Electrode catalyst of solid oxide fuel cell suitable for sulfur-containing fuel

Abstract

The invention belongs to the technical field of solid oxide fuel cells, and particularly relates to an electrode catalyst of a solid oxide fuel cell suitable for sulfur-containing fuel. The NiMo-YSZ electrode catalyst with the straight hole and spherical hole composite structure is prepared through a tape casting-phase conversion method and a vacuum-assisted impregnation process; the mass transfer efficiency and the specific surface area are improved by a composite pore structure in the obtained catalyst, and Mo actively captures sulfur by virtue of dual mechanisms of surface selective adsorption and bulk phase chemical sulfur fixation and can be dynamically regenerated. H2S can be reduced from 120 ppm to 14 ppm, and the removal rate reaches 88%; when the catalyst is operated in sulfur-containing hydrogen and methanol for 300 hours, the performance stability is respectively improved by 160% and 125%, the decline rate is as low as 0.4 mV / h, 98% of initial performance is regenerated and recovered, the tradeoff bottleneck of'activity-stability 'is broken through, and reliable support is provided for efficient and stable application of sulfur-containing hydrocarbon fuel SOFC (solid oxide fuel cell).

Description

Technical Field

[0001] This invention belongs to the field of solid oxide fuel cell technology, and specifically relates to an electrode catalyst suitable for solid oxide fuel cells containing sulfur fuels. Background Technology

[0002] Solid oxide fuel cells (SOFCs), as highly efficient electrochemical energy conversion devices, possess significant advantages such as high energy conversion efficiency, environmental friendliness, and wide fuel adaptability. SOFCs operate in a temperature range of 500-800°C, allowing for extremely flexible fuel selection—they can use not only pure hydrogen directly but also inexpensive and readily available hydrocarbon fuels such as natural gas, coal gas, and light alkanes. Compared to pure hydrogen, hydrocarbons have approximately three times the volumetric energy density, and operating costs can be reduced by 40%-60%. This characteristic allows SOFCs to significantly improve energy efficiency and economy while eliminating dependence on pure hydrogen. Therefore, developing SOFC technology using hydrocarbons as fuel is of significant practical importance for promoting the commercial application of this energy system.

[0003] During the operation of SOFCs, the anode must simultaneously meet the comprehensive requirements of chemical stability, structural stability, and electrocatalytic performance stability under operating conditions. However, compared with hydrogen fuel systems, the application of hydrocarbon fuels places more stringent requirements on the performance of SOFC anodes: trace sulfur impurities in hydrocarbons (such as ppm-level hydrogen sulfide, H2S) can significantly weaken the electrochemical catalytic activity and long-term stability of nickel (Ni)-based anodes, leading to anode sulfide poisoning. This has become one of the key bottlenecks restricting the large-scale application of SOFC technology.

[0004] Nickel (Ni)-based anodes have become the mainstream anode material for solid oxide fuel cells (SOFCs) due to their high electronic conductivity and excellent electrochemical catalytic activity. However, their high catalytic activity also makes them susceptible to trace sulfur impurities such as ppm-level H2S in hydrocarbon fuels, leading to sulfur poisoning and performance degradation. Current research has clarified that sulfur poisoning in Ni-based anodes mainly occurs through two mechanisms: two-dimensional surface adsorption and three-dimensional bulk sulfidation. Regarding the two-dimensional surface adsorption mechanism, H2S molecules are chemically adsorbed and dissociated on the surface of Ni active sites, forming adsorbed sulfur species such as S*, which directly inhibit the charge transfer process of the fuel oxidation reaction after covering the catalytic active center. To address this mechanism, researchers have proposed doping Ni with a second metal such as Cu or Co to form Ni... 1-x M xAlloy anodes (such as Chinese invention patents CN1443380A and CN113745541B). This strategy leverages the Ni-M intermetallic synergistic effect to modulate the Ni electronic structure, thereby reducing the H2S adsorption energy and inhibiting its surface adsorption and dissociation, thus improving sulfur tolerance. However, such alloys generally suffer from the problem of balancing electrochemical activity and long-term stability—excessive doping enhances sulfur tolerance but sacrifices the intrinsic catalytic activity of Ni; low doping levels cannot effectively suppress sulfur adsorption. Regarding the three-dimensional bulk sulfidation mechanism, sulfur atoms diffuse into the Ni lattice, forming NiS with Ni. x Bulk sulfides (x=1, 2) lead to lattice distortion, decreased electronic conductivity, and irreversible loss of catalytic activity in the anode. To address this mechanism, researchers have turned to developing Ni-free composite oxide anodes to fundamentally avoid NiS formation. x Inert products are formed. Representative materials include perovskite structures (such as La). 1-x Sr x Cr 1-y Mn y O 3-δ ), double perovskite structure (such as Sr2Mg) 2- x Mo x O 6-δ CeO2-based oxides (such as Chinese invention patents CN102593467B, CN114300722A, and CN113526547A) significantly improve sulfur resistance through the participation of lattice oxygen in the oxidation reaction. However, the electronic conductivity (typically <100 S / cm) and catalytic activity of these materials are much lower than those of metallic Ni-based anodes (conductivity >10 S / cm). 4 The power density (S / cm) is insufficient to meet the requirements of high power density SOFCs.

[0005] In summary, current research largely focuses on improving the sulfur resistance of SOFC anodes by inhibiting sulfur species adsorption or avoiding the formation of sulfide products, but has not yet achieved synergistic optimization of electrochemical activity and stability. Therefore, to address the issues of insufficient chemical catalytic performance and poor structural stability faced by existing internally catalytically reformed solid oxide fuel cells (SOFCs) in sulfur-containing hydrocarbon fuels, there is an urgent need to develop novel SOFC anode catalysts that combine high catalytic activity with high structural stability. Summary of the Invention

[0006] To overcome the shortcomings of the existing technology, this invention proposes a NiMo-YSZ anode design scheme with a straight pore + spherical pore structure: by controlling the composition of the anode catalyst (constructing a NiMo alloy and YSZ composite system) and optimizing the pore structure of the catalyst layer (using a straight pore + spherical pore design to improve mass transfer efficiency), a catalyst layer-supported SOFC single cell with both high catalytic activity and high structural stability is finally prepared, so as to solve the problems of insufficient chemical catalytic performance and poor structural stability faced by existing internal catalytic reforming solid oxide fuel cell (SOFC) single cells in sulfur-containing hydrocarbon fuels.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is as follows: The first aspect of this invention provides a method for preparing a SOFC single cell, the method comprising the following steps: S1. Preparation of electrode catalyst: S11. Mix NiO powder with YSZ powder and polymethyl methacrylate (PMMA) microspheres, add to solvent-binder system to make slurry, then cast the slurry onto the substrate surface, immerse the substrate in water, and initiate phase separation through solvent exchange to form a NiO-YSZ green film with oriented microchannel pore structure. S12. After phase separation, the NiO-YSZ green film is shaped and then calcined to remove organic components, thereby obtaining a porous NiO-YSZ support, i.e., an electrode catalyst. S2, Fabrication of the functional layer of a single cell: S21. A NiO-YSZ slurry is prepared by means of a powder component and an organic carrier system, wherein the powder component contains NiO powder and YSZ powder, and the organic carrier system is composed of α-terpineol, ethanol (Aladdin Chemistry Co. Ltd.) and B73210 binder (Ferro Electronics Materials); S22. The slurry of S21 is coated onto the surface of the electrode catalyst prepared in S1 by spin coating to form a NiO-YSZ anode functional layer. Then, a dense YSZ electrolyte layer is deposited on the surface of the anode functional layer by the same spin coating process. After each layer is coated, it is calcined at 600-800 ℃ for 20-40 minutes. S23. After assembly, co-fire at 1200-1500 ℃ in air for 3-6 hours, then use screen printing technology to sequentially prepare Ce on the electrolyte surface. 0.9 Gd 0.1 O 1.95 isolation layer and La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ cathode; S3. Introducing Mo: A vacuum-assisted impregnation method is used to impregnate the porous NiO-YSZ support after the preparation of the functional layer of the single cell with a molybdenum (Mo) precursor solution, thereby introducing molybdenum into the porous structure of the support, and finally forming a porous MoNi-YSZ support in the SOFC single cell, thus obtaining the SOFC single cell.

