A solid oxide fuel cell photocuring multi-material 3D printing method

Abstract

A kind of solid oxide fuel cell photocuring multi-material 3D printing method provides a kind of printing method suitable for solid oxide fuel cell, expands the application of 3D printing technology in the forming field of solid oxide fuel cell.It provides greater flexibility for the structure design of solid oxide fuel cell, can form the complex geometric structure that traditional manufacturing cannot realize, expands the space for improving the performance and efficiency of solid oxide fuel cell by structural optimization.And, by the method of photocuring printing, the microstructure of each functional layer of battery and the interface topography between adjacent functional layers can also be conveniently regulated, which is beneficial to improve and optimize battery performance.

Description

Technical Field

[0001] This invention relates to the field of fuel cell technology, and specifically to a photopolymerization multi-material 3D printing method for solid oxide fuel cells. Background Technology

[0002] Solid oxide fuel cells (SOFCs) are electrochemical devices that directly convert chemical energy into electrical energy through a chemical reaction between fuel (such as hydrogen or natural gas) and an oxidant (usually oxygen from the air). SOFCs use a solid oxide electrolyte to separate the fuel and oxidant, facilitating the transfer of ions between two electrodes. Due to the strong catalytic reaction capabilities of the electrodes at high temperatures, the fuel can be efficiently converted into electricity, resulting in very high energy conversion efficiency and low emissions. SOFCs have a variety of potential applications, including stationary power generation in buildings and remote areas, and transportation power for vehicles. However, this technology remains relatively expensive and requires further development before widespread adoption.

[0003] Compared to traditional manufacturing methods, the development of 3D printing technology has brought new possibilities to the molding of solid oxide fuel cells (SOFCs). 3D printing of SOFCs is an emerging technology with enormous potential, promising to revolutionize SOFC manufacturing and design. First, 3D printing offers greater design flexibility, enabling the molding of complex geometries that are impossible with traditional manufacturing, providing ample room for improving SOFC performance and efficiency through shape optimization. Second, 3D printing reduces material waste and costs by using only the necessary materials and minimizing excess material during the manufacturing process. Third, 3D printing can produce miniature SOFCs for use in portable or mobile devices. Finally, 3D printing can simplify manufacturing processes and reduce production costs.

[0004] However, 3D printing solid oxide fuel cell (SOFC) technology is still in the early research stage, and before it can be applied, there is still a problem that the applicable printing process is relatively limited. Summary of the Invention

[0005] This invention provides a photopolymerization multi-material 3D printing method for solid oxide fuel cells, expanding the application of 3D printing technology in the field of solid oxide fuel cell molding.

[0006] According to a first aspect, the present invention provides a method for photopolymerization multi-material 3D printing of solid oxide fuel cells, comprising the following steps:

[0007] The first electrode slurry for the solid oxide fuel cell was prepared according to the specified ratio;

[0008] The first electrode slurry is printed layer by layer using a photopolymerization 3D printing device to form the first electrode layer.

[0009] The first electrode layer is cleaned and then dried.

[0010] Prepare electrolyte slurry for solid oxide fuel cells according to the specified ratio;

[0011] The electrolyte slurry is printed layer by layer on the first electrode layer using a photopolymerization 3D printing device to form an electrolyte layer.

[0012] After the first electrode layer and electrolyte layer that have been printed are cleaned and dried, they are then degreased and sintered to form a solid oxide fuel cell.

[0013] The second electrode slurry for the solid oxide fuel cell is prepared according to the specified ratio, and the second electrode slurry is shaped on the side of the electrolyte layer away from the first electrode layer to form the second electrode layer. After post-processing, a full cell is formed.

[0014] According to a second aspect, the present invention provides a method for photopolymerization multi-material 3D printing of solid oxide fuel cells, comprising the following steps:

[0015] Prepare electrolyte slurry for solid oxide fuel cells according to the specified ratio;

[0016] The electrolyte slurry is printed layer by layer using a photopolymerization 3D printing device to form an electrolyte layer.

[0017] The electrolyte layer is cleaned and then dried.

[0018] The first electrode slurry for the solid oxide fuel cell was prepared according to the specified ratio;

[0019] The first electrode slurry is printed layer by layer on the electrolyte layer using a photopolymerization 3D printing device to form the first electrode layer.

[0020] After the first electrode layer and electrolyte layer that have been printed are cleaned and dried, they are then degreased and sintered to form a solid oxide fuel cell.

[0021] The second electrode slurry for the solid oxide fuel cell is prepared according to the specified ratio, and the second electrode slurry is shaped on the side of the electrolyte layer away from the first electrode layer to form the second electrode layer. After post-processing, a full cell is formed.

[0022] In one embodiment, the method further includes using a photopolymerization 3D printing device to print a transition layer on the first electrode layer, and then printing the electrolyte slurry layer by layer on the first electrode layer to form an electrolyte layer.

[0023] The printing of the transition layer includes:

[0024] The first electrode slurry and electrolyte slurry are mixed in a certain ratio to form a transition layer slurry; the cleaned first electrode layer is used as the substrate, and the transition layer slurry is printed layer by layer on the first electrode layer to form a transition layer, and then the electrolyte slurry is printed layer by layer on the first electrode layer to form an electrolyte layer.

[0025] Alternatively, using the cleaned first electrode layer as a substrate, the first electrode slurry and electrolyte slurry are printed layer by layer or alternately on the first electrode layer to form a transition layer containing a three-dimensional structure of the first electrode-electrolyte interface, and then the electrolyte slurry is printed layer by layer on the first electrode layer to form an electrolyte layer.

[0026] In one embodiment, the step of preparing the second electrode slurry for a solid oxide fuel cell according to the specified ratio, and molding the second electrode slurry on the side of the electrolyte layer away from the first electrode layer to form the second electrode layer, is as follows:

[0027] The second electrode composite material is mixed according to the specified ratio and pretreated.

[0028] The photosensitive resin monomer, dispersant, and photoinitiator are mixed evenly according to the formula to form the second electrode photosensitive resin;

[0029] The pretreated second electrode composite material was added to the second electrode photosensitive resin in several batches, and after being mixed evenly, the second electrode slurry was obtained by filtration and defoaming treatment.

[0030] The second electrode layer is formed by using a photopolymerization 3D printing device to mold the second electrode slurry on the side of the electrolyte layer away from the first electrode layer.

[0031] The pretreatment includes calcining the second electrode composite material that is mixed evenly according to the formula to roughen the second electrode composite material, wet grinding the roughened second electrode composite material, and then successively passing it through filtration, drying and grinding processes to obtain the second electrode composite material that meets the particle size requirements.

