CN111403768B - Integrated structure, battery/electrolytic cell and preparation method of battery stack - Google Patents

Integrated structure, battery/electrolytic cell and preparation method of battery stack Download PDF

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Publication number
CN111403768B
CN111403768B CN202010246229.9A CN202010246229A CN111403768B CN 111403768 B CN111403768 B CN 111403768B CN 202010246229 A CN202010246229 A CN 202010246229A CN 111403768 B CN111403768 B CN 111403768B
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pore
forming agent
metal powder
powder
connector
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CN111403768A (en
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李成新
李甲鸿
康思远
李长久
张山林
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Xian Jiaotong University
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Xian Jiaotong University
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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
    • H01M8/02—Details
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/11—Making porous workpieces or articles
    • B22F3/1121—Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/002—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of porous nature
    • B22F7/004—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of porous nature comprising at least one non-porous part
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0206—Metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0258—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/2404—Processes or apparatus for grouping fuel cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/241—Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes
    • H01M8/2425—High-temperature 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
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/2457—Grouping of fuel cells, e.g. stacking of fuel cells with both reactants being gaseous or vaporised
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M2008/1293—Fuel cells with solid oxide electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention provides an integrated structure, a battery/electrolytic cell and a preparation method of a battery stack. The method comprises the following steps: the self-sealing connector and support integrated structure is prepared by designing pore-forming agents with different flow passage shapes, then spreading powder layer by layer and then utilizing a compression molding and powder metallurgy preparation method. And sequentially preparing an anode, an electrolyte and a cathode on the metal porous area of the support body and the connector integrated structure by using tape casting, wet process or spraying, so that the anode covers the metal porous area, the electrolyte covers the anode area, and finally preparing the self-sealing monocell/electrolytic cell. The preparation method effectively simplifies the manufacturing process of the cell stack, reduces the sealing workload of the cell stack, is beneficial to reducing the manufacturing cost of the cell, and is beneficial to the commercial popularization of the solid oxide cell.

Description

Integrated structure, battery/electrolytic cell and preparation method of battery stack
Technical Field
The invention relates to the technical field of energy sources, in particular to an integrated structure, a battery/electrolytic cell and a preparation method of a battery stack.
Background
A Solid Oxide Fuel Cell (SOFC) is an energy conversion device, which directly converts chemical energy of fuel into electric energy, and has the advantages of high power generation efficiency, no environmental pollution, no noise, and the like. A conventional SOFC single cell consists of an anode, an electrolyte, and a cathode. Depending on the type of support providing cell strength, an anode-supported SOFC, a cathode-supported SOFC, and an electrolyte-supported SOFC can be classified, each providing support by thickening (about 1mm) one of the components. The above-described supported SOFC is still not mechanically strong due to the inherent brittleness of the ceramic material, and thickening of the electrode or electrolyte components leads to a decrease in cell performance.
The metal-supported SOFC is a novel SOFC structure. An anode, an electrolyte and a cathode are sequentially prepared thereon using a porous metal as a support. Due to the adoption of the metal support body, the structure has good mechanical strength and thermal shock resistance, and the electrode and the electrolyte component can be made into a film form, so that the cost is reduced, and the output performance of the battery is improved.
SOFC single cells must be used by being secured to a metal connector that provides a gas flow path and conducts current. In the traditional anode-supported SOFC, the cathode-supported SOFC, the electrolyte-supported SOFC and the connecting body are connected and sealed mainly through a glass sealing material, so that the cost is high and the stability is poor. The metal support SOFC uses a metal support body, so that the support body and the connecting body can be connected by using a conventional welding technology, and the welding methods in the related technologies include brazing and laser welding.
However, the SOFC has an operating temperature of 600-800 ℃, and at such a high temperature, the welded joints have problems of non-uniform stress, non-uniform components, and the like, and the sealing property and oxidation resistance of the welded joints are weak, which affect the long-term stability of the battery, resulting in degraded battery performance.
Therefore, the connection and sealing problems between the connecting body and the support body still remain key problems in the field, and the development of the field is greatly promoted if the problems can be solved. Similarly, solid oxide electrolysis cells suffer from similar sealing problems.
Disclosure of Invention
The invention provides an integrated structure, a battery/electrolytic cell and a preparation method of a battery stack, which aim to solve the problems of connection and sealing between a metal support body and a connector in the problems.
In a first aspect, the present invention provides a method for preparing a support and connector integrated structure, the method comprising:
preparing a first pore-forming agent block and a second pore-forming agent block by utilizing pore-forming agent powder, wherein a plurality of pores are distributed in the first pore-forming agent block and the second pore-forming agent block;
mixing metal powder and pore-forming agent powder to prepare porous metal support body precursor powder;
placing the first pore-forming agent block in a mold, and laying the metal powder on the first pore-forming agent block to form a first metal powder layer;
placing the second pore former block on the first metal powder layer;
filling the metal powder into a plurality of pores of the second pore-forming agent block to obtain a filled second pore-forming agent block;
laying the porous metal support body precursor powder on the filled second pore-forming agent block to form a second metal powder layer to obtain a multilayer structure system;
filling the gap between the multilayer structure system and the mold with the metal powder to obtain a filled structure system in which the metal powder surrounds the second metal powder layer;
pressing the filling structure system to obtain a formed green body;
removing the pore-forming agent in the formed green body to obtain a processed green body;
and roasting the treated green body to obtain a connector and support body integrated structure.
Preferably, the shape of the plurality of internally distributed pores of the first pore former block is different from the shape of the plurality of internally distributed pores of the second pore former block; the shape determining factor includes at least the gas introduced and the flow rate of the gas.
Preferably, said pressing said filled structural system to obtain a shaped green body comprises:
pressing the filling structure system in a pressure pressing mode to obtain a formed green body; wherein the pressure range of the pressing is 100 MPa-1000 MPa; the pore-forming agent content in the porous metal support precursor powder is 0-20 wt%.
