CN112072137B - Anode catalysis layer support body of SOFC (solid oxide Fuel cell), preparation method and application thereof - Google Patents

Abstract

The invention relates to an SOFC, comprising an anode catalytic layer support body, wherein the anode catalytic layer support body comprises the following structure: (1) a zirconia support of tubular or flat structure having a porous structure; (2) ni_1‑xMo_x/Ce_1‑yCa_yO_2‑δCatalyst of said Ni_1‑xMo_x/Ce_1‑yCa_yO_2‑δA catalyst is filled in the pores of the porous structure, wherein the zirconia is zirconia previously stabilized with yttria. The invention also relates to a preparation method of the SOFC. The anode catalyst layer support body disclosed by the invention has an excellent catalytic action on complex hydrocarbon fuel and excellent structural stability, so that the anode catalyst layer support body has a wide application prospect in an SOFC (solid oxide fuel cell) of the complex hydrocarbon fuel.

Description

Anode catalysis layer support body of SOFC (solid oxide Fuel cell), preparation method and application thereof

Technical Field

The invention belongs to the field of Solid Oxide Fuel Cells (SOFC), and particularly relates to an anode catalyst layer support body of an SOFC, a preparation method and application thereof.

Background

A Solid Oxide Fuel Cell (SOFC) is an all-Solid-state energy conversion device that converts chemical energy in Fuel into electrical energy, and has the advantages of high energy conversion efficiency, safety, environmental friendliness, and the like. Intermediate temperature fuel cells are an important development in SOFC technology. The operating temperature of the medium-temperature SOFC is 500-800 ℃, and in the operating temperature range, hydrogen can be used as fuel, and hydrocarbon (such as natural gas, city gas and gasoline) can also be used as fuel. Compared with hydrogen (energy density of 370 kWh/m)³At a cost of

) The hydrocarbons have higher energy density and lower cost (e.g., the energy density of gasoline is 8982kWh/m³At a cost of

). Therefore, the development of the intermediate-temperature SOFC taking hydrocarbons such as gasoline as fuel is beneficial to reducing the volume and the operation cost of a cell system, and has important significance for the practical application of the intermediate-temperature SOFC technology.

The electrochemical performance and stability of the SOFC anode under the condition of hydrocarbon fuel are difficult to combine, and the problem is a bottleneck problem which restricts the technical development of the SOFC. For hydrocarbon fuel SOFCs, the anode is required to have high fuel catalytic activity and can efficiently convert complex hydrocarbons into H₂And CO, the anode is also required to have high electron-ion mixed conductivity and excellent electrochemical catalytic activity to realize electrochemical oxidation of the fuel gas, and the anode is also required to have excellent performance stability under the condition of hydrocarbon fuel. The prior SOFC anode is difficult to simultaneously meet the performance requirements. For example, the currently used metal nickel-based anode has excellent fuel catalytic activity and electrochemical catalytic activity, but carbon deposition is easily generated on the surface of the anode, and the electrochemical catalytic activity of the anode and the working stability of a battery are reduced. CN102903940A (201210401826.X) discloses a copper-based anode material, CN109888303A (201910159682.3) discloses a copper-based anode material (PrBa)_0.95Fe_{2-x- y}Cu_xNbyO_5+δNovel anode materials of perovskite structure, which exhibit excellent electrochemical performance stability under hydrocarbon fuel conditions. However, the catalytic activity and electron-ion mixing conductivity of the fuel are less than ideal compared to metal nickel-based anodes.

Researchers at home and abroad have carried out the design, preparation and performance research work of multilayer anode functional layers. CN103165903A (201110422373.4) prepares a layer of Cu-LSCM-CeO on the surface of a traditional SOFC anode₂A catalyst layer to improve fuel catalytic performance. However, the catalytic activity of Cu-based catalysts for complex hydrocarbon fuels is not yet ideal. CN110600775A (201910936331.9) discloses an in-situ reforming solid oxide fuel cell, which is prepared by preparing a metallic Ni-based catalyst on the surface of the SOFC anode to improve the catalytic activity of the catalytic layer. By usingNi-LaMnO₃The catalyst can improve the chemical catalytic performance of the SOFC, but the catalytic layer of the catalyst has low structural stability and is easy to crack, and the working stability of the cell is influenced.

Therefore, in the early research, researchers at home and abroad mainly take an SOFC electrochemical functional layer (including an electrode or an electrolyte) as a support body, and prepare a hydrocarbon fuel catalytic layer on the surface of a battery anode, so that the catalytic conversion of the hydrocarbon fuel is promoted, and the electrochemical performance and the performance stability of the SOFC anode are improved. However, in such a cell structure, the volume change of the catalytic layer during the anode catalytic reaction (volume expansion and contraction of the catalyst during oxidation-reduction) increases the internal stress in the cell structure, resulting in the generation of microcracks, which is disadvantageous for improving the operational performance stability of the SOFC.

