A self-sealing indirect internal reforming solid oxide fuel cell and a method of making the same

Abstract

The application discloses a self-sealing indirect internal reforming solid oxide fuel cell and a preparation method thereof, and belongs to the technical field of fuel cells. The preparation steps of the cell comprise the following steps: carrying out structure and function integrated design on the self-sealing indirect internal reforming solid oxide fuel cell; realizing integral forming of a connecting body reforming plate by using additive manufacturing technology on the composite material of the connecting body body high-temperature alloy material and the reforming porous area high-temperature alloy and high-activity catalyst; carrying out stress relief annealing and flattening treatment on the formed connecting body reforming plate; and adopting a plasma spraying method to sequentially deposit an anode layer, an electrolyte layer and a cathode layer on the side of the cell support porous area away from the reforming synthesis gas flow channel. The method realizes the integral forming of the connecting body reforming plate heterogeneous alloy gradient material by using the regional powder laying technology, is suitable for the preparation of a new type of complex structure fuel cell, the method is simple and easy to operate, has high precision, and can obtain a multifunctional fuel cell with high quality, high efficiency and long service life.

Description

Technical Field

[0001] This invention relates to the field of battery technology, and more specifically, to a self-sealed indirect internal reforming solid oxide fuel cell and its preparation method. Background Technology

[0002] Solid oxide fuel cells (SOFCs) are all-solid-state reaction devices that directly convert the chemical energy of fuel and oxidant into electrical energy. Their basic structural units mainly include the anode, cathode, and electrolyte. The most common SOFC stack configurations are planar and tubular. The former has a simple structure, is easy to modularly assemble, and has a short current conduction path, resulting in higher power density. However, this type of stack has drawbacks such as a large sealing area, difficulty in sealing at high temperatures, and thermal expansion mismatch between components.

[0003] Furthermore, solid oxide fuel cells (SOFCs) have the widest range of usable fuels due to their high operating temperatures. They can use not only hydrogen but also hydrocarbon fuels such as methane, syngas, and ethanol. When using hydrocarbon fuels, they typically need to be reformed into syngas before entering the anode for electrochemical reactions. While internal reforming reduces the complexity and cost of external reforming equipment, the very rapid, strongly endothermic chemical reactions require a large amount of heat, creating a significant temperature gradient within the cell. The resulting thermal stress can easily damage the cell structure and lead to performance degradation. Moreover, hydrocarbon fuels are highly susceptible to cracking during high-temperature internal reforming at the anode, forming carbon deposits that cover the anode active sites, causing a significant decrease in cell performance and even premature cell failure.

[0004] Therefore, designing novel planar solid oxide fuel cells with multiple functions and effectively solving problems such as battery sealing and anode carbon deposition are common technical challenges faced by researchers in the field of fuel cells. Furthermore, achieving precise fabrication of the complex internal structures of multifunctional solid oxide fuel cells is also a key fabrication technology that those skilled in the art urgently need to master.

[0005] In view of this, the present invention is proposed. Summary of the Invention

[0006] One of the objectives of this invention is to provide a method for preparing a self-sealing indirect internal reforming solid oxide fuel cell. This method uses regional powder spreading technology to achieve integrated molding of the connecting reforming plate heterogeneous alloy gradient material additive manufacturing. It can be applied to the preparation of novel fuel cells with complex structures. Furthermore, this method is simple to operate, has high precision, and can obtain high-quality multifunctional fuel cells, thus extending their service life.

[0007] A second objective of this invention is to provide an indirect internal reforming solid oxide fuel cell that is self-sealed with hydrocarbon fuel and reformed gas obtained by the above-described preparation method.

[0008] This application can be implemented as follows:

[0009] In a first aspect, the present invention provides a method for preparing a self-sealing indirect internal reforming solid oxide fuel cell, comprising the following steps:

[0010] S1: A structural-functional integrated design is carried out for a self-sealed indirect internal reforming solid oxide fuel cell. The self-sealed internal reforming solid oxide fuel cell includes a connecting weight reforming plate and a single cell. The connecting weight reforming plate includes a connecting body, the upper and lower surfaces of which are respectively provided with a battery support porous region and an oxidation gas flow channel. The lower surface of the battery support porous region is provided with a reforming reforming gas flow channel. A reforming porous region for catalytic reaction of reformed fuel is provided between the reforming reforming gas flow channel and the oxidation gas flow channel. The reforming porous region is separated from the reforming reforming gas flow channel and the oxidation gas flow channel by a leak-free wall to achieve sealing of the reformed fuel. The single cell includes an anode, an electrolyte, and a cathode.

[0011] S2: The integral plate for connecting weights is prepared using additive manufacturing technology. The preparation of the integral plate for connecting weights includes:

[0012] Sa: Preparation of Region A of the Connector Weight Reorganization Plate: Region A of the connector weight reorganization plate is a solid region located below the porous reorganization zone in the connector body. During preparation, high-temperature resistant oxide alloy powder is laid in the preset forming area of ​​Region A of the connector weight reorganization plate. The additive manufacturing process is used to form the connector body and the oxidizing gas flow channel layer by layer through the melting-solidification process.

[0013] Sb: Preparation of the connecting weight reorganizing plate B region: The connecting weight reorganizing plate B region includes a reforming porous region and a solid region of the connecting body with the same height as the reforming porous region. During preparation, on the upper surface of the connecting weight reorganizing plate A region, high-temperature resistant oxide alloy powder is laid in the solid region of the connecting weight reorganizing plate B region, and a composite powder composed of high-temperature resistant oxide alloy and a material with catalytic reforming properties is laid in the porous region. Using additive manufacturing process, the material is formed layer by layer through melting-solidification process to achieve gradient connection between the high-temperature alloy material in the solid region and the composite material in the porous region, thus completing the integral molding of the heterogeneous material of the connecting weight reorganizing plate B region.

[0014] Sc: Preparation of the C region of the connecting body weight reorganization plate: The C region of the connecting body weight reorganization plate includes the solid region located above the reorganization porous region in the connecting body body and the battery support porous region. During preparation, high temperature resistant oxide alloy powder is laid in the preset forming area of ​​the C region of the connecting body weight reorganization plate. The additive manufacturing process is used to form the solid region of the C region of the connecting body weight reorganization plate, the battery support porous region and the reorganization forming airflow channel through the melting-solidification process.