[0008] Preferably, in S11, the composition of the NiO powder, YSZ powder, and polymethyl methacrylate (PMMA) microspheres, by mass fraction, is as follows: NiO powder 50-60 wt.%, YSZ powder 30-40 wt.%, polymethyl methacrylate (PMMA) microspheres 7-15 wt.

[0009] Preferably, in S11, the solvent-binder system is composed of polyethersulfone (PESF, Amerco Performance Radel A-300), polyvinylpyrrolidone (PVP, Sigma-Aldrich), and 1-methyl-2-pyrrolidone.

[0010] Preferably, the solid content in the slurry in S11 is 40-60 wt.%.

[0011] Preferably, in S12, the calcination temperature is 900-1200 ℃ and the time is 2-5 hours.

[0012] Preferably, in S3, the molybdenum precursor solution is 0.3-1.0 mol / L ammonium heptamolybdate tetrahydrate ((NH4)6Mo7O). 24 Aqueous solution of 4H2O.

[0013] Preferably, in S3, the impregnation treatment is carried out under reduced pressure of 0.1-0.3 atm.

[0014] Preferably, in S3, based on the NiMo metallic phase, the Mo loading in the porous MoNi-YSZ support is 5%-50%wt.

[0015] Preferably, step S21 specifically involves: preparing a NiO-YSZ slurry with 15-20 wt.% powder component and 80-90 wt.% organic carrier system, wherein the powder component contains 7-9 wt.% NiO powder and 7-9 wt.% YSZ powder, and the organic carrier system consists of 30-35 wt.% α-terpineol, 20-30 wt.% ethanol and 20-30 wt.% B73210 binder.

[0016] Preferably, after the S3 impregnation treatment, the sample needs to be calcined in an air atmosphere at 600-800 ℃ for 1-3 hours.

[0017] The second aspect of the present invention also provides an SOFC single cell prepared using the preparation method described in the first aspect.

[0018] The third aspect of the present invention also provides the application of the SOFC single cell described in the second aspect in the preparation of sulfur-containing fuel solid oxide fuel cells.

[0019] The application scheme of this invention has the following core advantages: (1) Multi-dimensional regulation strategy: From material composition and microstructure to preparation process, synergistic optimization is achieved, breaking through the traditional anode "activity-stability" trade-off relationship; (2) Advantages of straight pore + spherical pore structure: The straight pore structure reduces mass transfer resistance by shortening the fuel diffusion path, significantly improving the transport efficiency of H2, hydrocarbon fuels and sulfur species (such as H2S) in the catalyst layer; the spherical pore structure increases the specific surface area of ​​the anode catalyst layer, providing sufficient space for the uniform dispersion and high loading of NiMo active components, and increasing the density of catalytic active sites per unit volume. The "high efficiency mass transfer-anti-clogging" characteristics of the straight pore and the "high specific surface area-active loading" advantages of the spherical pore complement each other, solving the problem of insufficient specific surface area of ​​a single straight pore and avoiding the defect of excessive mass transfer resistance of a single spherical pore, ultimately achieving a comprehensive improvement in the catalytic activity, sulfur tolerance and long-term stability of SOFC anode in sulfur-containing hydrocarbon fuels. (3) NiMo-YSZ synergistic effect: NiMo alloy provides high catalytic activity, while YSZ (yttrium-stabilized zirconium oxide) serves as the electrolyte framework to enhance structural stability and ion conduction capacity. The two work together to ensure the long-term stable operation of the battery in sulfur-containing hydrocarbon fuels.

[0020] Compared with the prior art, the beneficial effects of the present invention are: This application utilizes a casting-phase inversion method combined with a vacuum-assisted impregnation process to prepare a NiMo-YSZ anode catalyst with a composite structure of straight and spherical pores. The resulting catalyst possesses both unique structure and excellent properties: the composite pore structure synergistically enhances mass transfer efficiency and specific surface area; the NiMo alloy provides high catalytic activity; and Mo actively captures sulfur species through a dual mechanism of "surface selective adsorption + bulk chemical sulfur fixation," and can achieve dynamic desulfurization and regeneration with the aid of an oxygen source. Simultaneously, its performance advantages are significant, reducing the H2S content in fuel from 120 ppm to 14 ppm, achieving a removal rate of 88%. After 300 hours of operation in sulfur-containing H2 or methanol systems, its performance stability improves by 160% and 125%, respectively, with an electrochemical performance degradation rate as low as 0.4 mV / hour. After regeneration, it can recover 98% of its initial performance, breaking through the traditional technology's "activity-stability" trade-off bottleneck and providing reliable support for the efficient and stable application of sulfur-containing hydrocarbon fuel SOFCs. Therefore, compared with the prior art (which uses catalytic inert materials to improve the sulfur poisoning resistance of the anode), the anode catalyst provided by the present invention protects the metal Ni-based anode by actively absorbing sulfur, which is beneficial to obtaining SOFC anodes with both excellent electrochemical catalytic activity and stability. Attached Figure Description

[0021] Figure 1 The process flow diagram for the casting-phase transformation of YSZ support with straight holes and spherical holes is shown.

[0022] Figure 2 SEM images of different pore structures of porous NiO-YSZ carrier: (a) Anode prepared by conventional method: randomly distributed irregular pores, (b) Anode prepared by conventional method: randomly distributed spherical pores, (c) Anode prepared in Example 1: arranged microporous channels, (d) High-magnification image of arranged microporous channels of anode prepared in Example 1, (e) Anode prepared in Example 2: combination of arranged microporous channels and spherical pores, (f) High-magnification image of arranged microporous channels of anode prepared in Example 2.

[0023] Figure 3 The current-voltage relationship curves of SOFC single cells with different pore morphologies at 750℃ and in an atmosphere of 50% H2-50% N2 are shown (Example 1 is referred to as Example 1, Example 2 is referred to as Example 2, and subsequent examples are represented in the same way).

[0024] Figure 4 This is a graph showing the adsorption capacity of the anode for H2S under different pore structures.

[0025] Figure 5 This is a graph showing the adsorption capacity of Mo content in the anode metal NiMo for H2S.

[0026] Figure 6The effect of Mo on the regeneration performance of NiO-YSZ catalyst.

[0027] Figure 7 The performance stability of SOFC single cells with NiO-YSZ and MoNi-YSZ as anode layers was studied in an environment containing 120 ppm H2S hydrogen.

[0028] Figure 8 The performance stability of SOFC single cells with NiO-YSZ and MoNi-YSZ as anode layers in methanol containing 120 ppm H2S was investigated. Detailed Implementation

[0029] The specific embodiments of the present invention will be further described below. It should be noted that these descriptions are for the purpose of aiding understanding the present invention, but do not constitute a limitation thereof. Furthermore, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0030] Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods, and the experimental materials used in the following embodiments are all available through conventional commercial channels.