Therefore, there is a need to develop an anode having high fuel catalytic activity, high electrochemical catalytic activity, and high performance stability, and to apply it to the structure of an SOFC, thereby solving the above problems.

Disclosure of Invention

In order to solve the problems, the invention discloses an SOFC (solid oxide fuel cell), which comprises an anode catalysis layer support body, and a preparation method and application of the SOFC. The material of SOFC anode catalyst adopted by the invention is Ni in chemical structure_1-xMo_x/Ce_{1- y}Ca_yO_2-δ(x is more than 0 and less than or equal to 0.5, and y is more than or equal to 0.01 and less than or equal to 0.4), wherein the catalytic process comprises the following steps: (1) adsorption of hydrocarbons on the catalyst surface; (2) decomposition of hydrocarbons on the catalyst surface; (3) partial oxidation of hydrocarbons at the catalyst surface and reduction of the catalyst; (4) desorption of newly generated small molecule fuel gas on the surface of the catalyst; (5) catalyst traps oxygen sources (e.g., H)₂O or CO₂) And oxidized to an initial state. Wherein, the steps (1), (2) and (4) are mainly determined by the influence of the binding energy of NiMo metal in the catalyst relative to different gas molecules, and the steps (3) and (5) are mainly influenced by the ceramic phase (namely Ce) in the catalyst_1-yCayO_2-δ) Oxygen storage capacity and redox cycle performance. The present invention is based on the above Ni_1-xMo_x/Ce_1-yCayO_2-δThe catalyst material is applied to an anode catalyst layer support body of the SOFC and adjusted by Ni_1-xMo_x/Ce_1-yCayO_2-δThe composition and microstructure of the catalyst material are used for preparing an anode catalyst layer support body with electrochemical performance and stability; further, the anode catalytic layer support is applied in the structure of an SOFC. The anode catalyst layer support body disclosed by the invention has excellent catalytic action on complex hydrocarbon fuels (such as gaseous alkanes such as methane, methanol, ethanol and propane and liquid alkanes such as gasoline), and can efficiently convert the hydrocarbons into H through catalysis₂And CO for providing H for electrochemical reaction of SOFC anode₂And a CO reaction gas; meanwhile, the catalyst layer supported cell structure has excellent structural stability, so that the stability of the working performance of the SOFC is remarkably improved, and the SOFC has wide application prospect in the SOFC of complex hydrocarbon fuels.

The invention aims to provide an SOFC (solid oxide fuel cell), which is realized by the following technical means:

an SOFC, comprising an anode catalytic layer support comprising:

(1) a tubular structure or a flat plate structure of zirconia having a porous structure;

(2)Ni_1-xMo_x/Ce_1-yCa_yO_2-δcatalyst of said Ni_1-xMo_x/Ce_1-yCa_yO_2-δThe catalyst is filled in the pores of the porous structure,

wherein the zirconia is a zirconia previously stabilized with yttria.

Furthermore, in the tubular structure, the inner diameter of the tube is 1.0-5.0mm, and the outer diameter is 2.0-7.0 mm.

Furthermore, in the flat plate structure, the thickness of the flat plate is 0.5-1.5 mm.

Further, the pores have an average pore diameter of 2.0 to 3.0 μm.

Further, the porosity of the zirconia of the tubular structure or the flat plate structure is 30 to 43%.

Another object of the present invention is to provide a method for preparing the SOFC, comprising the steps of:

s1. with (ZrO)₂)_0.92(Y₂O₃)_0.08The powder and PMMA powder are used as raw materials, and are calcined to prepare a zirconium oxide support body with a tubular structure or a flat plate structure;

s2, sequentially preparing an anode current collection layer, an anode functional layer and a double-electrolyte layer on the zirconium oxide support body with the tubular structure or the flat plate structure to form a half cell;

s3, preparing a mixed solution A of cerium nitrate, calcium nitrate and citric acid, and soaking the half-cell in the mixed solution A to form a pretreated sample A;

s4, calcining the pretreated sample A in a heated air atmosphere to obtain an intermediate;

s5, repeating the operations S3-S4 until the Ce in the intermediate_1-yCa_yO_2-δThe content of (A) is 4.3-12.9 wt%;

s6, preparing a mixed solution B of nickel nitrate, ammonium paramolybdate and citric acid, and soaking the intermediate in the S4 in the mixed solution B to form a pretreated sample B;

s7, calcining the pretreated sample B in a heated air atmosphere to obtain a crude product;

s8, repeating the operation S6-S7 on the crude product until Ni in the crude product_1-xMo_xThe content of the anode catalyst layer reaches 0.7 to 2.1 weight percent, and a half cell comprising an anode catalyst layer support body is obtained;

and S9, preparing a cathode on the half cell comprising the anode catalyst layer support body to obtain the SOFC.