Wherein the pressed pressure value corresponds to the pore-forming agent content in the porous metal support precursor powder, and the pressed pressure value corresponds to the porosity of the porous support part in the integrated connector-support structure.
Preferably, the removing the pore-forming agent from the formed green body to obtain a treated green body comprises:
removing the pore-forming agent in the formed green body in a heating removal mode to obtain a processed green body; the heating temperature range is 100-400 ℃; the removing time is 1-4 h.
Preferably, in the process of roasting the treated green body, the roasting environment at least comprises one of low-pressure vacuum, reducing atmosphere and inert atmosphere; the roasting temperature range is 1000-1400 ℃; the roasting time is 4-6 h.
Preferably, the particle size of the metal powder is 10-80 μm, and the metal powder at least comprises one of iron-chromium alloy, nickel-chromium alloy and pure chromium.
Preferably, the pore-forming agent content in the porous metal support precursor powder is 0-20% wt.
Preferably, the pore-forming agent comprises at least: ammonium bicarbonate, soluble starch, sucrose, sodium chloride and carbon powder.
Preferably, the method for preparing the first pore-forming agent block and the second pore-forming agent block comprises the following steps: die pressing or screen printing.
In a second aspect, the present invention provides a method of making a solid oxide fuel cell/electrolyser, said method comprising:
preparing an integrated structure of the connecting body and the supporting body by adopting the method of the first aspect;
coating an anode material on the surface layer region of the connector and support body integrated structure to obtain an anode layer;
coating an electrolyte material on the surface of the anode layer to obtain an electrolyte layer;
coating a cathode material on the surface of the electrolyte layer to obtain a solid oxide fuel cell/electrolytic cell;
the second pore former block is removed to form an anode gas channel through which anode gas flows into the anode;
the first pore former block is removed to form a cathode gas passage through which cathode gas flows into the cathode.
Preferably, the method of coating comprises at least: tape casting and sintering, and atmospheric plasma spraying.
In a third aspect, the present invention provides a solid oxide fuel cell stack comprising two or more solid oxide fuel cells according to the second aspect;
the solid oxide fuel cell stack is prepared by the following steps:
bonding the cathode of the first solid oxide fuel cell and the anode of the second solid oxide fuel cell by using a bonding agent to obtain a plurality of accumulated solid oxide fuel cells;
and sintering the accumulated plurality of solid oxide cells to obtain the solid fuel cell stack.
According to the integrated structure, the battery/electrolytic cell, the structure and the preparation method of the battery stack, provided by the embodiment of the invention, the preparation process of the battery stack is effectively simplified, the sealing workload of the battery stack is reduced, the manufacturing cost of the battery is favorably reduced, and the commercial popularization of the solid oxide battery is favorably realized. Moreover, the preparation method provided by the invention also has the following advantages:
1. by designing the pore-forming agent blocks with two flow channel shapes, after the pore-forming agent is removed, the pore-forming agent blocks with the two flow channel shapes form a flow channel after being removed at low temperature, namely, an anode air channel and a cathode air channel can be automatically formed for an anode and a cathode respectively, and the purpose of one-step forming of an integrated structure of a connector and a support body is achieved. The traditional methods such as machining and the like need to prepare a connector, then prepare a support body and finally connect the connector and the support body, a connection interface is generated in the traditional method, extra sealing is needed at two ends of the support body, and the corresponding sealing position and the connecting position have the defects of uneven stress and uneven components at high temperature.
2. According to the preparation method provided by the embodiment of the invention, the gas can be uniformly distributed on the cathode or the anode when the cathode or anode gas reaches the cathode or the anode by adjusting different flow channel forms, namely preparing the pore-forming agent blocks in different flow channel forms, so that the purpose of adjusting the uniform distribution of the cathode or anode gas in respective electrodes is achieved, the potential difference in the electrodes is reduced, the internal resistance of the battery is reduced, and the performance of the battery is improved. The potential difference refers to that the potential at the position of the anode or the cathode is higher due to the higher concentration of the gas at the air hole, and the potential at other positions is lower, so that the potential difference is formed.
In addition, in the preparation method provided by the embodiment of the invention, when the pore-forming agent blocks in different flow channel forms are prepared, the flow channel form of the pore-forming agent block is determined by the flow rate of the gas and/or the gas introduced into the gas channel, and when the regulated gas reaches the anode or the cathode, the regulated gas can be uniformly distributed.
3. The preparation method of the invention realizes the purpose of preparing the cathode air passage and the anode air passage in a non-mechanical processing mode by designing two pore-forming agent blocks which flow to the shape, overcomes the complexity of a processing technology for preparing the flow passage (air passage) by mechanical processing and achieves the purpose of simplifying the preparation technology.
4. According to the invention, the framework of the integrated structure of the connector and the support body is prepared by the preparation method of one-step pressing and one-step sintering, and the connector and the support body are sintered by one-step molding through powder metallurgy, so that the problem of uneven welding seams caused by welding connection is avoided, the sealing and connecting problems of the support body and the connector do not need to be considered when the cell stack is prepared, and the stability of the combination between the support body and the connector is greatly improved.
5. According to the preparation method, the two pore-forming agent blocks with the length and width smaller than the preset mold are designed, so that the prepared framework has the characteristic that the connector wraps the support, and the problem that the sealing performance and the connection point stability are poor due to the fact that the connector and the support are connected by adopting a welding technology is solved.
6. According to the preparation method, due to the adoption of the one-step forming and firing method, the obtained connector-support body integrated structure has no welding line, has the characteristics of uniform material components, high temperature resistance, strong oxidation resistance and the like in each region inside the structure, solves the problems of poor sealing property and oxidation resistance of the welding line at high temperature and the like caused by the defects of non-uniform stress and non-uniform components at the welding connection part in the welding method, improves the long-term stability of the battery, and overcomes the problem of performance attenuation of the battery.
