Integrated plate type metal support solid oxidation fuel cell or electrolytic tank and preparation method thereof

Abstract

The invention provides an integrated plate type metal support solid oxidation fuel cell or electrolytic tank and a preparation method, and relates to the technical field of solid oxide cells. The preparation method comprises the following steps: carrying out structure and function integrated design on the integrated plate type metal support solid oxidation fuel cell or electrolytic tank; preparing a metal support body by adopting an additive manufacturing technology; forming insulating layers on the upper and lower surfaces of the metal support body respectively; sequentially depositing an anode, an electrolyte and a cathode on the insulating layer and at the position corresponding to the ventilation through hole region; and depositing a conductive connecting layer in the local exposed region of the anode and the adjacent cell cathode partial region. The method is suitable for preparing a novel fuel cell with a complex structure, and is simple and easy to operate, high in precision, good in sealing performance and high in preparation efficiency, and the multifunctional fuel cell with high quality, high efficiency and long service life can be obtained.

Description

Technical Field

[0001] The present invention relates to the technical field of solid oxide fuel cells, and in particular to an integrated plate-type metal-supported solid oxide fuel cell or electrolytic cell and a preparation method thereof. Background Art

[0002] Solid oxide fuel cell (SOFC) is a fully solid-state reaction device that directly converts the chemical energy of fuel and oxidant into electrical energy. Its basic structural unit mainly includes anode, cathode and electrolyte. Solid oxide electrolyzer (SOEC) is the reverse process of solid oxide fuel cell in terms of operating principle. Therefore, SOFC and SOEC have the same cell and cell stack structure type, and will be collectively referred to as SOC in the future.

[0003] At present, the integrated plate SOC is mainly prepared by extrusion molding technology. The extrusion molding has high production efficiency and can be automated and continuously produced, but the material has low strength, is easy to deform, and may produce surface pits and bubbles, cracks and internal cracks. 2 O 4 、ZrO 2 -3Y 2 O 3 The insulating ceramic supports formed by extrusion of ceramic materials have no function other than mechanical support, which increases the gas resistance and weight of the battery and reduces the power-to-weight ratio of the battery. The supports formed by extrusion of anode materials with reforming functions such as NiO are not only bulky, but also greatly increase the cost. These supports can only be arranged with single-function straight or rotating gas flow channels, and it is difficult to control the porous shape and distribution for ventilation and / or reforming reactions. The gas flow resistance is large and it is impossible to achieve the molding of special structures.

[0004] The battery active membrane, anode, electrolyte and cathode are prepared on the support by screen printing. After multiple steps of high-temperature sintering, an integrated plate-type solid oxide battery SOC can be obtained. The porous support surface and side areas between adjacent cells need to be sealed, which increases the technical difficulty. After the battery stack is composed of multiple integrated plate-type solid oxide battery SOCs, the air distribution cavity at the inlet and outlet ends of the support also needs to be sealed. For smaller micro SOCs, because their hollow porous flat tube walls are very thin and difficult to manufacture, the pressure applied during the screen printing process can easily cause the hollow flat tube to collapse.

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

[0006] The objectives of the present invention include, for example, providing an integrated plate-type metal-supported solid oxide fuel cell or electrolytic cell and a preparation method, which can be applicable to the preparation of new complex structure fuel cells and improve the battery power-to-weight ratio; can avoid the adverse effects of the sintering process on the metal support body; 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: In a first aspect, the present invention provides a method for preparing an integrated plate-type metal-supported solid oxidation fuel cell or electrolytic cell, comprising: S1: structural and functional integration design of an integrated plate-type metal-supported solid oxidation fuel cell or electrolytic cell; the integrated plate-type metal-supported solid oxidation fuel cell or electrolytic cell comprises a metal support, an insulating layer and a battery cell; 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 a plurality of air-permeable through-hole areas; the air-permeable through-hole areas are connected to the flow channel; the battery cell comprises an anode, an electrolyte and a cathode; the insulating layer is provided between the metal support and the battery cell; S2: Preparing the metal support body by using additive manufacturing technology, comprising: Alloy powder is laid in the preset forming area of ​​the metal support body, and the metal support body is formed layer by layer through melting and solidification by using additive manufacturing process; wherein the flow channel is formed in the forming process; the air holes in the air permeable through hole area can be formed in the forming process or formed by subsequent secondary processing; S3: forming an insulating layer on the first surface and / or the second surface of the metal support body opposite to each other in the thickness direction; wherein, if the vent holes in the vent hole area are formed by subsequent secondary processing, the vent holes are directly formed on the metal support body by secondary processing 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 by secondary processing; S4: depositing an anode, an electrolyte and a cathode in sequence on the insulating layer and at positions corresponding to the air permeable through hole area, and the electrode layers of adjacent cells are not connected to each other, except that the anode is partially exposed for power supply connection, and the remaining anode and insulating layer areas are completely covered by the electrolyte to achieve self-sealing of the fuel gas path; S5: depositing a conductive connection layer on the partially exposed area of ​​the anode and the adjacent battery cathode area.

