CN114976102B - Preparation method of integrated connector supported electric symbiotic solid oxide fuel cell/cell stack reactor - Google Patents
Preparation method of integrated connector supported electric symbiotic solid oxide fuel cell/cell stack reactor Download PDFInfo
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- CN114976102B CN114976102B CN202210581376.0A CN202210581376A CN114976102B CN 114976102 B CN114976102 B CN 114976102B CN 202210581376 A CN202210581376 A CN 202210581376A CN 114976102 B CN114976102 B CN 114976102B
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- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 22
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- 229910002939 BaZr0.8Y0.2O3−δ Inorganic materials 0.000 claims description 6
- 229910002132 La0.6Sr0.4Co0.2Fe0.8O3-δ Inorganic materials 0.000 claims description 6
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- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 6
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- DTDCCPMQHXRFFI-UHFFFAOYSA-N dioxido(dioxo)chromium lanthanum(3+) Chemical compound [La+3].[La+3].[O-][Cr]([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Cr]([O-])(=O)=O DTDCCPMQHXRFFI-UHFFFAOYSA-N 0.000 claims description 3
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- 230000031068 symbiosis, encompassing mutualism through parasitism Effects 0.000 description 1
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Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Fuel Cell (AREA)
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: pore formers with different flow channel shapes are designed and prepared, then powder is paved layer by layer, and then a self-sealing integrated connector blank structure is pressed by using a compression molding method. And sequentially printing anode slurry, electrolyte slurry and cathode slurry on the porous area on the upper surface of the connector blank by utilizing a screen printing mode, so that the anode covers the porous area on the upper surface of the connector, the electrolyte covers the anode functional layer, and then the self-sealing battery reactor is prepared through presintering, glue discharging, roasting, shrinkage forming and the like. The preparation method of the invention 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 commercialization and 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 electric 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 in the conversion process. Unlike traditional Solid Oxide Fuel Cells (SOFCs) which only generate and supply power, an electric energy-value added chemical symbiotic SOFC is a special fuel cell reactor, and can generate power and obtain valuable chemicals. Compared with other reactors, the symbiotic SOFC reactor provides internal reforming conditions, has small polarization resistance, higher utilization rate of fuel gas, stable output of electric energy and the like. Therefore, in recent years, research on the cell structure and the composition of the symbiotic SOFC is active, and the fuel gas is selected more abundantly, so that the research of the symbiotic SOFC has practical value.
By constructing an symbiotic proton conductor SOFC, ethane is subjected to selective oxidative conversion at the anode side instead of complete oxidation, not only can power generation be realized under the condition of no CO 2 emission, but also value-added chemical ethylene can be obtained. In addition, the proton conductor electrolyte has higher ionic conductivity than the oxygen ion conductor electrolyte, and can be operated at medium and low temperatures. Further, since the fuel electrode does not generate water, the fuel circulation is not required.
However, most of the research on proton conductor SOFC symbiotic reactors at present is focused on the development and design of functional layer materials, especially anode materials, and little research on the structure and preparation method of the proton conductor SOFC symbiotic reactors is available. Thus, researchers are urgently required to develop a method of preparing a reactor for electrical symbiosis.
Disclosure of Invention
In order to solve the problems in the related art, the application provides a preparation method of an integrated connector-supported electric symbiotic solid oxide fuel cell/cell stack reactor, which can effectively simplify the preparation process of the reactor and improve the preparation efficiency of the reactor, and the specific contents are as follows:
In a first aspect, the present invention provides a method of making an integrated connector supported electrical co-occurrence solid oxide fuel cell reactor, the method comprising:
Placing an oxidizing gas flow channel filling body in the middle area of the bottom of a die, 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 die 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 passage filling body;
Further, laying a second precursor powder on the first ceramic powder layer to form a second ceramic powder layer;
Further, placing a reducing gas flow passage filling body in an intermediate area above the second ceramic powder layer, laying first precursor powder into holes of the reducing gas flow passage filling body, and laying second precursor powder between the edge of the die and the reducing gas flow passage filling body; the first precursor powder and the second precursor powder are identical in laying height and larger than the reducing gas runner filling body; the first precursor powder has a lay-up area greater than 90% of the lay-up area of the first precursor powder and the second precursor powder;
further, pressing the connector composite powder body to obtain a connector blank;
Further, anode slurry and electrolyte slurry are respectively printed on the upper surface of the connector blank, and are dried and solidified to form a first semi-finished product of the solid oxide fuel cell reactor supported by the connector;
Further, presintering and first roasting are carried out on the first semi-finished product of the solid oxide fuel cell reactor supported by the connector, so as 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 product of the solid oxide fuel cell reactor supported by the connecting body to form a third semi-finished product of the solid oxide fuel cell reactor supported by the connecting body;
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 a binder;
the anode slurry comprises anode powder which is a catalytic material capable of catalyzing hydrocarbon fuel to perform dehydrogenation oxidation;
the electrolyte slurry includes an electrolyte powder that is a proton conductor material.
Alternatively, the method according to claim 1, wherein the first precursor powder has a particle size of 50 μm to 300 μm and the second precursor powder has a particle size of 50 μm to 300 μm;
wherein, in the first precursor powder, the mass ratio of the ceramic powder, the binder and the pore-forming agent is 65-90:5-15:5-20, the particle size of the ceramic powder is 0.5-10 mu m, and the particle size of the pore-forming agent is 1-5 mu m;
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 mu m.
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), ethylcellulose, 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 as follows: baCe 1-xYxO3-δ、BaZr1-xYxO3-δ, and Ba (Ce, zr) 1-yYyO3-δ, wherein x is equal to or more than 0.1 and equal to or less than 0.9, and y is equal to or more than 0.1 and equal to or less than 0.9.
Optionally, the catalytic material comprises at least one component of SrTiO 3、La0.7Sr0.3 TiO and La 0.7Sr0.3CrO3;
the proton conductor material includes any one of components BaZr 0.8Y0.2O3–δ、BaZr0.1Ce0.7Y0.2O3–δ and BaZr 0.1Ce0.7Y0.1Yb0.1O3–δ;
The cathode slurry comprises cathode powder, wherein the cathode powder comprises the following components in percentage by mass: 1 with La 0.6Sr0.4Co0.2Fe0.8O3-δ, or the cathode powder consists of the following components in mass ratio 1: 1. is composed of Ba 0.5Sr0.5Co0.8Fe0.2O3-δ and electrolyte powder.
