Method for manufacturing a tubular solid oxide fuel cell half-cell, a full cell and a cell assembly

Abstract

The present application relates to a method for preparing a tubular solid oxide fuel half-cell, a method for preparing a full cell and a battery assembly, and belongs to the technical field of solid oxide fuel cells. The method aims to solve the technical problem that in the preparation process of the existing round tube structure cell, the coating area of each structure layer needs to be accurately controlled on the circumference, resulting in a complex process, and it is difficult to balance efficiency and quality. The technical solution is as follows: the support body is prepared into a multi-prism tube structure; in the preparation of the half-cell, the conductive layer slurry and the electrolyte layer slurry are respectively coated on the different outer wall surfaces of the support body, and the half-cell is formed after sintering; in the preparation of the full cell, the barrier layer and the cathode layer or the anode layer are respectively coated on the electrolyte layer of the half-cell, and the full cell is prepared after sintering again; the prepared full cell can be directly connected in series with the electrode layer of the adjacent cell through the conductive layer to form a battery assembly.

Description

Technical Field

[0001] This invention relates to the field of tubular solid oxide fuel cells, and specifically to a method for preparing a tubular solid oxide fuel cell half-cell, a method for preparing a full cell, and a battery assembly. Background Technology

[0002] Solid oxide fuel cells (SOFCs) have advantages such as high power generation efficiency, low emissions, wide adaptability to various fuel gases, and high waste heat utilization value. Solid oxide fuel cells are mainly of tubular and planar types, with the tubular structure being the most commonly used form at present.

[0003] Currently, the most common tubular solid oxide fuel cells are circular tubular coaxial stacked structures. For example, Chinese patent CN106207221B, applied for by Shanxi University on August 11, 2016, discloses a method for preparing a tubular solid oxide fuel cell, which is a structure in which the anode support, electrolyte layer, and other structural layers are coaxially stacked.

[0004] However, during battery use, both the anode and cathode layers of the full cell require external devices. Therefore, the anode and cathode layers are exposed on the outer surface of the full cell. In other words, the structural layers on the outer layer of the full cell cannot completely cover the inner structural layers. For example, Suzhou Nage Optoelectronics Technology Co., Ltd. filed a Chinese patent application on March 27, 2019, entitled "Supported Microtubular Solid Oxide Fuel Cell and its Preparation Method Thereof," with authorization announcement number CN109921050B. This patent application indicates that the length of the cathode layer is shorter than the length of the electrolyte layer. Therefore, there is a section on the surface of the electrolyte layer that is not covered by the cathode layer.

[0005] Therefore, when preparing a full cell, it is necessary to precisely control the coating or preparation length of each structural layer, which places high demands on the production process. If the coating speed is increased in pursuit of efficiency, the coating edges will be blurred and the quality requirements will not be met. Therefore, ensuring the simplicity of the preparation process of each structural layer while ensuring the coating quality of the battery has been a long-standing technical problem in this field. Summary of the Invention

[0006] The purpose of this invention is to provide a method for preparing a tubular solid oxide fuel cell half-cell, a method for preparing a full cell, and a battery assembly. By forming a support into a multi-prism tubular structure and sintering conductive, anode, or cathode layers on different outer wall surfaces, this invention solves the technical problem of existing tubular solid oxide fuel cells where precise control of the coating area of ​​each structural layer is required during the preparation process, making it difficult to balance production efficiency and product quality. This invention also simplifies the preparation process of each structural layer, reduces manufacturing difficulty, and accelerates production efficiency.

[0007] To achieve the aforementioned objectives, the technical solution adopted by the present invention is as follows: A method for preparing a tubular solid oxide fuel cell includes the following steps: S1: Prepare an anode or cathode support slurry and process it into a multi-prism tube-shaped support green body. The support green body is then dried, degreased, and sintered in sequence to obtain an anode support or cathode support. S2: For the anode support, prepare conductive layer slurry and electrolyte layer slurry, coat the conductive layer slurry and electrolyte layer slurry on different outer wall surfaces of the support, and dry to form conductive layer green and electrolyte layer green. For the cathode support, a conductive layer slurry, a barrier layer slurry, and an electrolyte layer slurry are prepared. The conductive layer slurry and the barrier layer slurry are coated on different outer wall surfaces of the support, and dried to form a conductive layer green body and a barrier layer green body. The electrolyte layer slurry is coated on the outer surface of the barrier layer green body and dried to form an electrolyte layer green body. S3: The anode support or cathode support coated with conductive layer green blank and electrolyte layer green blank is sintered to obtain an anode support half cell or cathode support half cell with conductive layer and electrolyte layer.

[0008] Preferably, in S1, the polyhedral tubular support blank is formed by extrusion molding or slip casting. If extrusion molding is used, the support slurry is injected into the extruder and the polyhedral tube-shaped support preform is directly extruded, or the round tube-shaped support preform is first extruded and then processed to form the polyhedral tube-shaped support preform. If the slurry casting method is used, the slurry for the support body is injected into the cavity of the mold. After the slurry for the support body dries, it is demolded to directly form a polyhedral tube-type support body blank, or it is first demolded to form a round tube-type support body blank, and then processed to form a polyhedral tube-type support body blank.