[0008] In an optional embodiment, the content of the structural and functional integrated design also includes: The flow channel includes a material inlet and a reaction porous zone connected thereto and used for catalytic reaction of reformed fuel; wherein the reaction porous 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 air permeable hole is connected to the reaction porous zone; wherein the metal support body includes a first layer structure, a second layer structure and a third layer structure divided along the thickness direction; wherein the first layer structure is between the reaction porous zone and the second surface, the height of the second layer structure is the thickness of the reaction porous zone, and the third layer structure is between the reaction porous zone and the first surface; Step S2 includes: S21, S22 and S23; S21: preparation of the first layer structure of the support body: the first layer structure of the support body includes a solid area in the metal support body located below the reactive porous area; during preparation, alloy powder is laid in a preset molding area of ​​the first layer structure of the support body, and an additive manufacturing process is adopted to complete the molding of the first layer structure of the support body through melting, solidification and layer-by-layer molding; wherein, if a breathable through hole area is provided in the first layer structure, the breathable through hole area is integrally molded in the molding of the first layer structure, or the breathable through hole area is secondary processed and molded after the solid body of the first layer structure is completed; or the breathable through hole area is secondary processed and molded after the insulating layer is formed on the second surface; S22: Preparation of the second layer structure of the support body: the second layer structure of the support body includes a reaction porous area and a solid area of ​​the support body with the same height as the reaction porous area; during preparation, on the upper surface of the first layer structure of the support body, alloy powder is laid in the solid area of ​​the second layer structure of the support body, and composite powder composed of alloy and material with catalytic reforming performance is laid in the reaction porous area, and an additive manufacturing process is adopted to form layer by layer through melting and solidification to achieve a gradient connection between the alloy material in the solid area of ​​the second layer structure and the composite material in the reaction porous area, thereby completing the heterogeneous material integrated forming of the second layer structure of the support body; S23: Preparation of the third layer structure of the support body: The third layer structure of the support body includes a solid area in the metal support body located above the reaction porous area; during preparation, alloy powder is laid in the preset molding area of ​​the third layer structure of the support body, and an additive manufacturing process is adopted to complete the molding of the third layer structure of the support body through melting and solidification layer by layer; wherein, if a breathable through hole area is provided in the third layer structure, the breathable through hole area is integrally formed in the molding of the third layer structure, or the breathable through hole area is secondary processed and molded after the solid body of the third layer structure is completed; or the breathable through hole area is secondary processed and molded after the insulating layer is formed on the first surface.

[0009] In an optional embodiment, the structural and functional integrated design includes: The spatial structure design of the metal support, including the design of the reaction porous area, the air permeable through-hole area, the support structure, the flow disturbance structure, the material inlet, the material outlet, the material distribution area, the material collection area, the gas distribution and guide body, and the catalyst material of the reaction porous area; The stacking design of the anode, electrolyte and cathode of the battery cell and the design of the conductive connecting layer.

[0010] In an optional embodiment, in step S22, an additive manufacturing process is used, and in the process of melting, solidification and layer-by-layer molding: A material inlet, a material outlet and a gas distribution and guiding body are reserved in the solid area of ​​the second layer structure of the support body, and the material inlet and the material outlet are respectively connected to the reaction porous area; the gas distribution and guiding body is located between the material inlet and the reaction porous area and between the material outlet and the reaction porous area; The support structure and the spoiler structure are formed in the reaction porous region in the second layer structure of the support body.

[0011] In an optional embodiment, step S3 includes: S31: forming a transition metal layer on the lower surface of the first layer structure and the upper surface of the third layer structure of the metal support body 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: Using plasma spraying technology to form an insulating layer on the surface of the transition metal layer, the insulating layer is made of Al 2 O 3 MgAl 2 O 4 , Y 2 O 3 -ZrO 2 or one or more of electrolyte materials.

[0012] In an optional embodiment, before step S31, it also includes S24: performing stress relief annealing and flattening on the formed metal support body, and performing surface activation treatment on the first surface and the second surface of the metal support body to obtain a fresh, clean and roughened surface required for the thermal spraying technology deposited coating; the surface activation treatment includes at least one of sandblasting and laser cleaning.

[0013] In an optional embodiment, in step S2, the additive manufacturing technology adopts selective laser melting technology, selective electron beam melting technology or binder jet additive manufacturing technology; If the selective laser melting technology is used, among which: The process conditions of the solid part in the first layer structure, the second layer structure and the third layer structure 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; The process conditions of the reaction porous zone 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 process conditions of the air permeable through hole area in the first layer structure and the third layer structure 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.

[0014] In a second aspect, the present invention provides an integrated plate-type metal-supported solid oxidation fuel cell or electrolytic cell, which is manufactured using the preparation method of an integrated plate-type metal-supported solid oxidation fuel cell or electrolytic cell as described in any one of the aforementioned embodiments.

[0015] In an optional embodiment, the preparation material of the metal support comprises an iron-based or chromium-based alloy material; preferably comprises at least one of SUS430, Croferr22, ZMG232 and T441; and / or, the catalyst is a highly active nanocatalyst, more preferably comprises Al 2 O 3 、NiO、CeO 2 and La 2 O 3 At least one of .

[0016] In an optional embodiment, 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 loaded on the surface of the reaction porous zone is 0.5-10 μm.