Optionally, the oxidizing gas runner filling body and the reducing gas runner filling body are formed by powder pressing or mould pressing and laser processing of runner filling body powder, and the runner filling body powder is at least one of PMMA, ammonium bicarbonate, starch, sucrose and carbon powder.
Optionally, the pressure value range of pressing the connector composite powder body is 50-200 MPa.
Optionally, the catalytic material is one or more of doped strontium titanate and doped strontium chromate;
the proton conductor material includes: baCe 1-xYxO3-δ、BaZr1-xYxO3-δ, and Ba (Ce, zr) 1-yYyO3-δ, wherein x is equal to or more than 0.1 and equal to or less than 0.9, and y is equal to or more than 0.1 and equal to or less than 0.9.
Optionally, the anode paste, the electrolyte paste and the cathode paste are prepared on the connector blank by screen printing, wherein the mesh number of the screen printing is 180-350 mesh, the scraper speed of the screen printing is 5cm/s, and the scraper angle of the screen printing is 55-85 ℃.
Optionally, the presintering temperature ranges from 100 ℃ to 600 ℃ and the presintering time ranges from 1h to 10h;
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 integrated connector-supported electric symbiotic solid oxide fuel cell stack reactor, the cell stack reactor is composed of two or more cell reactors prepared by the method in the second aspect, and the preparation method of the cell stack reactor comprises the following steps:
The cathode of one cell reactor is contacted and sealed with the integrated connector of the next cell reactor to form a connector supported electrosymbiotic solid oxide fuel cell reactor.
Compared with the related art, the preparation method of the integrated connector-supported electric symbiotic solid oxide fuel cell/cell stack reactor has at least the following advantages:
1. In the integrated connector-supported electric symbiotic solid oxide fuel cell reactor 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 of difficult sealing of the ceramic connector, simplify the sealing process of the solid oxide fuel cell reactor and improve the long-term operation stability. In addition, the ceramic anode material with good catalytic performance and excellent carbon deposition resistance is adopted to prepare the connector with the supporting function, so that a heterogeneous interface between the connector and the anode layer is avoided, the thermal matching and the structural matching are good, and the high-efficiency output and the stability of the reactor in the long-term service process can be obviously improved; the connector can fully catalyze and dehydrogenate fuel gas while playing its own role, and can efficiently and selectively convert ethane into ethylene at low temperature and generate electric energy.
2. According to the invention, the integrated connector green body structure with the self-sealing structure characteristic is pressed by optimizing the particle size ratio of the connector powder, the content regulation and control of pore-forming agents and the powder laying sequence design and combining a die. And sequentially printing anode slurry, electrolyte slurry and cathode slurry on the upper surface of the connector blank by utilizing a screen printing mode, and roasting to obtain the battery reactor with self-sealing effect. The preparation method provided by the invention can prepare the battery reactor with the self-sealing function, effectively simplifies the manufacturing process of the electric appliance symbiotic battery reactor, reduces the sealing workload of the battery reactor, is beneficial to reducing the manufacturing cost of the battery and promotes the commercialized popularization of the solid oxide battery.
3. The full ceramic solid oxide fuel cell/cell stack reactor prepared by the preparation method has the advantages of good structural chemical stability, good heat and corrosion resistance, capability of running at a high temperature of more than 800 ℃ and excellent reactor output performance.
Drawings
In order to more clearly illustrate the embodiments of the application or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 illustrates a flow chart of a method of making an integrated connector supported electrical co-occurrence solid oxide fuel cell reactor made in accordance with an embodiment of the present invention;
FIG. 2 is a schematic structural view showing an oxidizing gas flow channel filler prepared by an embodiment of the present invention;
FIG. 3 is a schematic structural view showing a reducing gas flow passage filling body prepared by an embodiment of the present invention;
FIG. 4 shows a schematic structural diagram of a connector prepared according to an embodiment of the present invention;
FIG. 5 illustrates a schematic structural view of an integrated connector supported electrical co-occurrence solid oxide fuel cell stack reactor prepared in accordance with an embodiment of the present invention;
Fig. 6 shows a schematic structural diagram of a connector supported integrated electrical symbiotic solid oxide fuel cell stack reactor prepared in accordance with an embodiment of the present invention.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
Specific experimental steps or conditions are not noted in the examples and may be performed in accordance with the operation or conditions of conventional experimental steps described in the prior art in the field. The reagents used, as well as other instruments, are conventional reagent products available commercially, without the manufacturer's knowledge.
Ethylene, the most produced organic compound worldwide, is generally obtained by thermally cracking hydrocarbons in high temperature steam with high energy consumption. Catalytic dehydrogenation of ethane to an endothermic process requires the combustion of a large amount of hydrocarbon fuel to supplement heat thereto, which in turn generates CO 2 greenhouse gases, thus, due to limitations in its high heat absorption, carbon deposition and thermodynamic equilibrium, researchers are motivated to seek a more efficient, safe and environmentally friendly method to increase ethane conversion efficiency. Partial oxidative dehydrogenation of ethane converts the endothermic process of catalytic dehydrogenation of ethane into an exothermic oxidation reaction, thereby having a greater thermodynamic driving force for the reaction and enabling the reaction to be operated at a lower temperature. The exothermic nature of the partial oxidative dehydrogenation of ethane and the lower operating temperature requirements, compared to conventional steam cracking catalysts, can save more than 30% of energy, but under oxygen-containing conditions ethane is readily oxidized thoroughly to carbon dioxide.
And by constructing an symbiotic proton conductor Solid Oxide Fuel Cell (SOFC), ethane is subjected to selective oxidation conversion at an anode instead of complete oxidation, so that high-efficiency clean power generation (without CO 2 emission) by using ethane can be realized, and yield-increasing and value-increasing chemical ethylene can be obtained. In addition, the proton conductor electrolyte has higher ionic conductivity than the oxygen ion conductor electrolyte, and thus can be operated at medium and low temperatures, and the fuel has very little water generation without fuel circulation.