[0031] To alleviate sulfur poisoning, researchers both domestically and internationally are actively developing sulfur-resistant anode materials. Current main research directions and progress are as follows: 1) Research on metal-modified nickel-based anodes: One core approach is to replace nickel with sulfur-inert metals (iron, cobalt, copper, etc.) to reduce sulfur reactivity. Copper has attracted significant attention due to its lower sulfur adsorption energy (-80 kJ / mol, compared to -160 kJ / mol for nickel) and its inertness to hydrogen sulfide cracking. Single cells based on copper-modified anodes exhibit excellent stability at high hydrogen sulfide concentrations (up to 500 ppm), but the low electrochemical activity of copper limits the battery's output power density, and its low melting point easily leads to particle coarsening during long-term operation. Research on nickel alloy catalysts is also progressing simultaneously. Alloying nickel with metals such as cobalt and iron, which have low affinity for sulfur, can improve sulfur resistance to some extent, but sulfur-induced deactivation still exists during long-term operation, failing to completely solve the sulfur poisoning problem. Despite significant progress in metal-modified nickel-based anodes, practical applications are still limited by challenges such as insufficient sulfur resistance stability and long-term performance degradation. 2) Protective coating strategy for nickel anode surfaces: Coating the nickel surface with a thin, uniform oxide layer such as cerium dioxide or niobium oxide can reduce sulfur adsorption and prevent direct formation of nickel-sulfur bonds, improving tolerance to high hydrogen sulfide environments. However, these oxides are mostly electrically insulating, and excessive coating thickness will increase resistance; over-coverage can also limit the active area of ​​nickel, hinder gas transport, and lead to decreased catalytic activity and loss of initial performance. 3) Development of nickel-free conductive oxide anodes: La 1- xSr x Cr 1-y Mn y O 3-δ (LSCM), Strontium titanate compounds and Sr2M 2-x Mo x O 6-δ Nickel-free anode materials (such as those containing Ti, Mg, and Fe) exhibit superior chemical stability and resistance to sulfur poisoning in reducing environments. However, compared to nickel-based anodes, their catalytic activity is insufficient (especially in hydrocarbon fuel systems), and their poor electronic conductivity leads to increased ohmic losses, thus limiting battery performance.

[0032] In summary, current research often mitigates sulfidation problems at the expense of initial electrochemical performance. Addressing the shortcomings of existing research, this invention proposes a solution to anodic sulfur poisoning from the perspective of controllable sulfur absorption and desulfurization: leveraging the multi-valence variable properties of Mo-based catalysts, dynamic control of sulfur poisoning can be achieved by dynamically regulating the adsorption-sulfur fixation-oxidation-desorption process of sulfur species. Accordingly, this invention proposes a novel strategy: utilizing the chalcophilic material molybdenum to actively adsorb H2S in a sulfur-polluted environment, preferentially capturing sulfur over nickel to protect the nickel active sites of the Ni-YSZ anode. Simultaneously, the generated layered MoS... x The phase not only has a high sulfur adsorption capacity, but also has structural reversibility, and its catalytic function can be restored through regeneration after sulfidation.

[0033] The molybdenum-modified Ni-YSZ anode with a hybrid straight-hole + round-hole structure designed in this invention can reduce the H2S content in the fuel stream by 88% (from 120 ppm to 14 ppm). In a hydrogen or methanol system containing 120 ppm H2S, after 300 hours of cyclic poisoning-regeneration testing, its performance stability is improved by 160% and 125%, respectively, and the electrochemical performance degradation rate is reduced to 0.4 mV / hour. This dynamically regenerable design combines high electrochemical performance with strong sulfur resistance, providing a feasible path for the practical application of high-sulfur hydrocarbon fuel SOFCs.

[0034] The specific design concept is as follows: (1) Two-dimensional surface adsorption regulation mechanism By modifying metallic Ni with Mo to prepare composite catalysts, the surface adsorption energy can be adjusted by relying on the electronic effect of Mo to achieve selective adsorption of sulfur: the 4d orbital of Mo forms a stronger interaction with the 3p orbital of S, weakening the hybridization effect of Ni-3d and S-3p, promoting the preferential adsorption of sulfur species such as H2S on the active sites of Mo, and reducing the poisoning of Ni catalytic centers; at the same time, it inhibits sulfur dissociation: the introduction of Mo can increase the dissociation energy barrier of H2S on the catalyst surface, reduce the surface diffusion rate of sulfur atoms, and further protect the electrochemical active sites of Ni.

[0035] (2) Three-dimensional bulk sulfurization regulation mechanism At SOFC operating temperatures of 500-800℃, Mo can react with sulfur species to form MoS. x Layered sulfides achieve long-term sulfur capture through chemical intercalation. Layered MoS₂ x Sulfur atoms can be accommodated through lattice expansion, preventing the formation of NiS. x The reaction produces inert catalytic products and is reversible, allowing sulfides to decompose again under oxygen-rich conditions, laying the foundation for subsequent desulfurization and regeneration. Its advantages lie in the fact that, compared to traditional alloying or composite oxide strategies, Mo-based catalysts utilize a dual pathway of "surface selective adsorption + bulk chemical sulfur fixation" to improve sulfur resistance while maintaining high catalytic activity, thus overcoming the trade-off between "activity and stability."

[0036] (3) Dynamic desulfurization function of Mo-based catalyst: oxygen source-driven oxidation and regeneration of sulfur species In the SOFC anode reaction, products such as H2O and CO2 increase the local oxygen partial pressure. Mo-based catalysts can utilize this environmental characteristic to trigger catalytic desulfurization and regeneration. The oxygen source capture mechanism is due to the variable valence characteristics of Mo (e.g., Mo2O2). 4+ / Mo 6+ (Circulation) enables it to efficiently activate O in the anolyte environment. 2- OH - Oxygen species, activated oxygen oxidizes adsorbed sulfur or bulk sulfides into gaseous products such as SO2, which are then discharged from the battery system via gas flow. This dynamic process endows Mo-based catalysts with dual capabilities of "sulfur filtration" and "self-repair": it selectively removes sulfur impurities from fuel as a sulfur storage carrier, and achieves dynamic sulfur management through in-situ oxidation, eliminating the need for additional desulfurization devices.

[0037] In general, the catalyst layer mixed pore supported SOFC single cell provided by the present invention includes the following two parts: (1) Preparation of straight-pore-spherical-pore catalyst support ( Figure 1 First, a NiO-YSZ ceramic matrix with a straight-pore-spherical pore composite structure was prepared by using a casting-phase inversion method with polymethyl methacrylate (PMMA) microspheres as a pore-forming agent. Then, the matrix was treated by solid-state sintering to obtain porous NiO-YSZ ceramic.

[0038] (2) Preparation of porous catalyst layer supported SOFC single cell: NiO-YSZ anode functional layer and dense YSZ electrolyte layer were spin-coated on porous MoNi-YSZ support by spin coating. Then, straight-pore-spherical-pore YSZ supported SOFC half cell was obtained by high-temperature co-firing process. Finally, Ce was prepared on the surface of dense YSZ electrolyte by screen printing process. 0.9 Gd 0.1 O 2-δ isolation layer and La 0.6 Sr0.4 Co 0.2 Fe 0.8 O 3-δ The cathode layer was constructed, ultimately resulting in a SOFC single cell supported by a straight-pore-spherical pore catalytic layer. Finally, Mo was loaded onto the pore wall surface of the porous NiO-YSZ using an impregnation process, ultimately forming a porous MoNi-YSZ support in the SOFC single cell.