[0009] Preferably, in S1, the drying, degreasing, and sintering treatment of the support green body includes: The green support body is dried at room temperature; and / or, The dried support green body is degreased by heating it to 500–600°C in air; and / or, The degreased support green body is heated to 1000-1100℃ and held for 2-3 hours for sintering.

[0010] Preferably, for the anode support half-cell: When the conductive layer slurry is applied to adjacent outer wall surfaces of the anode support, the conductive layer slurry on these adjacent outer wall surfaces is continuous, and after drying, it forms a conductive layer green body that continuously covers the adjacent outer wall surfaces; and / or, When the electrolyte layer slurry is coated on the adjacent outer wall surface of the anode support, the electrolyte layer slurry on the adjacent outer wall surface is continuous, and after drying, it forms an electrolyte layer green blank that continuously covers the adjacent outer wall surface. For cathode support half-cells: When the conductive layer slurry is applied to adjacent outer wall surfaces of the cathode support, the conductive layer slurry on these adjacent outer wall surfaces is continuous, and after drying, it forms a conductive layer green body that continuously covers the adjacent outer wall surfaces; and / or, When the barrier layer slurry is applied to adjacent outer wall surfaces of the cathode support, the barrier layer slurry on the adjacent outer wall surfaces is continuous, and after drying, it forms a barrier layer green body that continuously covers the adjacent outer wall surfaces; and / or, When the electrolyte layer slurry is applied to the barrier layer green body on the adjacent outer wall surface, the electrolyte layer slurry on the adjacent outer wall surface is continuous, and after drying, it forms an electrolyte layer green body that continuously covers the barrier layer green body on the adjacent outer wall surface.

[0011] Preferably, the preparation of the anode support slurry includes: using NiO powder and YSZ powder as main raw materials, mixing them with solvent, binder, plasticizer and dispersant, ball milling to prepare the anode support slurry; and / or, The preparation of the cathode support slurry includes: using LSCF powder and GDC powder as main raw materials, mixing them with solvent, binder, plasticizer and dispersant, ball milling to prepare the cathode support slurry; and / or, The preparation of the conductive layer slurry includes: using LST powder as the main raw material, mixing it with solvent, binder, plasticizer and dispersant, ball milling to prepare the conductive layer slurry; and / or, The preparation of the electrolyte layer slurry includes: using YSZ powder as the main raw material, mixing it with solvent, binder, plasticizer and dispersant, centrifuging to remove bubbles, ball milling, and preparing the electrolyte layer slurry; and / or, The preparation of the barrier layer slurry includes: using GDC powder as the main raw material, mixing it with solvent, binder, plasticizer and dispersant, ball milling to prepare the barrier layer slurry.

[0012] A method for preparing a tubular solid oxide fuel cell, comprising any of the above-mentioned methods for preparing a tubular solid oxide fuel cell, further comprising the following steps: S4: If the half-cell is an anode support half-cell, then prepare a barrier layer slurry and a cathode layer slurry. Coat the barrier layer slurry on the outer surface of the electrolyte layer and dry it to form a barrier layer green blank. Coat the cathode layer slurry on the middle area of ​​the outer surface of the barrier layer green blank and dry it to form a cathode layer green blank. If the half-cell is a cathode support half-cell, then an anode layer slurry is prepared, and the anode layer slurry is coated on the middle area of ​​the outer surface of the electrolyte layer and dried to form an anode layer green blank. S5: Sintering is performed on the anode support half-cell with a cathode layer green blank or the cathode support half-cell with an anode layer green blank to obtain an anode support full cell or a cathode support full cell.

[0013] Preferably, for the anode support half-cell: When the barrier layer slurry is applied to the electrolyte layer on adjacent outer wall surfaces, the barrier layer slurry on the adjacent outer wall surfaces is continuous, and after drying, it forms a barrier layer green body that continuously covers the electrolyte layer on the adjacent outer wall surfaces; and / or, When the cathode layer slurry is coated onto the barrier layer green body on the adjacent outer wall surface, the cathode layer slurry on the adjacent outer wall surface is continuous, and after drying, it forms a cathode layer green body that continuously covers the barrier layer green body on the adjacent outer wall surface. For cathode support half-cells: When the anode layer slurry is applied to the electrolyte layer on the adjacent outer wall surface, the anode layer slurry on the adjacent outer wall surface is continuous, and after drying, it forms an anode layer green blank that continuously covers the electrolyte layer on the adjacent outer wall surface.

[0014] Preferably, the preparation of the cathode layer slurry includes: using LSCF powder and GDC powder as the main raw materials, mixing them with solvent, binder, plasticizer and dispersant, centrifuging to remove bubbles, ball milling, and preparing the cathode layer slurry; The preparation of the anode layer slurry includes: using NiO powder and YSZ powder as the main raw materials, mixing them with solvent, binder, plasticizer and dispersant, ball milling to prepare the anode layer slurry.

