Integrated plate-type metal-supported solid oxidation fuel cell or electrolyzer and its preparation method

Abstract

This application provides an integrated plate-type metal-supported solid oxide fuel cell or electrolyzer and its fabrication method, relating to the field of solid oxide battery technology. The fabrication method includes: performing integrated structural and functional design on the integrated plate-type metal-supported solid oxide fuel cell or electrolyzer; fabricating a metal support using additive manufacturing technology; forming insulating layers on the upper and lower surfaces of the metal support; sequentially depositing an anode, electrolyte, and cathode on the insulating layers at positions corresponding to the permeable pore areas; and depositing a conductive connection layer in the partially exposed area of ​​the anode and the adjacent cathode portion. This method is suitable for fabricating novel complex fuel cells. It is simple to operate, highly precise, has good sealing properties, and high fabrication efficiency, resulting in high-quality, high-efficiency, and long-life multifunctional fuel cells.

Description

Technical Field

[0001] This invention relates to the field of solid oxide fuel cell technology, and more specifically, to an integrated plate-type metal-supported solid oxide fuel cell or electrolyzer and its preparation method. Background Technology

[0002] A solid oxide fuel cell (SOFC) is an all-solid-state reaction device that directly converts the chemical energy of fuel and oxidant into electrical energy. Its basic structural units mainly include an anode, a cathode, and an electrolyte. A solid oxide electrolyzer (SOEC) operates on the reverse process of a solid oxide fuel cell; therefore, SOFCs and SOECs share the same cell and stack structure, and will be referred to collectively as SOCs from now on.

[0003] Currently, integrated plate-type SOCs primarily utilize ceramic matrix supports manufactured through extrusion molding. While extrusion molding offers high production efficiency and allows for automated continuous production, it suffers from drawbacks such as low material strength, susceptibility to deformation, and potential defects like surface pitting, blistering, cracking, and internal fissures. Insulating ceramic supports extruded from materials like MgO, MgAl2O4, and ZrO2-3Y2O3 offer no functional benefits beyond mechanical support, increasing battery gas resistance and weight, and reducing the battery's power-to-weight ratio. Supports obtained through extrusion molding using anode materials with reforming capabilities, such as NiO, result in not only bulky batteries but also significantly increased costs. These supports can only accommodate single-function straight or rotary gas channels, and it's difficult to control the shape and distribution of pores used for permeability and / or reforming reactions, leading to high gas flow resistance and hindering the creation of specialized structures.

[0004] The active film, anode, electrolyte, and cathode of a battery are fabricated on a support using screen printing. After multiple high-temperature sintering processes, an integrated plate-type solid oxide battery (SOC) can be obtained. Sealing is required on the porous support surface and its side areas between adjacent individual cells, increasing the technical difficulty. After multiple integrated plate-type SOCs are assembled into a stack, the gas distribution chambers located at the gas inlet and outlet ends of the support also require sealing. For smaller micro-SOCs, the hollow porous flat tubes have very thin walls, making fabrication difficult. During the screen printing process, the applied pressure can easily cause the hollow flat tubes to collapse.

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

[0006] The objectives of this invention include, for example, providing an integrated plate-type metal-supported solid oxide fuel cell or electrolyzer and its preparation method, which is applicable to the preparation of novel complex structure fuel cells, improves the power-to-weight ratio of the cell, avoids the adverse effects of sintering processes on the metal support, has good sealing performance, and improves the reliability and preparation efficiency of the integrated plate-type metal-supported solid oxide fuel cell.

[0007] The embodiments of the present invention can be implemented as follows:

[0008] In a first aspect, the present invention provides a method for preparing an integrated plate-type metal-supported solid oxidation fuel cell or electrolyzer, comprising:

[0009] S1: An integrated plate-type metal-supported solid oxidation fuel cell or electrolyzer is designed with integrated structure and function; the integrated plate-type metal-supported solid oxidation fuel cell or electrolyzer includes a metal support, an insulating layer, and battery cells; the metal support is provided with a flow channel for the flow of reaction medium materials; the surface of the metal support is provided with multiple venting perforated areas; the venting holes in the venting perforated areas are connected to the flow channels; the battery cells include an anode, an electrolyte, and a cathode; the insulating layer is disposed between the metal support and the battery cells;

[0010] S2: The metal support is prepared using additive manufacturing technology, including:

[0011] Alloy powder is laid in the preset forming area of ​​the metal support, and the metal support is formed layer by layer through melting and solidification using additive manufacturing process; wherein, the flow channel is formed during the forming process; the vent holes in the vent area can be formed during the forming process or formed through subsequent secondary processing.

[0012] S3: An insulating layer is formed on the first and / or second surfaces of the metal support body that are opposite each other along the thickness direction; wherein, if the vent holes in the vent area are formed by subsequent secondary processing, the vent holes are formed directly on the metal support body after the metal support body is formed; or, after step S3, the vent holes are formed on the metal support body and the insulating layer through secondary processing.

[0013] S4: An anode, electrolyte, and cathode are deposited sequentially on the insulating layer at the position corresponding to the vent hole area, and the electrode layers of adjacent batteries are not connected to each other. Except for the partial exposure of the anode for power supply connection, the remaining anode and insulating layer areas are completely covered by electrolyte to achieve self-sealing of the fuel gas path.

[0014] S5: Deposit a conductive connection layer between the partially exposed area of ​​the anode and the adjacent cathode portion of the battery.