Furthermore, in the mixed solution A, the concentration of cerium nitrate is 0.3-0.7mol/L, the concentration of calcium nitrate is 0.033-0.078mol/L, and the concentration of citric acid is 1.0-2.0 mol/L;

furthermore, in the mixed liquid B, the concentration of nickel nitrate is 0.4-1.3mol/L, the concentration of ammonium paramolybdate is 0.0095-0.031mol/L, and the concentration of citric acid is 1.0-2.0 mol/L.

Further, the mass ratio of the zirconia in the tubular structure or the flat plate structure to the mixed solution A is 1:100-10: 100.

Further, the mass ratio of the intermediate to the mixed liquid B is 1:100-10: 100.

The invention has the following beneficial effects:

(1) the invention provides an SOFC (solid oxide fuel cell), which has an anode catalyst layer support body structure, wherein zirconia with a tubular structure or a flat plate structure is used as the support body of the anode catalyst layer, so that the matrix of the SOFC has good chemical and structural stability; ni_1-xMo_x/Ce_1-yCa_yO_2-δCatalyst particles are attached to the inner surfaces of pores of the porous zirconia support body, so that the problem of cracking of a catalyst layer structure in the traditional configuration is solved;

(2) in the SOFC, the anode catalyst layer has good thermal expansion matching performance with other functional layers of the cell at the temperature range of room temperature to 800 ℃;

(3) in SOFC structures containing an anode catalytic layer support of the SOFC, hydrocarbon fuel may be catalytically converted to H in the anode catalytic layer support₂And electrochemical active gases such as CO and the like are beneficial to improving the electrochemical performance and stability of the battery; and the composite material has the dual advantages of 'catalytic reforming of hydrocarbon fuel' and 'high structural stability', and can effectively improve the discharge performance stability of the SOFC in complex hydrocarbon fuel. Research results show that the single continuous stable running time of the battery can be improved from 10-20h to 30h by adopting the novel battery configuration. Meanwhile, in the battery configuration, the anode of the battery can adopt a traditional active metal Ni-based material, so that the high output power density and the discharge performance stability of the battery can be obtained.

Drawings

Fig. 1 shows the porosity of the anode catalytic layer support as a function of the pore former PMMA content for the tubular SOFCs of examples 1-5.

Fig. 2 shows the fracture strength of the anode catalytic layer support of the tube-in-tube SOFC in examples 1-5 as a function of the pore former PMMA content.

Figure 3 shows an SEM microstructure photograph of the tube-in-tube SOFC in example 2.

Figure 4 shows a diagram of a test setup for an example of a tubular SOFC for examples 1-5 of the invention.

Fig. 5(a) shows fuel conversion, H, of the tubular SOFC in example 2₂Graph of yield and CO yield over time.

FIG. 5(b) shows fuel conversion, H, for tubular SOFCs in examples 1-3₂Yield and CO yield as a function of catalyst content.

Fig. 6(a) shows a tubular SOFC in example 2 at H₂And current-voltage-power density profile in isooctane fuel.

Fig. 6(b) shows the maximum output power density of the tubular SOFC in examples 1-5 as a function of PMMA pore former content in hydrogen and isooctane fuels.

Fig. 7 shows a graph comparing the discharge performance stability in isooctane/air for a tube-in-tube SOFC and a conventional anode-supported SOFC in example 2.

Figure 8 shows a diagram of a test setup for an example of a flat SOFC for examples 6-10 of the invention.

FIG. 9(a) shows fuel conversion, H, of a planar SOFC in example 7₂Graph of yield and CO yield over time.

FIG. 9(b) shows fuel conversion, H, for planar SOFCs in examples 6-8₂Yield and CO yield as a function of catalyst content.

FIG. 10(a) shows SOFC at H with a catalyst loading of 10 wt% in example 7₂And a plot of current density versus SOFC voltage in isooctane fuel.

FIG. 10(b) shows a planar SOFC in H in examples 6-10₂And the maximum output power density in isooctane fuel as a function of PMMA pore former content.

Fig. 11 shows a graph comparing the discharge performance stability in isooctane/air for a planar SOFC and a conventional anode-supported SOFC in example 7.