7. According to the preparation method, the layers are sequentially filled in the mold, and the space between the pore-forming agent block body and the mold is filled with the metal powder serving as the connector, so that the connector and the support body integrated structure with the connector wrapping the periphery of the support body are realized, the self-sealing purpose is achieved, and the traditional methods such as mechanical welding and the like are not needed.
Drawings
FIG. 1 is a schematic cross-sectional view of an integrated structure of a support and a connector prepared according to an embodiment of the present invention;
FIG. 2 is a schematic cross-sectional view showing an integrated structure of a support and a connector prepared in example 2 of the present invention;
FIG. 3 is a schematic sectional view showing the integrated structure of a support and a connector prepared in example 3 of the present invention;
FIG. 4 is a schematic structural diagram of a pore former block of a first flow channel structure made in accordance with an embodiment of the present invention;
FIG. 5 is a schematic structural view of a pore former block of a first flow channel structure prepared in accordance with an embodiment of the present invention;
FIG. 6 is a schematic view of a scanning electron microscope showing the positional relationship among a connector, a support and an anode gas channel in an integrated structure of a connector and a support prepared by an embodiment of the present invention;
FIG. 7 is a flow chart illustrating an embodiment of a method for manufacturing a support and connector integrated structure according to the present invention;
fig. 8 is a schematic sectional view showing a cell stack having an integrated structure of supports and connectors, prepared in example 7 of the present invention;
FIG. 9 shows a schematic diagram of a conventional connection of a metal-supported solid oxide fuel cell in an embodiment of the invention;
fig. 10 shows a schematic view of the scanning electron microscope schematic view shown in fig. 6 corresponding to a specific position in fig. 1.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in further detail below. The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
In the prior art, the metal support SOFC uses a metal support body, so that the support body and the connector can be connected and sealed by using a conventional welding technology, and the welding technologies adopted in the related technologies include brazing and laser welding. However, the working temperature of the conventional SOFC is between 600-. Therefore, the connection and sealing problems between the connecting body and the support body still remain key problems in the field, and the development of the field is greatly promoted if the problems can be solved. Similarly, solid oxide electrolysis cells suffer from similar sealing problems. The welding technique operating region in the related art is shown in fig. 9.
The following provides a detailed description of the process flow of the present invention for preparing the integrated structure of support and connector, the cell stack and the electrolytic cell.
First, fig. 1 to 3 will be explained by taking a solid oxide fuel cell as an example:
referring to fig. 1, a cross-sectional view of an integrated structure of a support and a connector prepared according to an embodiment of the present invention is shown. As shown in the figure: 1-1 is a metal connector, 1-2 is a porous metal support, 1-3 is an anode gas passage, 1-4 is a cathode gas passage, wherein, as shown in figure 1, the cathode gas passage and the anode gas passage are separated by a compact transverse section of the connector, and in the same-side electrode (such as a cathode below figure 1), each flow passage is also separated by a longitudinal compact metal of the connector, so that gas can only flow in the flow passage. In addition, the support body is wrapped by the connecting body, so that the aim of sealing is fulfilled, and the connecting body is connected with the support body in a welding mode.
FIG. 2 is a schematic cross-sectional view showing the integrated structure of the support and the connector prepared in example 2 of the present invention. As shown in the figure: 2-1 is a metal connector, 2-2 is a porous metal support, 2-3 is an anode, 2-4 is an electrolyte layer, 2-5 is a cathode, and 2-6 is a gas channel. Wherein, the support body only has a very thin layer and is used for supporting the electrode, one part of the connector constructs an air flue, and the other part separates the cathode air flue from the anode air flue so as to prevent the mixed flow of the anode gas and the cathode gas.
FIG. 3 is a schematic cross-sectional view showing the integrated structure of the support and the connector prepared in example 3 of the present invention. As shown in the figure: 3-1 is a metal connector, 3-2 is an anode side porous metal support, 3-3 is an anode, 3-4 is an electrolyte layer, 3-5 is a cathode, 3-6 is a gas channel, and 3-7 is a cathode side porous metal support. The connecting body only has the function of separating the cathode air passage from the anode air passage, the support body not only has the function of supporting the electrode, but also has the function of constructing the air passage, as shown in the constructed anode air passage 3-6, and when the air passage is constructed by adopting the support body, because the porous metal support body precursor powder for preparing the support body contains the pore-forming agent, after the pore-forming agent is removed, the support body is composed of porous metal, the pore passage in the porous metal also has the function of a flow passage, gas can flow in the pore passage in the porous metal, so that the gas can be more uniformly distributed on the electrode surface when reaching the electrode, the potential difference in the electrode is reduced, and the performance of the battery is improved.
Fig. 4 and 5 respectively show structural schematic diagrams of pore-forming agent blocks of two flow channel structures prepared by the embodiment of the invention. As shown in the figure: the pore-forming agent block with the flow channel structure is formed by pressing a formed die, the length, the width, the thickness and the flow channel shape of the prepared pore-forming agent block can be adjusted according to actual requirements, the die corresponding to the pore-forming agent block with the required flow channel shape is prepared in advance, and then the pore-forming agent with the required flow channel shape is prepared by a pressing method. And, as shown in fig. 4 and 5, the right side of the channel-shaped pore-forming agent block is designed with a gas channel, so that the anode gas or the cathode gas can be introduced through the channel after the entire sealed connector and support integrated structure is successfully prepared.
Fig. 6 is a schematic scanning electron microscope showing the positional relationship among the connector, the support and the anode gas channel in the integrated structure of the connector and the support prepared in the embodiment of the present invention. As shown in fig. 6, the connecting body of the present invention covers the support body, the edge of the support body forms a self-sealing, and the anode air channel is a flow channel formed by removing the pore-forming agent block with a flow channel shape at a low temperature. Since fig. 6 is photographed by a scanning electron microscope, only a part of the entire integrated structure of the connecting body and the supporting body can be cut out and photographed, and thus fig. 6 shows a part of the entire integrated structure, as shown in fig. 10.