[0015] S3: Stress-relieving annealing and leveling treatment is performed on the formed connecting weight plate;

[0016] S4: Using plasma spraying technology, the anode layer, electrolyte layer and cathode layer are sequentially deposited on the side of the porous area of ​​the battery support away from the recombination gas flow channel. The electrolyte layer completely covers all areas of the anode layer and the upper surface of the connector body, realizing the self-sealing of the recombination gas flow channel.

[0017] In an optional implementation, the integrated structural and functional design includes: the spatial structure of the connecting weight reforming plate, the surface micro-features of the reforming porous region, the battery support porous region, the upper surface of the connecting body and the oxidation gas flow channel, the stacking of the battery functional layers, and the design of the catalyst material for the reforming porous region and the high-temperature conductive chromium protective coating for the oxidation gas flow channel.

[0018] In optional implementations, the additive manufacturing technology employs selective laser melting, selective electron beam melting, or binder jet additive manufacturing.

[0019] Preferably, selective laser melting technology is used, wherein:

[0020] The process conditions for the solid parts in each region of the connecting weight-reinforcing plate include: laser power of 200-250W, scanning speed of 1000-1150mm / s, scanning spacing of 0.05-0.1mm, spot size of 30-80μm, and laser wavelength of 900-1070nm.

[0021] The process conditions for the reforming porous region in region B of the connecting reforming plate include: laser power of 150-190W, scanning speed of 750-900mm / s, scanning spacing of 0.1-0.2mm, spot size of 30-80μm, and laser wavelength of 900-1070nm.

[0022] The process conditions for the battery support porous area in the C region of the connecting weight reorganization plate include: laser power of 80-100W, scanning speed of 500-700mm / s, scanning spacing of 0.12-0.15mm, spot size of 30-80μm, and laser wavelength of 900-1070nm.

[0023] In an optional implementation, stress-relief annealing and leveling are performed in a vacuum heat treatment furnace.

[0024] In an optional embodiment, the annealing temperature is 500-900°C, and / or the annealing time is 4-6 hours.

[0025] In an optional implementation, between S3 and S4, the method further includes: pre-treating the upper and lower surfaces of the connecting weight remodeling plate to obtain a fresh, clean, roughened surface required for plasma spraying deposition.

[0026] In an optional implementation, the pretreatment includes at least one of sandblasting and laser cleaning.

[0027] In an optional embodiment, in S4, the electrolyte layer is prepared by vacuum plasma spraying.

[0028] In an optional embodiment, S5 is also included: depositing a high-temperature conductive chromium protective coating on the surface of the side of the connecting weight-reforming plate with an oxidation airflow channel using a plasma spraying method.

[0029] Secondly, this application provides a solid oxide fuel cell, which is prepared by any of the preparation methods described in the foregoing embodiments.

[0030] In an optional embodiment, the material used to prepare the main body of the solid oxide fuel cell includes iron-based or chromium-based alloy materials; more preferably, it includes at least one of SUS430, Croferr22, ZMG232 and T441.

[0031] And / or, the catalyst is a highly active nanocatalyst, preferably including at least one of Al2O3, NiO, CeO2 and La2O3;

[0032] And / or, the materials used to prepare the high-temperature conductive chromium protective coating include at least one of rare earth perovskite and spinel.

[0033] In an optional embodiment, the rare earth perovskite includes at least one of (La,Sr)CrO3, (La,Sr)MnO3, and (La,Sr)CoO3.

[0034] In an optional embodiment, the spinel includes at least one of (Mn,Co)3O4 and (Mn,Cu)3O4.

[0035] In optional embodiments, the thickness of the connecting reforming plate is 2.5-5.0 mm; and / or, the thickness of the anode layer is 15-40 μm; and / or, the thickness of the electrolyte layer is 15-30 μm; and / or, the thickness of the cathode layer is 20-40 μm; and / or, the thickness of the catalyst supported on the surface of the reforming porous region is 0.5-10 μm; and / or, the thickness of the protective coating is 30-60 μm.

[0036] The beneficial effects of this application include:

[0037] The self-sealing indirect internal reforming solid oxide fuel cell fabrication method provided in this application can realize the integrated molding of the connecting reforming plate, especially the integrated additive manufacturing of heterogeneous alloy gradient materials in region B of the connecting reforming plate. It can be applied to the fabrication of novel fuel cells with complex structures. Furthermore, the method is simple to operate, has high precision, and can obtain high-quality multifunctional fuel cells, thus extending their service life.

[0038] The resulting solid oxide fuel cell is smaller in size and lower in cost. It not only solves the problems of anode carbon buildup covering catalytic active sites and reducing anode activity, but also avoids the risk of excessive thermal stress caused by the rapid, strongly endothermic catalytic reforming reaction leading to a low anode temperature at the fuel inlet, thus preventing the formation of a large temperature gradient and increasing the risk of structural damage. Furthermore, it addresses the issue of structural damage caused by direct contact between the gaseous medium and the electrode functional layer surface, leading to the separation of heterogeneous interfaces within the battery. Attached Figure Description

[0039] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0040] Figure 1 A partial structural schematic diagram of the self-sealing indirect internal reforming solid oxide fuel cell structure provided in this application;

[0041] Figure 2 for Figure 1 A schematic diagram of the structure of the connecting weight-integrating plate.

[0042] Icons: 10-Connector weight reforming plate; 11-Connector body; 111-First side; 112-Second side; 113-Third side; 114-Fourth side; 115-Reformation gas inlet; 116-Reformation gas outlet; 117-Oxidation gas inlet; 118-Oxidation gas outlet; 119-Reformation fuel inlet; 120-Reformation fuel outlet; 12-Porous area of ​​battery support; 13-Reformation gas flow channel; 14-Reformation porous area; 15-Oxidation gas flow channel; 20-Anode; 30-Electrolyte; 40-Cathode. Detailed Implementation

[0043] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0044] The solid oxide fuel cell and its preparation method provided in this application are described in detail below.