[0032] In one embodiment, the step of preparing the second electrode slurry for a solid oxide fuel cell according to the specified ratio, and molding the second electrode slurry on the side of the electrolyte layer away from the first electrode layer to form the second electrode layer, is as follows:

[0033] The second electrode composite material was mixed with solvent, binder and pore-forming agent in proportion to prepare a second electrode slurry.

[0034] The second electrode slurry is coated on the side of the electrolyte layer away from the first electrode layer to form a second electrode layer.

[0035] In one embodiment, the method for preparing the first electrode paste is as follows:

[0036] The first electrode composite material was mixed according to the specified ratio and pretreated.

[0037] The photosensitive resin monomer, dispersant, and photoinitiator are mixed evenly according to the formula to form the electrode photosensitive resin.

[0038] The pretreated first electrode composite material was added to the electrode photosensitive resin in several batches, and after being mixed evenly, the first electrode slurry was obtained by filtration and defoaming treatment.

[0039] The pretreatment includes calcining the first electrode composite material that is mixed evenly according to the formula to roughen the first electrode composite material, wet grinding the roughened first electrode composite material, and then passing it through the filtering, drying and grinding processes in sequence to obtain the first electrode composite material that meets the particle size requirements.

[0040] The method for preparing the electrolyte slurry is as follows:

[0041] The electrolyte powders were mixed according to the specified ratio and then dried and sieved in sequence.

[0042] The photosensitive resin monomer, dispersant, and photoinitiator are mixed evenly according to the formula to form an electrolyte layer photosensitive resin.

[0043] The sieved electrolyte powder is added to the photosensitive resin of the electrolyte layer in several batches, and after being mixed evenly, the electrolyte slurry is obtained by filtration and defoaming treatment.

[0044] In one embodiment, the electrolyte slurry further includes a sintering aid to adjust the sintering densification temperature of the electrolyte layer so that the sintering temperature of the electrolyte layer is close to the sintering temperature of the co-fired electrode layer.

[0045] In one embodiment, the first electrode slurry and the second electrode slurry further include microsphere material to increase the solid content of the first electrode slurry and the second electrode slurry, thereby reducing heat treatment volume shrinkage and adjusting the porosity of the first electrode layer and the second electrode layer, respectively.

[0046] In one embodiment, the post-processing includes using pressure sintering to suppress warping during co-sintering, including stacking and pressure sintering.

[0047] In one embodiment, the first electrode slurry and the second electrode slurry are respectively an anode slurry and a cathode slurry, and the first electrode layer and the second electrode layer are respectively an anode layer and a cathode layer.

[0048] In one embodiment, the solid content of the first electrode slurry and the second electrode slurry is 10-30% by volume, and the solid content of the electrolyte slurry is 20-50% by volume.

[0049] Based on the solid oxide fuel cell photopolymerization multi-material 3D printing method in the above embodiments, a printing method suitable for solid oxide fuel cells is provided, which expands the application of 3D printing technology in the field of solid oxide fuel cell molding, solves the problem of the single printing method of solid oxide fuel cells, and is conducive to realizing the mass production of solid oxide fuel cells. In addition, the photopolymerization printing method can also easily control the microstructure of each functional layer of the battery and the interface morphology between adjacent functional layers, which is beneficial to improving and optimizing battery performance. Attached Figure Description

[0050] Figure 1 This is a flowchart of Example 1 of a photopolymerization multi-material 3D printing method for solid oxide fuel cells;

[0051] Figure 2 This is a schematic diagram of the printing process in Example 1;

[0052] Figure 3 Flowchart for anode slurry preparation;

[0053] Figure 4 This is a flowchart of Example 2 of the photopolymerization multi-material 3D printing method for solid oxide fuel cells;

[0054] Figure 5 This is a flowchart of Example 3 of a photopolymerization multi-material 3D printing method for solid oxide fuel cells;

[0055] Figure 6 This is a flowchart of the printing process for the transition layer between the anode layer and the electrolyte layer in Example 3;

[0056] Figure 7 This is a schematic diagram of the printing of the transition layer between the anode layer and the electrolyte layer in Example 3;

[0057] Figure 8 A schematic diagram of the printed full-cell structure;

[0058] Figure 9 This is a flowchart of Example 4 of a photopolymerization multimaterial 3D printing method for solid oxide fuel cells. Detailed Implementation

[0059] The present invention will now be described in further detail with reference to specific embodiments and accompanying drawings. Similar elements in different embodiments are referred to by associated similar element reference numerals. In the following embodiments, many details are described to facilitate a better understanding of this application. However, those skilled in the art will readily recognize that some features may be omitted in different situations, or may be replaced by other elements, materials, or methods. In some cases, certain operations related to this application are not shown or described in the specification. This is to avoid obscuring the core parts of this application with excessive description. For those skilled in the art, detailed description of these related operations is not necessary; they can fully understand the related operations based on the description in the specification and general technical knowledge in the art.

[0060] Furthermore, the features, operations, or characteristics described in the specification can be combined in any suitable manner to form various embodiments, and the operational steps involved in each embodiment can also be rearranged or adjusted in a manner that is obvious to those skilled in the art. Therefore, the specification and drawings are only for clearly describing a particular embodiment and do not imply that they represent the necessary components and / or order.

[0061] The serial numbers assigned to components in this document, such as "first" and "second," are used only to distinguish the described objects and have no sequential or technical meaning. The terms "connection" and "linkage" used in this application, unless otherwise specified, include both direct and indirect connections (linkages).

[0062] This application provides a photopolymerization multi-material 3D printing method for solid oxide fuel cells, which is a new method for printing solid oxide fuel cells. It expands the application of 3D printing technology in the field of solid oxide fuel cell molding, solves the problem of the single battery printing method, and can also realize the mass production of batteries.

[0063] This method primarily utilizes photopolymerization 3D printing equipment, offering advantages such as high precision, good controllability, and suitability for forming complex three-dimensional structures. The 3D printing equipment includes at least a printing platform 3, a lifting device mounted on the printing platform 3, multiple resin tanks positioned below the printing platform 3, a cleaning device 5, a drying device 6, and a moving mechanism. The moving mechanism can move the printing platform 3 to corresponding resin tanks, and the lifting device can adjust the height of the printing platform 3 and the distance between it and the resin tanks, allowing the printing platform 3 to extend or retract into the resin tanks for printing. The resin tanks are used to hold different resin slurries.

