Solid oxide fuel cell with bionic alveolar structure and preparation method of solid oxide fuel cell

Abstract

The invention relates to a solid oxide fuel cell with a bionic alveolar structure and a preparation method of the solid oxide fuel cell. The preparation method comprises the following steps: step 1, printing electrolyte slurry based on a bionic alveolar model by adopting DLP printing equipment to obtain an electrolyte green body with the bionic alveolar structure; 2, the bionic alveolar structure electrolyte green body is placed in a muffle furnace to be subjected to gradient sintering, and the bionic alveolar structure electrolyte is obtained; thirdly, the anode slurry is soaked in the inner side of the bionic alveolar structure electrolyte, and then the electrolyte is placed in a muffle furnace to be sintered; and 4, dipping the cathode slurry on the outer side of the bionic alveolar structure electrolyte, and sintering in a muffle furnace to obtain the solid oxide fuel cell with the bionic alveolar structure. The solid oxide fuel cell is prepared by the preparation method. The solid oxide fuel cell has high specific surface area, high structural degree of freedom and high reliability, and the electrochemical performance of the cell can be effectively enhanced.

Description

Technical Field

[0001] This invention relates to a solid oxide fuel cell with a biomimetic alveolar structure and its preparation method, belonging to the field of solid oxide fuel cell technology. Background Technology

[0002] The extraction and use of fossil fuels have contributed to the development of human society, but their use is usually based on the Carnot cycle, which not only has low energy conversion efficiency but also causes serious environmental pollution. Solid oxide fuel cells (SOFCs), as an energy conversion device, can efficiently convert chemical energy into electrical energy. SOFCs have attracted widespread attention due to their high power generation efficiency and environmental friendliness. The core component of an SOFC, the single cell, consists of a porous cathode, an anode, and a dense electrolyte. The electrolyte layer typically uses ceramic materials such as yttrium-stabilized zirconia (YSZ) because of its high ionic conductivity and excellent mechanical and chemical stability, making it widely used in chemical, mechanical, aerospace, and biomedical engineering fields. Improving the electrolyte layer is crucial for enhancing SOFC performance.

[0003] Currently, there are various processes for preparing electrolytes, including tape casting, screen printing, and sol-gel methods. However, traditional methods for preparing ceramics often suffer from drawbacks such as long processing times and high costs, and it is difficult to produce ceramic components with complex structures. On the other hand, due to the extremely high hardness and brittleness of ceramics, machining is extremely difficult, and defects such as cracks may occur in ceramic components. It is also difficult to control the thickness of the electrolyte, and the surface structure design of the electrolyte is also challenging.

[0004] Photopolymerization technology is a core additive manufacturing and coating technology that utilizes light radiation of a specific wavelength to induce a rapid and controllable chemical reaction in a liquid photosensitive resin system, thereby transforming it from a liquid to a solid state. The basic principle of Digital Light Processing (DLP) 3D printing technology is to project a digital light source onto the surface of the liquid photosensitive resin until all the resin material solidifies. Rapid light switching and overall projection shorten printing time with DLP technology. Furthermore, it can achieve very high dimensional accuracy, reaching 50μm. DLP technology has been widely used in ceramic manufacturing, producing high-quality zirconia structural components with Vickers hardness comparable to components prepared using conventional methods. However, in successfully printed green bodies, the lack of a synergistic mechanism between resin removal and ceramic particle densification during sintering results in insufficient interlayer bonding, easy interlayer cracking, and inadequate electrolyte densification. Summary of the Invention

[0005] To overcome the above-mentioned defects of the prior art, the present invention provides a solid oxide fuel cell with a biomimetic alveolar structure and a method for preparing the same. The electrolyte of the solid oxide fuel cell has a high specific surface area and high reliability, which can effectively solve the problem of electrochemical performance degradation caused by insufficient specific surface area in traditional SOFCs during service.

[0006] The technical solution adopted in this invention is: a method for preparing a solid oxide fuel cell with a biomimetic alveolar structure, comprising the following steps: Step 1: Preparation of biomimetic alveolar structure electrolyte green body: Electrolyte slurry is printed based on a biomimetic alveolar model using a DLP printing device to obtain a biomimetic alveolar structure electrolyte green body; Step 2: Preparation of biomimetic alveolar structure electrolyte: The biomimetic alveolar structure electrolyte green body is placed in a muffle furnace for gradient sintering to obtain the biomimetic alveolar structure electrolyte; Step 3: Anode and electrolyte bonding: The anode slurry is impregnated into the inner side of the biomimetic alveolar structure electrolyte using an impregnation method, and then placed in a muffle furnace for sintering; Step 4: Cathode and electrolyte bonding: The cathode slurry is impregnated onto the outside of the biomimetic alveolar structure electrolyte using an impregnation method, and then sintered in a muffle furnace to obtain a solid oxide fuel cell with a biomimetic alveolar structure.