[0045] This application proposes a method for preparing a solid oxide fuel cell, comprising the following steps:

[0046] S1: Integrate structural and functional design for a self-sealing indirect internal reforming solid oxide fuel cell.

[0047] A self-sealed, indirectly reformed solid oxide fuel cell includes a connecting reforming plate 10 and a single cell. Please refer to the following: Figure 1 and Figure 2 The connecting reforming plate 10 includes a connecting body 11. The upper and lower surfaces of the connecting body 11 are respectively provided with a battery support porous region 12 and an oxidation gas flow channel 15. The lower surface of the battery support porous region 12 is provided with a reforming reforming gas flow channel 13. A reforming porous region 14 for catalytic reaction of reformed fuel is provided between the reforming reforming gas flow channel 13 and the oxidation gas flow channel 15. The reforming porous region 14 is separated from the reforming reforming gas flow channel 13 and the oxidation gas flow channel 15 by a leak-free wall to achieve sealing of the reformed fuel.

[0048] The single cell includes an anode, an electrolyte, and a cathode. The anode 20, electrolyte 30, and cathode 40 are sequentially deposited on the side of the porous region 12 of the cell support away from the recombination gas flow channel 13.

[0049] The area of ​​the aforementioned battery support porous region 12 is smaller than the area of ​​the upper surface of the connector body 11. The battery support porous region 12 is connected to the recombination syngas flow channel 13 to allow the syngas to diffuse through the pores of the battery support porous region 12 to the anode 20 located on the upper surface of the battery support porous region 12.

[0050] Anode 20, electrolyte 30 and cathode 40 are sequentially deposited on the upper surface of the porous region 12 supporting the battery.

[0051] The anode 20 covers the upper surface of the porous region 12 supporting the battery, while the electrolyte 30 covers the entire connector body 11 and the upper surface of the anode 20. The projection of the cathode 40 coincides with the area occupied by the recombination gas flow channel 13.

[0052] In this application, the reorganized porous region 14 is a region having a polyhedral lattice unit structure. Exemplarily, the polyhedron can be, for example, a hexahedron or an octahedron.

[0053] In some embodiments, the number of reforming porous regions 14 may be only one. In other embodiments, the reforming porous region 14 includes at least two porous sub-regions. When the reforming porous region 14 includes at least two porous sub-regions, adjacent porous sub-regions are separated by ribs, and the multiple porous sub-regions are arranged sequentially along a direction perpendicular to the reforming fuel flow direction.

[0054] In this application, the porosity of each porous sub-region gradually decreases along the reformed fuel flow direction, preferably in a gradient decrease.

[0055] It should be noted that the internal reforming of fuel within the battery is a very fast, strongly endothermic chemical reaction that requires the absorption of a large amount of heat. This application, by setting the porosity to a gradient reduction mode, helps to avoid a large temperature gradient inside the battery during the reforming process, reducing the resulting thermal stress and preventing damage to the battery structure. Furthermore, this method not only prevents carbon deposits formed from hydrocarbon fuels from covering the surface of the anode 20 active sites, thus avoiding a significant decrease in battery performance, but also prevents structural damage such as separation of heterogeneous interfaces inside the battery.

[0056] For reference, the maximum porosity mentioned above shall not exceed 90%, and the minimum porosity shall not be less than 50%. The pore size of each pore in the reforming porous region 14 may be 100-1000 μm, and the total thickness of the reforming porous region 14 may be 0.5-2.0 mm.

[0057] For ease of understanding, the recombination airflow channel 13 can be a groove that is recessed from top to bottom. Similarly, the oxidation airflow channel 15 can be a groove that is recessed from the lower surface of the connector body 11.

[0058] Preferably, all surfaces in contact with the reformed fuel are provided with a catalyst for the reforming reaction of the hydrocarbon fuel. Alternatively, only certain parts of the surfaces in contact with the reformed fuel may be provided with a catalyst for the reforming reaction of the hydrocarbon fuel.

[0059] In this application, the connector body 11 is provided with at least one pair of through holes for the flow of at least one of hydrocarbon fuel, recombination gas and oxidizing gas.

[0060] In some specific embodiments, the connection body 11 and the through hole are arranged as follows: taking the connection body 11 as an example, which is quadrilateral (such as a rectangle), it has a first side 111, a second side 112, a third side 113 and a fourth side 114 connected end to end, wherein the first side 111 and the third side 113 are arranged opposite to each other, and the second side 112 and the fourth side 114 are arranged opposite to each other.

[0061] The through-hole includes a reforming gas inlet 115, a reforming gas outlet 116, an oxidizing gas inlet 117, an oxidizing gas outlet 118, a reforming fuel inlet 119, and a reforming fuel outlet 120.

[0062] The reforming gas inlet 115 is located near the first side 111 of the connecting body 11 and penetrates the upper and lower surfaces of the connecting body 11; the reforming gas outlet 116 is located near the third side 113 of the connecting body 11 and penetrates the upper and lower surfaces of the connecting body 11; the oxidation gas inlet 117 is located near the third side 113 of the connecting body 11 and penetrates the upper and lower surfaces of the connecting body 11; the oxidation gas outlet 118 is located near the first side 111 of the connecting body 11 and penetrates the upper and lower surfaces of the connecting body 11; the reforming fuel inlet 119 is located near the second side 112 of the connecting body 11 and penetrates the upper and lower surfaces of the connecting body 11; and the reforming fuel outlet 120 is located near the fourth side 114 of the connecting body 11 and penetrates the upper and lower surfaces of the connecting body 11.

[0063] The two ends of the reforming gas flow channel 13 are connected to the reforming gas inlet 115 and the reforming gas outlet 116, respectively. The two ends of the oxidation gas flow channel 15 are connected to the oxidation gas inlet 117 and the oxidation gas outlet 118, respectively. The two ends of the reforming porous region 14 are connected to the reforming fuel inlet 119 and the reforming fuel outlet 120, respectively.

[0064] For example, the recombination gas flow channel 13 can be formed by multiple spaced recombination gas sub-channels, and the extension direction of each recombination gas sub-channel is the flow direction of the recombination gas, specifically extending from the first side 111 to the third side 113. Similarly, the oxidation gas flow channel 15 can also be formed by multiple spaced oxidation gas sub-channels, and the extension direction of each oxidation gas sub-channel is the flow direction of the oxidation gas, specifically extending from the third side 113 to the first side 111.