In a first aspect, an embodiment of the present invention provides a method for preparing an integrated structure of a support and a connector, as shown in fig. 7, the method specifically includes:
s101, preparing a first pore-forming agent block and a second pore-forming agent block by utilizing pore-forming agent powder, wherein a plurality of pores are distributed in the first pore-forming agent block and the second pore-forming agent block;
description of the drawings: preparing the pore-forming agent powder into a block with a flow channel shape by a preparation process, and removing the pore-forming agent in the later roasting treatment process to form a middle flow channel; and the sizes of the prepared first pore-forming agent block body and the second pore-forming agent block body are smaller than that of the mould. Wherein the plurality of pores distributed within the first pore former block are shaped differently than the plurality of pores distributed within the second pore former block; the shape is determined by the gas introduced into the pores and/or the flow rate of the gas.
S102, mixing metal powder and pore-forming agent powder to prepare porous metal support body precursor powder;
description of the drawings: the connector-support body integration comprises a compact connector part and a porous support body part, and an anode, an electrolyte and a cathode are sequentially prepared on the support body. Precursor powder formed by mixing metal powder and pore-forming agent is used for preparing the porous metal support body, and the porous metal support body can be formed after the processes of powder laying, pressing and sintering at the later stage.
S103, placing the first pore-forming agent block in a mold, and laying the metal powder on the first pore-forming agent block to form a first metal powder layer;
the width of the first pore-forming agent block body is smaller than that of the used mold, so that a space exists between the pore-forming agent block body and the mold and is used as a metal powder filling area of the connecting body. Therefore, after the metal powder completely covers the pore-forming agent block, the gap between the mold and the pore-forming agent block can be continuously filled, and a compact structure is obtained;
the first metal powder layer obtained in this step is illustrated as a portion of the joint below the anode gas flow channels 1-3 in fig. 1; the pore-forming agent which is formed by covering the flow channel with metal powder is laid to separate the anode air channel from the cathode air channel after sintering (the transverse part between 1-3 and 1-4 in figure 1); the flow channel shape pore-forming agent laid in the step is used for forming a cathode flow channel (1-4 in figure 1) by post sintering,
s104, placing the second pore-forming agent block on the first metal powder layer;
the second pore former block was placed to obtain the anode gas flow channel after the pore former removal operation.
S105, filling the metal powder into the plurality of pores of the second pore-forming agent block to obtain a filled second pore-forming agent block;
illustratively, the metal powder is filled here to prepare a protruding portion in the connected body, which is connected to the support body (e.g., the protruding portion connected to the support body in the connected body 2-1 in FIG. 2).
S106, laying the porous metal support body precursor powder on the filled second pore-forming agent block to form a second metal powder layer to obtain a multilayer structure system;
in the specific implementation, the laid porous metal support precursor powder is used for preparing the anode support, and when laying the porous metal support precursor powder, it is noted that the width of the porous metal support precursor powder layer is equal to the width of the pore-forming agent block (as shown by the width 1-2 in FIG. 1, the width 2-2 in FIG. 2, and the width 3-2 in FIG. 3), then, the metal powder as a connecting body (shown as two ends of 1-1 in figure 1, two ends of 2-1 in figure 2, and two ends of 3-1 in figure 3) is filled around the porous metal support precursor powder layer to obtain a metal powder-surrounded porous metal support precursor powder layer, this results in a unitary structure (portions at both ends of the connector as shown in fig. 1, 2 and 3) with the connector wrapped around the support body such that a self-sealing structure is formed after post-sintering. (i.e. without welding to the support body two sides sealing, but directly laying the metal powder as connector, using metal powder to fill the support body and the mold space, forming a wrapped type integrated structure, automatic sealing the support body, preventing its air leakage)
S107, filling the metal powder into a gap between the multilayer structure system and the die to obtain a filling structure system in which the metal powder surrounds the second metal powder layer;
in the production method according to the present invention, the filling method of filling the metal powder into the gap between the multilayer structure system and the mold in step S107 is not limited to the description of this step, and the gap between the mold and the first pore-forming agent block may be completely filled in step S103, and the thickness of the first metal powder layer obtained on the first pore-forming agent block may be 1 to 3 mm.
S108, pressing the filling structure system to obtain a formed green body;
description of the drawings: the structure is pressed under certain pressure to form a pressed compact, on one hand, the pressed compact is convenient to take out of a mold, and on the other hand, the pressed compact is used for improving the sintering forming performance of the connector-support body integrated structure. In specific implementation, the filling structure system is pressed in a pressure pressing mode to obtain a formed green body; wherein the pressure range of the pressing is 100 MPa-1000 MPa; the pore-forming agent content in the porous metal support precursor powder is 0-20 wt%; the pressing pressure value corresponds to the pore-forming agent content in the porous metal support precursor powder, and the pressing pressure value corresponds to the porosity of the porous support part in the integrated connector-support structure, for example, when the pore-forming agent content in the porous metal support precursor powder is 0 wt%, the pressure value should be a small pressure (such as 100 MPa-400 MPa), and the metal powder should be metal powder with a large particle size (such as 60-80 μm), so as to ensure that the porosity in the prepared porous metal support reaches a required value of a gas channel as a void.
S109, removing the pore-forming agent in the formed green body to obtain a processed green body;
in specific implementation, the pore-forming agent in the formed green body is removed in a heating removal mode to obtain a processed green body; the heating temperature range is 100-400 ℃; the removing time is 1-4 h.
Description of the drawings: since a large amount of gas is generated when the pore-forming agent in the form of a flow channel is removed, the gas needs to be removed before the green compact is sintered to ensure the integral sintering and forming performance of the connector-support. Since the pore-forming agent in the form of a flow channel has a large volume, if it is directly introduced into the operation of S110, a large amount of material (the pore-forming agent rapidly volatilizes at a high temperature) is inevitably volatilized, which may affect the moldability of the integrated structure.