[0007] Preferably, the biomimetic alveolar model includes a cuboid frame, which is hollow and open at both ends along its length. A biomimetic alveolar structure is disposed within the cavity of the cuboid frame. The biomimetic alveolar structure is composed of multiple composite units arranged in a regular longitudinal and transverse pattern. Each composite unit includes a first module and a second module. Both the first and second modules consist of two modular units. Each modular unit includes three curved tubular units. The outer walls of one end of the three curved tubular units are connected, and the other ends of the three curved tubular units radiate outwards towards the connecting end. The connecting ends of the two modular units of the first module are connected and communicate with each other. The outward radiating ends extend in opposite directions, forming a structure that is wide at both ends and narrow in the middle. The outward radiating ends of the two module units of the second module are joined together, and the curved tubular units of the two module units are connected and interconnected one by one. The connecting ends of the two module units are in opposite directions, forming a structure that is narrow at both ends and wide in the middle. The first module and the second module are assembled to form the composite unit. The connecting ends of the two module units of the first module are located in the cavity formed by the joining of the two module units of the second module. Each curved tubular unit of the first module radiates outward from the gap between the corresponding two curved tubular units of the second module.

[0008] Preferably, the cuboid frame has inwardly extending channels on its sidewalls, and these channels connect to the curved tubular units of the biomimetic alveolar structure.

[0009] Preferably, the diameter of the middle part of the curved tubular unit is smaller than the diameter of the two ends, and the wall of the curved tubular unit has a smooth curved surface.

[0010] Preferably, the cross-section of one end of the curved tubular unit is fan-shaped with a central angle of 120°, which facilitates the connection of the outer walls of the three curved tubular units through the fan-shaped end.

[0011] Preferably, the composite units are arranged in two rows and two columns in a regular pattern to form the biomimetic alveolar structure.

[0012] Preferably, the thickness of the biomimetic alveolar structure electrolyte is 0.3 mm to 0.4 mm, and the porosity is 15% to 25%.

[0013] Preferably, the electrolyte slurry comprises, by mass parts, 70 to 85 parts of 8YSZ powder, 10 to 25 parts of resin polymer, 5 to 15 parts of electrolyte slurry dispersant, and 3 to 10 parts of photoinitiator, and the components are ball-milled in a ball mill to obtain the electrolyte slurry.

[0014] Preferably, the resin polymer is a mixture of 1,6-hexanediol diacrylate and trimethylolpropane diacrylate in a volume ratio of 1:1.

[0015] Preferably, the electrolyte slurry dispersant is amine succinate or amine dicarboxylic acid.

[0016] Preferably, the photoinitiator is 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

[0017] Preferably, the ball milling time for preparing the electrolyte slurry is 6h to 8h.

[0018] Preferably, the solid content of the electrolyte slurry is 60% to 80%.

[0019] Preferably, the DLP printing equipment includes a lifting platform, a doctor blade, a liquid tank, and an exposure module. The lifting platform is used to precisely control the vertical position of the printing platform to achieve layer-by-layer printing. The lifting platform preferably descends by 0.5 μm before each printing. The doctor blade is used to scrape a layer of the electrolyte slurry to be cured onto the printing platform before each printing. The liquid tank is used to hold the electrolyte slurry. The exposure module is used to adjust the spreading speed, light intensity, and exposure time according to the biomimetic alveolar model.

[0020] Preferably, in step one, the electrolyte slurry is loaded into the liquid tank of the DLP printing equipment, the biomimetic alveolar model is introduced, and printing is performed by controlling the exposure parameters and the material spreading speed.

[0021] Preferably, in step one, the exposure power of the DLP printing equipment when printing the electrolyte slurry is 60 mW / cm. 2 The exposure time is 2 seconds, and the material spreading speed is 3 seconds per layer.

[0022] Preferably, in step two, the biomimetic alveolar structure electrolyte green blank is ultrasonically cleaned with alcohol and then placed in a muffle furnace for gradient sintering.

[0023] Preferably, in step two, the final stage of gradient sintering is to hold at a temperature of 1400℃~1500℃ for 2h~3h.

[0024] Preferably, the gradient sintering includes three stages: the first stage heats the temperature to 500°C at a heating rate of 5°C / min and holds it for 1 hour; the second stage heats the temperature to 1000°C at a heating rate of 3°C / min and holds it for 1 hour; and the third stage heats the temperature to 1500°C at a heating rate of 5°C / min and holds it for 2 hours.