[0015] In an optional implementation, the integrated structural-functional design further includes:

[0016] The flow channel includes a material inlet and a porous reaction zone connected thereto for catalytic reaction of reformed fuel; wherein the porous reaction zone is located between the first surface and the second surface and is spaced apart from the first surface and the second surface respectively; the vent is connected to the porous reaction zone; wherein the metal support includes a first layer, a second layer and a third layer structure divided along the thickness direction; wherein the first layer structure is between the porous reaction zone and the second surface, the height of the second layer structure is the thickness of the porous reaction zone, and the third layer structure is between the porous reaction zone and the first surface;

[0017] Step S2 includes: S21, S22, and S23; S21: Preparation of the first layer structure of the support: The first layer structure of the support includes a solid region located below the reactive porous region in the metal support; During preparation, alloy powder is laid in the preset forming area of ​​the first layer structure of the support, and additive manufacturing process is used to form the first layer structure of the support layer by layer through melting and solidification; wherein, if the first layer structure is provided with a ventilated through-hole area, the ventilated through-hole area is integrally formed in the forming of the first layer structure, or the ventilated through-hole area is formed in a secondary processing after the solid body of the first layer structure is completed; or the ventilated through-hole area is formed in a secondary processing after the insulating layer is formed on the second surface;

[0018] S22: Preparation of the second layer structure of the support: The second layer structure of the support includes a reactive porous region and a solid support region of the same height as the reactive porous region; during preparation, alloy powder is laid in the solid region of the second layer structure and composite powder composed of alloy and material with catalytic reforming properties is laid in the reactive porous region on the upper surface of the first layer structure of the support. Using additive manufacturing process, the alloy material in the solid region and the composite material in the reactive porous region are formed layer by layer through melting and solidification to achieve gradient connection between the alloy material in the solid region and the composite material in the reactive porous region of the second layer structure, thus completing the integral molding of the heterogeneous materials of the second layer structure of the support;

[0019] S23: Preparation of the third layer structure of the support: The third layer structure of the support includes a solid region located above the reactive porous region in the metal support; during preparation, alloy powder is laid in the preset forming area of ​​the third layer structure of the support, and additive manufacturing process is adopted to form the third layer structure of the support layer by layer through melting and solidification; wherein, if the third layer structure is provided with a ventilated through-hole area, the ventilated through-hole area is integrally formed in the forming of the third layer structure, or the ventilated through-hole area is formed in a secondary process after the solid body of the third layer structure is completed; or the ventilated through-hole area is formed in a secondary process after the insulating layer is formed on the first surface.

[0020] In an optional implementation, the integrated structural-functional design includes:

[0021] The spatial structure design of the metal support includes the design of the reaction porous zone, the gas permeable pore zone, the support structure, the turbulence structure, the material inlet, the material outlet, the material distribution zone, the material collection zone, the gas distribution and guiding fluid, and the catalyst material of the reaction porous zone.

[0022] The design of the stacked design of the anode, electrolyte, and cathode of the solar cell, and the design of the conductive interconnect layer.

[0023] In an optional implementation, in step S22, an additive manufacturing process is used, involving melting, solidification, and layer-by-layer forming:

[0024] A material inlet, a material outlet, and a gas distribution guide are reserved in the solid area of ​​the second layer structure of the support. The material inlet and the material outlet are respectively connected to the porous reaction zone. The gas distribution guide is located between the material inlet and the porous reaction zone and between the material outlet and the porous reaction zone.

[0025] The support structure and the turbulence structure are formed in the reactive porous region of the second layer structure of the support.

[0026] In an optional implementation, step S3 includes:

[0027] S31: A transition metal layer is formed on the lower surface of the first layer structure and the upper surface of the third layer structure of the metal support, respectively; the material of the transition metal layer is a nickel-based alloy material, including one or more of NiCr, NiAl, NiCrAlY and NiCoCrAlY;

[0028] S32: An insulating layer is formed on the surface of the transition metal layer using plasma spraying technology. The material of the insulating layer is one or more of Al2O3, MgAl2O4, Y2O3-ZrO2, or an electrolyte material.

[0029] In an optional embodiment, before step S31, step S24 is further included: stress-relief annealing, leveling, and surface activation treatment of the first and second surfaces of the metal support after molding, so as to obtain a fresh, clean, roughened surface required for thermal spraying coating deposition; the surface activation treatment includes at least one of sandblasting and laser cleaning.

[0030] In an optional implementation, in step S2, the additive manufacturing technology employs selective laser melting, selective electron beam melting, or binder jet additive manufacturing.

[0031] If selective laser melting technology is used, then:

[0032] The process conditions for the solid parts in the first, second, and third layers of the metal support include: laser power of 190-230W, scanning speed of 900-1100mm / s, scanning spacing of 0.08-0.1mm, spot size of 30-80μm, and laser wavelength of 900-1070nm.

[0033] The process conditions for the reactive porous region in the second layer structure of the metal support include: laser power of 160-190W, scanning speed of 700-800mm / s, scanning spacing of 0.1-0.15mm, spot size of 30-80μm, and laser wavelength of 900-1070nm.

[0034] The process conditions for the ventilated perforated areas in the first and third layers of the metal support include: laser power of 80-100W, scanning speed of 500-700mm / s, scanning spacing of 0.1-0.13mm, spot size of 30-80μm, and laser wavelength of 900-1070nm.

[0035] In a second aspect, the present invention provides an integrated plate-type metal-supported solid oxidation fuel cell or electrolyzer, which is manufactured using the preparation method of the integrated plate-type metal-supported solid oxidation fuel cell or electrolyzer as described in any of the foregoing embodiments.

[0036] In optional embodiments, the metal support is prepared from iron-based or chromium-based alloy materials; preferably, it includes at least one of SUS430, Croferr22, ZMG232 and T441; and / or, the catalyst is a highly active nanocatalyst, more preferably including at least one of Al2O3, NiO, CeO2 and La2O3.