[0064] The above printing sequence allows for the continuous printing of both the anode and electrolyte layers without the need to switch equipment, thus improving production efficiency. Furthermore, the layer-by-layer printing with mixed slurry enables simultaneous printing of multiple materials, simplifying the production process. Compared to existing DIW and inkjet printing processes, photopolymerization printing offers higher precision, better controllability, and is suitable for forming complex three-dimensional structures.

[0065] Furthermore, the device also includes an ultraviolet projector 2, which uses ultraviolet light to irradiate and expose the material to ultimately form a variety of complex three-dimensional structures. The principle of this solution has been disclosed in other existing technologies and will not be elaborated here.

[0066] Corresponding to the printing equipment mentioned above, and based on the different structures and performance requirements of the battery, there are various printing methods for solid oxide fuel cells. The following describes these printing methods in detail through some examples.

[0067] Example 1

[0068] like Figure 1 The above is a flowchart illustrating the method provided in this embodiment, as shown below. Figure 2 The diagram shown is a printing illustration of this embodiment. The method includes the following steps:

[0069] S101: Prepare the first electrode slurry for solid oxide fuel cells according to the specified ratio. The composition and ratio of the battery slurry will vary depending on the characteristics of the battery. Therefore, after determining the type of battery to be printed, the required slurry can be determined according to that type.

[0070] Specifically, the preparation method of the first electrode slurry is as follows: the first electrode composite material is mixed according to the ratio and pretreated; the photosensitive resin monomer, dispersant and photoinitiator are mixed evenly according to the ratio to form the electrode photosensitive resin; the pretreated first electrode composite material is added to the electrode photosensitive resin in batches, mixed evenly, and then filtered and defoamed to obtain the first electrode slurry.

[0071] In this embodiment, the mixing methods used in preparing the electrode photosensitive resin include, but are not limited to, ball milling and magnetic stirring.

[0072] In this embodiment, the method of uniformly mixing the first electrode composite material and the electrode photosensitive resin includes, but is not limited to, ball milling and three-dimensional mixing machine.

[0073] In this embodiment, the defoaming treatment is performed by removing air bubbles through vacuuming, resulting in a more uniform slurry. Specifically, the defoaming is considered complete when no more air bubbles are expelled.

[0074] Furthermore, the pretreatment includes calcining the first electrode composite material that is uniformly mixed according to the formula to roughen the first electrode composite material, wet grinding the roughened first electrode composite material, and then sequentially passing it through filtration, drying and grinding processes to obtain the first electrode composite material that meets the particle size requirements.

[0075] Specifically, the first electrode composite material is mixed evenly by high-speed wet ball milling according to a certain ratio, and then filtered, dried and ground into powder. The ground powder material is calcined at a certain temperature, and then wet grinding process is used to improve the sphericity of the composite powder particles, improve its dispersion performance in photosensitive resin, further reduce the scattering of the first electrode slurry, and finally filtered, dried and ground to form the first electrode composite material.

[0076] In this embodiment, the preparation process of the first electrode composite material involves two steps of filtration, drying, and grinding. The first filtration, drying, and grinding is for the uniformly mixed powder material to obtain powder particles that are easy to calcinate. In the second filtration, drying, and grinding, the zirconium balls are first separated from the slurry using a filter screen to obtain a uniformly mixed first electrode slurry. Then, a vacuum filtration device is used to filter the mixed slurry to remove the finer particles. The larger particle size composite powder is dried and ground before being used for subsequent batching. Particles with too small a particle size are filtered out and discarded or used for other purposes.

[0077] Furthermore, the filter paper specifications used in vacuum filtration are determined according to the required final particle size, such as selecting 0.5-micron vacuum filtration filter paper.

[0078] In this embodiment, the first electrode composite material is calcined, which can coarsen the powder, reduce the shrinkage rate of the anode layer, increase the particle size of the calcined powder, reduce the scattering of the first electrode slurry, increase the curing thickness, and improve the curing performance. Furthermore, using pre-ball-milled and mixed composite powder for calcination instead of calcining different materials separately and then mixing them can retain a larger three-phase reaction interface of the first electrode layer while coarsening the particles.

[0079] It is understandable that batteries generally have two electrodes, namely an anode and a cathode, and the first electrode slurry can also correspond to an anode slurry or a cathode slurry.

[0080] If the first electrode paste is an anode paste, its preparation process is as follows: Figure 3As shown, the anode composite material is mixed according to the specified ratio and pretreated. The anode composite material is one or more of the following: nickel, nickel oxide (NiO, Ni2O3, etc.), yttrium-stabilized zirconium oxide (YSZ), gadolinium-doped cerium oxide (GDC), copper-doped cerium oxide (Cu-CeO2), copper and copper oxide (Cu, CuO, etc.). The selection can be made according to the specific battery to be prepared. The ratio is also mixed according to the final electrode composition. For example, the commonly used ratios for NiO-YSZ anodes are 50%:50%, 55%:45%, or 60%:40%. The photosensitive resin monomer, dispersant, and photoinitiator are mixed evenly according to the specified ratio to form the anode photosensitive resin. The photosensitive resin monomer in the anode photosensitive resin is 4-acryloylmorpholine (ACMO), butyl acrylate (BA), hydroxyethyl acrylate (HEA), and polyethylene glycol diacrylate (PEGD). A) One or more of the following: dipropylene glycol diacrylate (DPGDA), ditripropylene glycol diacrylate (TPGDA), hexanediol diacrylate (HDDA), triethylene glycol diacrylate (TEGDA), trimethylolpropane triacrylate (TMPTA) and its ethoxide, pentaerythritol tetraacrylate (PETA) and its ethoxide, 3(propoxy)propanetriol triacrylate (GPTA), urethane methacrylate (UDMA), polyurethane acrylate (PUA), and epoxy acrylate (EA); and one or more of the following: sodium citrate, sodium pyrophosphate, polyacrylic acid and its sodium salt, hydroxymethyl cellulose, polyvinyl alcohol, oleic acid (OA), stearic acid (SA), fatty alcohol polyoxyethylene ether (AEO), dodecyl phosphate ammonium, KH560, and commercial ceramic dispersants. The photoinitiators are 2,4,6-(trimethylbenzoyl)diphenylphosphine oxide (TPO), phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (819), ethyl 2,4,6-trimethylbenzoylphosphonate (TPO-L), 2-methyl-1-[4-methylthiophenyl]-2-morpholinyl-1-propanone (907), ethyl 4-dimethylaminobenzoate (EDB), and 1-hydroxy-cyclohexylphenyl ketone (…). One or more of the following: 184), 2-hydroxy-2-methyl-1-phenyl-1-propanone (1173), benzoin dimethyl ether (BDK), methyl o-benzoylbenzoate (OMBB), 4-chlorobenzophenone (CBP), 2-isopropylthioxanthone (ITX), benzophenone (BP), 4-phenylbenzophenone (PBZ), 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinobenzylphenyl)butanone (369).The pretreated anode composite material is added to the anode photosensitive resin in several batches. After being mixed evenly, the anode slurry is obtained by filtration and defoaming. During the pretreatment, the calcination temperature of the anode composite material varies depending on the type of material, the original particle size, etc., and is usually slightly lower than the temperature required for post-treatment. The calcination time is 1-5 hours. For example, NiO-YSZ composite powder is usually calcined at 1000-1400 degrees Celsius for 2-3 hours.