And S110, roasting the processed green body to obtain a connector and support body integrated structure.
Wherein the sintering environment comprises at least one of a low pressure vacuum, a reducing atmosphere, and an inert atmosphere; the sintering temperature range is 1000-1400 ℃; the sintering time is 4-6 h;
description of the drawings: and sintering the pressed compact formed by pressing the powder to form a structure that the connecting body and the supporting body are integrated.
In specific implementation, the particle size of the metal powder is 10-80 μm, and the metal powder at least comprises one of iron-chromium alloy, nickel-chromium alloy and pure chromium;
in specific implementation, the content of the pore-forming agent in the porous metal support precursor powder is 0-20 wt%;
in specific implementation, the pore-forming agent at least comprises: one of ammonium bicarbonate, soluble starch, sucrose and carbon powder;
in specific implementation, the method for preparing the first pore-forming agent block and the second pore-forming agent block comprises the following steps: die pressing or screen printing.
In a second aspect, the present invention provides a method of making a solid oxide fuel cell/electrolyser, said method comprising:
preparing an integrated structure of the connecting body and the supporting body by adopting the method of the first aspect;
coating an anode material on the surface layer region of the connector and support body integrated structure to obtain an anode layer;
coating an electrolyte material on the surface of the anode layer to obtain an electrolyte layer;
coating a cathode material on the surface of the electrolyte layer to obtain a solid oxide fuel cell/electrolytic cell;
the second pore former block is removed to form an anode gas channel through which anode gas flows into the anode;
removing the first pore former block to form a cathode gas passage through which cathode gas flows into the cathode;
wherein the method of coating comprises at least: tape casting and sintering, and atmospheric plasma spraying.
In a third aspect, the present invention provides a solid oxide fuel cell stack comprising two or more solid oxide fuel cells according to the second aspect;
the solid oxide fuel cell stack is prepared by the following steps:
bonding the cathode of the first solid oxide fuel cell and the anode of the second solid oxide fuel cell by using a bonding agent to obtain a plurality of accumulated solid oxide fuel cells;
and sintering the accumulated plurality of solid oxide cells to obtain the solid fuel cell stack.
According to the preparation method of the connector and support integrated structure provided by the embodiment of the invention, the connector and the support are prepared into the integrated structure (without welding) in a one-step forming mode, and the powder metallurgy technology is widely applied to the preparation of the solid oxide fuel cell by combining a pore-forming agent to press and then remove the pore-forming agent, so that the problems of poor sealing at high temperature, cell performance attenuation and the like in the welding technology are solved.
Wherein, partially porous means a portion 1-2 as in fig. 1 (i.e., a porous metal support), partially hollow means a portion 1-3, 1-4 as in fig. 1 (an anode gas flow channel and a cathode gas flow channel), and partially dense means a portion 1-1 as in fig. 1 (a metal interconnect). The support body and the connector structure are integrated by pressing and sintering, so that the integrated structure, the air passage, the support body and the connector are respectively partially hollow, partially porous and partially dense.
In order that those skilled in the art will better understand the present invention, the integrated structure, cell/electrolyser and method of making the cell stack of the present invention are illustrated below by way of a number of specific examples.
Example 1
An ammonium bicarbonate block having a shape of two runners as shown in fig. 4 and 5, which is an ammonium bicarbonate block of 8cm x 8cm, was prepared by a pressing method through a mold prepared in advance corresponding to the ammonium bicarbonate block having a shape of a runner as shown in fig. 4 and 5. And mixing the iron-chromium alloy metal powder with ammonium bicarbonate to obtain porous metal support body precursor powder, wherein the content of the ammonium bicarbonate is 20 wt%.
Placing an ammonium bicarbonate block with a runner shape as shown in fig. 4 at the bottom of a 10cm x 10cm die, laying ferrochrome metal powder with a particle size of about 20 μm on the ammonium bicarbonate with the runner shape as shown in fig. 4, and completely covering the ammonium bicarbonate with the runner shape as shown in fig. 4 (including a space between a filling die and the ammonium bicarbonate block) with the ferrochrome metal powder to form a first metal powder layer; then placing the ammonium bicarbonate with the shape of the runner as shown in fig. 5 on the first metal powder layer, and continuously filling iron-chromium alloy metal powder into a plurality of runners of the ammonium bicarbonate with the shape of the runner as shown in fig. 5 to obtain a filled ammonium bicarbonate block with the shape of the runner as shown in fig. 5; then, laying the prepared porous metal area precursor powder on the filled ammonium bicarbonate block with the shape of the flow channel shown in fig. 5, and finally filling the space between the ammonium bicarbonate block and the mold with the ferrochrome metal powder to obtain a complete filling structure system of the powder layer of the porous metal area precursor powder surrounded by the ferrochrome metal powder. Pressing the structural system with 500MPa pressure to form a green body to obtain a formed green body, and removing the pore-forming agent ammonium bicarbonate in the formed green body at 100 ℃ for 4 hours to obtain a treated green body; and sintering the treated green body for 6h in a vacuum environment with high temperature of 1100 ℃ to form an integrated structure of the connector and the support body.
Preparing a 30 mu m-thick Ni/YSZ anode on the surface layer region of the integrated structure of the connector and the support body by means of tape casting and sintering, completely covering the surface porous region, covering a 10 mu m-thick YSZ electrolyte layer on the anode, enabling the YSZ electrolyte layer to be in contact with the dense region at the edge of the connector (as shown in the position relation of 2-4 and 2-1 in figure 2), and spraying a 20 mu m-thick LSCF cathode after sintering to obtain a solid oxide fuel single cell which shows good voltage and power output.
Wherein YSZ refers to yttria partially stabilized zirconia; LSCF refers to lanthanum strontium cobalt iron electrode material. It should be noted that the cathode, the anode and the electrolyte material in the following embodiments are the same as those in embodiment 1, and the cathode, the anode and the electrolyte material selected in the present invention can be selected from commonly used materials, which is not limited in the present invention.