In addition, the inventors of the present invention have found through a great deal of research that when a metal material is used as a connector of an electric symbiotic solid oxide fuel cell reactor, the oxidation resistance, the sulfuration resistance and the carbon deposition resistance of the electric symbiotic solid oxide fuel cell reactor to the environment are insufficient, and compared with a component contacted with the electric symbiotic solid oxide fuel cell reactor, the thermal expansion coefficient of the electric symbiotic solid oxide fuel cell reactor is too large, and the mechanical property of the metal material is also drastically reduced along 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 integrated connector-supported electric co-occurrence solid oxide fuel cell reactor, fig. 1 shows a flowchart of a method for preparing an integrated connector-supported electric co-occurrence solid oxide fuel cell reactor according to an embodiment of the present invention, and as shown in fig. 1, the method comprises the steps of:
S1, placing an oxidizing gas flow channel filling body in the middle area of the bottom of a die, 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 die 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 passage filling body.
In specific implementation, in step S1 of this embodiment, the oxidizing gas runner filling body correspondingly prepares the oxidizing gas runner, 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 holes between the oxidizing gas runner and the runner are filled with the first precursor powder, so that in the reactor of the cell stack, the oxidizing gas diffuses through the porous connector region, the contact area between the oxidizing gas and the cathode is increased, and the reaction efficiency is improved.
S2, laying 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 flow channel and the oxidizing gas flow channel, and the dense connector region is prepared by filling with the second precursor powder, so that an independent space between the reducing gas flow channel and the oxidizing gas flow channel is realized.
S3, placing a reducing gas flow passage filling body in the middle area above the second ceramic powder layer, laying first precursor powder in holes of the reducing gas flow passage filling body, and laying second precursor powder between the edge of the die and the reducing gas flow passage filling body to form a connector composite powder body; the first precursor powder and the second precursor powder are identical in laying height and larger than the reducing gas runner filling body; the first precursor powder has a lay-up area greater than 90% of the lay-up area of the first precursor powder and the second precursor powder.
In step S3 of this embodiment, the reducing gas runner filling body correspondingly prepares the reducing gas runner, in order to ensure that the reducing gas smoothly diffuses to the upper surface of the connector, contacts with the anode layer and generates catalytic dehydrogenation reaction, so as to improve the catalytic dehydrogenation reaction efficiency of hydrocarbon fuel, and achieve self-sealing on the structure of the connector.
Fig. 2 shows a schematic structural diagram of an oxidizing gas runner filling body prepared by an embodiment of the present invention, and fig. 3 shows a schematic structural diagram of a reducing gas runner filling body prepared by an embodiment of the present invention, as shown in fig. 2, the runner filling body is formed by pressing a molding die, and the length, width, thickness and runner shape of a prepared pore-forming agent block can be adjusted according to actual requirements, and a die corresponding to the pore-forming agent block with a desired runner shape is prepared in advance, and then a pore-forming agent with the desired runner shape is prepared by a pressing method. And, as shown in fig. 2, the diagonal sides of the flow-channel-shaped pore-forming agent block are designed with gas channels so that the entire sealing support integrated structure can be introduced with cathode oxidizing gas and anode fuel gas from the channels after the preparation is successful.
And S4, pressing the connector composite powder body to obtain a connector blank.
In step S4 of this embodiment, the composite powder body of the connector is pressed by a certain pressure to form a compact, which is convenient for taking out the mold on one hand, and is used for improving the sintering molding performance of the integrated structure of the support on the other hand.
And S5, respectively printing anode slurry and electrolyte slurry on the upper surface of the connector blank, and drying and solidifying to form a first semi-finished product of the solid oxide fuel cell reactor supported by the connector.
In step S5 of this embodiment, anode slurry is printed on the upper surface of the porous connector region of the connector body, and dried and cured to form an anode layer, and then electrolyte slurry is printed on the surface of the anode layer, and dried and cured to form an electrolyte layer.
S6, presintering and first roasting are carried out on the first semi-finished product of the solid oxide fuel cell reactor supported by the connector, so that the second semi-finished product of the solid oxide fuel cell reactor supported by the connector is obtained.
In step S6 of this embodiment, first, the first semi-finished product is pre-burned to remove the oxide gas flow channel filler and the reducing gas flow channel filler in the first semi-finished product, and further to remove part of the organic components in the anode layer and the electrolyte layer, so as to prevent the deformation and cracking phenomena caused by the large impact of the organic components in the electrode layer on the functional layer at high temperature during the subsequent baking process.
And secondly, the pre-baked blank is subjected to first roasting, so that the blank of the connector and the electrolyte layer are fully contracted to achieve a self-sealing effect, and in the firing process, the shrinkage rates of the connector and the electrolyte layer are controlled within a range of 12-20%, more preferably 15-17% (if the shrinkage rate of the connector is too small, the shrinkage rate of the electrolyte membrane is too large, and the shrinkage rates of the connector and the electrolyte layer are not matched to crack the electrolyte layer).
S7, printing cathode slurry on an 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, performing 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;
In step S8 of this embodiment, since the tolerance temperature of the cathode layer is lower than that of the electrolyte layer, in order to make the electrolyte layer fully contracted and ensure the self-sealing effect of the connector, the invention adopts a secondary roasting to obtain the formed integrated connector-supported electric symbiotic solid oxide fuel cell reactor, wherein the first roasting obtains a semi-finished product with the connector fully contracted with the electrolyte layer, and the second roasting makes the cathode layer tightly combined with the electrolyte layer, and finally obtains the integrated connector-supported electric symbiotic solid oxide fuel cell reactor finished product 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 a binder; the anode slurry comprises anode powder which is a catalytic material capable of catalyzing hydrocarbon fuel to perform dehydrogenation and oxidation; the electrolyte slurry contains electrolyte powder which is proton conductor material.
In specific implementation, fig. 4 shows a schematic structural diagram of a connector prepared by the embodiment of the present invention, fig. 5 shows a schematic structural diagram of an integrated connector-supported electric symbiotic solid oxide fuel cell stack reactor prepared by 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. Wherein the connector is an integral whole of the full ceramic material, and has no heterogeneous interface structure; a dense connector area is arranged between the oxidizing gas flow channel and the reducing gas flow channel, so that the gas flowing in the oxidizing gas flow channel and the gas flowing in the reducing gas flow channel are prevented from being influenced mutually; the porous connector area is arranged above the reducing gas flow passage, so that the reducing gas (hydrocarbon fuel gas) can permeate to the anode functional layer above the porous connector area through the porous connector area, and is subjected to 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 an electrolyte layer formed by a proton conductor and are combined with oxygen to generate water, and the reactor has the functions of synthesizing chemicals with high added value and generating electric energy.