[0025] Preferably, the anode slurry comprises, by mass, 70 to 80 parts of NiO-8YSZ powder, 7 to 15 parts of anode slurry dispersant, and 12 to 22 parts of anode slurry binder, and the components are ball-milled in a ball mill to obtain the anode slurry.

[0026] Preferably, in the NiO-8YSZ powder, the mass ratio of NiO to 8YSZ is 6:4.

[0027] Preferably, the anode slurry dispersant is BYK-2013.

[0028] Preferably, the anode slurry binder is PVB (polyvinyl butyral).

[0029] Preferably, the ball milling time for preparing the anode slurry is 6h to 8h.

[0030] Preferably, the solid content of the anode slurry is 60%.

[0031] Preferably, in step three, the anode slurry is immersed in the inner side (inner side) of the curved tubular unit of the biomimetic alveolar structure electrolyte, and sintered at a temperature of 1100℃~1300℃ for 2h~3h.

[0032] Furthermore, the anode side is heated to 1300℃ at a rate of 10℃ / min and held at that temperature for 2 hours.

[0033] Preferably, the cathode slurry comprises, by mass, 70 to 80 parts of LSM-8YSZ powder, 7 to 15 parts of cathode slurry dispersant, and 12 to 22 parts of cathode slurry binder, and the cathode slurry is obtained by ball milling each component in a ball mill.

[0034] Preferably, in the LSM-8YSZ powder, the mass ratio of LSM to 8YSZ is 6:4.

[0035] Preferably, the cathode slurry dispersant is BYK-2013.

[0036] Preferably, the cathode slurry binder is PVB (polyvinyl butyral).

[0037] Preferably, the ball milling time for preparing the cathode slurry is 6h to 8h.

[0038] Preferably, the solid content of the cathode slurry is 60%.

[0039] Preferably, in step four, the cathode slurry is immersed on the outside (outer side of the tube) of the curved tubular unit of the biomimetic alveolar structure electrolyte, and sintered at a temperature of 1100℃~1200℃ for 2h~3h.

[0040] Furthermore, in step four, the cathode side is heated to 1200°C at a rate of 10°C / min and held at that temperature for 2 hours.

[0041] A solid oxide fuel cell with a biomimetic alveolar structure is prepared using any of the preparation methods for a solid oxide fuel cell with a biomimetic alveolar structure disclosed in this invention.

[0042] The beneficial effects of this invention are: (1) The solid oxide fuel cell of the present invention adopts a biomimetic alveolar structure electrolyte, which gives it high specific surface area, high structural freedom, high reliability and deformability, and can effectively solve the problem of insufficient specific surface area of ​​SOFC during service, which leads to a decline in electrochemical performance. (2) The preparation method of the present invention is novel, simple and low in cost. Through the synergy of material formulation and process parameters, it can effectively enhance the specific surface area of ​​electrolyte and significantly improve its reliability, which has important application value for the development of high-performance SOFC. (3) The biomimetic alveolar structure electrolyte of the present invention uses the alveoli in biology as a biomimetic model and is prepared by combining biomimetic design with 3D printing. It has a biomimetic alveolar structure and a significantly enhanced specific surface area compared with traditional solid electrolytes, which can effectively enhance the electrochemical performance of the battery. The biomimetic alveolar model of the present invention can be controlled by CAD software to make the prepared biomimetic alveolar structure electrolyte have an adjustable structure. It can change the distribution of alveolar structure and the thickness of electrolyte according to actual use needs, making it widely applicable, not only to SOFC, but also to other battery systems. Attached Figure Description

[0043] Figure 1 This is a flowchart of one embodiment of the preparation method of the present invention; Figure 2 This is an electron microscope image of the biomimetic alveolar model (CAD model) of the present invention; Figure 3 This is a flowchart of the construction of the biomimetic alveolar model of the present invention; Figure 4 This is a backscattered electron image of the thickness of the electrolyte green blank of the biomimetic alveolar structure in Embodiment 1 of the present invention; Figure 5 This is a backscattered electron image of the electrolyte thickness of the biomimetic alveolar structure in Embodiment 1 of the present invention; Figure 6 This is a backscattered electron image of the anode and electrolyte after bonding in Embodiment 1 of the present invention; Figure 7 This is a schematic diagram of the anode and cathode models of a solid oxide fuel cell with a biomimetic alveolar structure in Embodiment 1 of the present invention. Detailed Implementation

[0044] See Figure 1 This invention discloses a method for fabricating a solid oxide fuel cell (SOFC) with a biomimetic alveolar structure. Specifically, it discloses a method for fabricating a solid oxide fuel cell with a biomimetic alveolar structure based on photopolymerization ceramic 3D printing technology, including the following steps: S1: Preparation of electrolyte slurry: Weigh out 70-85 parts of 8YSZ powder, 10-25 parts of resin polymer, 5-15 parts of electrolyte slurry dispersant, and 3-10 parts of photoinitiator by weight, and place each component in a ball mill for 6-8 hours to obtain the electrolyte slurry.

