A high-temperature solid oxide fuel cell anode slurry and a method of preparing the same

Abstract

This invention discloses a method for preparing anode slurry for high-temperature solid oxide fuel cells, belonging to the field of material preparation technology. The method includes the following steps: S1: Nickel oxide powder, gadolinium-doped cerium oxide powder, and a pore-forming agent are placed in a ball mill jar. A dispersant and a solvent are added to the ball mill jar, and the mixture is ball-milled for a first predetermined time period to obtain mixture A. The nickel oxide powder has a particle size of 0.5–5 μm and a purity ≥99.5%; the gadolinium-doped cerium oxide powder has a particle size of 0.1–3 μm and a purity ≥99%; the pore-forming agent is added at 5%–20% of the total mass of the nickel oxide powder and gadolinium-doped cerium oxide powder; the dispersant is added at 0.5%–5% of the total mass of the nickel oxide powder, gadolinium-doped cerium oxide powder, and pore-forming agent; and the solvent is added at 30%–80% of the total mass of the nickel oxide powder, gadolinium-doped cerium oxide powder, and pore-forming agent. This method facilitates material recycling and reuse, saves material costs, and reduces environmental impact.

Description

Technical Field

[0001] This invention relates to the field of materials preparation technology, and more specifically, to a high-temperature solid oxide fuel cell anode slurry and its preparation method. Background Technology

[0002] A fuel cell is a device that directly converts chemical energy into electrical energy. It boasts advantages such as high energy conversion efficiency and clean, pollution-free operation, and is considered a modern energy technology with enormous potential. Based on different operating temperatures and electrolyte types, fuel cells are mainly classified into five categories: proton exchange membrane fuel cells (PEMFC), alkaline fuel cells (AFC), high-temperature solid oxide fuel cells (SOFC), molten carbonate fuel cells (MCFC), and phosphoric acid fuel cells (PAFC). Among these, high-temperature solid oxide fuel cells (SOFC) exhibit broad application prospects in distributed power generation, residential combined heat and power (CHP), large-scale power plants, and transportation due to their significant advantages such as high power density, high energy conversion efficiency, no need for precious metal catalysts, and wide applicability to a wide range of fuels (directly using hydrogen, carbon monoxide, methane, and other fuels).

[0003] The core components of a high-temperature solid oxide fuel cell (HSOFC) include the anode, electrolyte, and cathode. The anode, as the site of electrochemical oxidation of the fuel, directly affects the overall output performance of the cell due to its microstructure and electrochemical performance. Currently, the most widely used anode materials for HSOFCs are nickel-based ceramic composite systems. Nickel (Ni) serves as the electronically conductive phase and catalytically active component, while gadolinium-doped cerium oxide (GDC) or yttrium-stabilized zirconium oxide (YSZ) serves as the ionicly conductive phase and structural support component. These anode materials are typically prepared into anode slurries using processes such as casting, screen printing, and spraying, which are then dried and sintered to form a porous anode structure. The composition and preparation process of the anode slurry have a decisive influence on key properties such as the anode's microstructure, porosity, pore size distribution, conductivity, and thermal compatibility with the electrolyte.

[0004] In the existing technology, high-temperature solid oxide fuel cell anode slurry mostly uses organic solvent systems, such as ethanol, toluene, methyl ethyl ketone, terpineol, etc. as solvents, combined with polyvinyl butyral (PVB), ethyl cellulose, etc. as binders, and dibutyl phthalate (DBP), etc. as plasticizers. While these organic solvent systems can achieve good dispersion and film-forming properties, they suffer from the following technical drawbacks: First, a large amount of organic solvents volatilize during slurry preparation, casting, and drying, resulting in solvent waste, potential occupational health hazards for operators, and environmental burden from volatile organic compound (VOC) emissions, requiring expensive exhaust gas treatment equipment. Second, waste liquid from organic solvent systems is difficult to treat, requiring solvent recovery or specialized incineration, leading to high processing costs. Third, organic solvents impose strict fire and explosion protection requirements on the production environment, increasing equipment investment and operating costs. Furthermore, in the manufacturing process of high-temperature solid oxide fuel cells, waste materials such as scraps and substandard green bodies generated during casting are difficult to effectively recover and reuse using organic solvent systems, typically requiring disposal as waste, resulting in low material utilization and further increasing manufacturing costs. Although some researchers have attempted to replace organic solvent systems with aqueous systems, aqueous anode slurries still face numerous technical challenges in terms of dispersion stability, film uniformity, and drying process control, making it difficult to achieve comprehensive performance comparable to organic solvent systems. Summary of the Invention

[0005] (a) Technical problems to be solved To address the shortcomings of existing technologies, this invention provides a high-temperature solid oxide fuel cell anode slurry and its preparation method, thus solving the aforementioned problems.