[0017] The beneficial effects of the embodiments of the present invention include, for example: 1. The method for preparing an integrated plate-type metal-supported solid oxidation fuel cell or electrolytic cell provided in an embodiment of the present invention adopts additive manufacturing technology to prepare a metal support body, which can form a complex structure inside the support body, has good flow channel sealing, and has high preparation efficiency.

[0018] 2. In the battery stack structure formed by this method, there is no need to seal the side of the metal support, which reduces the process difficulty and has good reliability. The metal support has good thermal shock resistance and fast start-stop speed.

[0019] 3. The anode, electrolyte and cathode of the battery cell are formed by a deposition process to avoid the impact of the sintering process on the metal support.

[0020] The integrated plate-type metal-supported solid oxidation fuel cell or electrolytic cell provided in the embodiment of the present invention is conducive to improving the start-stop speed, improving the thermal shock resistance, improving the power-to-weight ratio, improving the battery performance, and has reliable sealing, reduced difficulty in the preparation process, and high preparation efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for use in the embodiments are briefly introduced below. It should be understood that the following drawings only show certain embodiments of the present invention and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other related drawings can be obtained based on these drawings without creative work.

[0022] Figure 1 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; 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; Figure 3 for Figure 2 A partial enlarged schematic diagram of the M in the middle; Figure 4 A schematic structural diagram of a metal support body of an integrated plate-type metal-supported solid oxidation fuel cell provided in an embodiment of the present invention.

[0023] Icon: 100-integrated plate-type metal-supported solid oxide fuel cell; 110-metal support body; 101-first surface; 102-second surface; 103-first layer structure; 104-second layer structure; 105-third layer structure; 111-reaction porous area; 112-air permeable through hole area; 1121-air permeable hole; 113-material inlet; 114-material outlet; 115-support structure; 120-insulating layer; 121-transition metal layer; 130-battery cell; 131-anode; 132-electrolyte; 133-cathode; 140-conductive connecting layer; 141-solid segment; 142-porous segment. DETAILED DESCRIPTION

[0024] In order to make the purpose, 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 in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Generally, the components of the embodiments of the present invention described and shown in the drawings here can be arranged and designed in various different configurations.

[0025] Therefore, the following detailed description of the embodiments of the present invention provided in the accompanying drawings is not intended to limit the scope of the invention claimed for protection, but merely represents selected embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0026] It should be noted that similar reference numerals and letters denote similar items in the following drawings, and therefore, once an item is defined in one drawing, further definition and explanation thereof is not required in subsequent drawings.

[0027] In the description of the present invention, it should be noted that if the terms "upper", "lower", "inside", "outside", etc. appear to indicate an orientation or position relationship, they are based on the orientation or position relationship shown in the accompanying drawings, or are the orientation or position relationship in which the product of the invention is usually placed when used. They are only for the convenience of describing the present invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as a limitation on the present invention.

[0028] In addition, the terms “first”, “second”, etc., if used, are merely used to distinguish between the descriptions and should not be understood as indicating or implying relative importance.

[0029] It should be noted that, in the absence of conflict, the features in the embodiments of the present invention may be combined with each other.

[0030] 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 electrolytic cell, which mainly includes the following steps: S1: Perform structural and functional integration design on the integrated plate-type metal-supported solid oxidation fuel cell 100 or electrolytic cell.

[0031] The integrated plate-type metal-supported solid oxidation fuel cell 100 or electrolytic cell comprises a metal support 110, an insulating layer 120 and a battery sheet 130; the metal support 110 has a first surface 101 and a second surface 102 arranged opposite to each other, namely, an upper surface and a lower surface. The metal support 110 is provided with a reaction porous area 111 for catalytic reaction of the reformed fuel and a gas permeable through-hole area 112 as a synthetic gas flow channel. Among them, the reaction porous area 111 is located between the first surface 101 and the second surface 102 and is spaced from the first surface 101 and the second surface 102 respectively. Such a configuration has a compact structure and a small volume, which can not only solve the problem that the carbon deposition of the anode 131 covers the catalytic active sites and reduces the activity of the anode 131, and solve the problem that the carbon deposition of the anode 131 generates expansion stress to damage the battery structure, but also can avoid the rapid reaction of the catalytic reforming reaction, which directly leads to a low temperature of the anode 131 located at the fuel inlet, forming a large temperature gradient and generating excessive thermal stress to increase the risk of damaging the battery structure. In addition, the problem of the gas medium directly contacting the electrode surface of the battery cell 130, causing the separation of the heterogeneous interface inside the battery and damaging the battery structure, can also be solved.

[0032] The first surface 101 and the second surface 102 are respectively provided with a plurality of air holes 1121 to form an air-permeable through-hole area 112, and the air holes 1121 are connected to the reaction porous area 111. The hydrocarbon fuel gas undergoes a catalytic reforming reaction in the reaction porous area 111 to generate synthesis gas, and the synthesis gas reaches the anode 131 through the air holes 1121 to undergo an electrochemical reaction. The metal support 110 has a material inlet 113 and a material outlet 114 connected to the reaction porous area 111. Except for the material inlet 113, the material outlet 114 and the air holes 1121, the rest of the metal support 110 is a dense surface without leakage, thereby ensuring the sealing of the gas flow channel.