[0081] If the first electrode paste is a cathode paste, its preparation process refers to that of the anode paste. The cathode composite material used in the cathode paste preparation is lanthanum-strontium-manganese (LSM), lanthanum-strontium-cobalt (LSC), yttrium-stabilized zirconium oxide (YSZ), Ln(Sr)CoO3, Ln(Sr)FeO3, (la,Co)FeO4 (LCF), (La,Co)FeO4 (LSCF), (BaSr)CoFeO4 (BSCF), Mn 1.5 Co 1.5 One or more of O4 and CuCo2O4, the photosensitive resin, dispersant and initiator are the same as those of the anode slurry. The calcination temperature of the cathode composite material varies depending on the type of material, the original particle size, etc., and is usually slightly lower than the temperature required for post-treatment. The calcination time is 1-5 hours. For example, LSM-YSZ cathode slurry composite powder is usually calcined at 900-1200 degrees Celsius for 2-3 hours.

[0082] S102: Using a photopolymerization 3D printing device, the first electrode paste is printed layer by layer to form the first electrode layer; Reference Figure 2 The prepared first electrode paste 1 is placed into the corresponding resin tank. The printing platform 3 is positioned at the resin tank using the moving mechanism. The corresponding printing parameters are set. The lifting device lowers the printing platform 3 into the resin tank to print the first electrode layer. As the printing process progresses, the lifting device continuously raises the height of the printing platform 3 to achieve the printing of the first electrode layer layer by layer.

[0083] S103: Clean the first electrode layer and then dry it; when printing the next layer, to prevent the paste adhering to the previous layer from affecting the interface bonding of the print and thus affecting the performance after printing, the first electrode layer should be cleaned after printing. Figure 2 As shown, the printing platform 3 is raised above the resin tank using a lifting device, and then moved to the cleaning device 5 using a moving mechanism for ultrasonic cleaning with cleaning fluid 4. After cleaning, it is moved to the drying device 6 for drying with compressed air.

[0084] S104: Prepare electrolyte slurry for solid oxide fuel cells according to the specified ratio; the preparation method of electrolyte slurry is as follows: mix electrolyte powder according to the specified ratio, and dry and sieve it in sequence; mix photosensitive resin monomer, dispersant and photoinitiator evenly according to the specified ratio to form electrolyte layer photosensitive resin; slowly and gradually add the sieved electrolyte powder to the electrolyte layer photosensitive resin, mix evenly, and then obtain electrolyte slurry through filtration and defoaming treatment.

[0085] Specifically, when mixing the electrolyte powder and the photosensitive resin of the electrolyte layer evenly, ball milling, three-dimensional mixer or other methods can be used. After the slurry is evenly mixed, the zirconium balls are removed by filtration, and then the bubble is removed by vacuuming to obtain a bubble-free and uniform electrolyte slurry.

[0086] Furthermore, the electrolyte powder is a ceramic powder material composed of one or more of the following: yttrium-stabilized zirconium oxide (YSZ), yttrium zirconate (YZr2O7), cerium dioxide (CeO2), gadolinium-doped cerium dioxide (Gd-CeO2), yttrium-doped cerium dioxide (Y-CeO2), samarium-doped cerium dioxide (Sm-CeO2), bismuth oxide (BiO2) and BiO2-based doped electrolytes, scandium oxide-stabilized zirconium oxide (ScSZ), lanthanum gallium oxide (LSGM) and LSGM-based doped electrolytes, gallium titanate (Gd2Ti2O7), LaGaO3-based solid electrolytes, BaCeO3, and BaZrO3.

[0087] Furthermore, the electrolyte slurry also includes a sintering aid to adjust the sintering densification temperature of the electrolyte layer, so that the sintering temperature of the electrolyte layer is close to the sintering temperature of the co-fired electrode layer (such as the anode layer and / or cathode layer). The electrolyte slurry sintering aid is one or a mixture of several of alumina (Al2O3), yttrium oxide (Y2O3), calcium oxide (CaO), zinc oxide (ZnO), copper oxide (CuO), nickel oxide (NiO), and titanium dioxide (TiO2).

[0088] Specifically, the amount of sintering aid can be determined based on the sintering temperature experiment of the co-fired electrode layer.

[0089] Furthermore, the raw material preparation method of the photosensitive resin of the electrolyte layer is the same as that of the anode slurry mentioned above. The specific ratio is selected according to the solid content (content of electrolyte powder) requirement of the electrolyte slurry, that is, it is determined according to the performance of the battery to be prepared. The optimal solid content can be determined by experiment, and then the preparation of electrolyte slurry in subsequent batch production is guided by the solid content.

[0090] Furthermore, the filtration and defoaming methods used in the preparation of the electrolyte slurry are the same as those used in the preparation of the anode slurry. In both cases, the zirconium balls are separated from the slurry through a filter screen, and then a uniform, bubble-free electrolyte slurry is obtained by vacuuming until no more bubbles are discharged.

[0091] S105: Using a photopolymerization 3D printing device, the electrolyte slurry is printed layer by layer onto the first electrode layer to form an electrolyte layer; for example... Figure 2 As shown, the printing platform 3 is positioned and moved to the corresponding electrolyte slurry resin tank, the electrolyte printing parameters are set, and the operation of printing the anode layer is repeated to complete the electrolyte layer printing.