Example 2
And mixing the pure chromium metal powder with ammonium bicarbonate to obtain porous metal support body precursor powder, wherein the content of the ammonium bicarbonate is 9 wt%. The ammonium bicarbonate block in this embodiment is an ammonium bicarbonate block of 8cm x 16 cm.
Preparing a pore-forming agent (ammonium bicarbonate) with a flow channel shape as shown in figure 4, placing the pore-forming agent (ammonium bicarbonate) at the bottom of a mold with the temperature of 10cm and 20cm, laying pure chromium metal powder with the particle size of about 40 mu m on the pore-forming agent (ammonium bicarbonate) with the flow channel shape, covering the pore-forming agent, placing the pore-forming agent (ammonium bicarbonate) with the flow channel shape as shown in figure 5 on the pore-forming agent and laying the pure chromium metal powder, then laying the porous metal area precursor powder on the uppermost layer, and finally filling the space around the mold and the porous metal area precursor powder layer with metal powder to surround the porous metal area precursor powder layer to obtain a filling structure system. Pressing the obtained filling structure system with the pressure of 1000MPa to form a green body, and removing the pore-forming agent ammonium bicarbonate in the green body at the temperature of 110 ℃ for 2 hours to obtain a treated green body; and sintering the treated green body for 6h in an inert atmosphere environment at 1400 ℃ to form an integrated structure of the connecting body and the supporting body.
Preparing a 30 mu m-thick Ni/YSZ anode on the surface layer region by an atmospheric plasma spraying method, enabling the Ni/YSZ anode to completely cover the surface layer porous region, covering a 15 mu m-thick YSZ electrolyte layer on the anode and contacting with the edge dense region, and spraying a 30 mu m-thick LSCF cathode after sintering to obtain a solid oxide fuel single cell which shows good voltage and power output.
Example 3
Mixing the iron-nickel alloy metal powder with ammonium bicarbonate to obtain porous metal support body precursor powder, wherein the content of the ammonium bicarbonate is 12 wt%. The ammonium bicarbonate block in this embodiment is 4cm x 4cm ammonium bicarbonate block.
Preparing a pore-forming agent with a flow channel shape as shown in FIG. 5, placing the pore-forming agent at the bottom of a mold of 5cm x 5cm, filling the obtained porous metal support precursor powder into the gap of the pore-forming agent with a flow channel shape as shown in FIG. 5 (obtaining a cathode metal support structure 3-7), laying an iron-nickel alloy metal powder with a particle size of about 15 μm on the pore-forming agent with a flow channel shape, covering the pore-forming agent (laying metal powder to cover the flow channel shape to separate an anode gas channel from a cathode gas channel after sintering (a transverse part between 3-2 and 3-7 in FIG. 3)), placing the pore-forming agent with a flow channel shape as shown in FIG. 4 thereon (the flow channel shape agent laid at this step is to form an anode gas flow channel for post-sintering (shown in 3-6 in FIG. 3)), and filling iron-nickel alloy metal powder around the pore-forming agent (obtaining a structure of 3-1 wrapping 3-2), then, the porous metal area precursor powder is laid in the gap of the pore-forming agent in the shape of the flow channel shown in fig. 4 (to obtain an anode metal support structure 3-2), the porous metal area precursor powder is laid on the uppermost layer, and finally, the space around the mold and the porous metal area precursor powder layer is filled with the metal powder to surround the porous metal area precursor powder layer, so that a filling structure system is obtained. Pressing the filling structure system with a pressure of 500MPa to form a green body, and obtaining a formed green body; removing the pore-forming agent ammonium bicarbonate in the formed green body at 200 ℃ for 1h to obtain a processed green body; and sintering the green body for 4h in a reducing atmosphere environment at 1050 ℃ to form an integrated structure of the connecting body and the supporting body.
Preparing a Ni/YSZ anode with the thickness of 20 microns on the surface layer area by an atmospheric plasma spraying method, enabling the Ni/YSZ anode to completely cover the porous area of the surface layer, covering a YSZ electrolyte layer with the thickness of 20 microns on the anode and contacting with the edge dense area, and spraying an LSCF cathode with the thickness of 20 microns to obtain a solid oxide fuel single cell, wherein the single cell shows good voltage and power output.
Example 4
The alloy powder selected in the embodiment is ferrochrome metal powder with the grain diameter of about 30 mu m, and the carbon powder block is a carbon powder block of 12cm x 12 cm.
Preparing a pore-forming agent with the shape of a flow channel shown in the figure 5, placing the pore-forming agent at the bottom of a die with the density of 15cm and the density of 15cm, and mixing ferrochrome metal powder with carbon powder to obtain porous metal support body precursor powder, wherein the content of the carbon powder is 15% wt. Laying ferrochrome metal powder on a pore-forming agent with a flow channel shape, covering the pore-forming agent, then placing the pore-forming agent with the flow channel shape shown in figure 4 on the pore-forming agent, laying ferrochrome metal powder, then laying porous metal area precursor powder on the uppermost layer, finally filling the space around the die and the porous metal area precursor powder layer with metal powder, and enclosing the porous metal area precursor powder layer to obtain a filling structure system. Pressing the filling structure system with a pressure of 350MPa to form a green body, and obtaining a formed green body; removing pore-forming agent carbon powder in the formed green body at 400 ℃ for 3h to obtain a processed green body; and sintering the green body for 6h in a reducing atmosphere at 1300 ℃ to form an integrated structure of the connecting body and the support body.
Preparing a Ni/YSZ fuel electrode with the thickness of 25 mu m on the surface layer area by an atmospheric plasma spraying method or a tape-casting and sintering method, completely covering the porous area of the surface layer, covering a YSZ electrolyte layer with the thickness of 10 mu m on the anode and contacting with the edge compact area, and spraying an LSM air electrode with the thickness of 20 mu m after sintering to obtain the solid oxide fuel electrolytic cell which shows good voltage and power output.