[0037] In optional embodiments, the thickness of the metal support is 2-10.0 mm; and / or, the thickness of the anode is 15-40 μm; and / or, the thickness of the electrolyte is 10-30 μm; and / or, the thickness of the cathode is 20-40 μm; and / or, the thickness of the catalyst supported on the surface of the porous reaction region is 0.5-10 μm.

[0038] The beneficial effects of the embodiments of the present invention include, for example:

[0039] 1. The method for preparing an integrated plate-type metal-supported solid oxidation fuel cell or electrolyzer provided in this embodiment of the invention uses additive manufacturing technology to prepare the metal support, which can form a complex internal structure of the support, with good flow channel sealing and high preparation efficiency.

[0040] 2. The battery stack structure formed by this method eliminates the need for sealing the sides of the metal support, reducing manufacturing complexity and improving reliability. The use of a metal support provides excellent thermal shock resistance and rapid start-up and shutdown.

[0041] 3. The anode, electrolyte, and cathode of the battery cell are formed using a deposition process to avoid the impact of the sintering process on the metal support.

[0042] The integrated plate-type metal-supported solid oxidation fuel cell or electrolyzer provided in this invention is beneficial for improving start-up and shutdown speed, enhancing thermal shock resistance, increasing power-to-weight ratio, improving battery performance, and ensuring reliable sealing. It also reduces the difficulty of the manufacturing process and increases manufacturing efficiency. Attached Figure Description

[0043] 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.

[0044] Figure 1 This is a schematic diagram of the structure of an integrated plate-type metal-supported solid oxidation fuel cell provided in an embodiment of the present invention;

[0045] Figure 2 A schematic diagram of the cross-sectional structure of an integrated plate-type metal-supported solid oxidation fuel cell provided in an embodiment of the present invention;

[0046] Figure 3 for Figure 2 A magnified view of a portion of point M in the middle;

[0047] Figure 4 This is a schematic diagram of the structure of the metal support for an integrated plate-type metal-supported solid oxidation fuel cell provided in an embodiment of the present invention.

[0048] Icons: 100 - Integrated plate-type metal-supported solid oxidation fuel cell; 110 - Metal support; 101 - First surface; 102 - Second surface; 103 - First layer structure; 104 - Second layer structure; 105 - Third layer structure; 111 - Porous reaction zone; 112 - Permeable zone; 1121 - Permeable pore; 113 - Material inlet; 114 - Material outlet; 115 - Support structure; 120 - Insulating layer; 121 - Transition metal layer; 130 - Cell; 131 - Anode; 132 - Electrolyte; 133 - Cathode; 140 - Conductive connection layer; 141 - Solid section; 142 - Porous section. Detailed Implementation

[0049] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. The components of the embodiments of the present invention described and shown in the accompanying drawings can generally be arranged and designed in various different configurations.

[0050] Therefore, the following detailed description of the embodiments of the invention provided in the accompanying drawings is not intended to limit the scope of the claimed invention, but merely to illustrate selected embodiments of the invention. All other embodiments obtained by those skilled in the art based on the embodiments of the invention without inventive effort are within the scope of protection of the invention.

[0051] It should be noted that similar labels and letters in the following figures indicate similar items. Therefore, once an item is defined in one figure, it does not need to be further defined and explained in subsequent figures.

[0052] In the description of this invention, it should be noted that if terms such as "upper," "lower," "inner," or "outer" are used to indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings, or the orientation or positional relationship in which the product of this invention is usually placed, they are only for the convenience of describing this invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation of this invention.

[0053] Furthermore, the terms "first" and "second" are used only to distinguish descriptions and should not be interpreted as indicating or implying relative importance.

[0054] It should be noted that, where there is no conflict, the features in the embodiments of the present invention can be combined with each other.

[0055] Combination Figures 1 to 4 This embodiment provides a method for preparing an integrated plate-type metal-supported solid oxidation fuel cell 100 or an electrolyzer, mainly including the following steps:

[0056] S1: Design the integrated plate-type metal-supported solid oxidation fuel cell 100 or electrolyzer with integrated structure and function.

[0057] An integrated plate-type metal-supported solid oxidation fuel cell 100 or electrolyzer includes a metal support 110, an insulating layer 120, and a battery cell 130. The metal support 110 has a first surface 101 and a second surface 102 arranged opposite to each other, i.e., an upper surface and a lower surface. The metal support 110 is provided with a reaction porous region 111 for catalytic reaction of reformed fuel and a permeable through-hole region 112 as a synthesis gas flow channel. The reaction porous region 111 is located between the first surface 101 and the second surface 102 and is spaced apart from the first surface 101 and the second surface 102, respectively. This arrangement results in a compact structure and small volume, which not only solves the problem of carbon buildup on the anode 131 covering the catalytic active sites and reducing the activity of the anode 131, and the problem of expansion stress caused by carbon buildup on the anode 131 damaging the battery structure, but also avoids the risk of excessive thermal stress caused by the rapid and strongly endothermic reaction of the catalytic reforming reaction directly leading to a low temperature of the anode 131 located at the fuel inlet, forming a large temperature gradient and increasing the risk of damage to the battery structure. In addition, it can also solve the problem of damage to the battery structure caused by the separation of heterogeneous interfaces inside the battery due to direct contact between the gas medium and the electrode surface of the battery cell 130.

[0058] The first surface 101 and the second surface 102 are each provided with a plurality of vent holes 1121 to form a vented perforated region 112, which are connected to the porous reaction region 111. Hydrocarbon fuel gas undergoes a catalytic reforming reaction in the porous reaction region 111 to generate syngas. The syngas passes through the vent holes 1121 to reach the anode 131, where an electrochemical reaction occurs. The metal support 110 has a material inlet 113 and a material outlet 114 connected to the porous reaction region 111. Except for the material inlet 113, the material outlet 114, and the vent holes 1121, the rest of the metal support 110 is a leak-free, dense surface, thus ensuring the airtightness of the gas flow channel.