[0015] A battery assembly comprising multiple full cells prepared by any of the above-described tubular solid oxide fuel cell preparation methods, wherein each full cell has the same support type and is connected in series. If the full cell is an anode-supported full cell, then the full cells are connected in series by sequentially attaching the conductive layer of the full cell to the cathode layer of the adjacent full cell. If the full cell is a cathode-supported full cell, then the full cells are connected in series by sequentially attaching the conductive layer of the full cell to the anode layer of the adjacent full cell.

[0016] Preferably, the central axes of each full cell are arranged parallel to each other; On a plane perpendicular to the central axis of the battery module, the individual cells are arranged in a straight line, a serpentine pattern, or a spiral pattern.

[0017] The beneficial effects of this invention are: By designing the support as a multi-prism tubular structure, when applying the slurry, the operator only needs to apply the slurry to the designated outer wall surface. Unlike traditional cylindrical batteries, there is no need to precisely control the coating area of ​​each structural layer on the outer periphery of the battery. This significantly simplifies the coating process, reduces the requirements for operational precision, and improves production efficiency and process stability.

[0018] Full cells are connected in series by directly attaching the conductive layer of one full cell to the electrode layer (anode layer or cathode layer) of the adjacent full cell. This connection method eliminates the need for additional connectors or wires, simplifies the connection process between cells, reduces assembly complexity, and makes the structure more stable. Attached Figure Description

[0019] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some examples or embodiments of this application. For those skilled in the art, other drawings can be obtained based on the provided drawings without creative effort, and this application can be applied to other similar scenarios based on the provided drawings. Unless obvious from the linguistic context or otherwise stated, the same reference numerals in the drawings represent the same structure or operation.

[0020] Figure 1 This is a flowchart of the half-cell manufacturing method in Embodiment 1 of this application; Figure 2 This is a flowchart of the full-cell fabrication method in Embodiment 2 of this application; Figure 3 This is a schematic diagram of the full battery structure fabricated according to Embodiment 2 of this application; Figure 4 This is a schematic diagram of the battery assembly in Embodiment 3 of this application.

[0021] Among them, 1-support, 2-conductive layer, 3-electrolyte layer, 4-cathode layer. Detailed Implementation

[0022] The present application will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely for explaining the relevant application and are not intended to limit the application. The described embodiments are only some embodiments of the present application, and not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present application without creative effort are within the scope of protection of the present application.

[0023] Example 1

[0024] See Figure 1This embodiment provides a method for preparing a tubular solid oxide fuel cell. The core of this method is to set up a multi-prism tubular support and coat its outer wall with a corresponding structural layer slurry, thereby simplifying the coating process, increasing production efficiency and improving the stability of the product. This method mainly includes the preparation of the support, the preparation of the conductive layer green body, the preparation of the electrolyte layer green body, and the sintering and forming of the half cell.

[0025] S1: Preparation of the support, including the preparation of anode support slurry or cathode support slurry, injecting the prepared support slurry into a molding device to form a polyhedral tubular support green body, and then subjecting the support green body to drying, degreasing and sintering treatment in sequence to obtain anode support or cathode support; The anode support slurry is prepared by using nickel oxide (NiO) powder and yttrium-stabilized zirconia (YSZ) powder as the main raw materials, and mixing them with solvents (such as terpineol, ethanol, etc.), binders (such as polyvinyl butyral, ethyl cellulose, etc.), plasticizers (such as dibutyl phthalate, polyethylene glycol, etc.) and dispersants (such as fish oil, castor oil, etc.) in a certain proportion, and then ball milling them to prepare an anode support slurry with suitable viscosity and flowability.

[0026] The preparation of the cathode support slurry involves using lanthanum strontium cobalt ferrite (LSCF) powder and gadolinium-doped cerium oxide (GDC) powder as the main raw materials. These materials are mixed with solvents (such as terpineol, ethanol, etc.), binders (such as polyvinyl butyral, ethyl cellulose, etc.), plasticizers (such as dibutyl phthalate, polyethylene glycol, etc.) and dispersants (such as fish oil, castor oil, etc.) in a certain proportion. The mixture is then ball-milled to produce a cathode support slurry with suitable viscosity and flowability.

[0027] The polyhedral tubular support preform can be formed using either extrusion molding or slip casting. The molding devices used are an extruder or a die, respectively. It should be noted that if extrusion molding is used, the solids content of the prepared support slurry is higher than that of slip casting, and it is easier to extrude. The support slurry should be a mud-like slurry. The specific manufacturing method is as follows: If extrusion molding is used, the support slurry is injected into the feed port of the extruder, and the polyhedral tube-shaped support green body is directly extruded by setting a multi-faceted tube-shaped exit die on the extruder; or, a conventional extruder can be used to extrude a round tube-shaped support green body, and then processed by cutting, grinding and other processing methods to form a polyhedral tube-shaped support green body. If the slip casting method is used, the slurry for the support body is injected into the cavity of a mold with a polygonal tubular cavity. After the slurry dries, it is demolded to directly form a polygonal tubular support body blank. Alternatively, the slurry for the support body is injected into the cavity of a conventional mold. After the slurry dries, it is demolded to form a round tubular support body blank, which is then processed by cutting, grinding and other methods to form a polygonal tubular support body blank.