Detailed Description

The present invention is further illustrated by the following specific examples, which are not intended to limit the invention in any way. The starting materials described in the examples of the present invention are commercially available and, unless otherwise specified, the starting materials and methods employed are those conventional in the art.

The zirconia used in the examples was previously yttria stabilized zirconia available from Tosoh Biotechnology Inc. under the model of TZ-8Y.

The specific operation method of the dip-draw method described in the examples is: and (3) immersing the sample into the prepared slurry, slowly pulling and taking out the sample after 30 seconds of immersion, wherein the pulling speed is 10 cm/second.

Example 1

SOFC, comprising an anode catalytic layer support comprising the structure:

(1) a tubular-structured zirconia support having a porous structure; wherein the inner diameter of the tube is 1.0mm, and the outer diameter is 2.0 mm; the average pore diameter of the pores of the porous structure was 2.0 μm; the porosity of the tubular structure zirconia was 30%;

(2)NiMo/Ce_0.9Ca_0.10O_2-δcatalyst of said NiMo/Ce_0.9Ca_0.10O_2-δThe catalyst is filled in the pores of the porous structure.

The preparation method of the SOFC comprises the following steps:

s1, mixing (ZrO)₂)_0.92(Y₂O₃)_0.08Mixing the powder and PMMA powder according to the mass ratio of 85:15, preparing a ceramic tube blank by adopting an extrusion molding process (the method of the extrusion molding process refers to the prior art: Preparation method and device of SOFC anode supported ceramic tube, CN106747578A), and calcining for 2 hours at 900 ℃ to obtain a porous zirconia support body with a tubular structure;

s2, preparing a half cell on the basis of the zirconia support body with the tubular structure. The method comprises the following specific steps:

(1) preparing a polyvinyl butyral-ethanol solution with the concentration of 10 wt%, and then adding 3 wt% of n-butanol into the solution to prepare organic slurry A;

(2) mixing NiO and zirconia powder according to a mass ratio of 80:20, performing ball milling and crushing to obtain NiO-zirconia powder, mixing the NiO-zirconia powder and organic slurry A according to a mass ratio of 1:9, and coating the slurry on the surface of a zirconia support body with a tubular structure by adopting a dipping-pulling method to obtain an anode current collection layer;

(3) mixing NiO and zirconia powder according to a mass ratio of 50:50, performing ball milling and crushing to obtain NiO-zirconia powder, mixing the NiO-zirconia powder and organic slurry A according to a mass ratio of 1:9, and coating the slurry on the surface of an anode current collection layer by adopting a dipping-pulling method to obtain an anode functional layer;

(4) uniformly mixing 25 wt% of organic slurry A, 50 wt% of terpineol and 25 wt% of ethanol to prepare organic slurry B;

(5) mixing zirconia powder and organic slurry B in a mass ratio of 20:80, and then coating the slurry on the surface of an anode functional layer by adopting a dipping-pulling method to obtain a zirconia electrolyte layer; then Ce is mixed_0.8Sm_0.2O_1.9Mixing the powder and the organic slurry B in a mass ratio of 20:80, and then coating the slurry on the surface of the zirconia electrolyte layer by adopting a dipping-pulling method to form Ce_0.8Sm_0.2O_1.9An electrolyte layer, thereby forming a dual electrolyte layer;

(6) and (3) placing the structure in a muffle furnace, and sintering at 1400 ℃ for 4h to obtain the half cell.

S3, preparing a mixed solution A of cerium nitrate, calcium nitrate and citric acid, wherein the concentration of the cerium nitrate in the mixed solution A is 0.30mol/L, the concentration of the calcium nitrate is 0.033mol/L, and the concentration of the citric acid is 1.0 mol/L. Soaking the half cell in the S2 in the mixed solution A (wherein the mass ratio of the zirconium oxide with the tubular structure to the mixed solution A is 1:100) to form a pretreated sample A, wherein the vacuum degree of soaking is 50 kPa; the soaking time is 0.5 h;

s4, calcining the pretreated sample A in an air atmosphere at 500 ℃ for 0.5h to obtain an intermediate;

s5, intermediate body is subjected toRepeating the operations S3-S4 until the Ce in the intermediate_0.95Ca_0.10O_2-δThe content of (A) reaches 4.3 wt%;

s6, preparing a mixed solution B of nickel nitrate, ammonium paramolybdate and citric acid, wherein the concentration of nickel nitrate in the mixed solution B is 0.4mol/L, the concentration of ammonium paramolybdate is 0.0095mol/L, and the concentration of citric acid is 1.0 mol/L. Soaking the intermediate in S5 in a mixed solution B (wherein the mass ratio of the intermediate to the mixed solution B is 1:100) to form a pretreated sample B, wherein the vacuum degree of soaking is 50 kPa; the soaking time is 0.5 h;

s7, calcining the pretreated sample B in an air atmosphere at 500 ℃ for 0.5h to obtain a crude product;

s8, repeating the operations S6-S7 on the crude product until the content of NiMo in the crude product reaches 0.7 wt%, and obtaining the half cell comprising the anode catalytic layer support, wherein NiMo-Ce_0.95Ca_0.10O_2-δThe catalyst content was 5.0 wt%.

