powder in a hole of the oxidation gas flow channel filling body, and laying second precursor powder between the edge of the bottom of the mold and the oxidation gas flow channel filling body to form a first ceramic powder layer; wherein the laying height of the first precursor powder and the second precursor powder is the same as the height of the oxidizing gas flow channel filling body;
further, laying a second precursor powder on the first ceramic powder layer to form a second ceramic powder layer;
further, a reducing gas flow channel filling body is placed in the middle area above the second ceramic powder layer, first precursor powder is laid in a hole of the reducing gas flow channel filling body, and second precursor powder is laid between the edge of the mold and the reducing gas flow channel filling body to form a connector composite powder body; wherein the laying heights of the first precursor powder and the second precursor powder are the same and are greater than the height of the reducing gas flow channel filling body; the first precursor powder has a placement area greater than 90% of the placement area of the first and second precursor powders;
further, pressing the connector composite powder body to obtain a connector green body;
further, anode slurry and electrolyte slurry are respectively printed on the upper surface of the connecting body blank, and are dried and cured to form a first semi-finished product of the solid oxide fuel cell reactor supported by the connecting body;
further, pre-burning and first roasting the first semi-finished product of the solid oxide fuel cell reactor supported by the connector to obtain a second semi-finished product of the solid oxide fuel cell reactor supported by the connector;
further, printing cathode slurry on the electrolyte layer of the second semi-finished solid oxide fuel cell reactor supported by the connector to form a third semi-finished solid oxide fuel cell reactor supported by the connector;
further, performing second roasting on the third semi-finished product of the solid oxide fuel cell reactor supported by the connector to obtain an integrated connector-supported electric symbiotic solid oxide fuel cell reactor;
the first precursor powder is obtained by mixing ceramic powder, a pore-forming agent and a binder, and the second precursor powder is obtained by mixing ceramic powder and the binder;
the anode slurry contains anode powder, and the anode powder is a catalytic material capable of catalyzing the dehydrogenation and oxidation of the hydrocarbon fuel;
the electrolyte slurry contains electrolyte powder, and the electrolyte powder is a proton conductor material.
2. The method according to claim 1, wherein the first precursor powder has a particle size of 50 μ ι η to 300 μ ι η, and the second precursor powder has a particle size of 50 μ ι η to 300 μ ι η;
in the first precursor powder, the mass ratio of the ceramic powder to the binder to the pore-forming agent is 65-90: 5-15: 5-20, the particle size of the ceramic powder is 0.5-10 μm, and the particle size of the pore-forming agent is 1-5 μm;
in the second precursor powder, the mass ratio of the ceramic powder to the binder is 95-85: 5-10, and the particle size of the ceramic powder is 0.5-5 μm.
3. The method of claim 1, wherein the ceramic powder is at least one of doped lanthanum titanate, doped lanthanum chromate;
the binder is at least one component of polyvinyl butyral (PVB), ethyl cellulose, polyvinylpyrrolidone (K60-K90) and polyvinyl alcohol (PVA);
the pore-forming agent is any one of graphite, starch, polymethyl methacrylate, ammonium bicarbonate and sucrose.
4. The method of claim 1, wherein the catalytic material is at least one of doped strontium titanate and doped strontium chromate;
the proton conductor material is: BaCe 1-x Y x O 3-δ 、BaZr 1-x Y x O 3-δ And Ba (Ce, Zr) 1-y Y y O 3-δ And any one of the above, wherein x is more than or equal to 0.1 and less than or equal to 0.9, and y is more than or equal to 0.1 and less than or equal to 0.9.
5. The method of claim 1, wherein the catalytic material comprises SrTiO 3 、La 0.7 Sr 0.3 TiO and La 0.7 Sr 0.3 CrO 3 At least one component of (a);
the proton conductor material comprises BaZr 0.8 Y 0.2 O 3–δ 、BaZr 0.1 Ce 0.7 Y 0.2 O 3–δ And BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3–δ Any one of the components of (a);
the cathode slurry contains cathode powder, and the cathode powder is prepared from the following components in a mass ratio of 1:1 with La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ Or the cathode powder consists of the following components in a mass ratio of 1:1 with Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ And (4) forming.
6. The method of claim 1 wherein the oxidizing gas flow channel fill and the reducing gas flow channel fill are powder press formed or die pressed and laser machined from a flow channel fill powder that is at least one of PMMA, ammonium bicarbonate, starch, sucrose, and carbon powder.
7. The method of claim 1, wherein the pressure at which the connected composite powder body is compacted ranges from 50MPa to 200 MPa.
8. The method as claimed in claim 1, wherein the anode paste, the electrolyte paste and the cathode paste are prepared on the green interconnector body by screen printing, the mesh number of the screen printing is 180-350 meshes, the squeegee speed of the screen printing is 5cm/s, and the squeegee angle of the screen printing is 55-85 ℃.
9. The method of claim 1, wherein the pre-sintering is performed at a temperature ranging from 100 ℃ to 600 ℃ for 1h to 10 h;
the temperature range of the first roasting is 1350-1600 ℃, and the time is 4-6 h;
the temperature range of the second roasting is 600-1200 ℃, and the time is 4-6 h.