[0045] S2: Preparation of biomimetic alveolar structure electrolyte green body: The electrolyte slurry is loaded into the liquid tank of a DLP printer, a pre-constructed biomimetic alveolar model is introduced, and printing is performed by controlling exposure parameters and material spread speed to obtain the biomimetic alveolar structure electrolyte preform. The biomimetic alveolar model is as follows: Figure 2 As shown.

[0046] S3: Preparation of biomimetic alveolar structure electrolytes: The biomimetic alveolar structure electrolyte green body is ultrasonically cleaned with alcohol and then placed in a muffle furnace for gradient sintering. The final stage of the gradient sintering is to hold at 1400℃~1500℃ for 2h~3h to obtain the biomimetic alveolar structure electrolyte.

[0047] S4: Preparation of anode slurry: Weigh 70-80 parts of NiO-8YSZ powder, 7-15 parts of anode slurry dispersant, and 12-22 parts of anode slurry binder according to the mass fraction. Place each component in a ball mill and ball mill for 6-8 hours to obtain the anode slurry.

[0048] S5: Anode and electrolyte bonding: The anode slurry is impregnated on the inner side of the biomimetic alveolar structure electrolyte (referring to the inner side of the curved tubular unit) using an impregnation method. The impregnated sample is placed in a muffle furnace and sintered at a temperature of 1100℃~1300℃ for 2h~3h to achieve the bonding of the anode and the electrolyte.

[0049] S6: Preparation of cathode paste: Weigh 70-80 parts of LSM-8YSZ powder, 7-15 parts of cathode slurry dispersant, and 12-22 parts of cathode slurry binder by mass, and place each component in a ball mill for 6-8 hours to obtain the cathode slurry.

[0050] S7: Cathode and electrolyte combination: The cathode slurry is impregnated onto the outside of the biomimetic alveolar structure electrolyte (referring to the outside of the curved tubular unit) using an impregnation method. The impregnated sample is placed in a muffle furnace and sintered at a temperature of 1100℃~1200℃ for 2h~3h to achieve the combination of cathode and electrolyte, thereby obtaining a solid oxide fuel cell with a biomimetic alveolar structure.

[0051] In step S1, the resin polymer is preferably a mixture of 1,6-hexanediol diacrylate and trimethylolpropane diacrylate in a 1:1 volume ratio; the electrolyte slurry dispersant is preferably amine succinate or a dicarboxylic acid amine; and the photoinitiator is preferably 2,4,6-trimethylbenzoyl diphenylphosphine oxide. The ball mill rotation speed can be 500 r / min. The solid content of the electrolyte slurry is preferably 60%~80%.

[0052] In S2, the biomimetic alveolar model preferably includes a cuboid frame, which is hollow and open at both ends along its length. A biomimetic alveolar structure is provided within the cavity of the cuboid frame. The biomimetic alveolar structure is composed of multiple composite units arranged in a regular longitudinal and transverse pattern. Each composite unit includes a first module and a second module. Both the first and second modules consist of two modular units. Each modular unit includes three curved tubular units. The outer walls of one end of each curved tubular unit are connected, and the other ends of each curved tubular unit radiate outwards towards the connecting end. The connecting ends of the two modular units of the first module are connected and interconnected. The outward radiating ends of the first module extend in opposite directions, forming a structure that is wide at both ends and narrow in the middle. The outward radiating ends of the two modules of the second module are joined together, and the curved tubular units of the two modules are connected one-to-one. The connecting ends of the two modules are in opposite directions, forming a structure that is narrow at both ends and wide in the middle. The first module and the second module are assembled to form the composite unit. The connecting ends of the two modules of the first module are located in the cavity formed by the joining of the two modules of the second module. Each curved tubular unit of the first module radiates outward from the gap between the corresponding two curved tubular units of the second module. The process of constructing the biomimetic alveolar model is as follows: Figure 3 As shown.

[0053] Preferably, the sidewalls of the cuboid frame are provided with inwardly extending channels, which connect to the curved tubular units of the biomimetic alveolar structure for the introduction of gas.

[0054] The diameter of the middle part of the curved tubular unit is preferably smaller than the diameter of the two ends, and the wall of the curved tubular unit is preferably a smooth curved surface.

[0055] The cross-section of one end of the curved tubular unit is preferably fan-shaped with a central angle of 120°, so that the outer walls of the three curved tubular units can be connected through the fan-shaped end.