[0006] (II) Technical Solution To achieve the above-mentioned objectives, the present invention provides the following technical solution: a high-temperature solid oxide fuel cell anode slurry and its preparation method, comprising the following steps: S1: Nickel oxide powder, gadolinium-doped cerium oxide powder, and a pore-forming agent are placed in a ball mill jar. A dispersant and a solvent are added to the ball mill jar, and the mixture is ball-milled for a first predetermined time period to obtain mixture A. The nickel oxide powder has a particle size of 0.5–5 μm and a purity ≥99.5%; the gadolinium-doped cerium oxide powder has a particle size of 0.1–3 μm and a purity ≥99%; the pore-forming agent is added at 5%–20% of the total mass of the nickel oxide powder and the gadolinium-doped cerium oxide powder; the dispersant is added at 0.5%–5% of the total mass of the nickel oxide powder, gadolinium-doped cerium oxide powder, and the pore-forming agent; and the solvent is added at 30%–80% of the total mass of the nickel oxide powder, gadolinium-doped cerium oxide powder, and the pore-forming agent. S2: Add binder, plasticizer, wetting agent, and solvent to mixture A, and ball mill and mix for a second predetermined time period to obtain mixture B; wherein, the amount of binder added is 5% to 15% of the total mass of the nickel oxide powder and the gadolinium-doped cerium oxide powder; the amount of plasticizer added is 10% to 50% of the mass of the binder; the amount of wetting agent added is 1% to 10% of the total mass of the nickel oxide powder and the gadolinium-doped cerium oxide powder; and the amount of solvent added is 10% to 40% of the total mass of the nickel oxide powder, gadolinium-doped cerium oxide powder, and pore-forming agent. S3: Add a surfactant and a defoaming agent to mixture B, and ball mill the mixture for a third predetermined time period to obtain mixture C; wherein the amount of surfactant added is 0.1% to 2% of the total mass of the nickel oxide powder and the gadolinium-doped cerium oxide powder; the amount of defoaming agent added is 0.1% to 2% of the total mass of the nickel oxide powder and the gadolinium-doped cerium oxide powder; S4: Filter mixture C to remove large, uncrushed powder particles and any impurities that may have been mixed in, to obtain mixture D; S5: Vacuum degassing treatment is performed on mixture D to remove air bubbles from the slurry and adjust the viscosity of the slurry to a predetermined range to obtain high-temperature solid oxide fuel cell anode slurry; The solvent is deionized water, which has a resistivity ≥18 MΩ·cm and a pH value of 6.5~7.5.

[0007] Preferably, the chemical formula of the gadolinium-doped cerium oxide powder is GdaCebO2-X; where a+b=1, the value of a ranges from 0.05 to 0.3, the value of b ranges from 0.7 to 0.95, and the value of X ranges from 0 to 0.5. Preferably, the value of a ranges from 0.1 to 0.2, and the value of b ranges from 0.8 to 0.9. The mass ratio of the nickel oxide powder to the gadolinium-doped cerium oxide powder is (40-70):(30-60). Preferably, the mass ratio of the nickel oxide powder to the gadolinium-doped cerium oxide powder is (50-60):(40-50). The amount of pore-forming agent added is 5% to 15% of the total mass of the nickel oxide powder and the gadolinium-doped cerium oxide powder. The pore-forming agent is selected from one or more of starch, polymethyl methacrylate, graphite powder, cellulose, polyvinyl butyral, polyethylene glycol, and polystyrene microspheres. The particle size of the pore-forming agent is 0.5 to 10 μm. The dispersant is selected from one or more of isopropanol, ethanol, polyethylene glycol, ammonium polyacrylate, polyvinylpyrrolidone, sodium polyacrylate, and sodium dodecyl sulfate. The amount of dispersant added is 1% to 3% of the total mass of the nickel oxide powder, gadolinium-doped cerium oxide powder, and pore-forming agent.