In addition, the side surface of the connector is a compact connector area, and the electrode layer is prepared on the porous connector area on the upper surface of the connector, and is contacted with and partially covered with the compact connector area on the side surface of the connector, so that the self-sealing effect of the electric symbiotic solid oxide fuel cell reactor on the structure is realized.
In particular, in order to ensure that the reducing gas in the reducing gas flow channel can smoothly diffuse and be 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%, and in order to ensure the mutual independence of the reducing gas flow channel and the oxidizing gas flow channel, the porosity of the dense connector region is less than 7%, and when the porosity is less than 7%, the pores can be considered as closed pores. Thus, the first precursor powder provided by the invention has a particle size of 50 μm to 300 μm and the second precursor powder has a particle size of 50 μm to 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 mu m, and the particle size of the pore-forming agent is 1-5 mu m; 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 mu m, so that the porosity of a porous connector area prepared from the second precursor powder is ensured to be 15-60%.
In some embodiments, the ceramic powder is at least one component of doped lanthanum titanate, doped lanthanum chromate;
The binder is at least one component of polyvinyl butyral (PVB), ethylcellulose, 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 and obtain the electric symbiotic solid oxide fuel cell reactor supported by the integrated connector, the invention prepares the connector with the supporting function by adopting ceramic powder with good catalytic property and excellent anti-carbon deposition property (the anode layer preparation material is the same as the preparation material of the connector in the invention), so that no heterogeneous interface exists between the connector and the anode layer, the connector has good thermal matching and structural matching properties, and the high-efficiency output and stability of the reactor in the long-term service process can be obviously improved; the anode functional layer can fully catalyze and dehydrogenate fuel gas while playing its own role, and can make hydrocarbon fuel ethane efficiently and selectively converted into ethylene at low temperature, and simultaneously generate electric energy.
In some embodiments, the method of preparing the ceramic powder includes: 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 runner filler and the reducing gas runner filler are formed from a runner filler powder that is at least one of PMMA, ammonium bicarbonate, starch, sucrose, and carbon powder by powder compression molding or die pressing and laser machining.
In the concrete implementation, the pore-forming agent is removed at high temperature in the presintering process of the oxidizing gas flow passage filling body and the reducing gas flow passage filling body which are formed by the pore-forming agent, so that a hollow oxidizing gas flow passage and a hollow reducing gas flow passage are formed.
In some embodiments, the pressure at which the connector composite powder body is compacted ranges from 50MPa to 200MPa.
In some embodiments, the catalytic material is one or more of doped strontium titanate and doped strontium chromate;
the proton conductor material is as follows: baCe 1-xYxO3-δ、BaZr1-xYxO3-δ, and Ba (Ce, zr) 1-yYyO3-δ, wherein x is equal to or more than 0.1 and equal to or less than 0.9, and y is equal to or more than 0.1 and equal to or less than 0.9.
In particular, the ceramic material of the connector is the same as the catalytic material forming the anode layer, so that the reducing gas (hydrocarbon such as ethane) can be subjected to catalytic dehydrogenation reaction under the action of the catalytic material to generate hydrogen protons in the process of diffusing and transmitting the hydrogen protons to the anode layer, and the proton conductor can transmit the hydrogen protons to the cathode layer side to react with the oxidizing gas (such as oxygen) to generate water, thereby realizing sufficient catalytic dehydrogenation of the reducing gas, enabling the hydrocarbon fuel ethane to be efficiently and highly selectively converted into ethylene at low temperature, and simultaneously generating electric energy.
In some embodiments, the catalytic material comprises at least one component of SrTiO 3、La0.7Sr0.3 TiO and La 0.7Sr0.3CrO3;
the proton conductor material includes any one of components BaZr 0.8Y0.2O3–δ、BaZr0.1Ce0.7Y0.2O3–δ and BaZr 0.1Ce0.7Y0.1Yb0.1O3–δ;
The cathode slurry comprises cathode powder, wherein the cathode powder comprises the following components in percentage by mass: 1 with La 0.6Sr0.4Co0.2Fe0.8O3-δ, or the cathode powder consists of the following components in mass ratio 1: 1. is composed of Ba 0.5Sr0.5Co0.8Fe0.2O3-δ and electrolyte powder.
In some embodiments, the anode paste, the electrolyte paste, and the cathode paste are prepared on the connector body by screen printing, the screen mesh of the screen printing is 180-350 mesh, the doctor blade speed of the screen printing is 5cm/s, and the doctor blade angle of the screen printing is 55-85 ℃.
In some embodiments, the pre-firing temperature ranges from 100 ℃ to 600 ℃ for a period of time ranging from 1h to 10h;
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 integrated connector-supported electric symbiotic solid oxide fuel cell stack reactor, the cell stack reactor is composed of two or more cell reactors prepared by the method in the first aspect, and the preparation method of the cell stack reactor comprises the following steps:
The cathode of one reactor is contacted and sealed with the integrated connector of the next reactor to form a connector supported electrosymbiotic solid oxide fuel cell stack reactor.
In the specific implementation, two or more than two electric symbiotic solid oxide fuel cell stack reactors supported by the prepared integrated connectors are accumulated, then a cell stack is formed, each cell is connected through Manganese Cobalt Oxide (MCO), namely manganese cobalt oxide can be prepared into slurry at normal temperature, then the slurry is smeared on the surface of a cathode, and then the cells are bonded layer by layer and sintered and solidified, so that the electric symbiotic solid oxide fuel cell stack reactor supported by the integrated connectors is obtained.
Fig. 6 shows a schematic structural diagram of an integrated electric symbiotic solid oxide fuel cell reactor supported by a connector prepared according to an embodiment of the present invention, and fig. 6 shows a reactor in which 5 single cells are accumulated.
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 whole ceramic material can ensure that the cell stack reactor stably operates 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 better understand the present invention, the following description will illustrate the preparation method of the ceramic flat tube supported solid oxide fuel cell/electrolytic cell with one end self-sealing according to the present invention through a plurality of specific examples.
Example 1
Ammonium bicarbonate blocks having the two runner shapes shown in fig. 2 and 3 were prepared by pressing with a mold prepared in advance corresponding to the runner shape ammonium bicarbonate blocks shown in fig. 2 and 3, the ammonium bicarbonate blocks being 8cm×8cm ammonium bicarbonate blocks. The strontium titanate ceramic powder was mixed with ammonium bicarbonate and polyvinyl butyral (PVB) to give a porous ceramic precursor powder, wherein the ammonium bicarbonate content was 20wt.%, and the PVB content was 5wt.%. The strontium titanate ceramic powder was mixed with polyvinyl butyral (PVB) to give a dense ceramic precursor powder with a PVB content of 5wt.%.