[0065] In some embodiments, there may be two recombination gas inlets 115 and one recombination gas outlet 116. In this case, one end of some recombination gas sub-channels is connected to one of the recombination gas inlets 115, one end of the remaining recombination gas sub-channels is connected to the remaining recombination gas inlet 115, and the other end of all recombination gas sub-channels is connected to the recombination gas outlet 116.

[0066] The connection relationships between oxidizing gas inlet 117, oxidizing gas outlet 118, and oxidizing gas sub-channels, as well as the connection relationships between reforming fuel inlet 119, reforming fuel outlet 120, and porous sub-regions, can be set with reference to the connection relationships between reforming gas inlet 115, reforming gas outlet 116, and reforming gas sub-channels.

[0067] It should be noted that in other embodiments, the shape of the connector body 11, as well as the location and number of through holes, can be adjusted according to actual needs. Furthermore, other aspects of solid fuel cells not detailed in this application can be found in the relevant prior art, and will not be elaborated upon here.

[0068] In this application, the integrated structural and functional design may include, for example, the spatial structure of the connecting weight reforming plate 10, the surface features of the reforming porous region 14, the battery support porous region 12, the upper surface of the connecting body 11 and the oxidation gas flow channel 15, the stacking of battery functional layers, and the design of the catalyst material of the reforming porous region 14 and the high-temperature conductive chromium protective coating of the oxidation gas flow channel 15.

[0069] Further, in step S2: the connecting weight integral plate 10 is prepared using additive manufacturing technology.

[0070] For reference, the preparation of the connecting weight-integrating plate 10 includes steps Sa to Sc.

[0071] Sa: Preparation of the connecting body weight-reinforcing plate A region: The connecting body weight-reinforcing plate A region is a solid region located below the reforming porous region 14 in the connecting body body 11. During preparation, high-temperature resistant oxide alloy powder is laid in the preset forming area of ​​the connecting body weight-reinforcing plate A region. The additive manufacturing process is used to form the connecting body body 11 and the oxidizing gas flow channel (oxidizing gas flow channel 15) layer by layer through the melting-solidification process.

[0072] Sb: Preparation of the connecting weight solid plate region B: The connecting weight solid plate region B includes a reforming porous region 14 and a solid region of the connecting body with the same height as the reforming porous region 14. During preparation, on the upper surface of the connecting weight solid plate region A, high-temperature resistant oxide alloy powder is laid in the solid region of the connecting weight solid plate region B, and composite powder composed of high-temperature resistant oxide alloy and materials with catalytic reforming properties (including one or more composite powders of Ni, Al, Al2O3, NiO, CeO2, La2O3, etc.) is laid in the porous region. Using additive manufacturing process, the material is formed layer by layer through melting-solidification process to achieve gradient connection between the high-temperature alloy material in the solid region and the composite material in the porous region, thus completing the integral molding of the heterogeneous material of the connecting weight solid plate region B.

[0073] In the aforementioned Sb, two different materials are laid in the reforming porous region 14 and the corresponding connector body 11 through a layer-by-layer powder-laying method. Different process parameters are used to form the solid region of the connector body and the catalytic reforming region. Specifically, the solid region and the porous region of the connector body are integrally connected by a gradient alloy / composite material; the connector body adopts a commonly used high-temperature resistant metal alloy, and the material of the reforming porous region is a high-temperature metal alloy and a composite material with catalytic reforming properties.

[0074] Sc: Preparation of the connecting weight reorganization plate C region: The connecting weight reorganization plate C region includes a solid region located above the reorganization porous region 14 in the connecting body and a battery support porous region 12. During preparation, high-temperature resistant oxide alloy powder is laid in the preset forming area of ​​the connecting weight reorganization plate C region. Using additive manufacturing process, it is formed layer by layer through melting-solidification process to complete the forming of the solid region of the connecting weight reorganization plate C region, the battery support porous region 12 and the reorganization forming airflow channel 13.

[0075] By integrating the connecting weight plate A region, connecting weight plate B region, and connecting weight plate C region into a single molding process, the self-sealing of the reformed hydrocarbon fuel gas path is achieved.

[0076] In this application, selective laser melting is preferred for additive manufacturing. However, other additive manufacturing methods, such as selective electron beam melting or binder jet additive manufacturing, are also permitted.

[0077] For reference, the process conditions for the solid portions in each region of the connecting weight plate 10 include: laser power of 200-250W (e.g., 200W, 210W, 220W, 230W, 240W, or 250W), scanning speed of 1000-1150mm / s (e.g., 1000mm / s, 1050mm / s, 1100mm / s, or 1150mm / s), scanning spacing of 0.05-0.1mm (e.g., 0.05mm, 0.06mm, 0.07mm, 0.08mm, 0.09mm, or 0.1mm), spot size of 30-80μm (e.g., 30μm, 40μm, 50μm, 60μm, 70μm, or 80μm), and laser wavelength of 900-1070nm.

[0078] The process conditions for the reforming porous region 14 in the B region of the connecting reforming plate include: laser power of 150-190W (e.g., 150W, 160W, 170W, 180W or 190W), scanning speed of 750-900mm / s (e.g., 750mm / s, 800mm / s, 850mm / s or 900mm / s), scanning spacing of 0.1-0.2mm (e.g., 0.1mm, 0.15mm or 0.2mm), spot size of 30-80μm (e.g., 30μm, 40μm, 50μm, 60μm, 70μm or 80μm), and laser wavelength of 900-1070nm.

[0079] Preferably, the surface features of the polyhedral lattice unit structure of the reformed porous region 14 are controlled by optimizing the scanning strategy to maximize its catalytic surface area.

[0080] The process conditions for the battery support porous region 12 in the C region of the connecting weight reorganization plate include: laser power of 80-100W (e.g., 80W, 85W, 90W, 95W or 100W), scanning speed of 500-700mm / s (e.g., 500mm / s, 550mm / s, 600mm / s, 650mm / s or 700mm / s), scanning spacing of 0.12-0.15mm (e.g., 0.12mm, 0.13mm, 0.14mm or 0.15mm), spot size of 30-80μm (e.g., 30μm, 40μm, 50μm, 60μm, 70μm or 80μm), and laser wavelength of 900-1070nm.