[0059] The solar cell 130 includes an anode 131, an electrolyte 132, and a cathode 133. The anode 131 completely covers the venting perforation area 112. An insulating layer 120 is disposed between the metal support 110 and the solar cell 130.

[0060] It can be understood that each reactive porous region 111 corresponds to a permeable pore region 112. Each metal support 110 has multiple reactive porous regions 111. The reactive porous region 111 is a region with a polyhedral lattice unit structure. Exemplarily, the polyhedron can be, for example, a hexahedron or an octahedron. The sum of the areas of the multiple permeable pore regions 112 above the metal support 110 is less than the area of ​​the first surface 101. The sum of the areas of the multiple permeable pore regions 112 below the metal support 110 is less than the area of ​​the second surface 102.

[0061] Optionally, depending on the type of fuel, if a reforming reaction is not required, the porous reaction zone 111 can be omitted. Only a flow channel for the reaction medium needs to be formed in the metal support 110. The flow channel includes a material inlet 113 and a material outlet 114.

[0062] The venting perforation area 112 can be provided only on the first surface 101 or the second surface 102, that is, the battery cell 130 can be arranged on one side or both sides on the metal support 110. The insulating layer 120 can also be designed as one side or both sides according to the arrangement of the battery cell 130, and no specific limitation is made here.

[0063] Optionally, the integrated structural and functional design includes: the spatial structure design of the metal support 110, including the design of the reaction porous region 111, the permeable through-hole region 112, the support structure 115, the turbulence structure, the material inlet 113, the material outlet 114, the material distribution region, the material collection region, the gas distribution and guiding fluid, and the catalyst material of the reaction porous region 111; the stacking design of the anode 131, electrolyte 132 and cathode 133 of the battery cell 130, and the design of the conductive connection layer 140.

[0064] Optionally, the material inlet 113 and the material outlet 114 are located on a set of opposite sides of the metal support 110. There is only one material inlet 113 and one material outlet 114. Multiple reactive porous regions 111 are distributed in a matrix. In the material flow direction, the porosity of each reactive porous region 111 gradually decreases, preferably in a gradient decrease. Since 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 embodiment, by setting the porosity to a gradient decrease, 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 avoids carbon deposits formed from hydrocarbon fuels covering the active sites of the anode 131, which would lead to a significant decrease in battery performance, but also avoids structural damage such as separation of heterogeneous interfaces inside the battery.

[0065] Optionally, among the above porosities, the maximum porosity shall not exceed 90%, and the minimum porosity shall not be less than 40%. The pore diameter of each pore in each reactive porous region 111 can be 100-1000 μm, and the total thickness of the reactive porous region 111 can be 0.5-2.5 mm.

[0066] S2: The metal support 110 is prepared by additive manufacturing technology. Alloy powder is laid in the preset forming area of ​​the metal support 110. The metal support 110 is formed layer by layer by melting and solidification using additive manufacturing process. The flow channel is formed during the forming process. The vent holes 1121 of the vent hole area 112 can be formed during the forming process or formed through subsequent secondary processing.

[0067] Optionally, the flow channel includes a material inlet 113 and a porous reaction zone 111 connected thereto for catalytic reaction of reformed fuel. The porous reaction zone 111 is located between the first surface 101 and the second surface 102 and is spaced apart from both surfaces. A vent 1121 communicates with the porous reaction zone 111. The metal support 110 includes a first layer structure 103, a second layer structure 104, and a third layer structure 105 divided along its thickness direction. The first layer structure 103 is located between the porous reaction zone 111 and the second surface 102; the height of the second layer structure 104 is the thickness of the porous reaction zone 111; and the third layer structure 105 is located between the porous reaction zone 111 and the first surface 101.

[0068] Step S2 includes: S21, S22 and S23.

[0069] S21: Preparation of the first layer structure 103 of the support: The first layer structure 103 of the support includes a solid region in the metal support 110 located below the reactive porous region 111, such as... Figure 4 As shown. During preparation, alloy powder, such as high-temperature resistant oxide alloy powder, is laid in the preset forming area of ​​the first layer structure 103 of the support. Using additive manufacturing, the powder is melted and solidified layer by layer to complete the forming of the first layer structure 103. If the first layer structure 103 has a venting perforation area 112, the venting perforation area 112 is integrally formed during the forming of the first layer structure 103, or the venting perforation area 112 is formed in a secondary processing step after the solid body of the first layer structure 103 is completed. Alternatively, the venting holes 1121 of the venting perforation area 112 are formed in a secondary processing step after an insulating layer is formed on the second surface 102. It can be understood that the venting holes 1121 can be integrally formed during 3D additive manufacturing, or they can be formed after the support is prepared using methods such as laser drilling or electron beam drilling.

[0070] S22: Preparation of the second layer structure 104 of the support: The second layer structure 104 of the support includes a reactive porous region 111 and a solid support region of equal height to the reactive porous region 111, such as... Figure 4 As shown. During preparation, alloy powder, such as high-temperature resistant oxide alloy powder, is laid on the solid area of ​​the second layer structure 104 of the support on the upper surface of the first layer structure 103, and composite powder composed of high-temperature resistant oxide alloy and material with catalytic reforming properties is laid on the reactive porous region 111. Using additive manufacturing process, the high alloy material in the solid area of ​​the second layer structure 104 and the composite material in the reactive porous region 111 are formed layer by layer through melting and solidification, so as to achieve gradient connection between the high alloy material in the solid area of ​​the second layer structure 104 and the composite material in the reactive porous region 111, thus completing the integral molding of the heterogeneous materials of the second layer structure 104 of the support.