S9, preparing a cathode on the half-cell comprising the anode catalyst layer support body, and specifically comprising the following steps: la_0.6Sr_0.4Co_0.2Fe_0.8O_3-δThe cathode powder was mixed with organic slurry A, in which La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δThe content of the cerium oxide is 15 wt%, and a dipping-pulling method is adopted to carry out on Ce_0.8Sm_0.2O_1.9Preparation of La on electrolyte surface_0.6Sr_0.4Co_0.2Fe_0.8O_3-δAnd a cathode layer, wherein the battery cathode is sintered at 1000 ℃ to obtain the SOFC.

Example 2

SOFC, comprising an anode catalytic layer support comprising the structure:

(1) a tubular-structured zirconia support having a porous structure; wherein the inner diameter of the tube is 2.3mm, and the outer diameter is 4.0 mm; the average pore diameter of the pores of the porous structure was 2.5 μm; the porosity of the tubular structure zirconia was 35%;

(2)NiMo/Ce_0.9Ca_0.10O_2-δcatalyst of said NiMo/Ce_0.9Ca_0.10O_2-δThe catalyst is filled in the pores of the porous structure.

The preparation method of the SOFC comprises the following steps:

s1, mixing (ZrO)₂)_0.92(Y₂O₃)_0.08Mixing the powder and PMMA powder in a mass ratio of 80:20, preparing a ceramic tube blank by adopting an extrusion molding process, and calcining for 2 hours at 900 ℃ to obtain a porous zirconia support body with a tubular structure;

s2, preparing a half cell on the basis of the zirconia support body with the tubular structure. The method comprises the following specific steps:

(1) preparing a polyvinyl butyral-ethanol solution with the concentration of 10 wt%, and then adding 3 wt% of n-butanol into the solution to prepare organic slurry A;

(2) mixing NiO and zirconia powder according to a mass ratio of 80:20, performing ball milling and crushing to obtain NiO-zirconia powder, mixing the NiO-zirconia powder and organic slurry A according to a mass ratio of 1:9, and coating the slurry on the surface of a zirconia support body with a tubular structure by adopting a dipping-pulling method to obtain an anode current collection layer;

(3) mixing NiO and zirconia powder according to a mass ratio of 50:50, performing ball milling and crushing to obtain NiO-zirconia powder, mixing the NiO-zirconia powder and organic slurry A according to a mass ratio of 1:9, and coating the slurry on the surface of an anode current collection layer by adopting a dipping-pulling method to obtain an anode functional layer;

(4) uniformly mixing 25 wt% of organic slurry A, 50 wt% of terpineol and 25 wt% of ethanol to prepare organic slurry B;

(5) mixing zirconia powder and organic slurry B in a mass ratio of 20:80, and then coating the slurry on the surface of an anode functional layer by adopting a dipping-pulling method to obtain a zirconia electrolyte layer; then Ce is mixed_0.8Sm_0.2O_1.9Mixing the powder and the organic slurry B in a mass ratio of 20:80, and then coating the slurry on the surface of the zirconia electrolyte layer by adopting a dipping-pulling method to form Ce_0.8Sm_0.2O_1.9An electrolyte layer, therebyForming a dual electrolyte layer;

(6) and (3) placing the structure in a muffle furnace, and sintering at 1400 ℃ for 4h to obtain the half cell.

S3, preparing a mixed solution A of cerium nitrate, calcium nitrate and citric acid, wherein the concentration of the cerium nitrate in the mixed solution A is 0.60mol/L, the concentration of the calcium nitrate is 0.066mol/L, and the concentration of the citric acid is 1.32 mol/L. Soaking the half cell in the S2 in the mixed solution A (wherein the mass ratio of the zirconium oxide with the tubular structure to the mixed solution A is 5:100) to form a pretreated sample A, wherein the vacuum degree of soaking is 50 kPa; the soaking time is 0.5 h;

s4, calcining the pretreated sample A in an air atmosphere at 500 ℃ for 0.5h to obtain an intermediate;

s5, repeating the operations S3-S4 until the Ce in the intermediate_0.95Ca_0.10O_2-δThe content of (A) reaches 8.6 wt%;