[0039] Specifically, the present invention includes the following steps: (1) Preparation of porous NiO-YSZ substrate: 1) Slurry preparation: Mix 50-60 wt.% NiO powder with 30-40 wt.% YSZ powder and 7-15 wt.% PMMA, and add a solvent-binder system composed of polyethersulfone (PESF, Amerco Performance Radel A-300), polyvinylpyrrolidone (PVP, Sigma-Aldrich) and 1-methyl-2-pyrrolidone. Control the solid content of the mixed slurry to be 40-60 wt.%.

[0040] 2) Casting and phase separation: The above slurry is cast onto the surface of a glass plate, and then the glass plate is immersed in water. Phase separation is initiated through solvent exchange to form a NiO-YSZ green film with a directional microchannel pore structure.

[0041] 3) Green blank forming: The NiO-YSZ green blank film after phase separation is punched into circular samples.

[0042] 4) Calcination treatment: Place the sample in a high-temperature furnace and calcine at 900-1200 ℃ for 2-5 hours to completely remove organic components (PESF, PVP, PMMA, etc.) and obtain a porous NiO-YSZ support.

[0043] (2) Fabrication of functional layers in single-cell cells: 1) Preparation of NiO-YSZ slurry: NiO-YSZ slurry was prepared with 15-20 wt.% powder component and 80-90 wt.% organic carrier system, wherein the powder component contained 7-9 wt.% NiO and 7-9 wt.% YSZ powder, and the organic carrier system consisted of 30-35 wt.% α-terpineol, 20-30 wt.% ethanol (Aladdin Chemistry Co. Ltd.), and 20-30 wt.% B73210 binder (Ferro Electronics Materials).

[0044] 2) Spin-coating NiO-YSZ anode functional layer: The above slurry is coated onto the surface of the porous NiO-YSZ support by spin coating (2000-5000 rpm, 30-60 seconds).

[0045] 3) Spin-coated YSZ electrolyte layer: A dense YSZ electrolyte layer is deposited on the surface of the anode functional layer using the same spin-coating process.

[0046] 4) Layer-by-layer calcination treatment: After each coating layer is applied, it is calcined at 600-800 ℃ for 20-40 minutes to reduce defects such as cracks and pinholes generated during the sintering process.

[0047] 5) Functional layer co-firing: The assembled functional layers (including the anode functional layer and the electrolyte layer) are co-firing in air at 1200-1500 ℃ for 3-6 hours.

[0048] 6) Screen-printed isolation layer and cathode: Ce is sequentially prepared on the electrolyte surface using screen printing technology. 0.9 Gd 0.1 O 1.95 isolation layer and La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ cathode.

[0049] (3) Introduction of Mo into porous NiO-YSZ substrate: 1) Preparation of precursor solution: Prepare 0.3-1.0 mol / L ammonium heptamolybdate tetrahydrate ((NH4)6Mo7O) 24 Aqueous solution of 4H2O was used as a precursor for the Mo catalyst.

[0050] 2) Vacuum-assisted impregnation: The screen-printed isolation layer and the porous NiO-YSZ substrate after cathode are placed in a vacuum chamber and impregnated under reduced pressure of 0.1-0.3 atm to promote the deep penetration of the precursor solution into the porous structure of the substrate.

[0051] 3) The impregnated samples are calcined in air at 600-800 ℃ for 1-3 hours; 4) Multiple impregnation cycles: By repeating the impregnation process multiple times, the Mo content in the NiMo metal phase in the YSZ substrate is ensured to reach 5-50 wt%.

[0052] The following detailed description, with reference to specific examples, illustrates the anode support NiO-YSZ and its application in SOFC single cells.

[0053] Example 1: Anode support NiO-YSZ (straight hole + Mo-free) and corresponding SOFC single cell (1) Preparation of porous NiO-YSZ support: 1) Slurry preparation: Mix 60 wt.% NiO powder with 40 wt.% YSZ powder (yttrium stabilized zirconium oxide, 8YSZ, i.e., 8 mol% Y2O3 doped ZrO2), and add 16 wt.% of a solvent-binder system consisting of polyethersulfone (PESF, Amerco Performance Radel A-300), 4 wt.% polyvinylpyrrolidone (PVP, Sigma-Aldrich), and 80 wt.% 1-methyl-2-pyrrolidone, so that the solid content of the mixed slurry is 50 wt.%.

[0054] 2) Casting and phase separation: The above slurry is cast onto the surface of a glass plate, and then the glass plate is immersed in deionized water for 2 hours. Phase separation is initiated through solvent exchange, thereby forming a NiO-YSZ green film with a directional microchannel pore structure and a film thickness of 1 mm.

[0055] 3) Green blank forming: The NiO-YSZ green blank film after phase separation is punched into circular samples with a diameter of 21 mm.

[0056] 4) Calcination treatment: The sample is placed in a high-temperature furnace and calcined at 1000 °C for 3 hours to completely remove organic components (PESF, PVP, PMMA, etc.) and finally obtain a porous NiO-YSZ support.

[0057] (2) Preparation of SOFC single cells: 1) Preparation of NiO-YSZ slurry: It is formulated from 17 wt.% powder component and 83 wt.% organic carrier system, wherein the powder component contains 8.5 wt.% NiO powder and 8.5 wt.% YSZ powder, and the organic carrier system consists of 33 wt.% α-terpineol, 25 wt.% anhydrous ethanol (Aladdin Chemistry Co. Ltd.) and 25 wt.% B73210 binder (FerroElectronics Materials).

[0058] 2) Spin-coating NiO-YSZ anode functional layer: The above slurry is coated onto the surface of the porous NiO-YSZ support by spin coating (3000 rpm, 40 seconds), with a thickness of about 20 μm.

[0059] 3) Preparation of YSZ slurry: It is formulated from 17 wt.% YSZ powder and 83 wt.% organic carrier system, wherein the organic carrier system consists of 33 wt.% α-terpineol, 25 wt.% anhydrous ethanol (Aladdin Chemistry Co. Ltd.) and 25 wt.% B73210 binder (Ferro Electronics Materials).

[0060] 4) Spin-coated YSZ electrolyte layer: A dense YSZ electrolyte layer with a thickness of approximately 20 μm is deposited on the surface of the anode functional layer using a spin-coating process.

[0061] 5) Layer-by-layer calcination treatment: After each coating layer is applied, it is calcined at 700 ℃ for 30 minutes to reduce defects such as cracks and pinholes generated during the sintering process.

[0062] 6) Functional layer co-firing: The assembled functional layers (including the anode functional layer and the electrolyte layer) are co-firing at 1400 °C in air atmosphere for 4 hours.

[0063] 7) Screen-printed isolation layer and cathode: Ce is sequentially prepared on the electrolyte surface using screen printing technology. 0.9 Gd 0.1 O 1.95 isolation layer and La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ Cathode (for specific operation details, see the literature "Zhao K, Lu J, LeL, et al. A high-performance intermediate temperature reversible solid oxide cell with a new barrier layer free oxygen electrode[J]. Applied Energy, 2024,361: 122962.").

[0064] Example 2: Anode support NiO-YSZ (straight hole + round hole + Mo-free) and corresponding SOFC single cell (1) Preparation of porous NiO-YSZ support: 1) Slurry preparation: Mix 54 wt.% NiO powder with 36 wt.% YSZ powder and 10 wt.% PMMA, and add 16 wt.% of a solvent-binder system consisting of polyethersulfone (PESF, Amerco Performance Radel A-300), 4 wt.% polyvinylpyrrolidone (PVP, Sigma-Aldrich) and 80 wt.% 1-methyl-2-pyrrolidone to make the solids content of the mixed slurry 50 wt.%.

[0065] 2) Casting and phase separation: The above slurry is cast onto the surface of a glass plate, and then the glass plate is immersed in deionized water. Phase separation is initiated through solvent exchange, thereby forming a NiO-YSZ green film with a directional microchannel pore structure and a film thickness of 1 mm.