[0071] Two different materials are laid in the reactive porous region 111 and the corresponding solid support region of equal height using a layer-by-layer powder-laying method. Different process parameters are used to form the solid region and the reactive porous region 111. The solid region of the support and the reactive porous region 111 are integrally connected by a gradient alloy / composite material. The solid region uses a commonly used alloy material, while the reactive porous region 111 is made of an alloy and a composite material with catalytic reforming properties.

[0072] Optionally, in step S22, during the additive manufacturing process, through melting and solidification layer-by-layer forming: Material inlet 113, material outlet 114, and gas distribution guide are reserved in the solid area of ​​the second layer structure 104 of the support body. Material inlet 113 and material outlet 114 are respectively connected to the porous reaction zone 111; the gas distribution guide is located between material inlet 113 and porous reaction zone 111, and between material outlet 114 and porous reaction zone 111. A support structure 115 and a turbulence-inducing structure are formed in the porous reaction zone 111 of the second layer structure 104 of the support body. The support structure 115 provides structural support and enhances structural strength. The turbulence-inducing structure is located in the area of ​​the porous reaction zone 111 other than the support structure 115, and is used to guide the reformed gas to the vent 1121. Multiple structural features inside the metal support 110 can be integrally formed using additive manufacturing technology, without structural limitations, resulting in high manufacturing efficiency, reliable structure, convenient operation, low process difficulty, and low cost.

[0073] S23: Preparation of the third layer structure 105 of the support: The third layer structure 105 of the support includes a solid region in the metal support 110 located above the reactive porous region 111, such as... Figure 4 As shown. During preparation, alloy powder, such as high-temperature resistant oxide alloy powder, is laid in the preset forming area of ​​the third layer structure 105 of the support. Using additive manufacturing, the powder is melted and solidified layer by layer to complete the forming of the third layer structure 105. If the third layer structure 105 has a venting perforation area 112, the venting holes 1121 of the venting perforation area 112 are integrally formed during the forming of the third layer structure 105. Alternatively, the venting holes 1121 of the venting perforation area 112 are formed after an insulating layer is formed on the second surface 102, and then further processed. The venting holes 1121 in the third layer structure 105 can be formed using powder metallurgy, additive manufacturing, laser drilling, or electron beam drilling. For example, they can be integrally formed in a 3D additive manufacturing process, or they can be formed after the support is prepared using laser drilling or electron beam drilling.

[0074] Optionally, in step S2, the additive manufacturing technology may employ selective laser melting, selective electron beam melting, or binder jet additive manufacturing. In this embodiment, selective laser melting technology is used. Optionally, the process conditions for the solid part of the three-layer structure of the metal support 110 include: laser power of 190-230W (such as 190W, 200W, 210W, 220W, 225W or 230W, etc.), scanning speed of 900-1100mm / s (such as 900mm / s, 950mm / s, 1000mm / s, 1050mm / s or 1100mm / s, etc.), scanning spacing of 0.08-0.1mm (such as 0.08mm, 0.09mm or 0.1mm, etc.), spot size of 30-80μm (such as 30μm, 40μm, 50μm, 60μm, 70μm or 80μm, etc.), and laser wavelength of 900-1070nm.

[0075] Optionally, the process conditions for the reactive porous region 111 in the second layer structure 104 of the metal support 110 include: laser power of 160-190W (e.g., 160W, 170W, 180W, or 190W), scanning speed of 700-800mm / s (e.g., 700mm / s, 750mm / s, or 800mm / s), scanning spacing of 0.1-0.15mm (e.g., 0.1mm, 0.11mm, 0.13mm, or 0.15mm), spot size of 30-80μm (e.g., 30μm, 40μm, 50μm, 60μm, 70μm, or 80μm), and laser wavelength of 900-1070nm. Optionally, the surface characteristics of the polyhedral lattice unit structure of the reactive porous region 111 can be controlled by optimizing the scanning strategy to maximize its catalytic surface area.

[0076] Optionally, the process conditions for the ventilated perforation area 112 in the first layer structure 103 and the third layer structure 105 of the metal support 110 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 0.1-0.13mm (e.g., 0.1mm, 0.11mm, 0.12mm or 0.13mm), spot size of 30-80μm (e.g., 30μm, 40μm, 50μm, 60μm, 70μm or 80μm), and laser wavelength of 900-1070nm.

[0077] By integrally molding the first layer structure 103, the second layer structure 104, and the third layer structure 105 of the metal support 110, a self-sealing of the reformed hydrocarbon fuel gas path is achieved. The shape and position distribution of the reaction porous region 111 and the vent 1121 are easily controlled in the additive manufacturing process, are not limited by special structures, and have low airflow resistance.

[0078] For example, in this embodiment, the ventilation holes 1121 in the first layer structure 103 and the third layer structure 105 of the metal support 110 are formed by subsequent secondary processing, such as laser drilling, which has high forming accuracy, high efficiency, smooth hole walls, and low airflow resistance.

[0079] Optionally, the vent holes 1121 in the first layer structure 103 and the third layer structure 105 are made by laser drilling. The laser drilling process parameters are: laser power of 10W~1000W; laser frequency of 0.1Hz~1MHz; and pulse width of 5ps~100ms.

[0080] Optionally, the vent holes 1121 in the first layer structure 103 and the third layer structure 105 are drilled using an electron beam drilling method. The process parameters for electron beam drilling are: pulse power of 0.2kW~15kW, pulse frequency of 0.2kHz~10kHz, operating current of 1mA~150mA, and pulse duration of 50us~100ms.