s6, preparing a mixed solution B of nickel nitrate, ammonium paramolybdate and citric acid, wherein the concentration of nickel nitrate in the mixed solution B is 0.8mol/L, the concentration of ammonium paramolybdate is 0.019mol/L, and the concentration of citric acid is 1.5 mol/L. Soaking the intermediate in S5 in a mixed solution B (wherein the mass ratio of the intermediate to the mixed solution B is 5:100) to form a pretreated sample B, wherein the vacuum degree of soaking is 50 kPa; the soaking time is 0.5 h;

s7, calcining the pretreated sample B in an air atmosphere at 500 ℃ for 0.5h to obtain a crude product;

s8, repeating the operations S6-S7 on the crude product until the content of NiMo in the crude product reaches 1.4 wt%, and obtaining the half cell comprising the anode catalytic layer support, wherein NiMo-Ce_0.95Ca_0.10O_2-δThe catalyst content was 10 wt%.

S9, preparing a cathode on the half-cell comprising the anode catalyst layer support body, and specifically comprising the following steps: la_0.6Sr_0.4Co_0.2Fe_0.8O_3-δThe cathode powder was mixed with organic slurry A, in which La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δThe content of the cerium oxide is 15 wt%, and a dipping-pulling method is adopted to carry out on Ce_0.8Sm_0.2O_1.9Preparation of La on electrolyte surface_0.6Sr_0.4Co_0.2Fe_0.8O_3-δAnd a cathode layer, wherein the battery cathode is sintered at 1000 ℃ to obtain the SOFC.

Example 3

SOFC, comprising an anode catalytic layer support comprising the structure:

(1) a tubular-structured zirconia-based support having a porous structure; wherein the inner diameter of the tube is 5.0mm, and the outer diameter is 7.0 mm; the average pore diameter of the pores of the porous structure was 3.0 μm; the porosity of the tubular structure zirconia was 43%;

(2)NiMo/Ce_0.9Ca_0.10O_2-δcatalyst of said NiMo/Ce_0.9Ca_0.10O_2-δThe catalyst is filled in the pores of the porous structure.

The preparation method of the SOFC comprises the following steps:

s1, mixing (ZrO)₂)_0.92(Y₂O₃)_0.08Mixing the powder and PMMA powder in a mass ratio of 75:25, preparing a ceramic tube blank by adopting an extrusion molding process, and calcining for 2 hours at 900 ℃ to obtain a porous zirconia support body with a tubular structure;

s2, preparing a half cell on the basis of the zirconia support body with the tubular structure. The method comprises the following specific steps:

(1) preparing a polyvinyl butyral-ethanol solution with the concentration of 10 wt%, and then adding 3 wt% of n-butanol into the solution to prepare organic slurry A;

(2) mixing NiO and zirconia powder according to a mass ratio of 80:20, performing ball milling and crushing to obtain NiO-zirconia powder, mixing the NiO-zirconia powder and organic slurry A according to a mass ratio of 1:9, and coating the slurry on the surface of a zirconia support body with a tubular structure by adopting a dipping-pulling method to obtain an anode current collection layer;

(3) mixing NiO and zirconia powder according to a mass ratio of 50:50, performing ball milling and crushing to obtain NiO-zirconia powder, mixing the NiO-zirconia powder and organic slurry A according to a mass ratio of 1:9, and coating the slurry on the surface of an anode current collection layer by adopting a dipping-pulling method to obtain an anode functional layer;

(4) uniformly mixing 25 wt% of organic slurry A, 50 wt% of terpineol and 25 wt% of ethanol to prepare organic slurry B;

(5) mixing zirconia powder and organic slurry B in a mass ratio of 20:80, and then coating the slurry on the surface of an anode functional layer by adopting a dipping-pulling method to obtain a zirconia electrolyte layer; then Ce is mixed_0.8Sm_0.2O_1.9Mixing the powder and the organic slurry B in a mass ratio of 20:80, and then coating the slurry on the surface of the zirconia electrolyte layer by adopting a dipping-pulling method to form Ce_0.8Sm_0.2O_1.9An electrolyte layer, thereby forming a dual electrolyte layer;

(6) and (3) placing the structure in a muffle furnace, and sintering at 1400 ℃ for 4h to obtain the half cell.