[0033] The battery cell 130 includes an anode 131, an electrolyte 132 and a cathode 133. The anode 131 completely covers the air permeable through hole area 112. The insulating layer 120 is disposed between the metal support 110 and the battery cell 130.

[0034] It can be understood that each reaction porous area 111 corresponds to a permeable through hole area 112. A plurality of reaction porous areas 111 are provided on each metal support 110. The reaction porous area 111 is an area having a polyhedral lattice unit structure. Exemplarily, the polyhedron can be, for example, a hexahedron or an octahedron. The sum of the areas of the plurality of permeable through hole areas 112 above the metal support 110 is less than the area of ​​the first surface 101. The sum of the areas of the plurality of permeable through hole areas 112 below the metal support 110 is less than the area of ​​the second surface 102.

[0035] Optionally, depending on the type of fuel, if no reforming reaction is required, the reaction porous zone 111 can be omitted. It is only necessary to form a flow channel for the reaction medium material to flow in the metal support 110. The flow channel includes a material inlet 113 and a material outlet 114.

[0036] The ventilation hole area 112 can be only provided on the first surface 101 or the second surface 102, that is, the battery cell 130 can be arranged on one side or on both sides on the metal support 110. The insulating layer 120 can also be designed to be single-sided or double-sided according to the arrangement of the battery cell 130, which is not specifically limited here.

[0037] Optionally, the structural and functional integrated design includes: the spatial structure design of the metal support body 110, including the reaction porous area 111, the air permeable through-hole area 112, the support structure 115, the spoiler structure, the material inlet 113, the material outlet 114, the material distribution area, the material collection area, the gas distribution and conduction fluid, and the catalyst material design of the reaction porous area 111; the stacking design of the anode 131, the electrolyte 132 and the cathode 133 of the battery cell 130 and the design of the conductive connecting layer 140.

[0038] Optionally, the material inlet 113 and the material outlet 114 are arranged on a set of opposite sides of the metal support 110. And there is only one material inlet 113 and one material outlet 114. Multiple reaction porous areas 111 are distributed in a matrix. In the flow direction of the material, the porosity of each reaction porous area 111 gradually decreases, preferably decreasing in a gradient. Since the internal reforming of the fuel occurring inside the battery is a highly endothermic chemical reaction with a very fast rate and requires the absorption of a large amount of heat, this embodiment helps to avoid the reforming process causing a large temperature gradient inside the battery by setting the porosity to a gradient reduction mode, reducing the thermal stress formed therein and avoiding damage to the battery structure. In addition, this method can not only avoid the carbon deposits formed by hydrocarbon fuels covering the surface of the active sites of the anode 131, resulting in a significant decrease in battery performance, but also avoid the separation of the heterogeneous interface inside the battery and other destructive structures.

[0039] Optionally, among the above porosities, the maximum porosity is not more than 90%, and the minimum porosity is not less than 40%. The pore size of each pore in each reaction porous zone 111 may be 100-1000 μm, and the total thickness of the reaction porous zone 111 may be 0.5-2.5 mm.

[0040] S2: The metal support body 110 is prepared by using additive manufacturing technology, alloy powder is laid in the preset molding area of ​​the metal support body 110, and the metal support body 110 is molded layer by layer through melting and solidification by using additive manufacturing process; wherein, the flow channel is formed in the molding process; the air pores 1121 of the air permeable through hole area 112 can be formed in the molding process or formed by subsequent secondary processing.

[0041] Optionally, the flow channel includes a material inlet 113 and a reaction porous area 111 connected thereto and used for catalytic reaction of the reformed fuel. The reaction porous area 111 is located between the first surface 101 and the second surface 102 and is spaced from the first surface 101 and the second surface 102 respectively. The air vents 1121 are connected to the reaction porous area 111; wherein the metal support 110 includes a first layer structure 103, a second layer structure 104 and a third layer structure 105 divided along the thickness direction. The first layer structure 103 is between the reaction porous area 111 and the second surface 102, the height of the second layer structure 104 is the thickness of the reaction porous area 111, and the third layer structure 105 is between the reaction porous area 111 and the first surface 101.

[0042] Step S2 includes: S21, S22 and S23.

[0043] S21: Preparation of the first layer structure 103 of the support body: The first layer structure 103 of the support body includes a solid area located below the reaction porous area 111 in the metal support body 110, such as Figure 4 As shown. During preparation, alloy powder, such as high temperature oxidation resistant alloy powder, is laid in the preset molding area of ​​the first layer structure 103 of the support body, and the additive manufacturing process is adopted to complete the molding of the first layer structure 103 of the support body through melting and solidification layer by layer. Wherein, if a breathable through hole area 112 is provided in the first layer structure 103, the breathable through hole area 112 is integrally formed in the molding of the first layer structure 103, or the breathable through hole area 112 is secondary processed and molded after the solid body of the first layer structure 103 is completed. Alternatively, the breathable through hole area 1121 of the breathable through hole area 112 is secondary processed and molded after the insulating layer is formed on the second surface 102. It can be understood that the features of the breathable holes 1121 can be integrally formed in the 3D additive manufacturing process, or can be formed by laser drilling, electron beam drilling, etc. after the preparation of the support body is completed.