[0092] S106: After cleaning and drying the printed first electrode layer and electrolyte layer, degreasing and sintering are performed to form a solid oxide fuel cell. The cleaning and drying steps can refer to the steps in S103 above. After cleaning and drying, since the first electrode layer and electrolyte layer contain binders during preparation, they need to be removed. Therefore, degreasing is performed by high-temperature pyrolysis to remove the binders. For example, degreasing is performed by heat treatment in a certain atmosphere for 5-30 hours at a temperature below 800°C. The atmosphere during degreasing is a vacuum atmosphere, atmospheric atmosphere at normal pressure, or an inert gas atmosphere.

[0093] Meanwhile, since batteries fabricated using multi-material printing may warp during sintering, pressure sintering is performed on the integrated two-layer structure formed by the first electrode layer and the electrolyte layer to suppress warping and improve the flatness of the half-cell preform. The sintering method includes stacking or gravity-pressurized sintering of the half-cells. The sintering temperature and time can be selected according to different materials, generally sintering at temperatures of 800-1600℃, followed by heat treatment in a specific atmosphere for 2-10 hours; the sintering atmosphere is either an oxidizing atmosphere or ordinary atmospheric atmosphere.

[0094] Specifically, the stacked sintering method involves stacking multiple half-cells together for sintering, while the gravity-pressurized sintering method (also known as pressure sintering) involves placing a heavy object (such as a ceramic sheet) on the half-cell for sintering, using the gravity of the heavy object to achieve the purpose of warpage suppression.

[0095] It is understood that the stacking and sintering is performed using gravity for pressing. Therefore, while ensuring the stacking and sintering effect and preventing the bottom layer of battery cells from cracking, there is no specific limit to the number of cells stacked. Preferably, the number of cells stacked during the stacking and sintering process is 5-15.

[0096] S107: Prepare the second electrode slurry for the solid oxide fuel cell according to the formula, and shape the second electrode slurry on the side of the electrolyte layer away from the first electrode layer to form the second electrode layer, and then form a full cell through post-processing.

[0097] In one possible implementation, the step of preparing the second electrode slurry for a solid oxide fuel cell according to the specified ratio, and molding the second electrode slurry on the side of the electrolyte layer away from the first electrode layer to form the second electrode layer, comprises: mixing the second electrode composite material according to the specified ratio and pretreating it; mixing the photosensitive resin monomer, dispersant, and photoinitiator uniformly according to the specified ratio to form the second electrode photosensitive resin; adding the pretreated second electrode composite material to the second electrode photosensitive resin in batches, mixing them uniformly, and then filtering and defoaming to obtain the second electrode slurry; and using a photopolymerization 3D printing device to mold the second electrode slurry on the side of the electrolyte layer away from the first electrode layer to form the second electrode layer.

[0098] Specifically, the pretreatment includes calcining the second electrode composite material that is mixed evenly according to the formula to roughen the second electrode composite material, wet grinding the roughened second electrode composite material, and then successively passing it through filtration, drying and grinding processes to obtain the second electrode composite material that meets the particle size requirements.

[0099] It is understandable that the first electrode layer and the second electrode layer serve as the two poles of the battery, corresponding to the anode layer and the cathode layer, respectively. The method for preparing the second electrode slurry can refer to the method for preparing the first electrode slurry described above, and will not be repeated here.

[0100] By using the above-described embodiment to print the first electrode layer, electrolyte layer, and second electrode layer using a photopolymerization 3D printing device, continuous battery printing can be achieved, saving production steps and improving production efficiency. At the same time, since all three layers of the battery structure are 3D printed, the corresponding printing parameters can be adjusted according to the battery's structure and performance, realizing microscopic control of the battery structure. This enables the printing and molding of different three-dimensional structures, achieving the production of complex structures and high-performance batteries.

[0101] Specifically, the printing parameters mentioned above include the settings for exposure energy, exposure time, and layer thickness. It's understandable that each type of slurry will typically exhibit different cured thickness and scattering levels (corresponding to printing accuracy; lower scattering results in higher printing accuracy) under different printing parameters (exposure energy, exposure time). Generally, higher exposure energy and longer exposure time result in greater cured thickness and more severe scattering (lower accuracy). Therefore, these parameters are used during printing to control and optimize battery performance, such as reducing the electrolyte layer thickness, adjusting the interface morphology between the anode and electrolyte layers, adjusting the anode layer thickness, and regulating the microstructure through cured thickness.

[0102] Preferably, to ensure interlayer bonding in the printed preform, the cured thickness of the electrode layer and the electrolyte layer should be at least 2-3 times their respective layer thicknesses. For example, to ensure interlayer bonding between the anode layer and the electrolyte layer, the cured thickness of the anode layer and the electrolyte layer should be at least 2-3 times their respective layer thicknesses.

[0103] Understandably, since different materials have different properties, and different batteries require different performance characteristics, printing parameters can be determined through printing tests when printing each type of battery. Specifically, a single-layer printing test can be conducted first, printing a test model with a series of different printing parameters. Then, the cured thickness and scattering degree under different parameters can be compared. Considering both sufficient cured thickness and high printing accuracy, the optimal printing parameters can be selected as the printing parameters for subsequent production.

[0104] Of course, since the first electrode layer, electrolyte layer and second electrode layer are all printed in the above embodiment, the degreasing and sintering process in step S106 can be placed after the second electrode layer is printed in S107. That is, the degreasing and sintering process is performed after all three layers of the battery structure are printed, which saves the process in S106 while ensuring the flatness of the battery.

[0105] Furthermore, since the electrode layer requires a porous and breathable structure and the electrolyte layer requires a dense structure, in this embodiment, the solid content of the first electrode slurry and the second electrode slurry is relatively low, while the solid content of the electrolyte layer is relatively high. The solid content of the first electrode slurry and the second electrode slurry is 10-30% by volume, and the solid content of the electrolyte slurry is 20-50% by volume.

[0106] Because the solid content of the first and second electrode layers is lower than that of the electrolyte layer, and their shrinkage rates are greater, the printed batteries are prone to warping or even interlayer delamination during direct heat treatment. Therefore, in order to further reduce the interlayer difference between the electrolyte layer and the electrode layer, improve the interlayer shrinkage matching, and optimize battery performance, the solid content of the first and second electrode slurries can be appropriately increased to reduce the volume shrinkage of the first and second electrode layers during post-processing, while the solid content of the electrolyte layer can be reduced to increase its volume shrinkage, thereby reducing the difference in shrinkage rates between the electrode layer and the electrolyte layer. For example, the solid content of the first and second electrode slurries can be 20-30% by volume, and the solid content of the electrolyte slurry can be 20%-40% by volume.