Placing an ammonium bicarbonate block in the shape of a runner as shown in fig. 2 at the bottom of a mould with the size of 10cm multiplied by 10cm, paving porous ceramic precursor powder with the particle size of 20 mu m in holes of the ammonium bicarbonate block in the shape of the runner as shown in fig. 2, and paving dense ceramic precursor powder in a region between the mould and the ammonium bicarbonate block to form a first ceramic powder layer, wherein the paving 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 ammonium bicarbonate with the flow channel shape shown in fig. 3 on the second ceramic powder layer, continuously filling porous ceramic precursor powder into a plurality of flow channel holes of the ammonium bicarbonate with the flow channel shape shown in fig. 3, filling the space between the ammonium bicarbonate block and the mould with compact ceramic precursor powder, and obtaining a composite powder layer filling structure system with the compact ceramic precursor powder surrounding the porous ceramic precursor powder. Pressing the structural system with pressure of 500MPa to form a blank body, and obtaining the connector blank body.
At this time, an anode functional layer and an electrolyte are formed on the surface of the green body of the connection body by a screen printing method, and fired together with the support. After firing, the length of the connector body changes, and therefore, the shrinkage of the connector body during firing is preferably in the range of 12 to 20%, more preferably 15 to 17%. The shrinkage of the body of the connector is too small, the shrinkage of the electrolyte membrane is too large, and the shrinkage of the body of the connector is not matched with the shrinkage of the electrolyte membrane, so that the electrolyte layer is cracked.
Specifically, an anode layer was prepared on the porous region of the connector body using a screen printing method, and the coating range is shown in fig. 5. The main components of the anode functional layer were 50wt% SrTiO 3, 2.5wt% binder, 0.5wt% dispersant and 47wt% organic solvent, the SrTiO 3 particle size D 50 =200 nm. The anode functional layer slurry is ball-milled for 24 hours and then screen-printed to prepare the anode functional layer, wherein the mesh number of the 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 the anode functional layer is dried at 80 ℃ after printing. The anode current collector area was 8cm by 8cm.
Specifically, an electrolyte layer was prepared on the anode functional layer using a screen printing method, and the coating range is shown in fig. 5. The electrolyte layer was composed of BaZr 0.8Y0.2O3–δ (BZY 20) and 2.5wt% binder, 0.5wt% dispersant and 47wt% organic solvent as the main components, and the particle size of BaZr 0.8Y0.2O3–δ used was D 50 =100 nm. The electrolyte layer slurry is ball-milled for 24 hours and then screen printing is carried out to prepare the electrolyte layer, the mesh number of the 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 the electrolyte layer is dried at 80 ℃ after printing. The electrolyte area was 8.2cm×8.2cm, and the electrolyte layer was in contact with the dense region of the edge of the connector (as shown by the positional relationship of 2-4 and 2-1 in fig. 2).
Further, a step-by-step heating method is adopted to heat the intermediate of the reactor to 300 ℃ at a speed of 1 ℃/min for 4 hours of glue discharging in the air, so as to remove pore-forming agent ammonium bicarbonate in the intermediate of the reactor, and a reducing gas flow passage filling body and an oxidizing gas flow passage filling body, wherein glue discharging is carried out from 300 ℃ to 600 ℃ at a heating rate of 1 ℃/min for 8 hours, and then the intermediate of the reactor is sintered and molded in the air at a heating rate of 2 ℃/min for 4 hours at 1550 ℃.
The cathode paste was printed over the electrolyte using a screen mesh of preferably 180 mesh, a doctor blade speed of 5.0cm/s, a doctor blade angle of preferably 70 deg.c, a cathode functional layer thickness of 10±3 μm, and drying at 80 deg.c by the same operation as the printing method of the anode functional layer described above, with a main component of the cathode paste being 60wt% La 0.6Sr0.4Co0.2Fe0.8O3-δ/BaZr0.8Y0.2O3–δ (mass ratio 1:1), 2wt% binder, 0.5wt% dispersant, and 37.5wt% organic solvent. The cathode area was 8cm by 8cm.
And further adopting a step heating method to heat the intermediate of the reactor to 300 ℃ at a speed of 1 ℃/min for 4 hours in air, discharging the intermediate of the reactor from 300 ℃ to 600 ℃ at a speed of 1 ℃/min for 8 hours, and then preserving the temperature in the air for 4 hours at 1200 ℃ at a speed of 2 ℃/min for sintering and forming.
The cathode, anode and electrolyte materials selected in the present invention may be any common materials, and are not limited in the present invention.
Example 2
The soluble starch block having the two runner shapes shown in fig. 2 and 3 was prepared by pressing through a previously prepared mold corresponding to the soluble starch block having the runner shape shown in fig. 2 and 3, and the soluble starch block was 9cm×18cm. Mixing La 0.7Sr0.3TiO3 ceramic powder with soluble starch and polyvinylpyrrolidone (K60-K90) to obtain porous ceramic precursor powder, wherein the content of the soluble starch is 9wt.% and the content of the polyvinylpyrrolidone (K60-K90) is 6wt.%. La 0.7Sr0.3TiO3 ceramic powder with a particle size of about 30 μm was mixed with polyvinylpyrrolidone (K60-K90) to obtain a dense ceramic precursor powder with a polyvinylpyrrolidone (K60-K90) content of 6wt.%.
Placing the soluble starch block in the shape of a runner as shown in fig. 2 at the bottom of a mold with the size of 10cm multiplied by 20cm, paving porous ceramic precursor powder in holes of the soluble starch block in the shape of the runner as shown in fig. 2, and paving dense ceramic precursor powder in a region between the mold 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; placing soluble starch with the flow channel shape shown in fig. 3 on the second ceramic powder layer, continuously filling porous ceramic precursor powder into a plurality of flow channel holes of the soluble starch block with the flow channel shape shown in fig. 3, and filling compact ceramic precursor powder into the space between the soluble starch block and the die to obtain a composite powder layer filling structure system in which the compact ceramic precursor powder surrounds the porous ceramic precursor powder; pressing the structural system by using 300MPa pressure to form a blank body, and obtaining the connector blank body.