[0066] 3) Green blank forming: The NiO-YSZ green blank film after phase separation is punched into circular samples with a diameter of 21 mm.

[0067] 4) Calcination treatment: The green sample is placed in a high-temperature furnace and calcined at 1000 °C for 3 hours to completely remove organic components (PESF, PVP, PMMA, etc.) and finally obtain a porous NiO-YSZ support.

[0068] (2) Preparation of SOFC single cells: 1) Preparation of NiO-YSZ slurry: It is formulated from 17 wt.% powder component and 83 wt.% organic carrier system, wherein the powder component contains 8.5 wt.% NiO powder and 8.5 wt.% YSZ powder, and the organic carrier system consists of 33 wt.% α-terpineol, 25 wt.% anhydrous ethanol (Aladdin Chemistry Co. Ltd.) and 25 wt.% B73210 binder (FerroElectronics Materials).

[0069] 2) Spin-coating NiO-YSZ anode functional layer: The above slurry is coated onto the surface of the porous NiO-YSZ support by spin coating (3000 rpm, 40 seconds), with a thickness of about 20 μm.

[0070] 3) Preparation of YSZ slurry: It is formulated from 17 wt.% YSZ powder and 83 wt.% organic carrier system, wherein the organic carrier system consists of 33 wt.% α-terpineol, 25 wt.% anhydrous ethanol (Aladdin Chemistry Co. Ltd.) and 25 wt.% B73210 binder (Ferro Electronics Materials).

[0071] 4) Spin-coated YSZ electrolyte layer: A dense YSZ electrolyte layer with a thickness of approximately 20 μm is deposited on the surface of the anode functional layer using a spin-coating process.

[0072] 5) Layer-by-layer calcination treatment: After each coating layer is applied, it is calcined at 700 ℃ for 30 minutes to reduce defects such as cracks and pinholes generated during the sintering process.

[0073] 6) Functional layer co-firing: The assembled functional layers (including the anode functional layer and the electrolyte layer) are co-firing at 1400 °C in air atmosphere for 4 hours.

[0074] 7) Screen-printed isolation layer and cathode: Ce is sequentially prepared on the electrolyte surface using screen printing technology. 0.9 Gd 0.1 O 1.95 isolation layer and La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ cathode.

[0075] Example 3: Anode support NiO-YSZ (straight holes + containing 16% Mo) and corresponding SOFC single cell (1) Preparation of porous NiO-YSZ support: 1) Slurry preparation: Mix 60 wt.% NiO powder with 40 wt.% YSZ powder, and add 16 wt.% of a solvent-binder system consisting of polyethersulfone (PESF, Amerco Performance Radel A-300), 4 wt.% polyvinylpyrrolidone (PVP, Sigma-Aldrich) and 80 wt.% 1-methyl-2-pyrrolidone, so that the solid content of the mixed slurry is 50 wt.%.

[0076] 2) Casting and phase separation: The above slurry is cast onto the surface of a glass plate, and then the glass plate is immersed in deionized water. Phase separation is initiated through solvent exchange, thereby forming a NiO-YSZ green film with a directional microchannel pore structure and a film thickness of 1 mm.

[0077] 3) Green blank forming: The NiO-YSZ green blank film after phase separation is punched into circular samples with a diameter of 21 mm.

[0078] 4) Calcination treatment: The green sample is placed in a high-temperature furnace and calcined at 1000 °C for 3 hours to completely remove organic components (PESF, PVP, PMMA, etc.) and finally obtain a porous NiO-YSZ support.

[0079] (2) Preparation of SOFC single cells: 1) Preparation of NiO-YSZ slurry: It is formulated from 17 wt.% powder component and 83 wt.% organic carrier system, wherein the powder component contains 8.5 wt.% NiO powder and 8.5 wt.% YSZ powder, and the organic carrier system consists of 33 wt.% α-terpineol, 25 wt.% anhydrous ethanol (Aladdin Chemistry Co. Ltd.) and 25 wt.% B73210 binder (FerroElectronics Materials).

[0080] 2) Spin-coating NiO-YSZ anode functional layer: The above slurry is coated onto the surface of the porous NiO-YSZ support by spin coating (3000 rpm, 40 seconds), with a thickness of about 20 μm.

[0081] 3) Preparation of YSZ slurry: It is formulated from 17 wt.% YSZ powder and 83 wt.% organic carrier system, wherein the organic carrier system consists of 33 wt.% α-terpineol, 25 wt.% anhydrous ethanol (Aladdin Chemistry Co. Ltd.) and 25 wt.% B73210 binder (Ferro Electronics Materials).

[0082] 4) Spin-coated YSZ electrolyte layer: A dense YSZ electrolyte layer with a thickness of approximately 20 μm is deposited on the surface of the anode functional layer using a spin-coating process.

[0083] 5) Layer-by-layer calcination treatment: After each coating layer is applied, it is calcined at 700 ℃ for 30 minutes to reduce defects such as cracks and pinholes generated during the sintering process.

[0084] 6) Functional layer co-firing: The assembled functional layers (including the anode functional layer and the electrolyte layer) are co-firing at 1400 °C in air atmosphere for 4 hours.

[0085] 7) Screen-printed isolation layer and cathode: Ce is sequentially prepared on the electrolyte surface using screen printing technology. 0.9 Gd 0.1 O 1.95 isolation layer and La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ cathode.

[0086] (3) Introduction of Mo into porous NiO-YSZ substrate 1) Preparation of precursor solution: Prepare 0.5 mol / L ammonium heptamolybdate tetrahydrate ((NH4)6Mo7O) 24Aqueous solution of 4H2O was used as a precursor for the Mo catalyst.

[0087] 2) Vacuum-assisted impregnation: The screen-printed isolation layer and the porous NiO-YSZ substrate after cathode are placed in a vacuum chamber and impregnated under reduced pressure of about 0.1 atm to promote the deep penetration of the precursor solution into the porous structure of the substrate.

[0088] 3) The impregnated sample was calcined at 700 °C in air for 1 hour.

[0089] 4) Multiple impregnation cycles: By repeating the impregnation process multiple times, the final Mo loading in NiMo is ensured to be 16%, and a porous MoNi-YSZ support is finally formed in the SOFC single cell.

[0090] Example 4: NiO-YSZ anode support (straight holes + round holes + containing 5% Mo) and corresponding SOFC single cell (1) Preparation of porous NiO-YSZ support: 1) Slurry preparation: Mix 54 wt.% NiO powder with 36 wt.% YSZ powder and 10 wt.% PMMA, and add 16 wt.% of a solvent-binder system consisting of polyethersulfone (PESF, Amerco Performance Radel A-300), 4 wt.% polyvinylpyrrolidone (PVP, Sigma-Aldrich) and 80 wt.% 1-methyl-2-pyrrolidone to make the solids content of the mixed slurry 50 wt.%.

[0091] 2) Casting and phase separation: The above slurry is cast onto the surface of a glass plate, and then the glass plate is immersed in deionized water. Phase separation is initiated through solvent exchange, thereby forming a NiO-YSZ green film with a directional microchannel pore structure and a film thickness of 1 mm.

[0092] 3) Green blank forming: The NiO-YSZ green blank film after phase separation is punched into circular samples with a diameter of 21 mm.

[0093] 4) Calcination treatment: The green sample is placed in a high-temperature furnace and calcined at 1000 °C for 3 hours to completely remove organic components (PESF, PVP, PMMA, etc.) and finally obtain a porous NiO-YSZ support.