Example 5
Two runner-shaped soluble starch blocks as shown in fig. 4 and 5 were prepared in advance by screen printing, and the soluble starch blocks were 8cm x 8 cm. Mixing chromium powder with the grain diameter of 40 mu m and soluble starch to obtain porous metal support body precursor powder, wherein the content of the soluble starch is 15 wt%.
Placing a soluble starch block with the shape of a runner as shown in figure 4 at the bottom of a die with the density of 10cm and the density of 10cm, laying chromium powder with the grain size of 40 mu m on the soluble starch with the shape of the runner as shown in figure 4, and completely covering the soluble starch with the shape of the runner as shown in figure 4 with the chromium powder with the grain size of 40 mu m to form a first metal powder layer; then placing the soluble starch block with the shape of the runner as shown in figure 5 on the first metal powder layer, and continuously laying chromium powder with the particle size of 40 mu m to form a second metal powder layer; and then, laying the prepared porous metal area precursor powder on a second metal powder layer, and finally filling the space around the die and the porous metal area precursor powder layer with metal powder to surround the porous metal area precursor powder layer to obtain a filling structure system. Pressing the filling structure system with 100MPa pressure to form a green body to obtain a formed green body, and removing pore-forming agent soluble starch in the formed green body at 400 ℃ for 4h to obtain a treated green body; and sintering the treated green body at the high temperature of 1000 ℃ for 6h to form an integrated structure of the connector and the support body.
Preparing a 30 mu m-thick Ni/YSZ anode on the surface layer region of the integrated structure of the connector and the support body by means of tape casting and sintering, completely covering the surface porous region, covering a 10 mu m-thick YSZ electrolyte layer on the anode, enabling the YSZ electrolyte layer to be in contact with the dense region at the edge of the connector (as shown in the position relation of 2-4 and 2-1 in figure 2), and spraying a 20 mu m-thick LSCF cathode after sintering to obtain a solid oxide fuel single cell which shows good voltage and power output.
Example 6
Two kinds of sodium chloride blocks with flow channel shapes as shown in fig. 4 and 5 are prepared in advance by adopting a screen printing mode, and the sodium chloride blocks are 3cm of sodium chloride blocks of 3cm x 3 cm. Mixing iron-nickel alloy metal powder with the particle size of about 80 mu m with sodium chloride to obtain porous metal support body precursor powder, wherein the content of ammonium bicarbonate is 0 wt%.
Preparing a pore-forming agent with a flow channel shape as shown in figure 5, placing the pore-forming agent at the bottom of a mold with 5cm x 5cm, filling porous metal support precursor powder into a gap of the pore-forming agent with a flow channel shape as shown in figure 5, laying iron-nickel alloy metal powder with a particle size of about 10 microns on the pore-forming agent with a flow channel shape, covering the pore-forming agent, placing the pore-forming agent with a flow channel shape as shown in figure 4 on the pore-forming agent, laying the iron-nickel alloy metal powder, laying porous metal area precursor powder in the gap of the pore-forming agent with a flow channel shape as shown in figure 4, laying porous metal area precursor powder on the uppermost layer, filling the space around the mold and the porous metal area precursor powder layer with metal powder, and surrounding the porous metal area precursor powder layer to obtain a filling structure system. Pressing the structural system with a pressure of 1000MPa to form a green body, and obtaining a formed green body; removing the pore-forming agent sodium chloride in the formed green body at 200 ℃ for 2h to obtain a processed green body; and sintering the green body for 6h in a reducing atmosphere environment at 1050 ℃ to form an integrated structure of the connector and the support body.
Preparing a Ni/YSZ anode with the thickness of 20 microns on the surface layer area by an atmospheric plasma spraying method, enabling the Ni/YSZ anode to completely cover the porous area of the surface layer, covering a YSZ electrolyte layer with the thickness of 20 microns on the anode and contacting with the edge dense area, and spraying an LSCF cathode with the thickness of 20 microns to obtain a solid oxide fuel single cell, wherein the single cell shows good voltage and power output.
Example 7
Two kinds of flow channel-shaped ammonium bicarbonate blocks as shown in fig. 4 and 5 were prepared in advance by screen printing, and the ammonium bicarbonate block was 7cm x 7cm ammonium bicarbonate. Mixing nickel-chromium alloy metal powder with the grain diameter of 50 mu m with cane sugar to obtain porous metal support body precursor powder, wherein the content of the cane sugar is 20 wt%.
Placing the sucrose block with the flow channel shape shown in the figure 4 at the bottom of a die with the density of 10cm and the density of 10 mu m, laying the nichrome metal powder with the grain diameter of 10 mu m on the sucrose with the flow channel shape shown in the figure 4, and completely covering the sucrose with the flow channel shape shown in the figure 4 with the nichrome metal powder with the grain diameter of 10 mu m to form a first metal powder layer; putting the cane sugar with the shape of the runner as shown in figure 5 on the first metal powder layer, and continuously laying the nickel-chromium metal powder with the particle size of 10 mu m to form a second metal powder layer; and then, laying the prepared porous metal area precursor powder on a second metal powder layer, and finally filling the space around the die and the porous metal area precursor powder layer with metal powder to surround the porous metal area precursor powder layer to obtain a filling structure system. Pressing the structural system with 100MPa pressure to form a green body to obtain a formed green body, and removing pore-forming agents ammonium bicarbonate and sucrose in the formed green body at 400 ℃ for 4h to obtain a treated green body; and sintering the treated green body at the high temperature of 1400 ℃ for 4h to form an integrated structure of the connector and the support body.