Further, an anode layer and an electrolyte layer are formed on the surface of the green body of the connection body by a screen printing method, and fired together with the support body. After firing, the length of the connector body changes, and therefore, the shrinkage of the connector body during firing is preferably in the range of 12 to 20%, more preferably 15 to 17%. The shrinkage of the body of the connector is too small, the shrinkage of the electrolyte membrane is too large, and the shrinkage of the body of the connector is not matched with the shrinkage of the electrolyte membrane, so that the electrolyte layer is cracked.
Specifically, an anode functional layer was prepared on the porous region of the connector body using a screen printing method, and the coating range is shown in fig. 5. The main components of the anode functional layer are 50wt% of La 0.7Sr0.3TiO3, 2.5wt% of binder, 0.5wt% of dispersing agent and 47wt% of organic solvent, and La 0.7Sr0.3TiO3 particle size D 50 =200 nm is used. The anode functional layer slurry is ball-milled for 24 hours and then screen-printed to prepare the anode functional layer, wherein the mesh number of the 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 the anode functional layer is dried at 80 ℃ after printing. The anode functional layer area was 9cm×18cm.
Specifically, an electrolyte layer was prepared on the anode functional layer using a screen printing method, and the coating range is shown in fig. 5. The electrolyte layer was composed of BaZr 0.1Ce0.7Y0.2O3–δ (BZCY) and 2.5wt% binder, 0.5wt% dispersant and 47wt% organic solvent as the main components, and the particle size of BaZr 0.1Ce0.7Y0.2O3–δ used was D 50 =100 nm. The electrolyte layer slurry is ball-milled for 24 hours and then screen printing is carried out to prepare the electrolyte layer, the mesh number of the screen is preferably 300 meshes, the scraper speed is 5.0cm/s, the scraper angle is preferably 70 ℃, the thickness of the electrolyte layer is 15+/-3 mu m, and the electrolyte layer is dried at 80 ℃ after printing. The electrolyte area was 9.2 cm. Times.18.2 cm, and the electrolyte layer was in contact with the dense region of the edge of the connector (as shown by the positional relationship of 2-4 and 2-1 in FIG. 2).
Further, a step-by-step heating method is adopted to heat the intermediate of the reactor to 300 ℃ at a speed of 1 ℃/min for 4 hours in air, soluble starch of pore-forming agents in the blank of the reactor, including fuel gas and oxidizing gas runner filling bodies, are removed, the glue is discharged from 300 ℃ to 600 ℃ at a speed of 1 ℃/min for 8 hours, and then the intermediate of the reactor is sintered and molded in air at a speed of 2 ℃/min for 4 hours at 1500 ℃.
The cathode paste was printed over the electrolyte using a screen mesh of preferably 180 mesh, a doctor blade speed of 5.0cm/s, a doctor blade angle of preferably 70 deg.c, a cathode functional layer thickness of 30±3 μm, and drying at 80 deg.c by the same operation as the above-described printing method of the anode functional layer, the main component of the cathode paste being La0.6Sr0.4Co0.2Fe0.8O3-δ/BaZr0.1Ce0.7Y0.2O3–δ( mass ratio of 1:1) of 60wt%, 2wt% of binder, 0.5wt% of dispersant, and 37.5wt% of organic solvent. The cathode area was 9cm by 18cm.
Further, a step heating method is adopted to heat the intermediate of the reactor to 300 ℃ at a speed of 1 ℃/min for 4 hours in air, heat the intermediate of the reactor from 300 ℃ to 600 ℃ at a speed of 1 ℃/min for 8 hours, and then the intermediate of the reactor is sintered and molded in the air at 1200 ℃ for 4 hours at a speed of 2 ℃/min.
The cathode, anode and electrolyte materials selected in the present invention may be any common materials, and are not limited in the present invention.
Example 3
Two runner-shaped polymethyl methacrylate (PMMA) blocks as shown in FIGS. 2 and 3 were prepared in advance by molding and laser machining, and the PMMA blocks were 12cm by 12cm. The La 0.7Sr0.3CrO3 ceramic powder was mixed with PMMA, polyvinyl alcohol (PVA), the content of PMMA being 9wt.%, the PVA content being 4wt.%, to obtain a porous ceramic precursor powder. La 0.7Sr0.3CrO3 ceramic powder with a particle size of about 30 μm was mixed with polyvinyl alcohol (PVA) to give a dense ceramic precursor powder with a PVB content of 4wt.%.
Placing a PMMA block in the shape of a runner as shown in FIG. 2 at the bottom of a mold with the size of 15cm multiplied by 15cm, paving porous ceramic precursor powder with the particle size of about 20 mu m in holes of the PMMA block in the shape of the runner as shown in FIG. 2, and paving a region between the mold and the PMMA block with compact ceramic precursor powder 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 PMMA block height; further laying a layer of compact ceramic precursor powder on the first ceramic powder layer to form a second ceramic powder layer; and placing PMMA with the flow channel shape shown in figure 3 on the second ceramic powder layer, continuously filling porous ceramic precursor powder into a plurality of flow channel holes of PMMA with the flow channel shape shown in figure 3, and filling the space between the PMMA block and the die with the 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, thus obtaining the connector blank body.
At this time, an anode functional layer and an electrolyte are formed on the surface of the green body of the connection body by a screen printing method, and fired together with the support. After firing, the length of the connector body changes, and therefore, the shrinkage of the connector body during firing is preferably in the range of 12 to 20%, more preferably 15 to 17%. The shrinkage of the body of the connector is too small, the shrinkage of the electrolyte membrane is too large, and the shrinkage of the body of the connector is not matched with the shrinkage of the electrolyte membrane, so that the electrolyte layer is cracked.
Specifically, an anode functional layer was prepared on the porous region of the connector body using a screen printing method, and the coating range is shown in fig. 5. The main components of the anode functional layer are 50wt% of La 0.7Sr0.3CrO3, 2.5wt% of binder, 0.5wt% of dispersing agent and 47wt% of organic solvent, and La 0.7Sr0.3CrO3 particle size D 50 =200 nm is used. The anode functional layer slurry is ball-milled for 24 hours and then screen-printed to prepare the anode functional layer, wherein the mesh number of the 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 the anode functional layer is dried at 80 ℃ after printing. The anode current collector area was 12cm by 12cm.