[0028] The drying, degreasing, and sintering of the green support body can be performed using one or more of the following three steps: The green support was placed in a dry environment and dried at room temperature. The dried support green body is placed in a sintering equipment such as a muffle furnace and heated to 500-600℃ in an air atmosphere at a certain heating rate to remove organic binders, plasticizers and dispersants in the support slurry to a certain extent. The degreased support green body is heated to 1000-1100℃ for 2-3 hours and then sintered to obtain a support body with sufficient mechanical strength.

[0029] S2: For both the anode and cathode supports, the conductive layer slurry and conductive layer green body are prepared using the same method. However, for the anode support, an electrolyte layer slurry also needs to be prepared. The conductive layer slurry and electrolyte layer slurry are coated onto different outer wall surfaces of the support and dried to form the conductive layer green body and electrolyte layer green body, respectively. For the cathode support, conductive layer slurry, barrier layer slurry, and electrolyte layer slurry also need to be prepared. The conductive layer slurry and barrier layer slurry are coated onto different outer wall surfaces of the support and dried to form the conductive layer green body and barrier layer green body, respectively. The electrolyte layer slurry is then coated onto the outer surface of the barrier layer green body and dried to form the electrolyte layer green body. The specific methods are as follows: The preparation of the conductive layer green body includes preparing a conductive layer slurry, coating it on a portion of the outer wall surface of the anode support or cathode support, and drying it to form the conductive layer green body; The preparation of the conductive layer slurry involves using lanthanum strontium titanium ferrite (LST) powder as the main raw material, mixing it with solvents (such as terpineol, ethanol, etc.), binders (such as polyvinyl butyral, ethyl cellulose, etc.), plasticizers (such as dibutyl phthalate, polyethylene glycol, etc.) and dispersants (such as fish oil, castor oil, etc.) in a certain proportion, and then ball milling it to prepare a conductive layer slurry with suitable viscosity and flowability.

[0030] Since the support body is a multi-prism tubular structure, when applying the conductive layer slurry, the operator only needs to apply the slurry to one or more designated outer wall surfaces, without the need to precisely control the coating boundary of the slurry in the length direction of the support body, which significantly reduces the difficulty of operation.

[0031] When the conductive layer slurry is applied to adjacent outer wall surfaces, the conductive layer slurry can be applied to the edges between the adjacent outer wall surfaces to make the conductive layer slurry on the adjacent outer wall surfaces continuous. After drying, it forms a continuous conductive layer green body connected by the slurry at the edges.

[0032] For the anode support: The electrolyte layer slurry is prepared by using yttrium-stabilized zirconia (YSZ) powder as the main raw material, and mixing it with solvents (such as terpineol, ethanol, etc.), binders (such as polyvinyl butyral, ethyl cellulose, etc.), plasticizers (such as dibutyl phthalate, polyethylene glycol, etc.) and dispersants (such as fish oil, castor oil, etc.) in a certain proportion. The mixture is first centrifuged to remove air bubbles, and then ball-milled to produce a fine and uniform electrolyte layer slurry. The prepared electrolyte layer slurry is then coated onto the outer wall surface of the green blank without a conductive layer on the support, and dried to form the electrolyte layer green blank. During coating, the properties of the polygonal prism are also utilized to facilitate coating on the designated outer wall surface. When the electrolyte layer slurry is applied to adjacent outer wall surfaces, the electrolyte layer slurry can be applied to the edges between the adjacent outer wall surfaces to make the electrolyte slurry on the adjacent outer wall surfaces continuous. After drying, the electrolyte layer green body located on the adjacent outer wall surfaces is continuous.

[0033] For the cathode support: The barrier layer slurry and electrolyte layer slurry are prepared by the same method as described above when the support is the anode support. For the preparation of the barrier layer slurry, gadolinium-doped cerium oxide (GDC) powder is used as the main raw material, and a small amount of iron oxide (such as Fe2O3) or cobalt oxide (such as Co3O4) is added as a sintering aid. The slurry is mixed with solvent (such as terpineol, ethanol, etc.), binder (such as polyvinyl butyral, ethyl cellulose, etc.), plasticizer (such as dibutyl phthalate, polyethylene glycol, etc.) and dispersant (such as fish oil, castor oil, etc.) in a certain proportion and ball-milled to prepare a barrier layer slurry with suitable viscosity and flowability.

[0034] The barrier layer slurry is coated on the outer wall of the support body without a conductive layer green body, and dried to form a barrier layer green body. Then, the electrolyte layer slurry is coated on the outer surface of the barrier layer green body and dried to form an electrolyte layer green body. To ensure the continuity of electrical connections, when the barrier layer slurry is applied to adjacent outer wall surfaces, the barrier layer slurry can be applied to the edges between the adjacent outer wall surfaces to make the barrier layer slurry on the adjacent outer wall surfaces continuous. After drying, the barrier layer green blanks on the adjacent outer wall surfaces are continuous. When the electrolyte layer slurry is applied to the barrier layer green blanks on adjacent outer wall surfaces, the electrolyte layer slurry can be applied to the edges between the adjacent barrier layer green blanks to make the electrolyte layer green blanks on the barrier layer on the adjacent outer wall surfaces continuous after drying.