[0044] S22: Preparation of the second layer structure 104 of the support body: The second layer structure 104 of the support body includes a reaction porous area 111 and a solid area of ​​the support body having the same height as the reaction porous area 111, such as Figure 4 During preparation, on the upper surface of the first layer structure 103 of the support body, alloy powders, such as high temperature oxidation resistant alloy powders, are laid in the solid areas of the second layer structure 104 of the support body, and composite powders composed of high temperature oxidation resistant alloys and materials with catalytic reforming performance are laid in the reaction porous area 111. The additive manufacturing process is adopted, and the high alloy material in the solid area of ​​the second layer structure 104 and the composite material in the reaction porous area 111 are formed layer by layer through melting and solidification, so as to achieve a gradient connection between the high alloy material in the solid area of ​​the second layer structure 104 and the composite material in the reaction porous area 111, and complete the heterogeneous material integrated forming of the second layer structure 104 of the support body.

[0045] Two different materials are laid in the reaction porous area 111 and the corresponding equal height support body solid area by layer-by-layer powder laying, and the solid area and the reaction porous area 111 are formed by different process parameters. Among them, the solid area of ​​the support body and the reaction porous area 111 are integrally connected by gradient alloy / composite materials. The solid area adopts commonly used alloy materials, and the reaction porous area 111 material is an alloy and a composite material with catalytic reforming performance.

[0046] Optionally, in step S22, an additive manufacturing process is used, and in the process of melting, solidification and layer-by-layer molding: the solid area in the second layer structure 104 of the support body is reserved with features such as a material inlet 113, a material outlet 114 and a gas distribution guide body, and the material inlet 113 and the material outlet 114 are respectively connected to the reaction porous area 111; the gas distribution guide body is located between the material inlet 113 and the reaction porous area 111 and between the material outlet 114 and the reaction porous area 111. A support structure 115 and a spoiler structure are formed in the reaction porous area 111 domain in the second layer structure 104 of the support body. The support structure 115 plays a structural support role and improves the structural strength. The spoiler structure is arranged in the area other than the support structure 115 in the reaction porous area 111, and is used to guide the reformed gas to the air vents 1121. The multiple structural features inside the metal support body 110 can be integrally formed using additive manufacturing technology, which is not subject to structural restrictions, has high preparation efficiency, reliable structure, convenient operation, low process difficulty and low cost.

[0047] S23: Preparation of the third layer structure 105 of the support body: The third layer structure 105 of the support body includes a solid area located above the reaction porous area 111 in the metal support body 110, such as Figure 4 As shown. During preparation, alloy powder, such as high temperature oxidation resistant alloy powder, is laid in the preset molding area of ​​the third layer structure 105 of the support body, and the additive manufacturing process is adopted to complete the molding of the third layer structure 105 of the support body through melting and solidification layer by layer. If a breathable through hole area 112 is provided in the third layer structure 105, the air holes 1121 of the breathable through hole area 112 are integrally formed in the molding of the third layer structure 105. Alternatively, the air holes 1121 of the breathable through hole area 112 are formed by secondary processing after the insulating layer is formed on the second surface 102. The characteristics of the air holes 1121 in the third layer structure 105 can be formed by powder metallurgy, additive manufacturing, laser drilling or electron beam drilling. For example, it can be integrally formed in a 3D additive manufacturing process, or it can be formed by laser drilling or electron beam drilling after the preparation of the support body is completed.

[0048] Optionally, in step S2, the additive manufacturing technology adopts selective laser melting technology, selective electron beam melting technology or binder jetting additive manufacturing technology. In this embodiment, the selective laser melting technology is adopted. Optionally, the process conditions of the solid part in the three-layer structure of the metal support 110 include: the laser power is 190-230W (such as 190W, 200W, 210W, 220W, 225W or 230W, etc.), the scanning speed is 900-1100mm / s (such as 900mm / s, 950mm / s, 1000mm / s, 1050mm / s or 1100mm / s, etc.), the scanning interval is 0.08-0.1mm (such as 0.08mm, 0.09mm or 0.1mm, etc.), the spot size is 30-80μm (such as 30μm, 40μm, 50μm, 60μm, 70μm or 80μm, etc.), and the laser wavelength is 900-1070nm.

[0049] Optionally, the process conditions of the reaction porous area 111 in the second layer structure 104 of the metal support 110 include: laser power of 160-190W (such as 160W, 170W, 180W or 190W, etc.), scanning speed of 700-800mm / s (such as 700mm / s, 750mm / s or 800mm / s, etc.), scanning spacing of 0.1-0.15mm (such as 0.1mm, 0.11mm, 0.13mm or 0.15mm, etc.), spot size of 30-80μm (such as 30μm, 40μm, 50μm, 60μm, 70μm or 80μm, etc.), laser wavelength of 900-1070nm. Optionally, the surface characteristics of the polyhedral lattice unit structure of the reaction porous area 111 are regulated by optimizing the scanning strategy so that it has the largest catalytic surface area.