[0107] Specifically, the preparation of the first and second electrode slurries further includes adding microspheres to the first and second electrode slurries obtained through filtration and defoaming treatment to increase the solid content of the first and second electrode slurries. The microspheres can be materials such as polymethyl methacrylate (PMMA), polyamide (PA), and polylactic acid (PLA). The particle size of the microspheres is selected according to the required pore size, generally 1-20 micrometers. There is no fixed ratio for the amount of microspheres added, which can be selected according to the final required porosity and solid content of the slurry. It needs to be determined experimentally and is generally 0-10% by mass of the composite material powder (anode composite material or cathode composite material).

[0108] It is understandable that the solid content of the first electrode slurry and the second electrode slurry will affect the shape and performance of the printed battery. Therefore, the addition of microsphere material can be done by adding it and mixing it before filtering and defoaming when preparing new slurry, or it can be added to the prepared and tested slurry according to the experimental situation. The amount added should be adjusted according to the previous experimental data to avoid the addition of microsphere material generating bubbles and uneven slurry. After the microsphere material is added, it can be mixed, filtered and defoamed again.

[0109] Specifically, the mixing methods can include, but are not limited to, ball milling, three-dimensional mixers, etc.

[0110] Furthermore, during the preparation of the electrolyte slurry, the solid content of the electrolytic layer can be reduced by decreasing the amount of electrolyte powder, thereby further improving the shrinkage matching between the electrolyte layer and the electrode layer. Specifically, this can be achieved by controlling the ratio of photosensitive resin to electrolyte powder in the electrolyte layer during the preparation of the electrolyte slurry; this ratio can also be determined experimentally.

[0111] In another possible implementation, the step of preparing the second electrode slurry of the solid oxide fuel cell according to the formula and forming the second electrode slurry on the side of the electrolyte layer away from the first electrode layer to form the second electrode layer is as follows: the second electrode composite material is mixed uniformly with solvent, binder and pore-forming agent in proportion to prepare the second electrode slurry; the second electrode slurry is coated on the side of the electrolyte layer away from the first electrode layer to form the second electrode layer.

[0112] Furthermore, the second electrode composite material refers to the second electrode composite material prepared in the above-mentioned second electrode slurry preparation, wherein the solvent includes solvents such as terpineol, benzyl alcohol, xylene, isopropanol, and n-butanol, the binder includes ethyl cellulose and polyvinyl butyral, and the pore-forming agent includes starch and graphite powder.

[0113] Specifically, if the second electrode slurry is a cathode slurry, one or more of the above-mentioned cathode composite materials are selected, mixed evenly, and then mixed with solvent, binder, and pore-forming agent in a certain proportion by ball milling to form a cathode slurry. This proportion is determined based on the solid content and porosity of the cathode slurry, and the solid content and porosity of the cathode slurry are the values ​​corresponding to the optimal performance of different batteries through multiple experiments.

[0114] Furthermore, the coating method includes screen printing, spin coating with a spin coater, and spray coating. The coating thickness of the cathode layer is set according to the battery material and performance. The specific setting is a conventional technology for solid oxide fuel cells, generally 10-50 μm.

[0115] Furthermore, in this embodiment, the first electrode layer and the electrolyte layer are 3D printed, and there is also shrinkage matching between them. The shrinkage matching can be improved by adjusting the solid content as described above, so as to improve battery performance.

[0116] This embodiment provides a photopolymerization multi-material 3D printing method for solid oxide fuel cells, offering a novel approach to solid oxide fuel cell printing and expanding the application of 3D printing technology in the field of solid oxide fuel cell molding. Using the electrode layer as a substrate and then printing the electrolyte layer, unlike methods that use the electrolyte layer as a substrate, effectively reduces the requirements for the thickness and support strength of the electrolyte layer. This facilitates thinner electrolyte layers, making it suitable for producing batteries with thinner electrolyte layers. Furthermore, it allows for easy adjustment of printing parameters to control the microstructure of the electrode layer and the interface morphology between the electrode and electrolyte layers, thereby improving battery performance.

[0117] Meanwhile, based on the printing method provided in this embodiment, once the printing parameters and slurry ratio are determined, it is beneficial to achieve batch preparation, improve production efficiency, and reduce production costs.

[0118] It is understood that the configuration order of the first electrode slurry, the second electrode slurry, and the electrolyte slurry in this embodiment is not unique and can be configured simultaneously according to the actual situation.

[0119] Example 2

[0120] like Figure 4 As shown, the printing method steps provided in this embodiment include:

[0121] S201: Prepare electrolyte slurry for solid oxide fuel cells according to the specified ratio;

[0122] S202: The electrolyte slurry is printed layer by layer using a photopolymerization 3D printing device to form an electrolyte layer;

[0123] S203: Clean the electrolyte layer and then dry it;

[0124] S204: Prepare the first electrode slurry for a solid oxide fuel cell according to the specified ratio;

[0125] S205: Using a photopolymerization 3D printing device, the first electrode slurry is printed layer by layer on the electrolyte layer to form the first electrode layer;

[0126] S206: After cleaning and drying the printed first electrode layer and electrolyte layer, degreasing and sintering are performed to form a solid oxide fuel cell.

[0127] S207: Prepare the second electrode slurry for the solid oxide fuel cell according to the formula, and shape the second electrode slurry on the side of the electrolyte layer away from the first electrode layer to form the second electrode layer, and then form a full cell through post-processing.

[0128] The printing steps and the configuration of each slurry in this embodiment are the same as in Embodiment 1. The difference between Embodiment 1 and Embodiment 1 is that the electrolyte layer is printed first, and then the first electrode layer and the second electrode layer are printed in sequence. The electrolyte layer is used as the printing substrate. Unlike using the electrode layer as the substrate, the thickness and support strength of the electrolyte layer are more important, which can achieve the printing of batteries with a thicker electrolyte layer.

[0129] Similarly, the microstructure of each layer can be optimized and adjusted according to the printing parameters to achieve optimal battery performance.

[0130] Example 3

[0131] like Figure 5 As shown, to further reduce the differences between the electrode layer and the electrolyte layer, improve the shrinkage matching between the electrolyte layer and the electrode layer, and improve the interlayer bonding to solve the problem of interlayer peeling and shedding, it is also possible to choose whether to print an interface microstructure, i.e., a transition layer, between the electrode layer and the electrolyte layer, depending on the situation. The determination process is as follows: Figure 6 As shown, the printing method steps for printing a transition layer include:

[0132] S301: Prepare the first electrode slurry for the solid oxide fuel cell according to the specified ratio.

[0133] S302: The first electrode slurry is printed layer by layer using a photopolymerization 3D printing device to form the first electrode layer.