Preparing a 30 mu m-thick Ni/YSZ anode on the surface layer region of the integrated structure of the connector and the support body by means of tape casting and sintering, completely covering the surface porous region, covering a 10 mu m-thick YSZ electrolyte layer on the anode, enabling the YSZ electrolyte layer to be in contact with the dense region at the edge of the connector (as shown in the position relation of 2-4 and 2-1 in figure 2), and spraying a 20 mu m-thick LSCF cathode after sintering to obtain a solid oxide fuel single cell which shows good voltage and power output.
Two or more prepared solid oxide fuel single cells are accumulated to form a cell stack, and the 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, then the cells are bonded layer by layer, and are sintered and cured to obtain the prepared solid oxide fuel cell stack, as shown in figure 8, the cell stack obtained by accumulating 4 single cells is shown in the figure.
It should be noted that, in the preparation method provided by the present invention, the pore-forming agent blocks with the same flow channel shape may also be used to prepare an integrated structure of the connector and the support body, so as to obtain the cathode air passage and the anode air passage with the same flow channel shape, and the preparation method is similar to that in the above examples 1 to 7; in the preparation method, the particle diameters of the metal powder of the support body and the metal powder of the connecting body can be the same or different, and the selected particle diameter can be adjusted according to actual requirements; the pore-forming agents used in the preparation process of the invention can be the same (for example, 1 to 6, one pore-forming agent is used) or different (for example, 7, two pore-forming agents are used).
The core of the invention is that the structure integrating the connector and the support body is prepared at one time by adopting the powder metallurgy technology, and because the used metal powder can become an integral structure after sintering, an additional connecting means is not needed for connection.
For simplicity of explanation, the method embodiments are described as a series of acts or combinations, but those skilled in the art will appreciate that the present invention is not limited by the order of acts, as some steps may occur in other orders or concurrently in accordance with the invention. Further, those skilled in the art will appreciate that the embodiments described in the specification are preferred embodiments and that the acts and elements referred to are not necessarily required to practice the invention.
The above detailed description of the integrated structure, the battery/electrolytic cell and the method for manufacturing the battery stack provided by the present invention, and the specific examples applied herein, have been provided to illustrate the principle and the embodiments of the present invention, and the above description of the examples is only provided to help understanding the method of the present invention and the core concept thereof; 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 preparation method of a support body and connector integrated structure is characterized by comprising the following steps:
preparing a first pore-forming agent block and a second pore-forming agent block by utilizing pore-forming agent powder, wherein a plurality of pores are distributed in the first pore-forming agent block and the second pore-forming agent block;
mixing metal powder and pore-forming agent powder to prepare porous metal support body precursor powder;
placing the first pore-forming agent block in a mold, and laying the metal powder on the first pore-forming agent block to form a first metal powder layer;
placing the second pore former block on the first metal powder layer;
filling the metal powder into the plurality of pores of the second pore-forming agent block to obtain a filled second pore-forming agent block;
laying the porous metal support body precursor powder on the filled second pore-forming agent block to form a second metal powder layer to obtain a multilayer structure system;
filling the gap between the multilayer structure system and the mold with the metal powder to obtain a filled structure system in which the metal powder surrounds the second metal powder layer;
pressing the filling structure system to obtain a formed green body;
removing the pore-forming agent in the formed green body to obtain a processed green body;
and roasting the treated green body to obtain a connector and support body integrated structure.
2. The method of claim 1, wherein the shape of the internally distributed plurality of pores of the first pore former block is different from the shape of the internally distributed plurality of pores of the second pore former block;
the shape determining factor includes at least the gas introduced and the flow rate of the gas.
3. The method of claim 1, wherein said pressing said filled structural system to provide a shaped green body comprises:
pressing the filling structure system in a pressure pressing mode to obtain a formed green body; wherein the pressure range of the pressing is 100 MPa-1000 MPa; the pore-forming agent content in the porous metal support precursor powder is 0-20 wt%;
and the pressed pressure value corresponds to the content of the pore-forming agent in the porous metal support body precursor powder, and the pressed pressure value corresponds to the porosity of the porous support body part in the integrated structure of the connector and the support body.
4. The method of claim 1, wherein removing the pore former from the shaped green body to provide a treated green body comprises:
removing the pore-forming agent in the formed green body in a heating removal mode to obtain a processed green body; the heating temperature range is 100-400 ℃; the removing time is 1-4 h.
5. The method of claim 1, wherein the firing environment comprises at least one of a low pressure vacuum, a reducing atmosphere, and an inert atmosphere during firing of the treated green body; the roasting temperature range is 1000-1400 ℃; the roasting time is 4-6 h.
6. The method according to claim 1, wherein the metal powder has a particle size of 10 to 80 μm, and the metal powder includes at least one of ferrochrome, nichrome, and pure chromium.
7. The method of claim 1, wherein the pore former comprises at least: ammonium bicarbonate, soluble starch, sucrose, sodium chloride and carbon powder.
8. The method of claim 1, wherein preparing the first and second pore former blocks comprises: die pressing or screen printing.
9. A method of making a solid oxide fuel cell/electrolyser, comprising:
preparing a structure integrating a connector and a support by using the method of any one of claims 1 to 8;
coating an anode material on the surface layer region of the connector and support body integrated structure to obtain an anode layer;
coating an electrolyte material on the surface of the anode layer to obtain an electrolyte layer;
coating a cathode material on the surface of the electrolyte layer to obtain a solid oxide fuel cell/electrolytic cell;
wherein the method of coating comprises at least: tape casting, or atmospheric plasma spraying.
10. A solid oxide fuel cell stack comprising two or more solid oxide fuel cells according to claim 9;
the solid oxide fuel cell stack is prepared by the following steps:
bonding the cathode of the first solid oxide fuel cell and the anode of the second solid oxide fuel cell by using a bonding agent to obtain a plurality of accumulated solid oxide fuel cells;
and sintering the accumulated plurality of solid oxide cells to obtain the solid fuel cell stack.
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CN114944498A (en) * 2022-05-26 2022-08-26 西安交通大学 Integrated connector supported electric symbiotic solid oxide fuel cell/cell stack reactor
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