[0081] In this solid oxide fuel cell, the material used to prepare the connector body may, by way of example, include iron-based or chromium-based alloy materials, such as at least one of SUS430, Croferr22, ZMG232 and T441.

[0082] The catalyst used in this application is preferably a highly active nanocatalyst, such as at least one of Al2O3, NiO, CeO2 and La2O3.

[0083] S3: Perform stress-relieving annealing and leveling treatment on the formed connecting weight plate 10.

[0084] The stress-relieving annealing and leveling processes described above can be carried out in a vacuum heat treatment furnace.

[0085] For reference, the annealing temperature can be 500-900℃, such as 500℃, 550℃, 600℃, 650℃, 700℃, 750℃, 800℃, 850℃, or 900℃, or any other value within the 500-900℃ range. The annealing time can be 4-6 hours, such as 4 hours, 5 hours, or 6 hours, or any other value within the 4-6 hour range.

[0086] Furthermore, the upper and lower surfaces of the connecting weight-integrating plate 10 are pretreated to obtain a fresh, clean, roughened surface required for plasma spraying deposition.

[0087] The aforementioned pretreatment may include at least one of sandblasting and laser cleaning.

[0088] The specific operation of this part can be referred to the relevant existing technology, and will not be elaborated on here.

[0089] S4: Using plasma spraying technology, the anode 20, electrolyte 30, and cathode 40 are sequentially deposited on the side of the porous region 12 of the battery support away from the recombination gas flow channel 13. The electrolyte 30 completely covers all areas of the anode 20 and the upper surface of the connector body 11, achieving self-sealing of the recombination gas flow channel. A dense electrolyte layer can be obtained by using vacuum plasma spraying.

[0090] Furthermore, it also includes S5: depositing a high-temperature conductive chromium protective coating on the surface of the side of the connecting weight-integration plate 10 with the oxidation airflow channel 15 using a plasma spraying method.

[0091] The materials used to prepare the aforementioned protective coating may include at least one of rare earth perovskites and spinels. Rare earth perovskites may, for example, include at least one of (La,Sr)CrO3, (La,Sr)MnO3, and (La,Sr)CoO3. Spinels may, for example, include at least one of (Mn,Co)3O4 and (Mn,Cu)3O4.

[0092] In addition, this application also provides a solid oxide fuel cell prepared by the above-described preparation method.

[0093] For reference, the thickness of the connecting weight plate 10 can be 2.5-5.0mm, such as 2.5mm, 3.0mm, 3.2mm, 3.5mm, 3.8mm, 4.0mm, 4.2mm, 4.5mm, 4.8mm or 5.0mm, or any other value within the range of 2.5-5.0mm.

[0094] The thickness of anode 20 can be 15-40μm, such as 15μm, 20μm, 25μm, 30μm, 35μm or 40μm, or any other value in the range of 20-40μm.

[0095] The thickness of electrolyte 30 can be 15-30 μm, such as 15 μm, 18 μm, 20 μm, 22 μm, 25 μm, 28 μm or 30 μm, or any other value within the range of 15-30 μm.

[0096] The thickness of the cathode 40 can be 20-40μm, such as 20μm, 25μm, 30μm, 35μm or 40μm, or any other value within the range of 20-40μm.

[0097] The thickness of the catalyst supported on the surface of the reformed porous region 14 can be 0.5-10 μm, such as 0.5 μm, 1 μm, 2 μm, 5 μm, 8 μm or 10 μm, or any other value in the range of 0.5-10 μm.

[0098] The thickness of the high-temperature conductive chromium protective coating can be 30-60μm, such as 30μm, 35μm, 40μm, 45μm, 50μm, 55μm or 60μm, or any other value within the range of 30-60μm.

[0099] As described above, the method provided in this application enables the integrated fabrication of the connecting weight reforming plate 10 with the above-described structure. It is applicable to structurally complex anti-carbon-deposit self-sealing internal reforming solid oxide fuel cells. Furthermore, the method is simple to operate, highly accurate, and can obtain high-quality anti-carbon-deposit self-sealing internal reforming solid oxide fuel cells, thereby improving efficiency and extending their service life.

[0100] The features and performance of the present invention will be further described in detail below with reference to embodiments.

[0101] Example 1

[0102] This embodiment provides a self-sealing indirect internal reforming solid oxide fuel cell, which includes a connecting reforming plate 10 and a single cell. The single cell includes an anode 20, an electrolyte 30, and a cathode 40.

[0103] The connecting reforming plate 10 includes a connecting body 11. The upper and lower surfaces of the connecting body 11 are respectively provided with a battery support porous region 12 and an oxidation gas flow channel 15. The lower surface of the battery support porous region 12 is provided with a reforming reforming gas flow channel 13. A reforming porous region 14 for catalytic reaction of reformed fuel is provided between the reforming reforming gas flow channel 13 and the oxidation gas flow channel 15. The reforming porous region 14 is separated from the reforming reforming gas flow channel 13 and the oxidation gas flow channel 15 by a leak-free wall to achieve sealing of the reformed fuel.

[0104] Anode 20, electrolyte 30 and cathode 40 are sequentially deposited on the side of the porous region 12 of the battery support away from the recombination gas flow channel 13.

[0105] The area of ​​the battery support porous region 12 is smaller than the area of ​​the upper surface of the connector body 11. The battery support porous region 12 is connected to the recombination gas flow channel 13 to allow the synthesis gas to diffuse through the pores of the battery support porous region 12 to the anode 20 located on the upper surface of the battery support porous region 12.

[0106] Anode 20, electrolyte 30 and cathode 40 are sequentially deposited on the upper surface of the porous region 12 supporting the battery.

[0107] The anode 20 covers the upper surface of the porous region 12 supporting the battery, while the electrolyte 30 covers the entire connector body 11 and the upper surface of the anode 20. The projection of the cathode 40 coincides with the area occupied by the recombination gas flow channel 13.