10. A method of making an integrally connected supported symbiotic solid oxide fuel cell reactor comprising two or more reactors prepared according to the method of any one of claims 1 to 9, the method comprising:
and contacting and sealing the cathode of one cell reactor with the integrated connector of the next cell reactor to form the connector supported electricity symbiotic solid oxide fuel cell stack reactor.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024061382A1 (en) * | 2023-04-12 | 2024-03-28 | 广东省科学院新材料研究所 | Anti-carbon-deposition self-sealing electricity-gas symbiotic solid oxide fuel cell structure |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050095483A1 (en) * | 2003-11-03 | 2005-05-05 | Korea Institute Of Energy Research | Anode-supported flat-tubular solid oxide fuel cell stack and fabrication method of the same |
| KR20170038553A (en) * | 2015-09-30 | 2017-04-07 | 한국전력공사 | Ceramic interconnects and method of manufacturing the same |
| EP3166167A1 (en) * | 2015-11-03 | 2017-05-10 | Institute of Nuclear Energy Research, Atomic Energy Council, Executive Yuan | Permeable metal substrate, metal-supported solid oxide fuel cell and their manufacturing methods |
| KR101892909B1 (en) * | 2017-05-11 | 2018-08-29 | 한국과학기술연구원 | A method for manufacturing protonic ceramic fuel cells |
| WO2019112115A1 (en) * | 2017-12-04 | 2019-06-13 | 한국전력공사 | Method of manufacturing support-type ceramic connecting material and support-type ceramic connecting material manufactured thereby |
| CN110880611A (en) * | 2019-11-22 | 2020-03-13 | 锐菁源(成都)科技有限公司 | Anode supporting plate type solid oxide fuel cell structure and preparation process thereof |
| CN111403768A (en) * | 2020-03-31 | 2020-07-10 | 西安交通大学 | Integrated structure, battery/electrolytic cell and preparation method of battery stack |
| CN111403767A (en) * | 2020-03-31 | 2020-07-10 | 西安交通大学 | Solid oxide fuel cell/electrolyzer and stack structure |
| CN112397752A (en) * | 2020-11-12 | 2021-02-23 | 济南大学 | Improved electric symbiosis electrochemical reactor and preparation method thereof |
-
2022
- 2022-05-26 CN CN202210581376.0A patent/CN114976102A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050095483A1 (en) * | 2003-11-03 | 2005-05-05 | Korea Institute Of Energy Research | Anode-supported flat-tubular solid oxide fuel cell stack and fabrication method of the same |
| KR20170038553A (en) * | 2015-09-30 | 2017-04-07 | 한국전력공사 | Ceramic interconnects and method of manufacturing the same |
| EP3166167A1 (en) * | 2015-11-03 | 2017-05-10 | Institute of Nuclear Energy Research, Atomic Energy Council, Executive Yuan | Permeable metal substrate, metal-supported solid oxide fuel cell and their manufacturing methods |
| KR101892909B1 (en) * | 2017-05-11 | 2018-08-29 | 한국과학기술연구원 | A method for manufacturing protonic ceramic fuel cells |
| WO2019112115A1 (en) * | 2017-12-04 | 2019-06-13 | 한국전력공사 | Method of manufacturing support-type ceramic connecting material and support-type ceramic connecting material manufactured thereby |
| CN110880611A (en) * | 2019-11-22 | 2020-03-13 | 锐菁源(成都)科技有限公司 | Anode supporting plate type solid oxide fuel cell structure and preparation process thereof |
| CN111403768A (en) * | 2020-03-31 | 2020-07-10 | 西安交通大学 | Integrated structure, battery/electrolytic cell and preparation method of battery stack |
| CN111403767A (en) * | 2020-03-31 | 2020-07-10 | 西安交通大学 | Solid oxide fuel cell/electrolyzer and stack structure |
| CN112397752A (en) * | 2020-11-12 | 2021-02-23 | 济南大学 | Improved electric symbiosis electrochemical reactor and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| GAO, Y等: "Impact of ionomer film on effective transport properties and performance of cathode catalyst layer of proton-exchange membrane fuel cells", 《IONICS》, vol. 26, no. 07, 14 March 2020 (2020-03-14), pages 3425 - 3435, XP037161691, DOI: 10.1007/s11581-020-03524-6 * |
| 安雷;张玢;郜建全;赵文广;安胜利;: "固体氧化物燃料电池La_(0.7)Sr_(0.3)Cr_(0.5)Mn_(0.5)O_(3-δ)-SDC复合阳极性能研究", 稀土, vol. 34, no. 03, 15 June 2013 (2013-06-15), pages 11 - 16 * |
| 樊赟等: "乙烷脱氢共生电能-增值化学品固体氧化物燃料电池研究进展", 《电化学》, vol. 26, no. 2, pages 243 - 252 * |
| 陈旭等: "等离子喷涂钛酸锶镧/金属复合涂层组织结构及性能的研究", 《热喷涂技术》, vol. 13, no. 02, 15 June 2021 (2021-06-15), pages 1 - 9 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024061382A1 (en) * | 2023-04-12 | 2024-03-28 | 广东省科学院新材料研究所 | Anti-carbon-deposition self-sealing electricity-gas symbiotic solid oxide fuel cell structure |
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