[0056] The composite units are preferably arranged in two rows and two columns to form the biomimetic alveolar structure.

[0057] The DLP printing equipment typically includes a lifting platform, a doctor blade, a liquid tank, and an exposure module. The lifting platform is used to precisely control the vertical position of the printing platform to achieve layer-by-layer printing. The lifting platform preferably lowers by 0.5 μm before each print. The doctor blade applies a layer of the electrolyte slurry to be cured onto the printing platform before each print. The liquid tank holds the electrolyte slurry. The exposure module adjusts the spread rate, light intensity, and exposure time according to the biomimetic alveolar model. The preferred exposure power when printing the electrolyte slurry using the DLP printing equipment is 60 mW / cm². 2 The preferred exposure time is 2 seconds, and the preferred material spreading speed is 3 seconds per layer.

[0058] In S3, the gradient sintering preferably includes three stages: the first stage is preferably heated to 500°C at a heating rate of 5°C / min and held for 1 hour; the second stage is preferably heated to 1000°C at a heating rate of 3°C / min and held for 1 hour; and the third stage is preferably heated to 1500°C at a heating rate of 5°C / min and held for 2 hours.

[0059] The thickness of the biomimetic alveolar structure electrolyte is preferably 0.3 mm to 0.4 mm, and the porosity is preferably 15% to 25%.

[0060] In step S4, the preferred mass ratio of NiO to 8YSZ in the NiO-8YSZ powder is 6:4. The preferred anode slurry dispersant is BYK-2013. The preferred anode slurry binder is PVB. The preferred solid content of the anode slurry is 60%.

[0061] In S5, the anode side is preferably heated to 1300°C at a rate of 10°C / min and held at that temperature for 2 hours.

[0062] In step S6, the preferred mass ratio of LSM to 8YSZ in the LSM-8YSZ powder is 6:4. The preferred cathode slurry dispersant is BYK-2013. The preferred cathode slurry binder is PVB. The preferred solid content of the cathode slurry is 60%.

[0063] In S7, the cathode side is preferably heated to 1200°C at a rate of 10°C / min and held at that temperature for 2 hours.

[0064] The present invention also discloses a solid oxide fuel cell with a biomimetic alveolar structure, which is prepared by any of the preparation methods of the solid oxide fuel cell with a biomimetic alveolar structure disclosed in the present invention.

[0065] Example 1: S1: Preparation of electrolyte slurry: Weigh 70g of 8YSZ powder, 20g of resin polymer, 15g of amine succinate and 3g of 2,4,6-trimethylbenzoyl diphenylphosphine oxide, and place each component in a ball mill and ball mill at 500r / min for 6h to obtain the electrolyte slurry.

[0066] The solid content of the electrolyte slurry is 80%.

[0067] S2: Preparation of biomimetic alveolar structure electrolyte green body: The electrolyte slurry was loaded into the liquid tank of the DLP printing equipment, and a biomimetic alveolar model was introduced. The thickness of the biomimetic alveolar structure electrolyte preform was set to 300 μm, and the exposure power was controlled at 60 mW / cm². 2 The exposure time was 2 seconds, the material laying speed was 3 seconds per layer, and the biomimetic alveolar structure electrolyte preform was obtained by printing. The backscattered electron image of its thickness is shown below. Figure 4 As shown.

[0068] S3: Preparation of biomimetic alveolar structure electrolytes: The biomimetic alveolar structure electrolyte preform was ultrasonically cleaned with alcohol and then placed in a muffle furnace. The furnace underwent gradient sintering with the following steps: first, a heating rate of 5°C / min to 500°C, held for 1 hour; second, a heating rate of 3°C / min to 1000°C, held for 1 hour; and third, a heating rate of 5°C / min to 1500°C, held for 2 hours, to obtain the biomimetic alveolar structure electrolyte. The backscattered electron micrograph of its thickness is shown in the image below. Figure 5 As shown.

[0069] S4: Preparation of anode slurry: Weigh 70g of NiO-8YSZ powder, 10g of BYK-2013 and 22g of PVB, and place each component in a ball mill and ball mill at 500r / min for 6h to obtain the anode slurry.

[0070] S5: Anode and electrolyte bonding: The anode slurry was impregnated onto the inner side of the biomimetic alveolar structure electrolyte using an impregnation method. The impregnated sample was placed in a muffle furnace, and the anode side was heated to 1300°C at a rate of 10°C / min and held for 2 hours to achieve bonding between the anode and the electrolyte. Backscattered electron microscopy images are shown below. Figure 6 As shown.