[0081] S24: The formed metal support 110 undergoes stress-relief annealing, leveling, and surface activation treatment. Stress-relief annealing and leveling can be performed in a vacuum heat treatment furnace. Optionally, the annealing temperature is 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 is 4-6 hours, such as 4 hours, 5 hours, or 6 hours, or any other value within the 4-6 hour range.

[0082] The first surface 101 and the second surface 102 of the metal support 110 are subjected to surface activation treatment to obtain a fresh, clean, roughened surface required for thermal spray coating deposition. Optionally, the surface activation treatment includes at least one of sandblasting and laser cleaning.

[0083] S3: Insulating layers 120 are formed on the lower surface of the first layer structure 103 and the upper surface of the third layer structure 105 of the metal support 110, respectively. These include:

[0084] S31: A transition metal layer 121 is formed on the lower surface of the first layer structure 103 and the upper surface of the third layer structure 105 of the metal support 110 using thermal spraying technology. Optionally, the transition metal layer 121 is prepared by plasma spraying or supersonic flame spraying. The material of the transition metal layer 121 is a nickel-based alloy material, including one or more of NiCr, NiAl, NiCrAlY, and NiCoCrAlY.

[0085] The process conditions for plasma spraying MCrAlY onto the transition metal layer 121 include: Ar flow rate 45-48 L / min, H2 flow rate 7-10 L / min, spraying distance 100-110 mm, spraying current 580-630 A, spraying voltage 70-72 V, and spraying power 40.6-45.5 kW. Alternatively, the process conditions for supersonic flame spraying MCrAlY onto the transition metal layer 121 include: oxygen flow rate 750-800 L / min, aviation kerosene 18-20 L / h, combustion chamber pressure 5.8-6.1 bar, and spraying distance 290-310 mm. Alternatively, the process conditions for the transition metal layer 121 using Ni20Cr include: Ar flow rate 42-47 L / min, H2 flow rate 6-10 L / min, spraying distance 105-115 mm, spraying current 600-650 A, spraying voltage 65-70 V, and spraying power 39-45.5 kW.

[0086] S32: An insulating layer 120 is deposited on the surface of the transition metal layer 121 using plasma spraying technology. The insulating layer 120 may be a ceramic insulating layer 120. The material of the insulating layer 120 is one or more of Al2O3, MgAl2O4, Y2O3-ZrO2 or an electrolyte material.

[0087] If the insulating layer 120 uses Al2O3, the process conditions include: Ar flow rate 38-43 L / min, H2 flow rate 10-12 L / min, spraying distance 110-120 mm, spraying current 620-650 A, spraying voltage 72-74 V, and spraying power 44.5-48.1 kW. Alternatively, if the insulating layer 120 uses ZrO2-8Y2O3, the process conditions include: Ar flow rate 43-45 L / min, H2 flow rate 10-12 L / min, spraying distance 110-120 mm, spraying current 580-630 A, spraying voltage 71-73 V, and spraying power 41.2-46 kW.

[0088] It is understandable that setting a transition metal layer 121 can reduce the difference in thermal expansion coefficients between the insulating layer 120 and the metal support 110, avoid structural delamination, and improve the reliability of the battery structure. The vent 1121 needs to penetrate through the transition metal layer 121 and the insulating layer 120 so that the gas after the reforming reaction can reach the anode 131 smoothly.

[0089] It should be noted that the vent holes 1121 in the first layer structure 103 and the third layer structure 105 can be drilled after the insulating layer 120 is formed. If holes are drilled directly on the metal support 110 before the insulating layer 120 is formed, the metal support 110 needs to undergo surface activation treatment. If holes are drilled on the insulating layer 120 after the insulating layer 120 is formed, and the vent holes 1121 extend into the metal support 110, then surface activation treatment of the insulating layer 120 is not required, and holes can be drilled directly on the insulating layer 120.

[0090] S4: Using plasma spraying technology, an anode 131, an electrolyte 132, and a cathode 133 are sequentially deposited on the insulating layer 120 at the position corresponding to the venting through-hole area 112. The electrodes of adjacent batteries are not connected to each other. Except for the partial exposed power supply connection of the anode 131, the remaining areas of the anode 131 and the insulating layer 120 are completely covered by the electrolyte 132, thereby achieving self-sealing of the fuel gas path.

[0091] S5: A conductive connection layer 140 is deposited in a partially exposed area of ​​the anode 131 and a partial area of ​​the adjacent battery cathode 133 using plasma spraying technology.

[0092] The conductive connection layer 140 includes a connected solid segment 141 and a porous segment 142. The porous segment 142 covers the side of the cathode 133 away from the electrolyte 132, and the solid segment 141 covers the exposed portion of the anode 131, achieving electrical connection between the anode 131 of one cell 130 and the cathode 133 of the adjacent cell 130. This connects all the cells 130 on both sides of the metal support 110 in series. It can be understood that the solid segment 141 and the electrolyte 132 together fill the gap between two adjacent anodes 131.

[0093] It is understandable that using plasma spraying technology to form the electrolyte 132 and the conductive connection layer 140 can improve the sealing of the gas flow channels inside the metal support 110.

[0094] Optionally, the metal support 110 is prepared from iron-based or chromium-based alloy materials, such as at least one of SUS430, Croferr22, ZMG232, and T441. The catalyst is a highly active nanocatalyst, such as at least one of Al2O3, NiO, CeO2, and La2O3.

[0095] Optionally, the thickness of the metal support 110 is 2-10.0 mm; such as 2 mm, 2.5 mm, 3.0 mm, 3.5 mm, 4.0 mm, 4.5 mm, 5.0 mm, 5.5 mm, 6 mm, 6.5 mm, 7 mm, 7.5 mm, 8 mm, 8.5 mm, 9 mm, 9.5 mm or 10.0 mm, or any other value within the range of 2-10 mm.