[0108] In this application, the reforming porous region 14 is a region with a polyhedral lattice unit structure. The reforming porous region 14 includes two porous sub-regions separated by ribs, and these two sub-regions are arranged sequentially along a direction perpendicular to the reforming fuel flow direction. The porosity of each porous sub-region decreases from 90% to 50% in a 10% gradient along the reforming fuel flow direction. The pore size of each pore in the reforming porous region 14 is 500 μm, and the total thickness of the reforming porous region 14 is 1.0 mm.

[0109] All surfaces in contact with reformed fuel are equipped with catalysts for the reforming reaction of hydrocarbon fuels.

[0110] The connector body 11 is provided with through holes for the flow of hydrocarbon fuel, recombination gas and oxidation gas.

[0111] The main body 11 of the connector is quadrilateral (such as a rectangle) in shape, and has a first side 111, a second side 112, a third side 113 and a fourth side 114 connected end to end. The first side 111 and the third side 113 are arranged opposite each other, and the second side 112 and the fourth side 114 are arranged opposite each other.

[0112] The through-hole includes a reforming gas inlet 115, a reforming gas outlet 116, an oxidizing gas inlet 117, an oxidizing gas outlet 118, a reforming fuel inlet 119, and a reforming fuel outlet 120.

[0113] The reforming gas inlet 115 is located near the first side 111 of the connecting body 11 and penetrates the upper and lower surfaces of the connecting body 11; the reforming gas outlet 116 is located near the third side 113 of the connecting body 11 and penetrates the upper and lower surfaces of the connecting body 11; the oxidation gas inlet 117 is located near the third side 113 of the connecting body 11 and penetrates the upper and lower surfaces of the connecting body 11; the oxidation gas outlet 118 is located near the first side 111 of the connecting body 11 and penetrates the upper and lower surfaces of the connecting body 11; the reforming fuel inlet 119 is located near the second side 112 of the connecting body 11 and penetrates the upper and lower surfaces of the connecting body 11; and the reforming fuel outlet 120 is located near the fourth side 114 of the connecting body 11 and penetrates the upper and lower surfaces of the connecting body 11.

[0114] The two ends of the reforming gas flow channel 13 are connected to the reforming gas inlet 115 and the reforming gas outlet 116, respectively. The two ends of the oxidation gas flow channel 15 are connected to the oxidation gas inlet 117 and the oxidation gas outlet 118, respectively. The two ends of the reforming porous region 14 are connected to the reforming fuel inlet 119 and the reforming fuel outlet 120, respectively.

[0115] The recombination gas flow channel 13 is formed by multiple spaced recombination gas sub-channels, each recombination gas sub-channel extending from the first side 111 to the third side 113. The oxidation gas flow channel 15 can also be formed by multiple spaced oxidation gas sub-channels, each oxidation gas sub-channel extending from the third side 113 to the first side 111.

[0116] There are two recombination gas inlets 115 and one recombination gas outlet 116. One end of each of the recombination gas sub-channels is connected to one of the recombination gas inlets 115, and one end of each of the remaining recombination gas sub-channels is connected to the remaining recombination gas inlet 115. The other end of all the recombination gas sub-channels is connected to the recombination gas outlet 116.

[0117] The connection relationships between oxidizing gas inlet 117, oxidizing gas outlet 118, and oxidizing gas sub-channels, as well as the connection relationships between reforming fuel inlet 119, reforming fuel outlet 120, and porous sub-regions, can be set with reference to the connection relationships between reforming gas inlet 115, reforming gas outlet 116, and reforming gas sub-channels.

[0118] The thickness of the aforementioned connecting reforming plate 10 is 4 mm, the thickness of the anode 20 is 30 μm, the thickness of the electrolyte 30 is 20 μm, the thickness of the cathode 40 is 30 μm, the thickness of the catalyst loaded on the surface of the reforming porous region 14 is 5 μm, and the thickness of the high-temperature conductive chromium protective coating is 45 μm.

[0119] Its preparation process is as follows:

[0120] (1) Industrial software is used to design the spatial structure of the connecting weight reforming plate 10, the surface features of the reforming porous region 14, the battery support porous region 12, the upper surface of the connecting body 11 and the oxidation gas flow channel 15, the stacking of the battery functional layers, the catalyst material of the reforming porous region 14 and the high temperature conductive chromium protective coating of the oxidation gas flow channel 15, and to integrate the structure and function.

[0121] (2) The integral plate 10 of the connecting weight is prepared by selective laser melting.

[0122] Sa: Preparation of the connecting body weight-reinforcing plate A region: The connecting body weight-reinforcing plate A region is a solid region located below the reforming porous region 14 in the connecting body body 11. During preparation, high-temperature resistant oxide alloy powder is laid in the preset forming area of ​​the connecting body weight-reinforcing plate A region. The additive manufacturing process is used to form the connecting body body 11 and the oxidizing gas flow channel (oxidizing gas flow channel 15) layer by layer through the melting-solidification process.

[0123] Sb: Preparation of the connecting weight solid plate region B: The connecting weight solid plate region B includes a reforming porous region 14 and a solid region of the connecting body with the same height as the reforming porous region 14. During preparation, high-temperature resistant oxide alloy powder is laid in the solid region of the connecting weight solid plate region B, and a composite powder composed of high-temperature resistant oxide alloy and a material with catalytic reforming properties is laid in the porous region. Using additive manufacturing process, the material is formed layer by layer through melting-solidification process to achieve gradient connection between the high-temperature alloy material in the solid region and the composite material in the porous region, thus completing the integral molding of the heterogeneous material of the connecting weight solid plate region B.

[0124] Sc: Preparation of the connecting weight reorganization plate C region: The connecting weight reorganization plate C region includes a solid region located above the reorganization porous region 14 in the connecting body and a battery support porous region 12. During preparation, high-temperature resistant oxide alloy powder is laid in the preset forming area of ​​the connecting weight reorganization plate C region. Using additive manufacturing process, it is formed layer by layer through melting-solidification process to complete the forming of the connecting weight reorganization plate C region, the battery support porous region 12 and the reorganization forming airflow channel 13.

[0125] By integrating the connecting plates A, B, and C into a single unit, the reformed hydrocarbon fuel gas path achieves self-sealing.