[0035] S3: Sintering of half-cell: The support with conductive layer and electrolyte layer is sintered at a temperature of 1300-1500℃ for 2-3 hours. Through the above sintering process, an anode or cathode support half-cell with conductive layer and electrolyte layer is obtained.

[0036] Example 2 See Figure 2 and Figure 3 This embodiment provides a method for preparing a tubular solid oxide fuel cell, including the method for preparing a tubular solid oxide fuel cell as described in any of Embodiment 1, and adding an electrode layer to the tubular solid oxide fuel cell. The so-called electrode layer is an anode layer or a cathode layer to form a complete cell.

[0037] S4: The preparation methods for electrode layer green bodies differ depending on the type of half-cell. The specific methods are as follows: Half-cell with anode support: Prepare a barrier layer slurry and a cathode layer slurry. Coat the barrier layer slurry onto the outer surface of the electrolyte layer and dry it to form a barrier layer green blank. Coat the cathode layer slurry onto the middle area of ​​the outer surface of the barrier layer green blank and dry it to form a cathode layer green blank. The preparation of the barrier layer slurry can be the same as that in Example 1. The preparation of the cathode layer slurry includes using lanthanum strontium cobalt ferrite (LSCF) powder and yttrium stabilized zirconium oxide (YSZ) powder as the main raw materials, mixing them with solvents (such as terpineol, ethanol, etc.), binders (such as polyvinyl butyral, ethyl cellulose, etc.), plasticizers (such as dibutyl phthalate, polyethylene glycol, etc.) and dispersants (such as fish oil, castor oil, etc.) in a certain proportion, and then ball milling them to prepare a cathode layer slurry with suitable viscosity and fluidity.

[0038] In this process, the cathode layer slurry is coated on the middle area of ​​the outer surface of the barrier layer green blank. That is, on the full cell subsequently sintered, the middle part of the barrier layer is covered by the cathode layer, so the two ends of the barrier layer are exposed. This is to facilitate sealing and fixing between the full cell and the battery stack shell during subsequent battery stack assembly.

[0039] When the barrier layer slurry is applied to the electrolyte layer on the adjacent outer wall surface, the barrier layer slurry is applied to the edge between the adjacent electrolyte layers. After drying, the barrier layer green blank on the electrolyte layer on the adjacent outer wall surface is continuous. When the cathode layer slurry is applied to the barrier layer green blank on the adjacent outer wall surface, the cathode layer slurry is applied to the edge between the adjacent barrier layer green blank. After drying, the cathode layer green blank on the barrier layer green blank on the adjacent outer wall surface is continuous.

[0040] Half-cell with cathode support: Then, an anode layer slurry is prepared, coated onto the middle region of the outer surface of the electrolyte layer, and dried to form a green anode layer. The preparation of the anode layer slurry involves using nickel oxide (NiO) powder and yttrium-stabilized zirconium oxide (YSZ) powder as the main raw materials, mixing them with solvents (such as terpineol, ethanol, etc.), binders (such as polyvinyl butyral, ethyl cellulose, etc.), plasticizers (such as dibutyl phthalate, polyethylene glycol, etc.) and dispersants (such as fish oil, castor oil, etc.) in a certain proportion, and then ball milling them to prepare an anode support slurry with suitable viscosity and flowability.

[0041] When the anode layer slurry is applied to the electrolyte layer located on the adjacent outer wall surface, the anode layer slurry is applied at the edge between the adjacent electrolyte layers. After drying, the anode layer green body on the electrolyte layer located on the adjacent outer wall surface is continuous.

[0042] S5: The half-cell with a cathode layer green blank or an anode layer green blank is sintered to obtain a full cell with an anode or cathode support.

[0043] Figure 3 The image shows a full cell produced according to the method described in Embodiment 2 of this application. The full cell includes a multi-prism tubular support 1. When the support 1 is an anode support, a conductive layer 2 is covered on part of its outer wall surface, an electrolyte layer 3 is covered on the remaining outer wall surface, a barrier layer is covered on the outer surface of the electrolyte layer 3, and a cathode layer 4 is covered in the middle area of ​​the outer surface of the barrier layer. Alternatively, support 1 is a cathode support, with a conductive layer covering part of its outer wall surface and a barrier layer covering the remaining outer wall surface. An electrolyte layer covers the outer surface of the barrier layer, and an anode layer covers the central region of the outer surface of the electrolyte layer.

[0044] Example 3 See Figure 4 This embodiment provides a battery assembly, including multiple full cells prepared by the tubular solid oxide fuel cell preparation method as described in Embodiment 2. Each full cell has the same support type, that is, they are all anode support full cells or all cathode support full cells, and the full cells are connected in series. If the full cell is an anode-supported full cell, then the full cells are connected in series by sequentially attaching the conductive layer 2 of the full cell to the cathode layer 4 of the adjacent full cell. If the full cell is a cathode-supported full cell, then the full cells are connected in series by sequentially attaching the conductive layer 2 of the full cell to the anode layer of the adjacent full cell, and so on.