[0050] Optionally, the process conditions of the first layer structure 103 and the breathable through hole area 112 in the third layer structure 105 of the metal support 110 include: laser power of 80-100W (such as 80W, 85W, 90W, 95W or 100W, etc.), scanning speed of 500-700mm / s (such as 500mm / s, 550mm / s, 600mm / s, 650mm / s or 700mm / s, etc.), scanning spacing of 0.1-0.13mm (such as 0.1mm, 0.11mm, 0.12mm or 0.13mm, etc.), spot size of 30-80μm (such as 30μm, 40μm, 50μm, 60μm, 70μm or 80μm, etc.), and laser wavelength of 900-1070nm.

[0051] The self-sealing of the reformed hydrocarbon fuel gas path is achieved by integrating the first layer structure 103, the second layer structure 104 and the third layer structure 105 of the metal support 110. The shape and position distribution of the reaction porous area 111 and the air vents 1121 are easy to control in the additive manufacturing process, are not limited by special structures, and have low airflow resistance.

[0052] Illustratively, the air holes 1121 in the first layer structure 103 and the third layer structure 105 of the metal support body 110 in this embodiment are formed by subsequent secondary processing, such as laser drilling, which has high forming accuracy, high efficiency, smooth hole walls, and low airflow resistance.

[0053] Optionally, the air holes 1121 in the first layer structure 103 and the third layer structure 105 are punched by laser, and the process parameters of the laser punching are: laser power of 10W to 1000W, laser frequency of 0.1Hz to 1MHz, and pulse width of 5ps to 100ms.

[0054] Optionally, the air holes 1121 in the first layer structure 103 and the third layer structure 105 are punched by electron beam. The process parameters of electron beam punching are: pulse power of 0.2kW-15kW, pulse frequency of 0.2kHz-10kHz, working current of 1mA-150mA, and pulse duration of 50us-100ms.

[0055] S24: The formed metal support 110 is subjected to stress relief annealing, flattening and surface activation treatment. Stress relief annealing and flattening treatment can be performed in a vacuum heat treatment furnace. Optionally, the annealing temperature is 500-900°C, such as 500°C, 550°C, 600°C, 650°C, 700°C, 750°C, 800°C, 850°C or 900°C, etc., or any other value within the range of 500-900°C. The annealing time is 4-6 hours, such as 4 hours, 5 hours or 6 hours, etc., or any other value within the range of 4-6 hours.

[0056] The first surface 101 and the second surface 102 of the metal support 110 are subjected to surface activation treatment to obtain fresh, clean and roughened surfaces required for depositing coatings by thermal spraying technology. Optionally, the surface activation treatment includes at least one of sandblasting and laser cleaning.

[0057] S3: forming an insulating layer 120 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. 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 by 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.

[0058] The process conditions for plasma spraying MCrAlY on the transition metal layer 121 include: Ar flow rate 45-48 L / min, H 2 Flow rate 7-10L / min, spraying distance 100-110mm, spraying current 580-630A, spraying voltage 70-72V, spraying power 40.6-45.5kW. Alternatively, the process conditions for supersonic flame spraying of MCrAlY for the transition metal layer 121 include: oxygen flow rate 750-800L / min, aviation kerosene 18-20L / h, combustion chamber pressure 5.8-6.1bar, spraying distance 290-310mm. Alternatively, the process conditions for the transition metal layer 121 using Ni20Cr include: Ar flow rate 42-47L / min, H 2 Flow rate 6-10L / min, spraying distance 105-115mm, spraying current 600-650A, spraying voltage 65-70V, spraying power 39-45.5kW.

[0059] S32: Using plasma spraying technology to deposit an insulating layer 120 on the surface of the transition metal layer 121. The insulating layer 120 can be a ceramic insulating layer 120. The material of the insulating layer 120 is Al 2 O 3 MgAl 2 O 4 , Y 2 O 3 -ZrO 2 or one or more of electrolyte materials.

[0060] If the insulating layer 120 is made of Al 2 O 3 The process conditions include: Ar flow rate 38-43L / min, H 2 Flow rate 10-12L / min, spraying distance 110-120mm, spraying current 620-650A, spraying voltage 72-74V, spraying power 44.5-48.1kW. Alternatively, if the insulating layer 120 is made of ZrO 2 -8Y 2 O 3 The process conditions include: Ar flow rate 43-45L / min, H 2Flow rate 10-12L / min, spraying distance 110-120mm, spraying current 580-630A, spraying voltage 71-73V, spraying power 41.2-46kW.

[0061] It can be understood that the provision of the transition metal layer 121 can reduce the difference in thermal expansion coefficients between the insulating layer 120 and the metal support 110, avoid structural stratification, and improve the reliability of the battery structure. The vent 1121 needs to penetrate the transition metal layer 121 and the insulating layer 120 so that the gas after the reforming reaction can smoothly reach the anode 131.

[0062] It should be noted that the air holes 1121 in the first layer structure 103 and the third layer structure 105 can be punched after the insulating layer 120 is formed. If the metal support 110 is directly punched before the insulating layer 120 is formed, the metal support 110 needs to be surface activated. If the insulating layer 120 is punched after the insulating layer 120 is formed and the air holes 1121 are made deep into the metal support 110, the insulating layer 120 does not need to be surface activated, and the holes can be directly punched.