[0134] S303: Clean the first electrode layer and then dry it.

[0135] S304: A transition layer is printed on the first electrode layer using a photopolymerization 3D printing device, and then the electrolyte slurry is printed layer by layer on the first electrode layer to form an electrolyte layer.

[0136] In one possible implementation, the printing of the transition layer includes: preparing a transition layer slurry by mixing the first electrode slurry and the electrolyte slurry in a certain ratio; using the cleaned first electrode layer as a substrate, printing the transition layer slurry layer by layer on the first electrode layer to form a transition layer, and then printing the electrolyte slurry layer by layer on the first electrode layer to form an electrolyte layer.

[0137] In another possible implementation, the printing of the transition layer includes: using the cleaned first electrode layer as a substrate, printing the first electrode slurry and electrolyte slurry layer by layer or alternately on the first electrode layer to form a transition layer containing a three-dimensional structure of the first electrode-electrolyte interface, and then printing the electrolyte slurry layer by layer on the first electrode layer to form an electrolyte layer.

[0138] Specifically, the first electrode layer and electrolyte layer are defined as being arranged sequentially from top to bottom, with the vertical direction being the direction perpendicular to it, and the horizontal direction being the direction perpendicular to it. If the first electrode layer is the anode layer, the schematic diagram printed layer by layer can be as follows: Figure 7 As shown, the printing is performed layer by layer in sequence. The specific steps are: (1) Print the planar part of the anode layer; (2) Print a layer of microstructure of the anode layer; (3) Clean and dry; (4) Print a layer of microstructure of the electrolyte layer; repeat the cleaning and drying process in (3); repeat (2), (3) and (4) until the interface microstructure is printed; (5) Print the planar part of the electrolyte layer; repeat the cleaning and drying process in (3) again; to obtain (6) half cell green blank.

[0139] S305: Prepare electrolyte slurry for solid oxide fuel cells according to the specified ratio;

[0140] S306: The electrolyte slurry is printed layer by layer on the first electrode layer using a photopolymerization 3D printing device to form an electrolyte layer;

[0141] S307: After cleaning and drying the printed first electrode layer and electrolyte layer, the solid oxide fuel cell is formed by degreasing and sintering.

[0142] S308: Prepare the second electrode slurry for the solid oxide fuel cell according to the formula, and shape the second electrode slurry on the side of the electrolyte layer away from the first electrode layer to form the second electrode layer, and then form a full cell through post-processing.

[0143] When the second electrode slurry is also formed by printing, an interfacial microstructure can be set between it and the electrolyte layer. The printing method is the same as that for the interfacial microstructure between the first electrode layer and the electrolyte layer, ultimately forming a structure like... Figure 8The full cell structure shown includes an anode layer 8, an electrolyte layer 9, and a cathode layer 10, as well as the microstructure between the anode layer 8 and the electrolyte layer 9, and the microstructure between the cathode layer 10 and the electrolyte layer 9.

[0144] Example 4

[0145] This embodiment uses an electrolyte as the substrate, and its implementation method is the same as in Embodiment 2, except that a transition layer is added between the electrode layer and the electrolyte layer to improve interface shrinkage matching and enhance battery performance. Figure 9 As shown, the steps include:

[0146] S401: Prepare electrolyte slurry for solid oxide fuel cells according to the specified ratio.

[0147] S402: The electrolyte slurry is printed layer by layer using a photopolymerization 3D printing device to form an electrolyte layer.

[0148] S403: Clean the electrolyte layer and then dry it.

[0149] S404: A transition layer is printed on the electrolyte layer using a photopolymerization 3D printing device, and then the first electrode slurry is printed layer by layer on the electrolyte layer to form the first electrode layer. The specific printing process can be referred to the method in Example 3.

[0150] S405: Prepare the first electrode slurry for a solid oxide fuel cell according to the specified ratio.

[0151] S406: The first electrode slurry is printed layer by layer on the electrolyte layer using a photopolymerization 3D printing device to form the first electrode layer.

[0152] S407: After cleaning and drying the printed first electrode layer and electrolyte layer, degreasing and sintering are performed to form a solid oxide fuel cell.

[0153] S408: Prepare a second electrode slurry for a solid oxide fuel cell according to the specified ratio, and shape the second electrode slurry on the side of the electrolyte layer away from the first electrode layer to form a second electrode layer, and then perform post-processing to form a full cell.

[0154] Similarly, a transition layer can be set between the second electrode layer and the electrolyte layer when printing the second electrode layer.

[0155] The above examples illustrate the present invention only to aid in understanding it and are not intended to limit the scope of the invention. Those skilled in the art can make various simple deductions, modifications, or substitutions based on the principles of this invention.

Claims

1. A method for photopolymerization of multiple materials in solid oxide fuel cells, characterized in that, Includes the following steps: The first electrode slurry for solid oxide fuel cells was prepared according to the specified ratio; The first electrode slurry is printed layer by layer using a photopolymerization 3D printing device to form the first electrode layer. The first electrode layer is cleaned and then dried. Prepare electrolyte slurry for solid oxide fuel cells according to the specified ratio; The electrolyte slurry is printed layer by layer on the first electrode layer using a photopolymerization 3D printing device to form an electrolyte layer. After the first electrode layer and electrolyte layer that have been printed are cleaned and dried, they are then degreased and sintered to form a solid oxide fuel cell. The second electrode slurry for the solid oxide fuel cell is prepared according to the specified ratio, and the second electrode slurry is shaped on the side of the electrolyte layer away from the first electrode layer to form the second electrode layer. After post-processing, a full cell is formed. The method for preparing the first electrode paste is as follows: The first electrode composite material was mixed according to the specified ratio and pretreated. The photosensitive resin monomer, dispersant, and photoinitiator are mixed evenly according to the formula to form the electrode photosensitive resin; The pretreated first electrode composite material was added to the electrode photosensitive resin in several batches, and after being mixed evenly, the first electrode slurry was obtained by filtration and defoaming treatment. The pretreatment includes calcining the first electrode composite material that is mixed evenly according to the formula to roughen the first electrode composite material, wet grinding the roughened first electrode composite material, and then passing it through the filtering, drying and grinding processes in sequence to obtain the first electrode composite material that meets the particle size requirements. The method for preparing the electrolyte slurry is as follows: The electrolyte powders were mixed according to the specified ratio and then dried and sieved sequentially. The photosensitive resin monomer, dispersant, and photoinitiator are mixed evenly according to the formula to form an electrolyte layer photosensitive resin. The sieved electrolyte powder is added to the photosensitive resin of the electrolyte layer in batches, and after being mixed evenly, the electrolyte slurry is obtained by filtration and defoaming. The first electrode slurry has a solid content of 10-30% by volume, and the electrolyte slurry has a solid content of 20-50% by volume. The first electrode slurry and the second electrode slurry also include microsphere material to increase the solid content of the first electrode slurry and the second electrode slurry, thereby reducing heat treatment volume shrinkage and adjusting the porosity of the first electrode layer and the second electrode layer, respectively.