S3, preparing a mixed solution A of cerium nitrate, calcium nitrate and citric acid, wherein the concentration of the cerium nitrate in the mixed solution A is 0.70mol/L, the concentration of the calcium nitrate is 0.078mol/L, and the concentration of the citric acid is 2.0 mol/L. Soaking the half cell in the S2 in the mixed solution A (wherein the mass ratio of the zirconium oxide with the tubular structure to the mixed solution A is 10:100) to form a pretreated sample A, wherein the vacuum degree of soaking is 50 kPa; the soaking time is 0.5 h;

s4, calcining the pretreated sample A in an air atmosphere at 500 ℃ for 0.5h to obtain an intermediate;

s5, repeating the operations S3-S4 until the Ce in the intermediate_0.95Ca_0.10O_2-δThe content of (A) reaches 12.9 wt%;

s6, preparing a mixed solution B of nickel nitrate, ammonium paramolybdate and citric acid, wherein the concentration of the nickel nitrate in the mixed solution B is 1.3mol/L, the concentration of the ammonium paramolybdate is 0.031mol/L, and the concentration of the citric acid is 2.0 mol/L. Soaking the intermediate in S5 in a mixed solution B (wherein the mass ratio of the intermediate to the mixed solution B is 10:100) to form a pretreated sample B, wherein the vacuum degree of soaking is 50 kPa; the soaking time is 0.5 h;

s7, calcining the pretreated sample B in an air atmosphere at 500 ℃ for 0.5h to obtain a crude product;

s8, repeating the operations S6-S7 on the crude product until the content of NiMo in the crude product reaches 2.1 wt%, and obtaining the half cell comprising the anode catalytic layer support, wherein NiMo-Ce_0.95Ca_0.10O_2-δThe catalyst content was 15.0 wt%.

S9, preparing a cathode on the half-cell comprising the anode catalyst layer support body, and specifically comprising the following steps: la_0.6Sr_0.4Co_0.2Fe_0.8O_3-δThe cathode powder was mixed with organic slurry A, in which La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δThe content of the cerium oxide is 15 wt%, and a dipping-pulling method is adopted to carry out on Ce_0.8Sm_0.2O_1.9Preparation of La on electrolyte surface_0.6Sr_0.4Co_0.2Fe_0.8O_3-δAnd a cathode layer, wherein the battery cathode is sintered at 1000 ℃ to obtain the SOFC.

Example 4

SOFC, comprising an anode catalytic layer support comprising the structure:

(1) a tubular-structured zirconia support having a porous structure; wherein the inner diameter of the tube is 1.0mm, and the outer diameter is 2.0 mm; the average pore diameter of the pores of the porous structure was 2.0 μm; the porosity of the tubular structure zirconia was 30%;

(2)NiMo/Ce_0.9Ca_0.10O_2-δcatalyst of said NiMo/Ce_0.9Ca_0.10O_2-δThe catalyst is filled in the pores of the porous structure.

The preparation method of the SOFC comprises the following steps:

s1, mixing (ZrO)₂)_0.92(Y₂O₃)_0.08Mixing the powder and PMMA powder according to a mass ratio of 90:10, preparing a ceramic tube blank by adopting an extrusion molding process, and calcining for 2 hours at 900 ℃ to obtain a porous zirconia support body with a tubular structure;

s2, preparing a half cell on the basis of the zirconia support body with the tubular structure. The method comprises the following specific steps:

(1) preparing a polyvinyl butyral-ethanol solution with the concentration of 10 wt%, and then adding 3 wt% of n-butanol into the solution to prepare organic slurry A;

(2) mixing NiO and zirconia powder according to a mass ratio of 80:20, performing ball milling and crushing to obtain NiO-zirconia powder, mixing the NiO-zirconia powder and organic slurry A according to a mass ratio of 1:9, and coating the slurry on the surface of a zirconia support body with a tubular structure by adopting a dipping-pulling method to obtain an anode current collection layer;

(3) mixing NiO and zirconia powder according to a mass ratio of 50:50, performing ball milling and crushing to obtain NiO-zirconia powder, mixing the NiO-zirconia powder and organic slurry A according to a mass ratio of 1:9, and coating the slurry on the surface of an anode current collection layer by adopting a dipping-pulling method to obtain an anode functional layer;

(4) uniformly mixing 25 wt% of organic slurry A, 50 wt% of terpineol and 25 wt% of ethanol to prepare organic slurry B;

(5) mixing zirconia powder and organic slurry B in a mass ratio of 20:80, and then coating the slurry on the surface of an anode functional layer by adopting a dipping-pulling method to obtain a zirconia electrolyte layer; then Ce is mixed_0.8Sm_0.2O_1.9Mixing the powder and the organic slurry B in a mass ratio of 20:80, and then coating the slurry on the surface of the zirconia electrolyte layer by adopting a dipping-pulling method to form Ce_0.8Sm_0.2O_1.9An electrolyte layer, thereby forming a dual electrolyte layer;

(6) and (3) placing the structure in a muffle furnace, and sintering at 1400 ℃ for 4h to obtain the half cell.