[0063] S4: The anode 131, the electrolyte 132 and the cathode 133 are sequentially deposited on the insulating layer 120 and at positions corresponding to the air-permeable through-hole area 112 using plasma spraying technology, and the electrodes of adjacent batteries are not connected to each other. Except for the partially exposed power supply connection of the anode 131, the remaining anode 131 and the insulating layer 120 area are completely covered by the electrolyte 132 to achieve self-sealing of the fuel gas path.

[0064] S5: using plasma spraying technology to deposit a conductive connection layer 140 on the partially exposed area of ​​the anode 131 and a partial area of ​​the adjacent battery cathode 133 .

[0065] 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 part of the anode 131, so as to realize the electrical connection between the anode 131 of one battery cell 130 and the cathode 133 of the adjacent battery cell 130. In this way, all battery cells 130 on both sides of the metal support 110 are connected in series. It can be understood that the solid segment 141 and the electrolyte 132 together fill the gap between two adjacent anodes 131.

[0066] It can be understood that the use of plasma spraying technology to form the electrolyte 132 and the conductive connection layer 140 can improve the sealing of the gas flow channel in the metal support 110.

[0067] Optionally, the preparation material of the metal support 110 includes an iron-based or chromium-based alloy material; such as at least one of SUS430, Croferr22, ZMG232 and T441. The catalyst is a highly active nanocatalyst, such as Al 2 O 3 、NiO、CeO 2 and La 2 O 3 At least one of .

[0068] 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, etc., or it can be any other value within the range of 2-10 mm.

[0069] The thickness of the 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 within the range of 20-40 μm.

[0070] The thickness of the 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 within the range of 15-30 μm.

[0071] The thickness of the cathode 133 is 20-40 μm, such as 20 μm, 25 μm, 30 μm, 35 μm or 40 μm, or any other value within the range of 20-40 μm.

[0072] The thickness of the catalyst loaded on the surface of the reaction porous zone 111 is 0.5-10 μm, such as 0.5 μm, 1 μm, 2 μm, 5 μm, 8 μm or 10 μm, etc., and may also be any other value within the range of 0.5-10 μm.

[0073] The embodiment of the present invention further provides an integrated plate-type metal-supported solid oxidation fuel cell 100 or electrolytic cell, which is manufactured using the preparation method of the integrated plate-type metal-supported solid oxidation fuel cell 100 or electrolytic cell as described in any of the aforementioned embodiments.

[0074] In summary, the integrated plate-type metal-supported solid oxidation fuel cell 100 or electrolytic cell and preparation method provided in the embodiments of the present invention have the following beneficial effects, for example: 1. The method for preparing the integrated plate-type metal-supported solid oxidation fuel cell 100 or electrolytic cell provided in the embodiment of the present invention adopts additive manufacturing technology to prepare the metal support body 110, which can form a complex structure inside the support body, has good flow channel sealing, and high preparation efficiency.

[0075] 2. In the battery stack structure formed by this preparation method, there is no need to seal the side of the support body, which reduces the process difficulty and improves reliability.

[0076] 3. The metal support body 110 is adopted, which has good thermal shock resistance and fast start and stop speed.

[0077] 4. A reactive porous area 111 is formed inside the metal support 110 to prevent carbon deposition on the anode 131, thereby improving battery performance and the battery power-to-weight ratio.

[0078] 5. The anode 131 , the electrolyte 132 and the cathode 133 of the battery cell 130 are formed by a deposition process to avoid the influence of the sintering process on the metal support 110 .

[0079] The method is simple and easy to operate with high precision, and can obtain a high-quality carbon deposition-resistant self-sealed internal reforming solid oxide fuel cell or electrolytic cell, thereby improving efficiency and extending its service life.

[0080] The integrated plate-type metal-supported solid oxidation fuel cell 100 or electrolytic cell provided in the embodiment of the present invention is conducive to improving the start-stop speed, improving thermal shock resistance, improving the power-to-weight ratio, reducing carbon deposition on the anode 131, and improving battery performance. It also has reliable sealing, reduced difficulty in the preparation process, and high preparation efficiency.

[0081] The above is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by a person skilled in the art within the technical scope disclosed by the present invention should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims.

Claims

1. A method for preparing an integrated plate-type metal-supported solid oxidation fuel cell or electrolytic cell, characterized in that: include: S1: structural and functional integration design of an integrated plate-type metal-supported solid oxidation fuel cell or electrolytic cell; the integrated plate-type metal-supported solid oxidation fuel cell or electrolytic cell comprises a metal support, an insulating layer and a battery cell; the metal support is provided with a flow channel for the flow of reaction medium materials; a plurality of air-permeable through-hole areas are provided on the surface of the metal support; the air-permeable through-hole areas are connected to the flow channel; the battery cell comprises an anode, an electrolyte and a cathode; The insulating layer is provided between the metal support and the battery cell; S2: Preparing the metal support body by using additive manufacturing technology, comprising: Alloy powder is laid in the preset forming area of ​​the metal support body, and the metal support body is formed layer by layer through melting and solidification by using additive manufacturing process; wherein the flow channel is formed in the forming process; the air holes in the air permeable through hole area can be formed in the forming process or formed by subsequent secondary processing; S3: forming an insulating layer on a first surface and / or a second surface opposite to the metal support along a thickness direction; Wherein, if the vent holes in the vent hole area are formed by subsequent secondary processing, the vent holes are directly formed on the metal support by secondary processing after the metal support is formed; or, after step S3, the vent holes are formed on the metal support and the insulating layer by secondary processing; S4: depositing an anode, an electrolyte and a cathode in sequence on the insulating layer and at positions corresponding to the air permeable through hole area, and the electrode layers of adjacent cells are not connected to each other, except that the anode is partially exposed for power supply connection, and the remaining anode and insulating layer areas are completely covered by the electrolyte to achieve self-sealing of the fuel gas path; S5: depositing a conductive connection layer on the partially exposed area of ​​the anode and the adjacent battery cathode area.