[0071] S6: Preparation of cathode paste: Weigh 70g of LSM-8YSZ powder, 10g of BYK-2013 and 22g of PVB, and place each component in a ball mill and ball mill at 500r / min for 6h to obtain the cathode slurry.

[0072] S7: Cathode and electrolyte combination: The cathode slurry was impregnated onto the outer side of the biomimetic alveolar structure electrolyte using an impregnation method. The impregnated sample was placed in a muffle furnace, and the cathode side was heated to 1200°C at a rate of 10°C / min and held for 2 hours to achieve bonding between the cathode and the electrolyte, thus obtaining a solid oxide fuel cell with a biomimetic alveolar structure. The model of the solid oxide fuel cell with the biomimetic alveolar structure is as follows. Figure 7 As shown.

[0073] The thickness of the biomimetic alveolar structure electrolyte obtained in this embodiment is 200 μm, which is comparable to the thickness of SOFC electrolytes currently reported, indicating that the method of this embodiment can obtain a high-quality biomimetic alveolar structure SOFC.

[0074] Example 2: S1: Preparation of electrolyte slurry: Weigh 80g of 8YSZ powder, 25g of resin polymer, 5g of dicarboxylic acid amine and 6g of 2,4,6-trimethylbenzoyl diphenylphosphine oxide, and place each component in a ball mill and ball mill at 500r / min for 6h to obtain the electrolyte slurry.

[0075] The solid content of the electrolyte slurry is 70%.

[0076] S2: Preparation of biomimetic alveolar structure electrolyte green body: The electrolyte slurry is loaded into the liquid tank of the DLP printing equipment and then introduced into a biomimetic alveolar model, as shown in the figure below. Figure 2 As shown, the thickness of the biomimetic alveolar structure electrolyte preform was set to 300 μm, and the exposure power was controlled at 60 mW / cm². 2 The exposure time was 2 seconds, the material laying speed was 3 seconds per layer, and the biomimetic alveolar structure electrolyte preform was obtained by printing.

[0077] S3: Preparation of biomimetic alveolar structure electrolytes: The biomimetic alveolar structure electrolyte preform was ultrasonically cleaned with alcohol and then placed in a muffle furnace. In the first stage, the temperature was increased to 500°C at a rate of 5°C / min and held for 1 hour. In the second stage, the temperature was increased to 1000°C at a rate of 3°C / min and held for 1 hour. In the third stage, the temperature was increased to 1500°C at a rate of 5°C / min and held for 2 hours to perform gradient sintering, thereby obtaining the biomimetic alveolar structure electrolyte.

[0078] S4: Preparation of anode slurry: Weigh 75g of NiO-8YSZ powder, 15g of BYK-2013 and 12g of PVB, and place each component in a ball mill and ball mill at 500r / min for 6h to obtain the anode slurry.

[0079] S5: Anode and electrolyte bonding: The anode slurry was impregnated into the inner side of the biomimetic alveolar structure electrolyte using an impregnation method. The impregnated sample was placed in a muffle furnace, and the anode side was heated to 1300°C at a rate of 10°C / min and held for 2 hours to achieve the bonding between the anode and the electrolyte.

[0080] S6: Preparation of cathode paste: Weigh 75g of LSM-8YSZ powder, 15g of BYK-2013 and 12g of PVB, and place each component in a ball mill and ball mill at 500r / min for 6h to obtain the cathode slurry.

[0081] S7: Cathode and electrolyte combination: The cathode slurry was impregnated onto the outside of the biomimetic alveolar structure electrolyte using an impregnation method. The impregnated sample was placed in a muffle furnace, and the cathode side was heated to 1200°C at a rate of 10°C / min and held for 2 hours to achieve the bonding of the cathode and electrolyte, thereby obtaining a solid oxide fuel cell with a biomimetic alveolar structure.

[0082] Example 3: S1: Preparation of electrolyte slurry: Weigh 85g of 8YSZ powder, 10g of resin polymer, 10g of amine succinate and 10g of 2,4,6-trimethylbenzoyl diphenylphosphine oxide, and place each component in a ball mill and ball mill at 500r / min for 6h to obtain the electrolyte slurry.

[0083] The solid content of the electrolyte slurry is 80%.

[0084] S2: Preparation of biomimetic alveolar structure electrolyte green body: The electrolyte slurry is loaded into the liquid tank of the DLP printing equipment and then introduced into a biomimetic alveolar model, as shown in the figure below. Figure 2 As shown, the thickness of the biomimetic alveolar structure electrolyte preform was set to 300 μm, and the exposure power was controlled at 60 mW / cm². 2 The exposure time was 2 seconds, the material laying speed was 3 seconds per layer, and the biomimetic alveolar structure electrolyte preform was obtained by printing.