[0045] Specifically, the central axes of each full cell are arranged parallel to each other, and the full cells are distributed in a straight line or in a grid pattern. Figure 4 The distribution shown is either serpentine or spiral-shaped.

[0046] Example 4 Based on the above embodiments 1 to 3, common improvements or common explanations are provided: It is not necessary to provide a conductive layer or an electrode layer (the electrode layer is an anode layer or a cathode layer) on the side wall of the support. That is, there may be a support side wall without a conductive layer or an electrode layer; however, preferably, the side wall of the support should be provided with one of a conductive layer or an electrode layer.

[0047] The sidewall of the support does not necessarily have to be a plane parallel to the axis of the support. Instead, it can be adapted to the specific processing technology and design scheme. For example, the sidewall of the support may have an inwardly recessed part and an outwardly protruding part, and the cross-section of the sidewall may be arc-shaped. The so-called sidewall is the surface located on the outer periphery of the support, between two adjacent edges.

[0048] The support is in the shape of a polygonal prism. Here, "polyprism" refers to the fact that the outer periphery of the tube has edges, but it does not require the support to be a regular polyhedral tube. That is, the edges of the support do not have to be parallel to the axis of the support.

[0049] The coating process described in this application can be achieved through methods such as screen printing, dipping, spraying, or PVD.

[0050] Example 5 Based on Embodiment 2 above, this embodiment provides a specific method for fabricating a full cell with an anode support tube: The anode support slurry was prepared by mixing nickel oxide powder, 3 mol yttrium oxide-stabilized zirconium oxide (YO) stabilized by 3 mol yttrium oxide (YO) stabilized by 8 mol YO stabilized by 8 mol ZO powder in a weight ratio of 11:8:1, with a total weight of 54 wt%. Ethanol and butanone were mixed in a weight ratio of 3:2, with a total weight of 36 wt%. The nickel oxide powder, 3YSZ powder, 8YSZ, ethanol, butanone, and 1 wt% fish oil were then ball-milled at 250 rpm for 6 hours using a planetary ball mill. Then, 4 wt% dibutyl phthalate and 5 wt% polyvinyl butyral were added, and the mixture was ball-milled at 200 rpm for 5 hours.

[0051] The prepared anode support slurry is injected into the feed port of the extruder, and the multi-faceted tube-shaped support green body is directly extruded by setting a multi-faceted tube-shaped outlet die on the extruder. The green support blank is placed in a dry environment and dried at room temperature. The dried green support blank is then placed in a sintering device such as a muffle furnace and heated to 550°C in air for degreasing for 5 hours. The degreased green support blank is then heated to 1150°C for 3 hours for sintering. The cooling and heating rates during the degreasing and sintering processes are 3°C / s. The anode support is then obtained.

[0052] A conductive layer paste was prepared using LST as the main raw material and screen-printed onto one outer wall of a support, then dried to form a conductive layer green body.

[0053] 3 wt% polyvinyl butyral was heated and stirred to dissolve in 24 wt% diethylene glycol monobutyl ether, then 70 wt% 8YSZ (8 mol yttrium oxide-stabilized zirconium oxide) powder was added, and finally 2 wt% polyethylene glycol and 1 wt% dispersant BYK-110 were added. The mixture was then centrifuged at 800 rpm, 1600 rpm and 800 rpm for 15 s, 60 s and 15 s respectively. The mixture was then passed through a three-roll mill in the order of 20 μm-10 μm-5 μm-3 μm four times. The particle size of the slurry was tested with a scraper fineness meter and found to be below 5 μm. The viscosity of the slurry was tested with a rheometer and found to be within the set target. The mixture was then vacuum degassed using a low-speed centrifuge to prepare the electrolyte slurry. Electrolyte slurry is screen-printed onto the outer wall of each support body without a conductive layer, forming an electrolyte layer preform. The support with a conductive layer and an electrolyte layer is sintered at a temperature of 1400°C for 3 hours. Through the above sintering process, an anode support half-cell with a conductive layer and an electrolyte layer is obtained.