[0094] (2) Preparation of SOFC single cells: 1) Preparation of NiO-YSZ slurry: It is formulated from 17 wt.% powder component and 83 wt.% organic carrier system, wherein the powder component contains 8.5 wt.% NiO powder and 8.5 wt.% YSZ powder, and the organic carrier system consists of 33 wt.% α-terpineol, 25 wt.% anhydrous ethanol (Aladdin Chemistry Co. Ltd.) and 25 wt.% B73210 binder (FerroElectronics Materials).

[0095] 2) Spin-coating NiO-YSZ anode functional layer: The above slurry is coated onto the surface of the porous NiO-YSZ support by spin coating (3000 rpm, 40 seconds), with a thickness of about 20 μm.

[0096] 3) Preparation of YSZ slurry: It is formulated from 17 wt.% YSZ powder and 83 wt.% organic carrier system, wherein the organic carrier system consists of 33 wt.% α-terpineol, 25 wt.% anhydrous ethanol (Aladdin Chemistry Co. Ltd.) and 25 wt.% B73210 binder (Ferro Electronics Materials).

[0097] 4) Spin-coated YSZ electrolyte layer: A dense YSZ electrolyte layer with a thickness of approximately 20 μm is deposited on the surface of the anode functional layer using a spin-coating process.

[0098] 5) Layer-by-layer calcination treatment: After each coating layer is applied, it is calcined at 700 ℃ for 30 minutes to reduce defects such as cracks and pinholes generated during the sintering process.

[0099] 6) Functional layer co-firing: The assembled functional layers (including the anode functional layer and the electrolyte layer) are co-firing at 1400 °C in air atmosphere for 4 hours.

[0100] 7) Screen-printed isolation layer and cathode: Ce is sequentially prepared on the electrolyte surface using screen printing technology. 0.9 Gd 0.1 O 1.95 isolation layer and La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ cathode.

[0101] (3) Introduction of Mo into porous NiO-YSZ substrate 1) Preparation of precursor solution: Prepare 0.5 mol / L ammonium heptamolybdate tetrahydrate ((NH4)6Mo7O) 24Aqueous solution of 4H2O was used as a precursor for the Mo catalyst.

[0102] 2) Vacuum-assisted impregnation: The screen-printed isolation layer and the porous NiO-YSZ substrate after cathode are placed in a vacuum chamber and impregnated under reduced pressure of about 0.1 atm to promote the deep penetration of the precursor solution into the porous structure of the substrate.

[0103] 3) The impregnated sample was calcined at 700 °C in air for 1 hour.

[0104] 4) Multiple impregnation cycles: By repeating the impregnation process multiple times, the final Mo loading in NiMo is ensured to be 5%, and a porous MoNi-YSZ support is finally formed in the SOFC single cell.

[0105] Example 5: NiO-YSZ anode support (straight holes + round holes + containing 16% Mo) and the corresponding SOFC single cell (1) Preparation of porous NiO-YSZ support: 1) Slurry preparation: Mix 54 wt.% NiO powder with 36 wt.% YSZ powder and 10 wt.% PMMA, and add 16 wt.% of a solvent-binder system consisting of polyethersulfone (PESF, Amerco Performance Radel A-300), 4 wt.% polyvinylpyrrolidone (PVP, Sigma-Aldrich) and 80 wt.% 1-methyl-2-pyrrolidone to make the solids content of the mixed slurry 50 wt.%.

[0106] 2) Casting and phase separation: The above slurry is cast onto the surface of a glass plate, and then the glass plate is immersed in deionized water. Phase separation is initiated through solvent exchange, thereby forming a NiO-YSZ green film with a directional microchannel pore structure and a film thickness of 1 mm.

[0107] 3) Green blank forming: The NiO-YSZ green blank film after phase separation is punched into circular samples with a diameter of 21 mm.

[0108] 4) Calcination treatment: The green sample is placed in a high-temperature furnace and calcined at 1000 °C for 3 hours to completely remove organic components (PESF, PVP, PMMA, etc.) and finally obtain a porous NiO-YSZ support.

[0109] (2) Preparation of SOFC single cells: 1) Preparation of NiO-YSZ slurry: It is formulated from 17 wt.% powder component and 83 wt.% organic carrier system, wherein the powder component contains 8.5 wt.% NiO powder and 8.5 wt.% YSZ powder, and the organic carrier system consists of 33 wt.% α-terpineol, 25 wt.% anhydrous ethanol (Aladdin Chemistry Co. Ltd.) and 25 wt.% B73210 binder (FerroElectronics Materials).

[0110] 2) Spin-coating NiO-YSZ anode functional layer: The above slurry is coated onto the surface of the porous NiO-YSZ support by spin coating (3000 rpm, 40 seconds), with a thickness of about 20 μm.

[0111] 3) Preparation of YSZ slurry: It is formulated from 17 wt.% YSZ powder and 83 wt.% organic carrier system, wherein the organic carrier system consists of 33 wt.% α-terpineol, 25 wt.% anhydrous ethanol (Aladdin Chemistry Co. Ltd.) and 25 wt.% B73210 binder (Ferro Electronics Materials).

[0112] 4) Spin-coated YSZ electrolyte layer: A dense YSZ electrolyte layer with a thickness of approximately 20 μm is deposited on the surface of the anode functional layer using a spin-coating process.

[0113] 5) Layer-by-layer calcination treatment: After each coating layer is applied, it is calcined at 700 ℃ for 30 minutes to reduce defects such as cracks and pinholes generated during the sintering process.

[0114] 6) Functional layer co-firing: The assembled functional layers (including the anode functional layer and the electrolyte layer) are co-firing at 1400 °C in air atmosphere for 4 hours.

[0115] 7) Screen-printed isolation layer and cathode: Ce is sequentially prepared on the electrolyte surface using screen printing technology. 0.9 Gd 0.1 O 1.95 isolation layer and La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ cathode.

[0116] (3) Introduction of Mo into porous NiO-YSZ substrate 1) Preparation of precursor solution: Prepare 0.5 mol / L ammonium heptamolybdate tetrahydrate ((NH4)6Mo7O) 24Aqueous solution of 4H2O was used as a precursor for the Mo catalyst.

[0117] 2) Vacuum-assisted impregnation: The screen-printed isolation layer and the porous NiO-YSZ substrate after cathode are placed in a vacuum chamber and impregnated under reduced pressure of about 0.1 atm to promote the deep penetration of the precursor solution into the porous structure of the substrate.

[0118] 3) The impregnated sample was calcined at 700 °C in air for 1 hour.

[0119] 4) Multiple impregnation cycles: By repeating the impregnation process multiple times, the final Mo loading in NiMo is ensured to be 16%, and a porous MoNi-YSZ support is finally formed in the SOFC single cell.

[0120] Example 6: NiO-YSZ anode support (straight holes + round holes + containing 50% Mo) and the corresponding SOFC single cell (1) Preparation of porous NiO-YSZ support: 1) Slurry preparation: Mix 54 wt.% NiO powder with 36 wt.% YSZ powder and 10 wt.% PMMA, and add 16 wt.% of a solvent-binder system consisting of polyethersulfone (PESF, Amerco Performance Radel A-300), 4 wt.% polyvinylpyrrolidone (PVP, Sigma-Aldrich) and 80 wt.% 1-methyl-2-pyrrolidone to make the solids content of the mixed slurry 50 wt.%.

[0121] 2) Casting and phase separation: The above slurry is cast onto the surface of a glass plate, and then the glass plate is immersed in deionized water. Phase separation is initiated through solvent exchange, thereby forming a NiO-YSZ green film with a directional microchannel pore structure and a film thickness of 1 mm.

[0122] 3) Green blank forming: The NiO-YSZ green blank film after phase separation is punched into circular samples with a diameter of 21 mm.