2. The method for photopolymerization of multiple materials in a solid oxide fuel cell as described in claim 1, characterized in that, It also includes using a photopolymerization 3D printing device to print a transition layer on the first electrode layer, and then printing the electrolyte slurry layer by layer on the first electrode layer to form an electrolyte layer; The printing of the transition layer includes: The first electrode slurry and electrolyte slurry are mixed in a certain ratio to form a transition layer slurry; the cleaned first electrode layer is used as the substrate, and the transition layer slurry is printed layer by layer on the first electrode layer to form a transition layer, and then the electrolyte slurry is printed layer by layer on the first electrode layer to form an electrolyte layer. Alternatively, using the cleaned first electrode layer as a substrate, the first electrode slurry and electrolyte slurry are printed layer by layer or alternately on the first electrode layer to form a transition layer containing a three-dimensional structure of the first electrode-electrolyte interface, and then the electrolyte slurry is printed layer by layer on the first electrode layer to form an electrolyte layer.

3. A method for photopolymerization of multiple materials in solid oxide fuel cells, characterized in that, Includes the following steps: Prepare electrolyte slurry for solid oxide fuel cells according to the specified ratio; The electrolyte slurry is printed layer by layer using a photopolymerization 3D printing device to form an electrolyte layer. The electrolyte layer is cleaned and then dried. The first electrode slurry for solid oxide fuel cells was prepared according to the specified ratio; The first electrode slurry is printed layer by layer on the electrolyte layer using a photopolymerization 3D printing device to form the first electrode layer. After the first electrode layer and electrolyte layer that have been printed are cleaned and dried, they are then degreased and sintered to form a solid oxide fuel cell. The second electrode slurry for the solid oxide fuel cell is prepared according to the specified ratio, and the second electrode slurry is shaped on the side of the electrolyte layer away from the first electrode layer to form the second electrode layer. After post-processing, a full cell is formed. The method for preparing the first electrode paste is as follows: The first electrode composite material was mixed according to the specified ratio and pretreated. The photosensitive resin monomer, dispersant, and photoinitiator are mixed evenly according to the formula to form the electrode photosensitive resin; The pretreated first electrode composite material was added to the electrode photosensitive resin in several batches, and after being mixed evenly, the first electrode slurry was obtained by filtration and defoaming treatment. The pretreatment includes calcining the first electrode composite material that is mixed evenly according to the formula to roughen the first electrode composite material, wet grinding the roughened first electrode composite material, and then passing it through the filtering, drying and grinding processes in sequence to obtain the first electrode composite material that meets the particle size requirements. The method for preparing the electrolyte slurry is as follows: The electrolyte powders were mixed according to the specified ratio and then dried and sieved sequentially. The photosensitive resin monomer, dispersant, and photoinitiator are mixed evenly according to the formula to form an electrolyte layer photosensitive resin. The sieved electrolyte powder is added to the photosensitive resin of the electrolyte layer in batches, and after being mixed evenly, the electrolyte slurry is obtained by filtration and defoaming. The first electrode slurry has a solid content of 10-30% by volume, and the electrolyte slurry has a solid content of 20-50% by volume. The first electrode slurry and the second electrode slurry also include microsphere material to increase the solid content of the first electrode slurry and the second electrode slurry, thereby reducing heat treatment volume shrinkage and adjusting the porosity of the first electrode layer and the second electrode layer, respectively.

4. A method for photopolymerization of multiple materials in solid oxide fuel cells as described in claim 1 or 3, characterized in that, The step of preparing the second electrode slurry for the solid oxide fuel cell according to the specified ratio, and shaping the second electrode slurry on the side of the electrolyte layer away from the first electrode layer to form the second electrode layer, is as follows: The second electrode composite material is mixed according to the specified ratio and pretreated. The photosensitive resin monomer, dispersant, and photoinitiator are mixed evenly according to the formula to form the second electrode photosensitive resin; The pretreated second electrode composite material was added to the second electrode photosensitive resin in several batches, and after being mixed evenly, the second electrode slurry was obtained by filtration and defoaming treatment. The second electrode layer is formed by using a photopolymerization 3D printing device to mold the second electrode slurry on the side of the electrolyte layer away from the first electrode layer. The pretreatment includes calcining the second electrode composite material that is mixed evenly according to the formula to roughen the second electrode composite material, wet grinding the roughened second electrode composite material, and then successively passing it through filtration, drying and grinding processes to obtain the second electrode composite material that meets the particle size requirements.

5. A method for photopolymerization of multiple materials in solid oxide fuel cells as described in claim 1 or 3, characterized in that, The step of preparing the second electrode slurry for the solid oxide fuel cell according to the specified ratio, and shaping the second electrode slurry on the side of the electrolyte layer away from the first electrode layer to form the second electrode layer, is as follows: The second electrode composite material was mixed with solvent, binder and pore-forming agent in proportion to prepare a second electrode slurry. The second electrode slurry is coated on the side of the electrolyte layer away from the first electrode layer to form a second electrode layer.

6. A method for photopolymerization of multiple materials in a solid oxide fuel cell as described in claim 1 or 3, characterized in that, The electrolyte slurry also includes sintering aids to adjust the sintering densification temperature of the electrolyte layer so that the sintering temperature of the electrolyte layer is close to that of the co-fired electrode layer.

7. A method for photopolymerization of multiple materials in solid oxide fuel cells as described in claim 1 or 3, characterized in that, The post-processing includes using pressure sintering to suppress warping during co-sintering, including stacking and pressure sintering.

8. A method for photopolymerization of multiple materials in solid oxide fuel cells as described in claim 1 or 3, characterized in that, The first electrode slurry and the second electrode slurry are respectively an anode slurry and a cathode slurry, and the first electrode layer and the second electrode layer are respectively an anode layer and a cathode layer.

9. A method for photopolymerization of multiple materials in solid oxide fuel cells as described in claim 1 or 3, characterized in that, The solid content of the second electrode slurry is 10-30% by volume.

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