[0054] 2 wt% polyvinyl butyral was dissolved in 35 wt% diethylene glycol monobutyl ether under heating and stirring. Then, 58.5 wt% gadolinium-doped cerium oxide powder and 1.5 wt% ferric oxide were added. Finally, 2 wt% polyethylene glycol and 1 wt% dispersant BYK-110 were added. The mixture was then centrifuged at 800 rpm, 1600 rpm and 800 rpm for 15 s, 60 s and 15 s respectively. The mixture was then passed through a three-roll mill four times in the order of 20 μm-10 μm-5 μm-3 μm. The particle size of the slurry was tested with a scraper fineness meter and found to be below 5 μm. The viscosity of the slurry was tested with a rheometer and found to be within the set target. The mixture was then vacuum degassed using a low-speed centrifuge to obtain the barrier layer slurry. The barrier layer slurry was then screen-printed onto the entire outer surface of each electrolyte layer and dried to form the barrier layer green body. The lanthanum-strontium-cobalt ferrite powder and cerium oxide-doped zirconium oxide powder were prepared in a weight ratio of 1.78:1, with a total weight ratio of 71.6 wt%. 7 wt% polyvinyl butyral was dissolved in 20 wt% diethylene glycol monobutyl ether by heating and stirring. Then, the lanthanum-strontium-cobalt ferrite powder and cerium oxide-doped zirconium oxide powder were added. Finally, 1.2 wt% adipic acid diester and 0.2 wt% stearic acid were added. The slurry is mixed at 800 rpm, 1600 rpm and 800 rpm for 15 seconds, 60 seconds and 15 seconds respectively. Then it is passed through a three-roll mill four times in the order of 20μm-10μm-5μm-3μm. The particle size of the slurry is tested with a scraper fineness meter and found to be below 5μm. The viscosity of the slurry is tested with a rheometer and found to meet the set target. Then it is vacuum degassed with a low-speed mixing and degassing machine to obtain the cathode layer slurry. The cathode layer slurry is screen printed on the middle area of ​​the outer surface of each barrier layer preform and dried to form the cathode layer preform.

[0055] The half-cell with a cathode layer was sintered at 1050℃ for 3 hours to obtain a full cell with an anode support.

[0056] In the description of the embodiments of this application, unless otherwise stated, "、" means "or". For example, A and B can mean A or B. "And" and "or" in this article are merely a description of the relationship between related objects, indicating that there can be three relationships. For example, A and or B can mean: A exists alone, A and B exist simultaneously, and B exists alone.

[0057] It should be noted that, for ease of description, only the parts relevant to the application are shown in the accompanying drawings; unless otherwise specified, the embodiments and features in the embodiments of this application can be combined with each other.

[0058] The above description is merely a preferred embodiment of this application and an explanation of the technical principles employed, and is not intended to limit this application. For those skilled in the art, this application can have various modifications and variations; the scope of this application is not limited to technical solutions formed by specific combinations of the above-described technical features, but should also cover other technical solutions formed by arbitrary combinations of the above-described technical features or their equivalents without departing from the above-described application concept; for example, technical solutions formed by substituting the above features with (but not limited to) technical features with similar functions disclosed in this application.

Claims

1. A method for preparing a tubular solid oxide fuel cell, characterized in that, Includes the following steps: S1: Prepare an anode or cathode support slurry and process it into a multi-prism tube-shaped support green body. The support green body is then dried, degreased, and sintered in sequence to obtain an anode support or cathode support. S2: For the anode support, prepare conductive layer slurry and electrolyte layer slurry, coat the conductive layer slurry and electrolyte layer slurry on different outer wall surfaces of the support, and dry to form conductive layer green and electrolyte layer green. For the cathode support, a conductive layer slurry, a barrier layer slurry, and an electrolyte layer slurry are prepared. The conductive layer slurry and the barrier layer slurry are coated on different outer wall surfaces of the support, and dried to form a conductive layer green body and a barrier layer green body. The electrolyte layer slurry is coated on the outer surface of the barrier layer green body and dried to form an electrolyte layer green body. S3: The anode support or cathode support coated with conductive layer green blank and electrolyte layer green blank is sintered to obtain an anode support half cell or cathode support half cell with conductive layer and electrolyte layer.

2. The method for preparing a tubular solid oxide fuel cell as described in claim 1, characterized in that: In S1, the polyhedral tubular support blank is processed and formed by extrusion molding or slip casting. If extrusion molding is used, the support slurry is injected into the extruder and the polyhedral tube-shaped support preform is directly extruded, or the round tube-shaped support preform is first extruded and then processed to form the polyhedral tube-shaped support preform. If the slurry casting method is used, the slurry for the support body is injected into the cavity of the mold. After the slurry for the support body dries, it is demolded to directly form a polyhedral tube-type support body blank, or it is first demolded to form a round tube-type support body blank, and then processed to form a polyhedral tube-type support body blank.

3. The method for preparing a tubular solid oxide fuel cell as described in claim 1, characterized in that: In S1, the drying, degreasing, and sintering treatments of the support green body include: Dry the support green body at room temperature; and / or The dried support green body is degreased by heating it to 500–600°C in air; and / or, The degreased support green body is heated to 1000-1100℃ and held for 2-3 hours for sintering.