[0126] The process conditions for the solid parts in each region of the connecting weight plate 10 include: laser power of 225W, scanning speed of 1000mm / s, scanning spacing of 0.08mm, spot size of 80μm, and laser wavelength of 1064nm.

[0127] The process conditions for connecting the reforming porous region 14 in region B of the reforming plate include: laser power of 180W, scanning speed of 900mm / s, scanning spacing of 0.15mm, spot size of 50μm, and laser wavelength of 1064nm.

[0128] The process conditions for connecting the battery support porous region 12 in region C of the weight-integrating plate include: laser power of 90W, scanning speed of 700mm / s, scanning spacing of 0.14mm, spot size of 80μm, and laser wavelength of 1064nm.

[0129] The main body of the connector is made of SUS430, and the composite powder is NiO and Al2O3.

[0130] (3) In a vacuum heat treatment furnace, the formed connecting weight plate 10 is subjected to stress relief annealing and flattening treatment.

[0131] The annealing temperature is 800℃ and the annealing time is 5 hours.

[0132] (4) The upper and lower surfaces of the connecting weight plate 10 are sandblasted and laser cleaned to obtain a clean and roughened surface required for plasma spraying deposition.

[0133] (5) Anode 20, electrolyte 30 and cathode 40 are sequentially deposited on the side of the porous region 12 of the battery support away from the recombination gas flow channel 13 by vacuum plasma spraying.

[0134] (6) A protective coating ((Mn,Co)3O4 coating) is deposited on the surface of the side of the connecting weight-integrating plate 10 with the oxidation gas flow channel 15 by vacuum plasma spraying.

[0135] Example 2

[0136] The difference between this embodiment and Embodiment 1 is that:

[0137] The thickness of the aforementioned connecting reforming plate 10 is 2.0 mm, the thickness of the anode 20 is 15 μm, the thickness of the electrolyte 30 is 15 μm, the thickness of the cathode 40 is 20 μm, the thickness of the catalyst loaded on the surface of the reforming porous region 14 is 0.5 μm, and the thickness of the protective coating is 30 μm.

[0138] The process conditions for the solid parts in each region of the connecting weight plate 10 include: laser power of 200W, scanning speed of 1050mm / s, scanning spacing of 0.05mm, spot size of 30μm, and laser wavelength of 900nm.

[0139] The process conditions for connecting the reforming porous region 14 in region B of the reforming plate include: laser power of 150W, scanning speed of 750mm / s, scanning spacing of 0.1mm, spot size of 30μm, and laser wavelength of 900nm.

[0140] The process conditions for connecting the battery support porous region 12 in region C of the weight-integrating plate include: laser power of 80W, scanning speed of 500mm / s, scanning spacing of 0.12mm, spot size of 30μm, and laser wavelength of 900nm.

[0141] The main body of the connector is made of Croferr22, and the composite powder is NiO and Al2O3.

[0142] The annealing temperature is 500℃ and the annealing time is 4 hours.

[0143] The anode 20 is deposited by atmospheric plasma spraying, the electrolyte 30 is deposited by vacuum plasma spraying, and the cathode 40 is deposited by atmospheric plasma spraying. The protective coating ((Mn,Cu)3O4 coating) is deposited by atmospheric plasma spraying.

[0144] Example 3

[0145] The difference between this embodiment and Embodiment 1 is that:

[0146] The thickness of the aforementioned connecting reforming plate 10 is 5.0 mm, the thickness of the anode 20 is 40 μm, the thickness of the electrolyte 30 is 30 μm, the thickness of the cathode 40 is 40 μm, the thickness of the catalyst loaded on the surface of the reforming porous region 14 is 10 μm, and the thickness of the protective coating is 60 μm.

[0147] The process conditions for the solid parts in each region of the connecting weight plate 10 include: laser power of 250W, scanning speed of 1150mm / s, scanning spacing of 0.1mm, spot size of 50μm, and laser wavelength of 1070nm.

[0148] The process conditions for connecting the reforming porous region 14 in region B of the reforming plate include: laser power of 190W, scanning speed of 800mm / s, scanning spacing of 0.2mm, spot size of 80μm, and laser wavelength of 1070nm.

[0149] The process conditions for connecting the battery support porous region 12 in region C of the weight-integrating plate include: laser power of 100W, scanning speed of 600mm / s, scanning spacing of 0.15mm, spot size of 50μm, and laser wavelength of 1070nm.

[0150] The main body of the connector is made of ZMG232, and the composite powder is NiO and CeO2.

[0151] The annealing temperature is 900℃ and the annealing time is 6 hours.

[0152] The anode 20 is deposited by atmospheric plasma spraying, the electrolyte 30 is deposited by vacuum plasma spraying, and the cathode 40 is deposited by atmospheric plasma spraying. The protective coating ((La,Sr)CrO3 coating) is deposited by atmospheric plasma spraying.

[0153] In summary, the solid oxide fuel cell method provided in this application can realize the integrated fabrication of the connecting weight reforming plate 10, which is applicable to structurally complex self-sealed indirect internal reforming solid oxide fuel cells. Furthermore, the method is simple to operate, low in cost, and can obtain high-quality self-sealed indirect internal reforming solid oxide fuel cells, thus extending their service life.