[0123] 4) Calcination treatment: The green sample is placed in a high-temperature furnace and calcined at 1000 °C for 3 hours to completely remove organic components (PESF, PVP, PMMA, etc.) and finally obtain a porous NiO-YSZ support.

[0124] (2) Preparation of SOFC single cells: 1) Preparation of NiO-YSZ slurry: It is formulated from 17 wt.% powder component and 83 wt.% organic carrier system, wherein the powder component contains 8.5 wt.% NiO powder and 8.5 wt.% YSZ powder, and the organic carrier system consists of 33 wt.% α-terpineol, 25 wt.% anhydrous ethanol (Aladdin Chemistry Co. Ltd.) and 25 wt.% B73210 binder (FerroElectronics Materials).

[0125] 2) Spin-coating NiO-YSZ anode functional layer: The above slurry is coated onto the surface of the porous NiO-YSZ support by spin coating (3000 rpm, 40 seconds), with a thickness of about 20 μm.

[0126] 3) Preparation of YSZ slurry: It is formulated from 17 wt.% YSZ powder and 83 wt.% organic carrier system, wherein the organic carrier system consists of 33 wt.% α-terpineol, 25 wt.% anhydrous ethanol (Aladdin Chemistry Co. Ltd.) and 25 wt.% B73210 binder (Ferro Electronics Materials).

[0127] 4) Spin-coated YSZ electrolyte layer: A dense YSZ electrolyte layer with a thickness of approximately 20 μm is deposited on the surface of the anode functional layer using a spin-coating process.

[0128] 5) Layer-by-layer calcination treatment: After each coating layer is applied, it is calcined at 700 ℃ for 30 minutes to reduce defects such as cracks and pinholes generated during the sintering process.

[0129] 6) Functional layer co-firing: The assembled functional layers (including the anode functional layer and the electrolyte layer) are co-firing at 1400 °C in air atmosphere for 4 hours.

[0130] 7) Screen-printed isolation layer and cathode: Ce is sequentially prepared on the electrolyte surface using screen printing technology. 0.9 Gd 0.1 O 1.95 isolation layer and La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ cathode.

[0131] (3) Introduction of Mo into porous NiO-YSZ substrate 1) Preparation of precursor solution: Prepare 0.5 mol / L ammonium heptamolybdate tetrahydrate ((NH4)6Mo7O) 24Aqueous solution of 4H2O was used as a precursor for the Mo catalyst.

[0132] 2) Vacuum-assisted impregnation: The screen-printed isolation layer and the porous NiO-YSZ substrate after cathode are placed in a vacuum chamber and impregnated under reduced pressure of about 0.1 atm to promote the deep penetration of the precursor solution into the porous structure of the substrate.

[0133] 3) The impregnated sample was calcined at 700 °C in air for 1 hour.

[0134] 4) Multiple impregnation cycles: By repeating the impregnation process multiple times, the final Mo loading in NiMo is ensured to be 50%, and a porous MoNi-YSZ support is finally formed in the SOFC single cell.

[0135] Experimental Example: Characterization and Performance Testing of NiO-YSZ Anode Support and Corresponding SOFC Single Cell The control sample used for SEM testing was a sample prepared by traditional dry pressing method using corn starch as a pore-forming agent (refer to the literature "Zhao K, Lee KS, Chen M, et al. Electrochemical performance of acopper-impregnated Ni–Ce"). 0.8 Sm 0.2 O 1.9 Anode running on methane[J]. Internationaljournal of hydrogen energy, 2013, 38(9): 3750-3756.”) and a support prepared by extrusion molding and high-temperature sintering with PMMA spherical pore-forming agent (see literature “Lin Z, Zhao K, Cheng G, et al. Catalyst layer supported solid oxide fuel cells running on methane[J]. Journal of Power Sources, 2021, 507: 230317.”).

[0136] Figure 2 The images show SEM images of the NiO-YSZ anodes. They reveal that the Ni-YSZ supports prepared using different methods all exhibit a porous structure with uniformly distributed pores. The porosity of each sample, measured by the Archimedes method, is between 40% and 50%. Among these, the sample prepared using corn starch as a pore-forming agent and the traditional dry pressing method (…) Figure 2(a) The support has randomly distributed irregular pores, and its tortuosity is measured to be 5.0–5.5 by a pore curvature tester; the support is prepared by extrusion molding and high-temperature sintering using PMMA spherical pore-forming agent. Figure 2 (b) results in regularly shaped spherical pores, with the tortuosity reduced to 3.5–4.0. In contrast, the support prepared using the phase transformation method of this invention ( Figure 2 (c) During solvent exchange, oriented microchannels are formed, and the tortuosity is significantly reduced to about 1.0. This ordered channel structure is beneficial for promoting gas transport within the anode; however, high-magnification images ( Figure 2 (d) shows that its channel wall microstructure is relatively dense, which may have an adverse effect on heterogeneous reactions. By incorporating PMMA microspheres during the phase transformation process, the resulting composite structure ( Figure 2 (e) and (f) successfully integrated two morphologies: directional microchannels and spherical pores, demonstrating the effective combination of the two pore structures.

[0137] Figure 3 The current-voltage relationship curves of SOFC single cells at 750℃ and in an atmosphere of 50% H2-50% N2 are shown. It can be seen that the open-circuit voltage of the cell is 1.07–1.08 V, consistent with the values ​​reported in the literature (see: Pei Y, Liu C, Han Z, et al. Revealing the impacts of metastable structure on the electrochemical properties: The case of MnS[J]. Journal of Power Sources, 2019, 431: 75-83.), confirming the effectiveness of the cell sealing. Among them, the peak power density of the cells with irregular pores and spherical pore structures is 517–542 mW·cm⁻¹. -2 Notably, by customizing the pore structure into ordered microchannels, battery performance was improved by approximately 25%, with a peak power density reaching 650–680 mW·cm⁻¹. -2 This significantly improves the electrochemical performance of the battery.

[0138] Figure 4 The absorption effects of different anodes on H2S were compared and studied. The specific testing method was as follows: the catalyst support was placed in the middle of a quartz tube reactor (inner diameter 16 mm), sealed with ceramic adhesive, and a K-type thermocouple was used to monitor the catalytic reaction temperature. Hydrogen gas (or methanol) containing 120 ppm H2S was introduced at the inlet, and the H2S content in the reformed gas was measured at the outlet. Figure 4It can be seen that the straight-hole Ni-YSZ anode can reduce the H2S concentration in the feed gas from 120 ppm to approximately 34 ppm. However, its performance begins to degrade after only 30 hours of operation. In contrast, introducing Mo into the catalyst to form a MoNi-YSZ layer can reduce the outlet H2S concentration by 29% to approximately 24 ppm and extend the stable operating time by 66% to approximately 50 hours. Furthermore, using a straight-hole + round-hole MoNi-YSZ anode can further reduce the H2S concentration to approximately 14 ppm and extend the stable operating time to approximately 60 hours.

[0139] Figure 5 The effect of Mo content on sulfur absorption efficiency in a straight-hole + round-hole NiMo anode was compared and analyzed. Under sulfidation conditions of 750℃ and 120ppm H2S, the sulfur absorption capacity of the low-Mo-content NiMo anode (5% Mo) was comparable to that of the pure Ni anode, reducing the H2S concentration from 120ppm to 28ppm. A higher Mo content (50%) did not improve sulfur absorption performance, only reducing the sulfur content in the reformed gas to 21ppm. In the NiMo anode system, the NiMo sample (16% Mo) exhibited the best sulfur absorption effect, significantly reducing the H2S concentration from 120ppm to 14ppm, achieving efficient absorption and conversion of sulfur components.