4. The method for preparing a tubular solid oxide fuel cell as described in claim 1, characterized in that: For anode-supported half-cells: When the conductive layer slurry is coated on the adjacent outer wall surface of the anode support, the conductive layer slurry on the adjacent outer wall surface is continuous, and after drying, it forms a conductive layer green blank that continuously covers the adjacent outer wall surface. And / or, When the electrolyte layer slurry is coated on the adjacent outer wall surface of the anode support, the electrolyte layer slurry on the adjacent outer wall surface is continuous, and after drying, it forms an electrolyte layer green blank that continuously covers the adjacent outer wall surface. For cathode support half-cells: When the conductive layer slurry is applied to adjacent outer wall surfaces of the cathode support, the conductive layer slurry on these adjacent outer wall surfaces is continuous, and after drying, it forms a conductive layer green body that continuously covers the adjacent outer wall surfaces; and / or, When the barrier layer slurry is applied to adjacent outer wall surfaces of the cathode support, the barrier layer slurry on the adjacent outer wall surfaces is continuous, and after drying, it forms a barrier layer green body that continuously covers the adjacent outer wall surfaces; and / or, When the electrolyte layer slurry is applied to the barrier layer green body on the adjacent outer wall surface, the electrolyte layer slurry on the adjacent outer wall surface is continuous, and after drying, it forms an electrolyte layer green body that continuously covers the barrier layer green body on the adjacent outer wall surface.

5. The method for preparing a tubular solid oxide fuel cell as described in claim 1, characterized in that: The preparation of the anode support slurry includes: using NiO powder and YSZ powder as main raw materials, mixing them with solvent, binder, plasticizer and dispersant, ball milling to prepare the anode support slurry; and / or, The preparation of the cathode support slurry includes: using LSCF powder and GDC powder as main raw materials, mixing them with solvent, binder, plasticizer and dispersant, ball milling to prepare the cathode support slurry; and / or, The preparation of the conductive layer slurry includes: using LST powder as the main raw material, mixing it with solvent, binder, plasticizer and dispersant, ball milling to prepare the conductive layer slurry; and / or, The preparation of the electrolyte layer slurry includes: using YSZ powder as the main raw material, mixing it with solvent, binder, plasticizer and dispersant, centrifuging to remove bubbles, ball milling, and preparing the electrolyte layer slurry; and / or, The preparation of the barrier layer slurry includes: using GDC powder as the main raw material, mixing it with solvent, binder, plasticizer and dispersant, ball milling to prepare the barrier layer slurry.

6. A method for preparing a tubular solid oxide fuel cell, characterized in that, The method for preparing a tubular solid oxide fuel cell as described in any one of claims 1-5 further includes the following steps: S4: If the half-cell is an anode support half-cell, then prepare a barrier layer slurry and a cathode layer slurry. Coat the barrier layer slurry on the outer surface of the electrolyte layer and dry it to form a barrier layer green blank. Coat the cathode layer slurry on the middle area of ​​the outer surface of the barrier layer green blank and dry it to form a cathode layer green blank. If the half-cell is a cathode support half-cell, then an anode layer slurry is prepared, and the anode layer slurry is coated on the middle area of ​​the outer surface of the electrolyte layer and dried to form an anode layer green blank. S5: Sintering is performed on the anode support half-cell with a cathode layer green blank or the cathode support half-cell with an anode layer green blank to obtain an anode support full cell or a cathode support full cell.

7. The method for preparing a tubular solid oxide fuel cell as described in claim 6, characterized in that: For anode-supported half-cells: When the barrier layer slurry is applied to the electrolyte layer on adjacent outer wall surfaces, the barrier layer slurry on the adjacent outer wall surfaces is continuous, and after drying, it forms a barrier layer green body that continuously covers the electrolyte layer on the adjacent outer wall surfaces; and / or, When the cathode layer slurry is coated onto the barrier layer green body on the adjacent outer wall surface, the cathode layer slurry on the adjacent outer wall surface is continuous, and after drying, it forms a cathode layer green body that continuously covers the barrier layer green body on the adjacent outer wall surface. For cathode support half-cells: When the anode layer slurry is applied to the electrolyte layer on the adjacent outer wall, the anode layer slurry on the adjacent outer wall is continuous, and after drying, it forms an anode layer green blank that continuously covers the electrolyte layer on the adjacent outer wall.

8. The method for preparing a tubular solid oxide fuel cell as described in claim 6, characterized in that: The preparation of the cathode layer slurry includes: using LSCF powder and GDC powder as the main raw materials, mixing them with solvent, binder, plasticizer and dispersant, centrifuging to remove bubbles, ball milling, and preparing the cathode layer slurry; The preparation of the anode layer slurry includes: using NiO powder and YSZ powder as the main raw materials, mixing them with solvent, binder, plasticizer and dispersant, ball milling to prepare the anode layer slurry.

9. A battery assembly, characterized in that: The invention includes multiple tubular solid oxide fuel cell full cells prepared by the method described in any one of claims 6-8, wherein each full cell has the same type of support and is connected in series. If the full cell is an anode-supported full cell, then the full cells are connected in series by sequentially attaching the conductive layer of the full cell to the cathode layer of the adjacent full cell. If the full cell is a cathode-supported full cell, then the full cells are connected in series by sequentially attaching the conductive layer of the full cell to the anode layer of the adjacent full cell.

10. The battery assembly as claimed in claim 9, characterized in that: The central axes of each full cell are set parallel to each other on a plane perpendicular to the central axis of the battery module. The full cells are arranged in a straight line, a serpentine pattern, or a spiral pattern.

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