[0008] Preferably, in S1, the rotational speed of the ball mill is 80–250 rpm, preferably 100–200 rpm, and the first predetermined time period is 1–8 hours, preferably 2–6 hours; in S2, the rotational speed of the ball mill is 80–250 rpm, preferably 100–200 rpm, and the second predetermined time period is 0.5–5 hours, preferably 1–3 hours; in S3, the rotational speed of the ball mill is 80–250 rpm, preferably 100–200 rpm, and the third predetermined time period is 12–96 hours, preferably 24–72 hours; the ball milling and mixing in S1, S2, and S3 are all carried out at room temperature, the ball mill jar material is selected from one of zirconium oxide, polyurethane, nylon, and stainless steel, the ball milling media are zirconium oxide balls or alumina balls, the diameter of the ball milling media is 3–20 mm, and the ball-to-material ratio is (1–5):1.

[0009] Preferably, in step S2, the binder is selected from one or more of polyacrylic acid, polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, ethyl cellulose, polymethyl methacrylate, and polyurethane, and the binder is added in solution form with a solution concentration of 10% to 50%; the plasticizer is selected from one or more of polyethylene glycol, dibutyl phthalate, dioctyl phthalate, glycerin, tributyl citrate, and dibutyl sebacate, and the amount of plasticizer added is 15% to 40% of the mass of the binder; the wetting agent is selected from one or more of glycerol, ethylene glycol, butanediol, polyoxyethylene ether, polyethylene glycol octylphenyl ether, and sodium dodecylbenzenesulfonate, and the amount of wetting agent added is 2% to 8% of the total mass of the nickel oxide powder and the gadolinium-doped cerium oxide powder.

[0010] Preferably, in step S3, the surfactant is selected from one or more of sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, polyoxyethylene sorbitan monooleate, octylphenol polyoxyethylene ether, hexadecyltrimethylammonium bromide, and polyethylene glycol octylphenyl ether; the defoamer is selected from one or more of tributyl phosphate, polydimethylsiloxane, polyoxypropylene glycerol ether, polyethylene glycol fatty acid ester, mineral oil, and silicone defoamer; the surfactant and defoamer are pre-dissolved in deionized water before addition to form a premixed solution with a concentration of 5% to 20%.

[0011] Preferably, in step S4, the filtration process employs one of the following methods: negative pressure filtration, centrifugal filtration, vibrating sieving filtration, or pressure filtration. The mesh size of the filter used during filtration is 80–600 mesh, preferably 100–500 mesh. In step S5, the vacuum degree of the vacuum degassing process is -0.08–-0.1 MPa, preferably -0.09–-0.1 MPa, and the vacuum degassing time is 2–30 hours, preferably 4–24 hours. During the vacuum degassing process, intermittent stirring or continuous slow stirring is performed at a stirring speed of 10–50 rpm. After the vacuum degassing process, the viscosity, solid content, and particle size distribution of the slurry are tested. The viscosity of the slurry is adjusted to 3000–8000 mPa·s, preferably 4000–7500 mPa·s, the solid content of the slurry is 40%–70%, and the particle size distribution D50 of the slurry is 0.5–5 μm.

[0012] Preferably, the pore-forming agent is starch or polymethyl methacrylate; the dispersant is isopropanol; the binder is polyacrylic acid; the plasticizer is polyethylene glycol; the wetting agent is glycerol; the surfactant and defoamer are added simultaneously; the surfactant is sodium dodecyl sulfate, and the defoamer is tributyl phosphate; the mass ratio of nickel oxide powder to gadolinium-doped cerium oxide powder is 60:40 or 50:50; the amount of pore-forming agent added is the ratio of nickel oxide powder to gadolinium oxide powder. The amount of the dispersant added is 10% of the total mass of the nickel oxide powder, gadolinium-doped cerium oxide powder, and pore-forming agent; the amount of the binder added is 10% to 12% of the total mass of the nickel oxide powder and the gadolinium-doped cerium oxide powder; the amount of the plasticizer added is 20% to 30% of the mass of the binder; and the amount of the wetting agent added is 3% to 6% of the total mass of the nickel oxide powder and the gadolinium-doped cerium oxide powder.

[0013] Preferably, the anode slurry is prepared by the method described in any one of claims 1 to 7 for preparing high-temperature solid oxide fuel cell anode slurry; the anode slurry uses deionized water as a solvent and contains nickel oxide, gadolinium-doped cerium oxide, pore-forming agent, dispersant, binder, plasticizer, wetting agent, surfactant, and defoamer; the anode slurry has a solid content of 40% to 70%, a particle size distribution D50 of 0.5 to 5 μm, a viscosity of 4000 to 7500 mPa·s, a pH value of 6.5 to 8.5, a viscosity of 5000 to 6500 mPa·s at 25°C, and a shear thinning index of 0.3 to 0.8.