[0096] The thickness of anode 131 is 15-40 μm; such as 15 μm, 20 μm, 25 μm, 30 μm, 35 μm or 40 μm, or any other value in the range of 20-40 μm.

[0097] The thickness of electrolyte 132 is 10-30 μm; such as 10 μm, 12 μm, 15 μm, 18 μm, 20 μm, 22 μm, 25 μm, 28 μm or 30 μm, or any other value in the range of 15-30 μm.

[0098] The thickness of cathode 133 is 20-40 μm; such as 20 μm, 25 μm, 30 μm, 35 μm or 40 μm, or any other value in the range of 20-40 μm.

[0099] The thickness of the catalyst supported on the surface of the porous reaction region 111 is 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.

[0100] The present invention also provides an integrated plate-type metal-supported solid oxidation fuel cell 100 or an electrolyzer, which is manufactured by the preparation method of the integrated plate-type metal-supported solid oxidation fuel cell 100 or electrolyzer as described in any of the foregoing embodiments.

[0101] In summary, the integrated plate-type metal-supported solid oxidation fuel cell 100 or electrolyzer and its preparation method provided in the embodiments of the present invention have the following beneficial effects, for example:

[0102] 1. The preparation method of the integrated plate-type metal-supported solid oxidation fuel cell 100 or electrolyzer provided in the embodiments of the present invention uses additive manufacturing technology to prepare the metal support 110, which can form a complex internal structure of the support, with good flow channel sealing and high preparation efficiency.

[0103] 2. The battery stack structure formed by this preparation method does not require sealing the sides of the support, which reduces the difficulty of the process and improves reliability.

[0104] 3. It adopts a metal support body 110, which has good thermal shock resistance and fast start-up and shutdown speed.

[0105] 4. The metal support 110 forms a porous reaction zone 111 inside, which prevents carbon buildup on the anode 131, improves battery performance, and increases the battery power-to-weight ratio.

[0106] 5. The anode 131, electrolyte 132 and cathode 133 of the battery cell 130 are formed by deposition process to avoid the influence of sintering process on metal support 110.

[0107] This method is simple to operate, highly accurate, and can produce high-quality anti-carbon-deposit self-sealing internal reforming solid oxide fuel cells or electrolyzers, thereby improving efficiency and extending their service life.

[0108] The integrated plate-type metal-supported solid oxide fuel cell 100 or electrolyzer provided in this embodiment of the invention is beneficial for improving start-up and shutdown speed, enhancing thermal shock resistance, increasing power-to-weight ratio, reducing carbon buildup on the anode 131, improving battery performance, and ensuring reliable sealing. It also reduces the difficulty of the manufacturing process and increases manufacturing efficiency.

[0109] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A method for preparing an integrated plate-type metal-supported solid oxidation fuel cell or electrolyzer, characterized in that, include: S1: An integrated plate-type metal-supported solid oxidation fuel cell or electrolyzer is designed with integrated structure and function; the integrated plate-type metal-supported solid oxidation fuel cell or electrolyzer includes a metal support, an insulating layer, and battery cells; the metal support is provided with a flow channel for the flow of reaction medium materials; the surface of the metal support is provided with multiple venting perforated areas; the venting holes in the venting perforated areas are connected to the flow channels; the battery cells include an anode, an electrolyte, and a cathode; The insulating layer is disposed between the metal support and the battery cell; S2: The metal support is prepared using additive manufacturing technology, including: Alloy powder is laid in the preset forming area of ​​the metal support, and the metal support is formed layer by layer through melting and solidification using additive manufacturing process; wherein, the flow channel is formed during the forming process; the vent holes in the vent area are formed during the forming process or through subsequent secondary processing. S3: An insulating layer is formed on the first and / or second surfaces of the metal support that are opposite each other along the thickness direction; If the vent holes in the vent area are formed through subsequent secondary processing, then after the metal support is formed, the vent holes are formed directly on the metal support through secondary processing; or, after step S3, the vent holes are formed on the metal support and the insulating layer through secondary processing. S4: An anode, electrolyte, and cathode are deposited sequentially on the insulating layer at the position corresponding to the vent hole area, and the electrode layers of adjacent batteries are not connected to each other. Except for the partial exposure of the anode for power supply connection, the remaining anode and insulating layer areas are completely covered by electrolyte to achieve self-sealing of the fuel gas path. S5: A conductive connection layer is deposited in both the partially exposed area of ​​the anode and the cathode portion of the adjacent battery.