Specifically, an electrolyte layer was prepared on the anode functional layer using a screen printing method, and the coating range is shown in fig. 5. The electrolyte layer was composed of BaZr 0.1Ce0.7Y0.1Yb0.1O3–δ (BZCYYb) and 2.5wt% binder, 0.5wt% dispersant and 47wt% organic solvent as the main components, and the particle size of BaZr 0.1Ce0.7Y0.1Yb0.1O3–δ used was D 50 =100 nm. The electrolyte layer slurry is ball-milled for 24 hours and then screen printing is carried out to prepare the electrolyte layer, the mesh number of the adopted screen is preferably 350 meshes, the scraper speed is 5.0cm/s, the scraper angle is preferably 70 ℃, the thickness of the electrolyte layer is 15+/-3 mu m, and the electrolyte layer is dried at 80 ℃ after printing. The electrolyte area was 12.2cm×12.2cm, and the electrolyte layer was in contact with the dense region of the edge of the connector (as shown by the positional relationship of 2-4 and 2-1 in fig. 2).
Further, a step-by-step heating method is adopted to heat the intermediate of the reactor to 300 ℃ at a speed of 1 ℃/min for 4 hours of glue discharging in the air, the pore-forming agent PMMA in the blank of the reactor is removed, the pore-forming agent PMMA comprises fuel gas and oxidizing gas runner filling bodies, glue discharging is carried out from 300 ℃ to 600 ℃ at a speed of 1 ℃/min for 8 hours, and then the mixture is sintered and molded in the air at a temperature of 1600 ℃ at a speed of 2 ℃/min.
The cathode paste was printed over the electrolyte using a screen mesh of preferably 180 mesh, a doctor blade speed of 5.0cm/s, a doctor blade angle of preferably 70 deg.c, a cathode functional layer thickness of 30±3 μm, and drying at 80 deg.c by the same operation as the above-described printing method of the anode functional layer, the main component of the cathode paste being La0.6Sr0.4Co0.2Fe0.8O3-δ/BaZr0.1Ce0.7Y0.1Yb0.1O3–δ( mass ratio of 1:1) of 60wt%, 2wt% of binder, 0.5wt% of dispersant, and 37.5wt% of organic solvent. The cathode area was 12cm by 12cm.
Further, a step heating method is adopted to heat the intermediate of the reactor to 300 ℃ at a speed of 1 ℃/min for 4 hours in air, heat the intermediate of the reactor from 300 ℃ to 600 ℃ at a speed of 1 ℃/min for 8 hours, and then the intermediate of the reactor is sintered and molded in the air at 1200 ℃ for 4 hours at a speed of 2 ℃/min.
The cathode, anode and electrolyte materials selected in the present invention may be any common materials, and are not limited in the present invention.
Example 4
The two runner-shaped carbon powder blocks shown in fig. 2 and 3 are prepared in advance by adopting a mould pressing sintering mode, and the ammonium bicarbonate blocks are 18cm multiplied by 18cm ammonium bicarbonate blocks. La 0.75Sr0.25Cr0.5Mn0.5O3 (LSCM) ceramic powder with the particle size of 80 μm is mixed with carbon powder and polyvinyl alcohol (PVA) to obtain porous ceramic precursor powder, wherein the content of the carbon powder is 20wt.% and the PVB content is 2wt.%. La 0.75Sr0.25Cr0.5Mn0.5O3 ceramic powder with a particle size of about 10 μm was mixed with polyvinyl alcohol (PVA) to give a dense ceramic precursor powder with a PVB content of 2wt.%.
Placing the runner-shaped carbon powder block shown in fig. 2 at the bottom of a mold with the size of 20cm multiplied by 20cm, paving porous ceramic precursor powder with the particle size of 20 mu m in holes of the runner-shaped carbon powder block shown in fig. 2, and paving dense ceramic precursor powder in a region between the mold and the carbon powder block to form a first ceramic powder layer, wherein the paving height of the porous ceramic precursor powder and the dense ceramic precursor powder is 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 continuing to fill porous ceramic precursor powder into the plurality of runner holes of the carbon powder block with the runner shape as shown in fig. 3, and filling the space between the carbon powder block and the die 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. Pressing the structural system by using 100MPa pressure to form a blank body, and obtaining the integrated connector blank body.
At this time, an anode functional layer, an anode, and an electrolyte are formed on the surface of the green body of the connection body by a screen printing method, and fired together with the support. After firing, the length of the connector body changes, and therefore, the shrinkage of the connector body during firing is preferably in the range of 12 to 20%, more preferably 15 to 17%. The shrinkage of the body of the connector is too small, the shrinkage of the electrolyte membrane is too large, and the shrinkage of the body of the connector is not matched with the shrinkage of the electrolyte membrane, so that the electrolyte layer is cracked.
Specifically, an anode functional layer was prepared on the porous region of the connector body using a screen printing method, and the coating range is shown in fig. 5. The main components of the anode functional layer were 50wt% La 0.75Sr0.25Cr0.5Mn0.5O3, 2.5wt% binder, 0.5wt% dispersant and 47wt% organic solvent, la 0.75Sr0.25Cr0.5Mn0.5O3 particle size D 50 =200 nm was used. The anode functional layer slurry is ball-milled for 24 hours and then screen-printed to prepare the anode functional layer, wherein the mesh number of the 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 the anode functional layer is dried at 80 ℃ after printing. The anode current collector area was 18cm by 18cm.
Specifically, an electrolyte layer was prepared on the anode functional layer using a screen printing method, and the coating range is shown in fig. 5. The electrolyte layer was composed of BaZr 0.1Ce0.7Y0.1Yb0.1O3–δ (BZCYYb) and 2.5wt% binder, 0.5wt% dispersant and 47wt% organic solvent as the main components, and the particle size of BaZr 0.1Ce0.7Y0.1Yb0.1O3–δ used was D 50 =100 nm. The electrolyte layer slurry is ball-milled for 24 hours and then screen printing is carried out to prepare the electrolyte layer, the mesh number of the adopted screen is preferably 350 meshes, the scraper speed is 5.0cm/s, the scraper angle is preferably 70 ℃, the thickness of the electrolyte layer is 15+/-3 mu m, and the electrolyte layer is dried at 80 ℃ after printing. The electrolyte area was 18.2 cm. Times.18.2 cm, and the electrolyte layer was in contact with the dense region of the edge of the connector (as shown by the positional relationship of 2-4 and 2-1 in FIG. 2).