[0140] In addition, the regeneration capacity of Ni-YSZ and MoNi-YSZ (Mo accounts for 16% in NiMo) catalyst layers under cyclic operating conditions was evaluated. The test conditions included (1) H2S absorption for 30 hours and (2) regeneration for 10 hours (the regeneration method was to convert the reaction gas into hydrogen gas without H2S for purging, thereby achieving regeneration). Figure 6 As shown, the Ni-YSZ layer exhibited stable performance during the first two cycles. After two cycles, H2S in the exhaust gas increased at a rate of 0.06 ppm / h, indicating a loss of sulfur fixation ability. When MoNi was applied to the porous YSZ support, the catalyst showed significantly improved regeneration capacity during five regeneration cycles, while H2S in the exhaust gas increased at a low rate of 0.013 ppm / h. These results indicate that Mo plays an effective role in improving stability.

[0141] Figure 7 The performance stability of SOFC single cells in an H2 atmosphere containing 120 ppm H2S was assessed. The cell using the Ni-YSZ anode exhibited good stability in the first two cycles. However, in subsequent test cycles, the cell's electrochemical performance declined by 1.6 mV·h. -1The degradation rate is significantly lower. Even with periodic regeneration, each cycle still exhibits an irreversible performance loss of 57%. In contrast, the single-cell performance degradation rate using the MoNi-YSZ anode is reduced by approximately 62%, with a degradation rate as low as 0.6 mV·h. -1 Furthermore, the regeneration process can restore 98% of the initial performance.

[0142] This study further verified the electrochemical performance of NiMo anodes in sulfur-containing fuels based on single-cell experiments in direct methanol fuel cells (SOFCs). The specific method was as follows: The electrochemical performance of SOFC single cells was studied using a high-temperature fuel cell testing device (see: Zhao K, NiMo-ceria-zirconia catalytic reforming layer for solid oxide fuel cells running on agasoline surrogate[J] Applied Catalysis B: Environmental, 2018, 224, 500-507). The battery samples were sealed with Al2O3-based ceramic sealant, and the battery temperature was raised to 750 °C for electrochemical performance testing. When hydrogen was used as fuel, 50 mL·min⁻¹ was directly applied. -1 Hydrogen gas is introduced into the anode port of the fuel cell; when methanol is used as fuel, a mixture of methanol and N2 is introduced into the anode port of the fuel cell, wherein the flow rate of liquid CH3OH is 0.09 mL·min. -1 The nitrogen flow rate is 100 mL / min. -1 This study employed standard current-voltage testing techniques to investigate the electrochemical performance of the battery, and constant current discharge techniques to study the stability of the battery's operating performance. Figure 8 For SOFC batteries in methanol fuel containing 120 ppm H2S, at a constant current density of 200 mA·cm⁻¹ -2 The electrochemical performance under the specified conditions was examined. It can be seen that the SOFC battery using Ni-YSZ as the anode had an initial voltage of 0.89 V. During subsequent cycle testing, the Ni-YSZ anode battery exhibited irreversible poisoning, resulting in an average performance degradation rate of 0.9 mV·h. -1 In contrast, SOFC cells employing molybdenum-modified nickel-yttrium stabilized zirconium oxide (MoNi-YSZ) anodes exhibited significantly improved durability. After regeneration, these cells were able to recover up to 98% of their initial performance, with the overall performance degradation rate reduced by more than 50%, down to 0.4 mV·h. -1 The above experimental results further verify the high tolerance of the MoNi-YSZ anode to sulfur-containing fuels.

[0143] The embodiments of the present invention have been described in detail above, but the present invention is not limited to the described embodiments. For those skilled in the art, various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principles and spirit of the present invention, and these variations still fall within the protection scope of the present invention.

Claims

1. A method for preparing an SOFC single cell, characterized in that, Includes the following steps: S1. Preparation of electrode catalyst: S11. Mix NiO powder with YSZ powder and polymethyl methacrylate microspheres, add to solvent-binder system to make slurry, then cast the slurry onto the substrate surface, then immerse the substrate in water, initiate phase separation through solvent exchange, and form a NiO-YSZ green film with oriented microchannel pore structure. S12. After phase separation, the NiO-YSZ green film is shaped and then calcined to remove organic components, thereby obtaining a porous NiO-YSZ support, i.e., an electrode catalyst. S2, Fabrication of the functional layer of a single cell: S21. A NiO-YSZ slurry is prepared by means of a powder component and an organic carrier system, wherein the powder component contains NiO powder and YSZ powder, and the organic carrier system is composed of α-terpineol, ethanol and B73210 binder. S22. The slurry of S21 is coated onto the surface of the electrode catalyst prepared in S1 by spin coating to form a NiO-YSZ anode functional layer. Then, a dense YSZ electrolyte layer is deposited on the surface of the anode functional layer by the same spin coating process. After each layer is coated, it is calcined at 600-800 ℃ for 20-40 minutes. S23. After assembly, co-fire at 1200-1500 ℃ in air for 3-6 hours, then use screen printing technology to sequentially prepare Ce on the electrolyte surface. 0.9 Gd 0.1 O 1.95 isolation layer and La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ cathode; S3. Introduction of Mo: A vacuum-assisted impregnation method is used to impregnate the porous NiO-YSZ support after the preparation of the functional layer of the single cell with a molybdenum precursor solution, thereby introducing molybdenum into the porous structure of the support, and finally forming a porous MoNi-YSZ support in the SOFC single cell, thus obtaining the SOFC single cell.

2. The method for preparing an SOFC single cell according to claim 1, characterized in that, In S11, the composition of the NiO powder, YSZ powder, and polymethyl methacrylate microspheres, by mass fraction, is as follows: NiO powder 50-60 wt.%, YSZ powder 30-40 wt.%, polymethyl methacrylate microspheres 7-15 wt.%.

3. The method for preparing an SOFC single cell according to claim 1, characterized in that, In S11, the solvent-binder system is composed of polyethersulfone, polyvinylpyrrolidone and 1-methyl-2-pyrrolidone.

4. The method for preparing an SOFC single cell according to claim 1, characterized in that, The solids content in the slurry described in S11 is 40-60 wt.%.

5. The method for preparing an SOFC single cell according to claim 1, characterized in that, In S12, the calcination temperature is 900-1200 ℃ and the time is 2-5 hours.

6. The method for preparing an SOFC single cell according to claim 1, characterized in that, In S3, the molybdenum precursor solution is an aqueous solution of ammonium heptamolybdate tetrahydrate at a concentration of 0.3-1.0 mol / L; the impregnation treatment is carried out under reduced pressure of 0.1-0.3 atm; and the Mo loading in the porous MoNi-YSZ support is 5%-50% wt, based on the NiMo metal phase.

7. The method for preparing an SOFC single cell according to claim 1, characterized in that, Step S21 specifically involves preparing a NiO-YSZ slurry with 15-20 wt.% powder components and 80-90 wt.% organic carrier system, wherein the powder components contain 7-9 wt.% NiO powder and 7-9 wt.% YSZ powder, and the organic carrier system consists of 30-35 wt.% α-terpineol, 20-30 wt.% ethanol and 20-30 wt.% B73210 binder.

8. The method for preparing an SOFC single cell according to claim 1, characterized in that, After the S3 impregnation treatment, the sample needs to be calcined in an air atmosphere at 600-800 ℃ for 1-3 hours.

9. A single SOFC cell prepared by the preparation method according to any one of claims 1-8.

10. The application of the SOFC single cell according to claim 9 in the preparation of solid oxide fuel cells containing sulfur fuel.

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