[0154] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method of making a self-sealing indirect internal reforming solid oxide fuel cell, characterized by, The method comprises the following steps: S1: performing structural and functional integrated design on a self-sealing indirect internal reforming solid oxide fuel cell, wherein the self-sealing internal reforming solid oxide fuel cell comprises a connecting body reforming plate and a single cell; the connecting body reforming plate comprises a connecting body, and the upper surface and the lower surface of the connecting body are respectively provided with a cell support porous area and an oxidizing gas flow channel; the lower surface of the cell support porous area is provided with a reforming synthesis gas flow channel; a reforming porous area for catalytic reaction of reforming fuel is arranged between the reforming synthesis gas flow channel and the oxidizing gas flow channel; the reforming porous area is separated from the reforming synthesis gas flow channel and the oxidizing gas flow channel by a leak-free wall surface to realize self-sealing of the reforming fuel; the single cell comprises an anode, an electrolyte and a cathode; The reforming porous area is a region with a polyhedral lattice unit structure; the reforming porous area comprises at least two porous sub-regions, and adjacent two porous sub-regions are separated by a rib; and a plurality of porous sub-regions are sequentially arranged along a direction perpendicular to the reforming fuel flow direction; the porosity of each porous sub-region gradually decreases along the reforming fuel flow direction; S2: preparing the connecting body reforming plate by using an additive manufacturing technology; the preparation of the connecting body reforming plate comprises: Sa: preparation of a connecting body reforming plate A region: the connecting body reforming plate A region is a solid region of the connecting body below the reforming porous area; in the preparation, high-temperature oxidation alloy powder is laid on a preset forming area of the connecting body reforming plate A region; a layer-by-layer forming process is performed through a melting-solidification process by using an additive manufacturing process to complete the forming of the connecting body and the oxidizing gas flow channel; Sb: preparation of a connecting body reforming plate B region: the connecting body reforming plate B region comprises the reforming porous area and a solid region of the connecting body at the same height as the reforming porous area; in the preparation, high-temperature oxidation alloy powder is laid on the solid region in the connecting body reforming plate B region and composite powder composed of high-temperature oxidation alloy and material with catalytic reforming performance is laid on the porous region on the upper surface of the connecting body reforming plate A region; a layer-by-layer forming process is performed through a melting-solidification process by using an additive manufacturing process to realize gradient connection between the high-temperature alloy material of the solid region and the composite material of the porous region and complete the integrally formed heterogeneous material of the connecting body reforming plate B region; Sc: preparation of a connecting body reforming plate C region: the connecting body reforming plate C region comprises a solid region of the connecting body above the reforming porous area and a cell support porous area; in the preparation, high-temperature oxidation alloy powder is laid on a preset forming area of the connecting body reforming plate C region; a layer-by-layer forming process is performed through a melting-solidification process by using an additive manufacturing process to complete the forming of the solid region of the connecting body reforming plate C region, the cell support porous area and the reforming synthesis gas flow channel; S3: performing stress relief annealing and flattening treatment on the formed connecting body reforming plate. S4: depositing an anode layer, an electrolyte layer and a cathode layer on the side of the cell support porous area away from the reforming syngas channel by using plasma spraying technology, and the electrolyte layer completely covers the anode layer and all areas on the upper surface of the connecting body body, realizing self-sealing of the reforming syngas channel.

2. The production method according to claim 1, characterized by, The structure and function integrated design content includes: the spatial structure of the connecting body reforming plate, the surface characteristics of the reforming porous area, the cell support porous area, the upper surface of the connecting body body and the oxidation gas channel, the stacking of the cell functional layer, the design of the reforming porous area catalyst material and the high-temperature conductive chromium coating of the oxidation gas channel.

3. The method of claim 1, wherein, The additive manufacturing technology adopts selective laser melting technology, selective electron beam melting technology or binder jet additive manufacturing technology.

4. The production method according to claim 3, characterized by, The selective laser melting technology is adopted, wherein: The process conditions of the solid part in each area of the connecting body reforming plate include: laser power is 200-250W, scanning speed is 1000-1150mm / s, scanning interval is 0.05-0.1mm, spot size is 30-80μm, and laser wavelength is 900-1070nm; The process conditions of the reforming porous area in the B area of the connecting body reforming plate include: laser power is 150-190W, scanning speed is 750-900mm / s, scanning interval is 0.1-0.2mm, spot size is 30-80μm, and laser wavelength is 900-1070nm; The process conditions of the cell support porous area in the C area of the connecting body reforming plate include: laser power is 80-100W, scanning speed is 500-700mm / s, scanning interval is 0.12-0.15mm, spot size is 30-80μm, and laser wavelength is 900-1070nm.

5. The preparation method according to claim 1, characterized in that, The stress relief annealing and flattening treatment is carried out in a vacuum heat treatment furnace.

6. The production method according to claim 5, wherein The annealing temperature is 500-900℃, and / or the annealing time is 4-6 hours.

7. The preparation method according to claim 1, characterized in that, Between S3 and S4, the upper surface and the lower surface of the connecting body reforming plate are also pretreated to obtain a fresh, clean and roughened surface required for plasma spraying deposition.

8. The preparation method according to claim 7, characterized in that, The pretreatment includes at least one of sandblasting and laser cleaning.

9. The method of claim 1, wherein, In S4, the electrolyte layer is prepared by using vacuum plasma spraying.

10. The method of claim 1, wherein, S5: depositing a high-temperature conductive chromium protective coating on the surface of the side of the connecting body reforming plate with the oxidation gas channel by using plasma spraying.

11. A solid oxide fuel cell, characterized by, Prepared by the preparation method of any one of claims 1-10.

12. The solid oxide fuel cell according to claim 11, characterized by The preparation material of the connecting body body includes iron-based or chromium-based alloy material in the solid oxide fuel cell; And / or, the catalyst is a high-activity nano catalyst, And / or, the preparation material of the high-temperature conductive chromium protective coating includes at least one of rare earth perovskite and spinel.

13. The solid oxide fuel cell of claim 12, wherein, The preparation material of the connecting body body includes at least one of SUS430, Croferr22, ZMG232 and T441.

14. The solid oxide fuel cell of claim 12, wherein, The catalyst includes at least one of Al2O3, NiO, CeO2 and La2O3.

15. The solid oxide fuel cell of claim 12, wherein, The rare earth perovskites include at least one of (La,Sr)CrO3, (La,Sr)MnO3, and (La,Sr)CoO3.

16. The solid oxide fuel cell of claim 12, wherein, The spinels include at least one of (Mn,Co)3O4 and (Mn,Cu)3O4.

17. The solid oxide fuel cell of claim 11, wherein, The thickness of the reforming plate of the connector is 2.5-5.0 mm; and / or, the thickness of the anode layer is 15-40 μm; and / or, the thickness of the electrolyte layer is 15-30 μm; and / or, the thickness of the cathode layer is 20-40 μm; and / or, the thickness of the surface loaded catalyst of the reforming porous region is 0.5-10 μm; and / or, the thickness of the high temperature electrically conductive chromium protective coating is 30-60 μm.

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