[0085] S3: Preparation of biomimetic alveolar structure electrolytes: The biomimetic alveolar structure electrolyte preform was ultrasonically cleaned with alcohol and then placed in a muffle furnace. In the first stage, the temperature was increased to 500°C at a rate of 5°C / min and held for 1 hour. In the second stage, the temperature was increased to 1000°C at a rate of 3°C / min and held for 1 hour. In the third stage, the temperature was increased to 1500°C at a rate of 5°C / min and held for 2 hours to perform gradient sintering, thereby obtaining the biomimetic alveolar structure electrolyte.

[0086] S4: Preparation of anode slurry: Weigh 80g of NiO-8YSZ powder, 7g of BYK-2013 and 17g of PVB, and place each component in a ball mill and ball mill at 500r / min for 6h to obtain the anode slurry.

[0087] S5: Anode and electrolyte bonding: The anode slurry was impregnated into the inner side of the biomimetic alveolar structure electrolyte using an impregnation method. The impregnated sample was placed in a muffle furnace, and the anode side was heated to 1300°C at a rate of 10°C / min and held for 2 hours to achieve the bonding between the anode and the electrolyte.

[0088] S6: Preparation of cathode paste: Weigh 80g of LSM-8YSZ powder, 7g of BYK-2013 and 17g of PVB, and place each component in a ball mill and ball mill at 500r / min for 6h to obtain the cathode slurry.

[0089] S7: Cathode and electrolyte combination: The cathode slurry was impregnated onto the outside of the biomimetic alveolar structure electrolyte using an impregnation method. The impregnated sample was placed in a muffle furnace, and the cathode side was heated to 1200°C at a rate of 10°C / min and held for 2 hours to achieve the bonding of the cathode and electrolyte, thereby obtaining a solid oxide fuel cell with a biomimetic alveolar structure.

[0090] Comparative example (taking the preparation of disc electrolytes as an example): S1: Preparation of electrolytes: Weigh 10g of YSZ powder, 0.2g of PVA, 0.1g of glycerol and 10g of anhydrous ethanol, place each component in a ball mill and ball mill at 500r / min for 12h, then dry in a drying oven to obtain electrolyte powder.

[0091] S2: Preparation of electrolyte green blank: Weigh a certain amount of the mixed powder and pour it evenly into the mold cavity; press it into tablets at a pressure of 10 MPa for 3 minutes to obtain the electrolyte green compact.

[0092] S3: Preparation of disc electrolytes: The electrolyte green body was placed in a muffle furnace and heated to 500°C at a rate of 2°C / min in the first stage and held for 2 hours; in the second stage, it was heated to 1500°C at a rate of 5°C / min and held for 2 hours to obtain the disc-structured electrolyte.

[0093] S4: Preparation of anode slurry: Weigh 10g of NiO-8YSZ powder, 0.2g of PVA, 0.1g of glycerol and 10g of anhydrous ethanol. Place each component in a ball mill and ball mill at 500r / min for 12h. Then dry in a drying oven to obtain the anode slurry.

[0094] S5: Anode and electrolyte bonding: The anode paste was screen-printed onto one side of the electrolyte. The coated sample was placed in a muffle furnace, and the anode side was heated to 1300°C at a rate of 10°C / min and held for 2 hours to achieve bonding between the anode and the electrolyte.

[0095] S6: Preparation of cathode paste: Weigh 10g of LSM-8YSZ powder, 0.2g of PVA, 0.1g of glycerin and 10g of anhydrous ethanol. Place each component in a ball mill and ball mill at 500r / min for 12h. Then dry in a drying oven to obtain an anion slurry.

[0096] S7: Cathode and electrolyte combination: The cathode slurry was screen-printed onto the other side of the electrolyte. The coated sample was placed in a muffle furnace, and the cathode side was heated to 1200°C at a rate of 10°C / min and held for 2 hours to achieve the bonding of the cathode and the electrolyte, thus obtaining a solid oxide fuel cell.

[0097] The electrolytes prepared in each embodiment have a biomimetic alveolar structure with multiple curved tubular units. Their specific surface area is the sum of the wall areas of each curved tubular unit. The specific surface area of ​​the conventional disc electrolyte prepared in the comparative example is the area of ​​the end cross-section (circular area) of the disc electrolyte. Through comparative analysis, under the condition that other parameters of the electrolyte (referring to the overall shape and size parameters, such as length, width, and height) are the same, the specific surface area of ​​the electrolytes prepared in each embodiment is at least 20 to 30 times that of the electrolyte prepared in the comparative example.

[0098] Unless otherwise specified or further limited to one preferred or optional technical means being another, the preferred and optional technical means disclosed in this invention can be arbitrarily combined to form several different technical solutions.