[0014] Preferably, the anode slurry is used to prepare an anode support or anode functional layer by processes such as casting, screen printing, spraying, dip coating, scraping, or spin coating. After the anode slurry is formed, it is dried and sintered. The drying temperature is 60-120℃, the drying time is 2-12 hours, the sintering temperature is 1200-1400℃, and the sintering time is 2-6 hours to obtain a porous anode structure. The porosity of the porous anode structure is 20%-50%, the pore size distribution is 0.5-5μm, and the electrical conductivity is ≥1000 S / cm at 800℃.

[0015] Preferably, the method is also applicable to the recycling and reuse of anode raw material waste generated during the manufacturing process of high-temperature solid oxide fuel cells. The waste includes one or more of the following: scraps generated during the casting process, unqualified green blanks, unsintered anode sheets after drying, and residues from slurry conveying pipelines. The specific steps for recycling and reuse include: crushing or pulverizing the waste to a particle size ≤ 5 mm, adding deionized water for stirring and dispersion at a stirring speed of 200–500 rpm for 1–4 hours, filtering through a 100–300 mesh filter to remove impurities, and then performing vacuum degassing treatment at a vacuum degree of -0.09–-0.1 MPa for 2–12 hours to obtain regenerated slurry. The regenerated slurry is then mixed with freshly prepared anode slurry in any proportion and reused for anode preparation.

[0016] (III) Beneficial Effects Compared with the prior art, the present invention provides a high-temperature solid oxide fuel cell anode slurry and its preparation method, which has the following beneficial effects: This invention relates to a high-temperature solid oxide fuel cell anode slurry and its preparation method. It uses deionized water instead of organic solvents such as ethanol as the slurry solvent, fundamentally eliminating the emission of volatile organic compounds (VOCs). This avoids the health hazards to operators and the pollution of the atmospheric environment caused by the volatilization of organic solvents. No explosion-proof modification or exhaust gas treatment equipment is required during the production process, making the operating environment safer and more friendly. The waste liquid generated during the preparation process is only an aqueous solution containing a small amount of additives, which can be harmlessly treated by low-temperature drying and evaporation. There is no need for complicated solvent recovery or incineration processes, which significantly reduces the cost of waste liquid treatment and the environmental burden, and is in line with the development concept of green manufacturing.

[0017] This invention discloses a high-temperature solid oxide fuel cell anode slurry and its preparation method. Based on an aqueous solvent system, it enables convenient recycling and reuse of anode raw material waste during the manufacturing process of high-temperature solid oxide fuel cells. The waste only needs to be crushed, mixed with deionized water, stirred, filtered, and degassed to be converted into regenerated slurry. This regenerated slurry can be mixed with fresh slurry and reused in anode preparation, increasing the material utilization rate to over 95% and reducing the overall manufacturing cost by 20% to 40%. Furthermore, through a staged ball milling process and optimized material ratio, the anode slurry prepared by this invention has a solid content of 40% to 70%, a viscosity of 4000 to 7500 mPa·s, a particle size distribution D50 of 0.5 to 5 μm, a porosity of 20% to 50% after sintering, and an electrical conductivity ≥1000 S / cm at 800℃, fully meeting the performance requirements of high-temperature solid oxide fuel cells for anode materials. Attached Figure Description

[0018] Figure 1 This is a flowchart of the preparation method of the present invention. Detailed Implementation

[0019] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0020] Please see Figure 1 The present invention provides a technical solution: A high-temperature solid oxide fuel cell anode slurry and its preparation method are disclosed. The nickel oxide powder has a particle size of 0.5–5 μm and a purity ≥99.5%; the gadolinium-doped cerium oxide powder has a particle size of 0.1–3 μm and a purity ≥99%; the deionized water has a resistivity ≥18 MΩ·cm and a pH value of 6.5–7.5. The ball milling equipment is a planetary ball mill, the grinding jar is made of zirconium oxide, the grinding media is zirconium oxide balls, the ball-to-material ratio is 3:1, and the diameter of the grinding media is 5 mm.