Further, a step heating method is adopted to heat the intermediate of the reactor to 300 ℃ at 1 ℃/min for 4 hours of glue discharging in the air, pore-forming agent carbon powder in the blank of the reactor is removed, the pore-forming agent carbon powder comprises fuel gas and oxidizing gas runner filling bodies, glue discharging is carried out from 300 ℃ to 600 ℃ at a heating rate of 1 ℃/min for 8 hours, and then sintering and forming are carried out in the air at 1550 ℃ for 4 hours at a heating rate of 2 ℃/min.
The cathode paste was printed over the electrolyte using a screen mesh of preferably 180 mesh, a doctor blade speed of 5.0cm/s, a doctor blade angle of preferably 70 deg.c, a cathode functional layer thickness of 30±3 μm, and drying at 80 deg.c by the same operation as the above-described printing method of the anode functional layer, the main component of the cathode paste being Ba0.5Sr0.5Co0.8Fe0.2O3-δ/BaZr0.1Ce0.7Y0.1Yb0.1O3–δ( mass ratio of 1:1) of 60wt%, 2wt% of binder, 0.5wt% of dispersant, and 37.5wt% of organic solvent. The cathode area was 18cm by 18cm.
Further, a step heating method is adopted to heat the intermediate of the reactor to 300 ℃ at a speed of 1 ℃/min for 4 hours in air, heat the intermediate of the reactor from 300 ℃ to 600 ℃ at a speed of 1 ℃/min for 8 hours, and then the intermediate of the reactor is sintered and molded in the air at 1200 ℃ for 4 hours at a speed of 2 ℃/min.
The above description is made in detail of a method for preparing an integrated connector-supported electric symbiotic solid oxide fuel cell/cell stack reactor, and specific examples are applied to illustrate the principles and embodiments of the present invention, and the above examples are only used to help understand the method and core ideas of the present invention; meanwhile, as those skilled in the art will have variations in the specific embodiments and application scope in accordance with the ideas of the present invention, the present description should not be construed as limiting the present invention in view of the above.
Claims (9)
1. A method for preparing an integrated connector supported electrical symbiotic solid oxide fuel cell reactor, the method comprising:
Placing an oxidizing gas flow channel filling body in the middle area of the bottom of a die, 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 die 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 passage filling body;
Further, laying second precursor powder on the first ceramic powder layer and the oxidizing gas flow channel filling body to form a second ceramic powder layer;
Further, a reducing gas flow passage filling body is placed in the middle area above the second ceramic powder layer, first precursor powder is paved in holes of the reducing gas flow passage filling body, and second precursor powder is paved between the edge of the die and the reducing gas flow passage filling body to form a connector composite powder body; the first precursor powder and the second precursor powder are identical in laying height and larger than the reducing gas runner filling body; the first precursor powder has a lay-up area greater than 90% of the lay-up area of the first precursor powder and the second precursor powder;
further, pressing the connector composite powder body to obtain a connector blank;
Further, anode slurry and electrolyte slurry are respectively printed on the upper surface of the connector blank, and are dried and solidified to form a first semi-finished product of the solid oxide fuel cell reactor supported by the connector;
Further, presintering and first roasting are carried out on the first semi-finished product of the solid oxide fuel cell reactor supported by the connector, so as 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 product of the solid oxide fuel cell reactor supported by the connecting body to form a third semi-finished product of the solid oxide fuel cell reactor supported by the connecting body;
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 ceramic powder is prepared by mixing at least one component of doped lanthanum titanate and doped lanthanum chromate, wherein 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 mu m, and the particle size of the pore-forming agent is 1-5 mu m; 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 mu m;
The anode slurry comprises anode powder, wherein the anode powder is a catalytic material capable of catalyzing hydrocarbon fuel to be subjected to dehydrogenation oxidation, and the catalytic material is at least one component of doped strontium titanate and doped strontium chromate;
The electrolyte slurry comprises electrolyte powder, wherein the electrolyte powder is a proton conductor material;
The oxidizing gas runner filling body and the reducing gas runner filling body are formed by runner filling body powder through powder compression molding or mould pressing and laser processing, and the runner filling body powder is at least one of polymethyl methacrylate (PMMA), ammonium bicarbonate, starch, sucrose and carbon powder;
The presintering temperature ranges from 100 ℃ to 600 ℃ and the presintering time ranges from 1h to 10h.
2. The method of claim 1, wherein the first precursor powder has a particle size of 50 μm to 300 μm and the second precursor powder has a particle size of 50 μm to 300 μm.
3. The method of claim 1, wherein the binder is at least one component of polyvinyl butyral PVB, ethylcellulose, polyvinyl pyrrolidone K60-K90, 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 proton conductor material is: either BaCe 1-xYxO3-δ、BaZr1- xYxO3-δ or Ba (Ce, zr) 1-yYyO3-δ, 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 at least one of SrTiO 3、La0.7Sr0.3 TiO and La 0.7Sr0.3CrO3;
The proton conductor material includes any one of components BaZr 0.8Y0.2O3–δ、BaZr0.1Ce0.7Y0.2O3–δ and BaZr 0.1Ce0.7Y0.1Yb0.1O3–δ;
The cathode slurry comprises cathode powder, wherein the cathode powder comprises the following components in percentage by mass: 1 with La 0.6Sr0.4Co0.2Fe0.8O3-δ, or the cathode powder consists of the following components in mass ratio 1:1 with Ba 0.5Sr0.5Co0.8Fe0.2O3-δ.
6. The method of claim 1, wherein the pressure at which the connector composite powder is compacted ranges from 50mpa to 200mpa.
7. The method of claim 1, wherein the anode paste, the electrolyte paste, and the cathode paste are prepared on the connector body by screen printing, the screen printing having a screen mesh of 180-350 mesh, the screen printing doctor blade speed of 5cm/s, and the screen printing doctor blade angle of 55-85 ℃.
8. The method of claim 1, wherein the first firing is at a temperature in the range 1350 ℃ to 1600 ℃ for a time in the range 4 hours to 6 hours;
the temperature range of the second roasting is 600-1200 ℃ and the time is 4-6 hours.
9. A method for preparing an integrated connector-supported electric symbiotic solid oxide fuel cell stack reactor, characterized in that the cell stack reactor consists of two or more cell reactors prepared by the method of any one of the claims 1-8, and the preparation method of the cell stack reactor comprises the following steps:
The cathode of one cell reactor is contacted and sealed with the integrated connector of the next cell reactor to form a connector supported electrosymbiotic solid oxide fuel cell reactor.
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