Claims

1. A method for preparing a solid oxide fuel cell with a biomimetic alveolar structure, characterized in that... Includes the following steps: Step 1: Preparation of biomimetic alveolar structure electrolyte green body: Electrolyte slurry is printed based on a biomimetic alveolar model using a DLP printing device to obtain a biomimetic alveolar structure electrolyte green body; Step 2: Preparation of biomimetic alveolar structure electrolyte: The biomimetic alveolar structure electrolyte green body is placed in a muffle furnace for gradient sintering to obtain the biomimetic alveolar structure electrolyte; Step 3: Anode and electrolyte bonding: The anode slurry is impregnated into the inner side of the biomimetic alveolar structure electrolyte using an impregnation method, and then placed in a muffle furnace for sintering; Step 4: Cathode and electrolyte bonding: The cathode slurry is impregnated onto the outside of the biomimetic alveolar structure electrolyte using an impregnation method, and then sintered in a muffle furnace to obtain a solid oxide fuel cell with a biomimetic alveolar structure.

2. The method for preparing a solid oxide fuel cell with a biomimetic alveolar structure according to claim 1, characterized in that... The biomimetic alveolar model includes a cuboid frame, which is hollow and open at both ends along its length. A biomimetic alveolar structure is housed within the cavity of the cuboid frame. This structure is composed of multiple composite units arranged in a regular, longitudinal and transverse pattern. Each composite unit includes a first module and a second module. Both the first and second modules consist of two modular units. Each modular unit includes three curved tubular units. The outer walls of one end of each curved tubular unit are connected, and the other ends of each curved tubular unit radiate outwards towards the connecting end. The connecting ends of the two modular units of the first module are connected and interconnected, and their outward radiating ends radiate in opposite directions. The outward radiating ends of the two modular units of the second module are aligned, and their curved tubular units are connected and interconnected one-to-one. Their connecting ends radiate in opposite directions. The first module and the second module are assembled to form the composite unit. The connecting ends of the two modular units of the first module are located within the cavity formed by the aligned two modular units of the second module. Each curved tubular unit of the first module radiates outwards from the gap between corresponding two curved tubular units of the second module.

3. The method for preparing a solid oxide fuel cell with a biomimetic alveolar structure according to claim 2, characterized in that... The cuboid frame has inwardly extending channels on its sidewalls, which connect to the curved tubular units of the biomimetic alveolar structure.

4. The method for preparing a solid oxide fuel cell with a biomimetic alveolar structure according to claim 3, characterized in that... The biomimetic alveolar structure electrolyte has a thickness of 0.3 mm to 0.4 mm and a porosity of 15% to 25%.

5. The method for preparing a solid oxide fuel cell with a biomimetic alveolar structure according to claim 1, characterized in that... The electrolyte slurry, by mass parts, comprises 70 to 85 parts of 8YSZ powder, 10 to 25 parts of resin polymer, 5 to 15 parts of electrolyte slurry dispersant, and 3 to 10 parts of photoinitiator. The components are ball-milled in a ball mill to obtain the electrolyte slurry.

6. The method for preparing a solid oxide fuel cell with a biomimetic alveolar structure according to claim 1, characterized in that... In step two, the final stage of gradient sintering is to hold the temperature at 1400℃~1500℃ for 2h~3h.

7. The method for preparing a solid oxide fuel cell with a biomimetic alveolar structure according to claim 6, characterized in that... The gradient sintering process includes three stages: the first stage involves heating to 500°C at a rate of 5°C / min and holding for 1 hour; the second stage involves heating to 1000°C at a rate of 3°C / min and holding for 1 hour; and the third stage involves heating to 1500°C at a rate of 5°C / min and holding for 2 hours.

8. The method for preparing a solid oxide fuel cell with a biomimetic alveolar structure according to claim 1, characterized in that... The anode slurry, by mass parts, comprises 70 to 80 parts of NiO-8YSZ powder, 7 to 15 parts of anode slurry dispersant, and 12 to 22 parts of anode slurry binder. The components are ball-milled in a ball mill to obtain the anode slurry.

9. The method for preparing a solid oxide fuel cell with a biomimetic alveolar structure according to claim 1, characterized in that... The cathode slurry, by mass, comprises 70 to 80 parts of LSM-8YSZ powder, 7 to 15 parts of cathode slurry dispersant, and 12 to 22 parts of cathode slurry binder. The components are ball-milled in a ball mill to obtain the cathode slurry.

10. A solid oxide fuel cell with a biomimetic alveolar structure, characterized in that... The solid oxide fuel cell with a biomimetic alveolar structure, as described in any one of claims 1-9, was prepared.

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