[0021] Example 1 S1: Take 60g of nickel oxide powder, 40g of gadolinium-doped cerium oxide powder (chemical formula: Gd0.2Ce0.8O1.9), and 10g of starch as a pore-forming agent and place them in a ball mill jar. Add 1.5g of isopropanol as a dispersant to 5g of deionized water and stir evenly. Add the stirred mixture to the ball mill jar and ball mill at a speed of 200rpm for 2 hours to obtain mixture A.

[0022] S2: Add 30% polyacrylic acid solution (35g) as binder, 2g polyethylene glycol (PEG600) as plasticizer, 5g glycerol as wetting agent, and 10g deionized water to mixture A. Ball mill the mixture at 200rpm for 1 hour to obtain mixture B.

[0023] S3: Add 0.5g sodium dodecyl sulfate as a surfactant and 0.5g tributyl phosphate as a defoaming agent to mixture B, add 5g deionized water and stir evenly, then add to a ball mill jar and ball mill at 200 rpm for 24 hours to obtain mixture C.

[0024] S4: Filter mixture C using a 200-mesh filter under negative pressure to remove large, uncrushed powder particles and impurities, and obtain mixture D.

[0025] S5: Mixture D was subjected to vacuum degassing at a vacuum level of -0.09 MPa for 4 hours, with intermittent stirring at 30 rpm during the degassing process, to obtain a high-temperature solid oxide fuel cell anode slurry. The slurry viscosity was measured to be 5200 mPa·s, the solid content to be 55%, and the particle size distribution D50 to be 1.2 μm.

[0026] Example 2 S1: Take 50g of nickel oxide powder, 50g of gadolinium-doped cerium oxide powder (chemical formula: Gd0.2Ce0.8O1.9), and 10g of starch as a pore-forming agent and place them in a ball mill jar. Add 1.5g of isopropanol as a dispersant to 5g of deionized water and stir evenly. Add the stirred mixture to the ball mill jar and ball mill at a speed of 100rpm for 4 hours to obtain mixture A.

[0027] S2: Add 30% polyacrylic acid solution (35g) as binder, 2g polyethylene glycol (PEG600) as plasticizer, 5g glycerol as wetting agent, and 10g deionized water to mixture A. Ball mill the mixture at 100rpm for 2 hours to obtain mixture B.

[0028] S3: Add 0.5g sodium dodecyl sulfate as a surfactant and 0.5g tributyl phosphate as a defoaming agent to mixture B, add 5g deionized water and stir evenly, then add to a ball mill jar and ball mill at 100 rpm for 24 hours to obtain mixture C.

[0029] S4: Filter mixture C using a 300-mesh filter under negative pressure to obtain mixture D.

[0030] S5: Mixture D was subjected to vacuum degassing at a vacuum level of -0.09 MPa for 4 hours to obtain a high-temperature solid oxide fuel cell anode slurry. The slurry viscosity was measured to be 4850 mPa·s, the solid content to be 53%, and the particle size distribution D50 to be 1.5 μm.

[0031] Example 3 S1: Take 60g of nickel oxide powder, 40g of gadolinium-doped cerium oxide powder (chemical formula: Gd0.1Ce0.9O1.95), and 10g of polymethyl methacrylate (PMMA) as pore-forming agents and place them in a ball mill jar. Add 1.5g of isopropanol as a dispersant to 5g of deionized water and stir evenly. Add the stirred mixture to the ball mill jar and ball mill at a speed of 200rpm for 4 hours to obtain mixture A.

[0032] S2: Add 30% polyacrylic acid solution (35g) as binder, 2g polyethylene glycol (PEG600) as plasticizer, 5g glycerol as wetting agent, and 10g deionized water to mixture A. Ball mill the mixture at 200rpm for 2 hours to obtain mixture B.

[0033] S3: Add 0.5g sodium dodecyl sulfate as a surfactant and 0.5g tributyl phosphate as a defoaming agent to mixture B, add 5g deionized water and stir evenly, then add to a ball mill jar and ball mill at 200 rpm for 72 hours to obtain mixture C.

[0034] S4: Filter mixture C using a 500-mesh filter under negative pressure to obtain mixture D.

[0035] S5: Mixture D was subjected to vacuum degassing at a vacuum level of -0.098 MPa for 12 hours to obtain a high-temperature solid oxide fuel cell anode slurry. The slurry viscosity was measured to be 6100 mPa·s, the solid content to be 58%, and the particle size distribution D50 to be 0.9 μm.