2. The method for preparing an integrated plate-type metal-supported solid oxidation fuel cell or electrolyzer according to claim 1, characterized in that, The integrated structural and functional design also includes: The flow channel includes a material inlet and a porous reaction zone connected thereto for catalytic reaction of reformed fuel; wherein the porous reaction zone is located between the first surface and the second surface and is spaced apart from the first surface and the second surface respectively; the vent is connected to the porous reaction zone; wherein the metal support includes a first layer, a second layer and a third layer structure divided along the thickness direction; wherein the first layer structure is between the porous reaction zone and the second surface, the height of the second layer structure is the thickness of the porous reaction zone, and the third layer structure is between the porous reaction zone and the first surface; Step S2 includes: S21, S22 and S23; S21: Preparation of the first layer structure of the support: The first layer structure of the support includes a solid region located below the reactive porous region in the metal support; during preparation, alloy powder is laid in the preset forming area of ​​the first layer structure of the support, and additive manufacturing process is adopted to form the first layer structure of the support layer by layer through melting and solidification; wherein, if the first layer structure is provided with a ventilated through-hole area, the ventilated through-hole area is integrally formed in the forming of the first layer structure, or the ventilated through-hole area is formed in a secondary processing after the solid body of the first layer structure is completed; or, the ventilated through-hole area is formed in a secondary processing after the insulating layer is formed on the second surface; S22: Preparation of the second layer structure of the support: The second layer structure of the support includes a reactive porous region and a solid support region of equal height to the reactive porous region; during preparation, alloy powder is laid in the solid region of the second layer structure and a composite powder composed of alloy powder and a material with catalytic reforming properties is laid in the reactive porous region on the upper surface of the first layer structure of the support. Using additive manufacturing process, the alloy powder is melted and solidified layer by layer to achieve gradient connection between the alloy material in the solid region and the composite material in the reactive porous region of the second layer structure, thus completing the integral molding of the heterogeneous materials of the second layer structure of the support. S23: Preparation of the third layer structure of the support: The third layer structure of the support includes a solid region located above the reactive porous region in the metal support; during preparation, alloy powder is laid in the preset forming area of ​​the third layer structure of the support, and additive manufacturing process is adopted to form the third layer structure of the support layer by layer through melting and solidification; wherein, if the third layer structure is provided with a ventilated through-hole area, the ventilated through-hole area is integrally formed in the forming of the third layer structure, or the ventilated through-hole area is formed in a secondary process after the solid body of the third layer structure is completed; or the ventilated through-hole area is formed in a secondary process after the insulating layer is formed on the first surface.

3. The method for preparing an integrated plate-type metal-supported solid oxidation fuel cell or electrolyzer according to claim 2, characterized in that, The integrated structural and functional design includes: The spatial structure design of the metal support includes the design of the reaction porous zone, the gas permeable pore zone, the support structure, the turbulence structure, the material inlet, the material outlet, the material distribution zone, the material collection zone, the gas distribution and guiding fluid, and the catalyst material of the reaction porous zone. The design of the stacked design of the anode, electrolyte, and cathode of the solar cell, and the design of the conductive interconnect layer.

4. The method for preparing an integrated plate-type metal-supported solid oxidation fuel cell or electrolyzer according to claim 3, characterized in that, In step S22, additive manufacturing is used, and the material is formed layer by layer through melting and solidification: A material inlet, a material outlet, and a gas distribution guide are reserved in the solid area of ​​the second layer structure of the support. The material inlet and the material outlet are respectively connected to the porous reaction zone. The gas distribution guide is located between the material inlet and the porous reaction zone and between the material outlet and the porous reaction zone. The support structure and the turbulence structure are formed in the reactive porous region of the second layer structure of the support.

5. The method for preparing an integrated plate-type metal-supported solid oxidation fuel cell or electrolyzer according to claim 1, characterized in that, Step S3 includes: S31: A transition metal layer is formed on the lower surface of the first layer structure and the upper surface of the third layer structure of the metal support, respectively. The material of the transition metal layer is a nickel-based alloy material, including one or more of NiCr, NiAl, NiCrAlY and NiCoCrAlY. S32: An insulating layer is formed on the surface of the transition metal layer using plasma spraying technology. The insulating layer is made of one or more of Al2O3, MgAl2O4, or an electrolyte material.

6. The method for preparing an integrated plate-type metal-supported solid oxidation fuel cell or electrolyzer according to claim 5, characterized in that, Before step S31, step S24 is also included: The formed metal support is subjected to stress-relief annealing, leveling, and surface activation treatment on the first and second surfaces of the metal support to obtain a fresh, clean, roughened surface required for thermal spray coating deposition; wherein the surface activation treatment includes at least one of sandblasting and laser cleaning.

7. The method for preparing an integrated plate-type metal-supported solid oxidation fuel cell or electrolyzer according to claim 2, characterized in that, In step S2, the additive manufacturing technology employs selective laser melting, selective electron beam melting, or binder jet additive manufacturing. If selective laser melting technology is used, then: The fabrication process conditions for the solid portions of the first, second, and third layers of the metal support include: laser power of 190-230W, scanning speed of 900-1100mm / s, scanning spacing of 0.08-0.10mm, spot size of 30-80μm, and laser wavelength of 900-1070nm. The fabrication process conditions for the reactive porous region in the second layer structure of the metal support include: laser power of 160-190W, scanning speed of 700-800mm / s, scanning spacing of 0.1-0.15mm, spot size of 30-80μm, and laser wavelength of 900-1070nm. The fabrication process conditions for the permeable pore areas in the first and third layers of the metal support include: laser power of 80-100W, scanning speed of 500-700mm / s, scanning spacing of 0.1-0.13mm, spot size of 30-80μm, and laser wavelength of 900-1070nm.

8. An integrated plate-type metal-supported solid oxidation fuel cell or electrolyzer, characterized in that, It is manufactured using the preparation method of the integrated plate-type metal-supported solid oxidation fuel cell or electrolyzer as described in any one of claims 1 to 7.

9. The integrated plate-type metal-supported solid oxidation fuel cell or electrolyzer according to claim 8, characterized in that, The materials used to prepare the metal support include iron-based or chromium-based alloy materials; including at least one of SUS430, Crofer22, ZMG232 and T441; And / or, the catalyst is a highly active nanocatalyst, including at least one of Al2O3, NiO, CeO2 and La2O3.

10. The integrated plate-type metal-supported solid oxidation fuel cell or electrolyzer according to claim 8, characterized in that, The thickness of the metal support is 2.0-10.0 mm; and / or, the thickness of the anode is 15-40 μm; and / or, the thickness of the electrolyte is 10-30 μm; and / or, the thickness of the cathode is 20-40 μm.

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