2. The method for preparing an integrated plate-type metal-supported solid oxidation fuel cell or electrolytic cell according to claim 1, characterized in that: The contents of the structural and functional integrated design also include: The flow channel includes a material inlet and a reaction porous zone connected thereto and used for catalytic reaction of reformed fuel; wherein the reaction porous 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 air permeable hole is connected to the reaction porous zone; wherein the metal support body includes a first layer structure, a second layer structure and a third layer structure divided along the thickness direction; wherein the first layer structure is between the reaction porous zone and the second surface, the height of the second layer structure is the thickness of the reaction porous zone, and the third layer structure is between the reaction porous zone and the first surface; Step S2 includes: S21, S22 and S23; S21: Preparation of the first layer structure of the support body: the first layer structure of the support body includes a solid area in the metal support body located below the reactive porous area; during preparation, alloy powder is laid in a preset molding area of ​​the first layer structure of the support body, and an additive manufacturing process is adopted to complete the molding of the first layer structure of the support body through melting, solidification and layer-by-layer molding; wherein, if a breathable through hole area is provided in the first layer structure, the breathable through hole area is integrally molded during the molding of the first layer structure, or the breathable through hole area is secondary processed and molded after the solid body of the first layer structure is completed; or the breathable through hole area is secondary processed and molded after the insulating layer is formed on the second surface; S22: Preparation of the second layer structure of the support body: the second layer structure of the support body includes a reaction porous area and a solid area of ​​the support body at the same height as the reaction porous area; during preparation, on the upper surface of the first layer structure of the support body, alloy powder is laid in the solid area of ​​the second layer structure of the support body, and composite powder composed of alloy powder and material with catalytic reforming performance is laid in the reaction porous area, and an additive manufacturing process is adopted to achieve gradient connection between the alloy material in the solid area of ​​the second layer structure and the composite material in the reaction porous area through melting and solidification, so as to complete the heterogeneous material integrated molding of the second layer structure of the support body; S23: Preparation of the third layer structure of the support body: The third layer structure of the support body includes a solid area in the metal support body located above the reaction porous area; during preparation, alloy powder is laid in the preset molding area of ​​the third layer structure of the support body, and an additive manufacturing process is adopted to complete the molding of the third layer structure of the support body through melting and solidification layer by layer; wherein, if a breathable through hole area is provided in the third layer structure, the breathable through hole area is integrally formed in the molding of the third layer structure, or the breathable through hole area is secondary processed and molded after the solid body of the third layer structure is completed; or the breathable through hole area is secondary processed and molded 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 electrolytic cell according to claim 2, characterized in that: The contents of the structural and functional integrated design include: The spatial structure design of the metal support, including the design of the reaction porous area, the air permeable through-hole area, the support structure, the flow disturbance structure, the material inlet, the material outlet, the material distribution area, the material collection area, the gas distribution and guide body, and the catalyst material of the reaction porous area; The stacking design of the anode, electrolyte and cathode of the battery cell and the design of the conductive connecting layer.

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

5. The method for preparing an integrated plate-type metal-supported solid oxidation fuel cell or electrolytic cell according to claim 1, characterized in that: Step S3 includes: S31: forming a transition metal layer on the lower surface of the first layer structure and the upper surface of the third layer structure of the metal support, respectively, wherein the material of the transition metal layer is a nickel-based alloy material, including one or more of NiCr, NiAl, NiCrAlY and NiCoCrAlY; S32: forming an insulating layer on the surface of the transition metal layer by plasma spraying technology, wherein the material of the insulating layer is one or more of Al2O3, MgAl2O4, Y2O3-ZrO2 or electrolyte material.

6. The method for preparing an integrated plate-type metal-supported solid oxidation fuel cell or electrolytic cell according to claim 5, characterized in that: Before step S31, the method further includes step S24: The formed metal support body is subjected to stress relief annealing, flattening, and surface activation treatment on the first surface and the second surface of the metal support body to obtain a fresh, clean, roughened surface required for the thermal spraying technology deposited coating; 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 electrolytic cell according to claim 2, characterized in that: In step S2, the additive manufacturing technology adopts selective laser melting technology, selective electron beam melting technology or binder jet additive manufacturing technology; If the selective laser melting technology is used, among which: The process conditions of the solid part in the first layer structure, the second layer structure and the third layer structure 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 process conditions of the reaction porous zone 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 process conditions of the air permeable through hole area in the first layer structure and the third layer structure 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: The integrated plate-type metal-supported solid oxidation fuel cell or electrolytic cell is manufactured by the preparation method according to 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 preparation material of the metal support body includes an iron-based or chromium-based alloy material; including at least one of SUS430, Croferr22, 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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