[0036] Example 4 S1: Take 55g of nickel oxide powder, 45g of gadolinium-doped cerium oxide powder (chemical formula: Gd0.1Ce0.9O1.95), and 6g of polymethyl methacrylate (PMMA) as pore-forming agents and place them in a ball mill jar. Add 1.5g of isopropanol as a dispersant to 5g of deionized water and stir evenly. Add the stirred mixture to the ball mill jar and ball mill at a speed of 120rpm for 4 hours to obtain mixture A.

[0037] S2: Add 30% polyacrylic acid solution (35g) as binder, 2g polyethylene glycol (PEG600) as plasticizer, 5g glycerol as wetting agent, and 10g deionized water to mixture A. Ball mill the mixture at 120rpm for 2 hours to obtain mixture B.

[0038] S3: Add 0.5g sodium dodecyl sulfate as a surfactant and 0.5g tributyl phosphate as a defoaming agent to mixture B, add 5g deionized water and stir evenly, then add to a ball mill jar and ball mill at 120 rpm for 48 hours to obtain mixture C.

[0039] S4: Filter mixture C using a 300-mesh filter under negative pressure to obtain mixture D.

[0040] S5: Mixture D was subjected to vacuum degassing at a vacuum level of -0.098 MPa for 24 hours to obtain a high-temperature solid oxide fuel cell anode slurry. The slurry viscosity was measured to be 5650 mPa·s, the solid content to be 56%, and the particle size distribution D50 to be 1.1 μm.

[0041] Example 5 500g of scrap and defective green blanks generated during the casting process of high-temperature solid oxide fuel cells were collected. The waste was crushed to a particle size ≤3 mm, and 500ml of deionized water was added. The mixture was dispersed at 300rpm for 2 hours. The dispersed slurry was then filtered through a 200-mesh screen to remove impurities. The filtered slurry was then subjected to vacuum degassing at -0.095MPa for 6 hours to obtain regenerated slurry.

[0042] The recycled slurry was mixed with the fresh anode slurry prepared in Example 1 at a 1:1 mass ratio. After stirring and dispersing, the mixture was used for casting to prepare green anode tapes. Testing showed that the viscosity, solid content, and particle size distribution of the mixed recycled and fresh slurries were essentially the same as those of the slurry in Example 1. The quality of the cast anode tapes was good, with a porosity of 32% and an electrical conductivity of 1120 S / cm at 800°C, comparable to the performance of anodes prepared using pure fresh slurry. Through the recycling method of this example, the material utilization rate was increased to 96%, and the overall manufacturing cost was reduced by approximately 30%.

[0043] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely preferred examples and are not intended to limit the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the present invention as claimed. The scope of protection of the present invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a high-temperature solid oxide fuel cell anode slurry, characterized in that, Includes the following steps: S1: Nickel oxide powder, gadolinium-doped cerium oxide powder, and a pore-forming agent are placed in a ball mill jar. A dispersant and a solvent are added to the ball mill jar, and the mixture is ball-milled for a first predetermined time period to obtain mixture A. The nickel oxide powder has a particle size of 0.5–5 μm and a purity ≥99.5%; the gadolinium-doped cerium oxide powder has a particle size of 0.1–3 μm and a purity ≥99%; the pore-forming agent is added at 5%–20% of the total mass of the nickel oxide powder and the gadolinium-doped cerium oxide powder; the dispersant is added at 0.5%–5% of the total mass of the nickel oxide powder, gadolinium-doped cerium oxide powder, and the pore-forming agent; and the solvent is added at 30%–80% of the total mass of the nickel oxide powder, gadolinium-doped cerium oxide powder, and the pore-forming agent. S2: Add binder, plasticizer, wetting agent, and solvent to mixture A, and ball mill and mix for a second predetermined time period to obtain mixture B; wherein, the amount of binder added is 5% to 15% of the total mass of the nickel oxide powder and the gadolinium-doped cerium oxide powder; the amount of plasticizer added is 10% to 50% of the mass of the binder; the amount of wetting agent added is 1% to 10% of the total mass of the nickel oxide powder and the gadolinium-doped cerium oxide powder; and the amount of solvent added is 10% to 40% of the total mass of the nickel oxide powder, gadolinium-doped cerium oxide powder, and pore-forming agent. S3: Add a surfactant and a defoaming agent to mixture B, and ball mill the mixture for a third predetermined time period to obtain mixture C; wherein the amount of surfactant added is 0.1% to 2% of the total mass of the nickel oxide powder and the gadolinium-doped cerium oxide powder; the amount of defoaming agent added is 0.1% to 2% of the total mass of the nickel oxide powder and the gadolinium-doped cerium oxide powder; S4: Filter mixture C to remove large, uncrushed powder particles and any impurities that may have been mixed in, to obtain mixture D; S5: Vacuum degassing treatment is performed on mixture D to remove air bubbles from the slurry and adjust the viscosity of the slurry to a predetermined range to obtain high-temperature solid oxide fuel cell anode slurry; The solvent is deionized water, which has a resistivity ≥18 MΩ·cm and a pH value of 6.5~7.

5.

2. The method for preparing high-temperature solid oxide fuel cell anode slurry according to claim 1, characterized in that, The gadolinium-doped cerium oxide powder has the chemical formula GdaCebO2-X; where a+b=1, a ranges from 0.05 to 0.3, b ranges from 0.7 to 0.95, and X ranges from 0 to 0.

5. Preferably, a ranges from 0.1 to 0.2, and b ranges from 0.8 to 0.

9. The mass ratio of the nickel oxide powder to the gadolinium-doped cerium oxide powder is (40-70):(30-60). Preferably, the mass ratio of the nickel oxide powder to the gadolinium-doped cerium oxide powder is (50-60):(40-50). The pore-forming agent... The amount of the added agent is 5% to 15% of the total mass of the nickel oxide powder and the gadolinium-doped cerium oxide powder. The pore-forming agent is selected from one or more of starch, polymethyl methacrylate, graphite powder, cellulose, polyvinyl butyral, polyethylene glycol, and polystyrene microspheres. The particle size of the pore-forming agent is 0.5 to 10 μm. The dispersant is selected from one or more of isopropanol, ethanol, polyethylene glycol, ammonium polyacrylate, polyvinylpyrrolidone, sodium polyacrylate, and sodium dodecyl sulfate. The amount of the dispersant added is 1% to 3% of the total mass of the nickel oxide powder, gadolinium-doped cerium oxide powder, and the pore-forming agent.

3. The method for preparing high-temperature solid oxide fuel cell anode slurry according to claim 1, characterized in that, In step S1, the ball mill rotates at a speed of 80–250 rpm, preferably 100–200 rpm, and the first predetermined time period is 1–8 hours, preferably 2–6 hours. In step S2, the ball mill rotates at a speed of 80–250 rpm, preferably 100–200 rpm, and the second predetermined time period is 0.5–5 hours, preferably 1–3 hours. In step S3, the ball mill rotates at a speed of 80–250 rpm, preferably 100–200 rpm, and the third predetermined time period is 12–96 hours, preferably 24–72 hours. The ball milling and mixing in steps S1, S2, and S3 are all carried out at room temperature. The ball mill jar is made of one of zirconium oxide, polyurethane, nylon, or stainless steel. The grinding media are zirconium oxide balls or alumina balls with a diameter of 3–20 mm and a ball-to-material ratio of (1–5):

1.

4. The method for preparing high-temperature solid oxide fuel cell anode slurry according to claim 1, characterized in that, In step S2, the binder is selected from one or more of polyacrylic acid, polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, ethyl cellulose, polymethyl methacrylate, and polyurethane, and is added in solution form with a solution concentration of 10% to 50%; the plasticizer is selected from one or more of polyethylene glycol, dibutyl phthalate, dioctyl phthalate, glycerin, tributyl citrate, and dibutyl sebacate, and the amount of plasticizer added is 15% to 40% of the mass of the binder; the wetting agent is selected from one or more of glycerol, ethylene glycol, butanediol, polyoxyethylene ether, polyethylene glycol octylphenyl ether, and sodium dodecylbenzenesulfonate, and the amount of wetting agent added is 2% to 8% of the total mass of the nickel oxide powder and the gadolinium-doped cerium oxide powder.

5. The method for preparing high-temperature solid oxide fuel cell anode slurry according to claim 1, characterized in that, In S3, the surfactant is selected from one or more of sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, polyoxyethylene sorbitan monooleate, octylphenol polyoxyethylene ether, hexadecyltrimethylammonium bromide, and polyethylene glycol octylphenyl ether; the defoamer is selected from one or more of tributyl phosphate, polydimethylsiloxane, polyoxypropylene glycerol ether, polyethylene glycol fatty acid ester, mineral oil, and silicone defoamer; the surfactant and defoamer are pre-dissolved in deionized water before addition to form a premixed solution with a concentration of 5% to 20%.

6. The method for preparing high-temperature solid oxide fuel cell anode slurry according to claim 1, characterized in that, In step S4, the filtration process employs one of the following methods: negative pressure filtration, centrifugal filtration, vibrating sieving filtration, or pressure filtration. The mesh size of the filter used during filtration is 80–600 mesh, preferably 100–500 mesh. In step S5, the vacuum degree of the vacuum degassing process is -0.08–-0.1 MPa, preferably -0.09–-0.1 MPa, and the vacuum degassing time is 2–30 hours, preferably 4–24 hours. During the vacuum degassing process, intermittent stirring or continuous slow stirring is performed at a stirring speed of 10–50 rpm. After the vacuum degassing process, the viscosity, solid content, and particle size distribution of the slurry are tested. The viscosity of the slurry is adjusted to 3000–8000 mPa·s, preferably 4000–7500 mPa·s, the solid content of the slurry is 40%–70%, and the particle size distribution D50 of the slurry is 0.5–5 μm.

7. The method for preparing high-temperature solid oxide fuel cell anode slurry according to claim 1, characterized in that, The pore-forming agent is starch or polymethyl methacrylate; the dispersant is isopropanol; the binder is polyacrylic acid; the plasticizer is polyethylene glycol; the wetting agent is glycerol; the surfactant and defoamer are added simultaneously; the surfactant is sodium dodecyl sulfate, and the defoamer is tributyl phosphate; the mass ratio of nickel oxide powder to gadolinium-doped cerium oxide powder is 60:40 or 50:50; the amount of pore-forming agent added is the ratio of nickel oxide powder to gadolinium-doped cerium oxide powder. The amount of cerium oxide powder is 10% of the total mass; the amount of dispersant is 1.5% to 2.5% of the total mass of nickel oxide powder, gadolinium-doped cerium oxide powder, and pore-forming agent; the amount of binder is 10% to 12% of the total mass of nickel oxide powder and gadolinium-doped cerium oxide powder; the amount of plasticizer is 20% to 30% of the mass of binder; and the amount of wetting agent is 3% to 6% of the total mass of nickel oxide powder and gadolinium-doped cerium oxide powder.

8. A high-temperature solid oxide fuel cell anode slurry, characterized in that, The anode slurry is prepared by the method described in any one of claims 1 to 7 for high-temperature solid oxide fuel cell anode slurry; the anode slurry uses deionized water as a solvent and contains nickel oxide, gadolinium-doped cerium oxide, pore-forming agent, dispersant, binder, plasticizer, wetting agent, surfactant and defoamer; the anode slurry has a solid content of 40% to 70%, a particle size distribution D50 of 0.5 to 5 μm, a viscosity of 4000 to 7500 mPa·s, a pH value of 6.5 to 8.5, a viscosity of 5000 to 6500 mPa·s at 25°C, and a shear thinning index of 0.3 to 0.

8.

9. The high-temperature solid oxide fuel cell anode slurry according to claim 8, characterized in that, The anode slurry is used to prepare anode supports or anode functional layers through processes such as casting, screen printing, spraying, dip coating, scraping, or spin coating. After the anode slurry is formed, it is dried and sintered. The drying temperature is 60-120℃ and the drying time is 2-12 hours. The sintering temperature is 1200-1400℃ and the sintering time is 2-6 hours to obtain a porous anode structure. The porosity of the porous anode structure is 20%-50%, the pore size distribution is 0.5-5μm, and the electrical conductivity is ≥1000 S / cm at 800℃.

10. The method for preparing high-temperature solid oxide fuel cell anode slurry according to claim 1, characterized in that, The method is also applicable to the recycling and reuse of anode raw material waste generated during the manufacturing process of high-temperature solid oxide fuel cells. The waste includes one or more of the following: scraps generated during the casting process, substandard green blanks, unsintered anode sheets after drying, and residues from slurry conveying pipelines. The specific steps for recycling and reuse include: crushing or pulverizing the waste to a particle size ≤ 5 mm, adding deionized water for stirring and dispersion at a stirring speed of 200–500 rpm for 1–4 hours, filtering through a 100–300 mesh filter to remove impurities, and then performing vacuum degassing treatment at a vacuum degree of -0.09–-0.1 MPa for 2–12 hours to obtain regenerated slurry. The regenerated slurry is then mixed with freshly prepared anode slurry in any proportion and reused for anode preparation.

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