S3, preparing a mixed solution A of cerium nitrate, calcium nitrate and citric acid, wherein the concentration of the cerium nitrate in the mixed solution A is 0.30mol/L, the concentration of the calcium nitrate is 0.033mol/L, and the concentration of the citric acid is 1.0 mol/L. Soaking the half cell in the S2 in the mixed solution A (wherein the mass ratio of the zirconium oxide with the tubular structure to the mixed solution A is 1:100) to form a pretreated sample A, wherein the vacuum degree of soaking is 50 kPa; the soaking time is 0.5 h;

s4, calcining the pretreated sample A in an air atmosphere at 500 ℃ for 0.5h to obtain an intermediate;

s5, repeating the operations S3-S4 until the Ce in the intermediate_0.95Ca_0.10O_2-δThe content of (A) reaches 4.3 wt%;

s6, preparing a mixed solution B of nickel nitrate, ammonium paramolybdate and citric acid, wherein the concentration of nickel nitrate in the mixed solution B is 0.4mol/L, the concentration of ammonium paramolybdate is 0.0095mol/L, and the concentration of citric acid is 1.0 mol/L. Soaking the intermediate in S5 in a mixed solution B (wherein the mass ratio of the intermediate to the mixed solution B is 1:100) to form a pretreated sample B, wherein the vacuum degree of soaking is 50 kPa; the soaking time is 0.5 h;

s7, calcining the pretreated sample B in an air atmosphere at 500 ℃ for 0.5h to obtain a crude product;

s8, repeating the operations S6-S7 on the crude product until the content of NiMo in the crude product reaches 0.7 wt%, and obtaining the half cell comprising the anode catalytic layer support, wherein NiMo-Ce_0.95Ca_0.10O_2-δThe catalyst content was 5.0 wt%.

S9, preparing a cathode on the half-cell comprising the anode catalyst layer support body, and specifically comprising the following steps: la_0.6Sr_0.4Co_0.2Fe_0.8O_3-δThe cathode powder was mixed with organic slurry A, in which La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δThe content of the cerium oxide is 15 wt%, and a dipping-pulling method is adopted to carry out on Ce_0.8Sm_0.2O_1.9Preparation of La on electrolyte surface_0.6Sr_0.4Co_0.2Fe_0.8O_3-δAnd a cathode layer, wherein the battery cathode is sintered at 1000 ℃ to obtain the SOFC.

Example 5

SOFC, comprising an anode catalytic layer support comprising the structure:

(1) a tubular-structured zirconia support having a porous structure; wherein the inner diameter of the tube is 5.0mm, and the outer diameter is 7.0 mm; the average pore diameter of the pores of the porous structure was 3.0 μm; the porosity of the tubular structure zirconia was 43%;

(2)NiMo/Ce_0.9Ca_0.10O_2-δcatalyst of said NiMo/Ce_0.9Ca_0.10O_2-δThe catalyst is filled in the pores of the porous structure.

The preparation method of the SOFC comprises the following steps:

s1, mixing (ZrO)₂)_0.92(Y₂O₃)_0.08Mixing the powder and PMMA powder according to a mass ratio of 70:30, preparing a ceramic tube blank by adopting an extrusion molding process, and calcining for 2 hours at 900 ℃ to obtain a porous zirconia support body with a tubular structure;

s2, preparing a half cell on the basis of the zirconia support body with the tubular structure. The method comprises the following specific steps:

(1) preparing a polyvinyl butyral-ethanol solution with the concentration of 10 wt%, and then adding 3 wt% of n-butanol into the solution to prepare organic slurry A;

(2) mixing NiO and zirconia powder according to a mass ratio of 80:20, performing ball milling and crushing to obtain NiO-zirconia powder, mixing the NiO-zirconia powder and organic slurry A according to a mass ratio of 1:9, and coating the slurry on the surface of a zirconia support body with a tubular structure by adopting a dipping-pulling method to obtain an anode current collection layer;

(3) mixing NiO and zirconia powder according to a mass ratio of 50:50, performing ball milling and crushing to obtain NiO-zirconia powder, mixing the NiO-zirconia powder and organic slurry A according to a mass ratio of 1:9, and coating the slurry on the surface of an anode current collection layer by adopting a dipping-pulling method to obtain an anode functional layer;

(4) uniformly mixing 25 wt% of organic slurry A, 50 wt% of terpineol and 25 wt% of ethanol to prepare organic slurry B;

(5) mixing zirconia powder and organic slurry B in a mass ratio of 20:80, and then coating the slurry on the surface of an anode functional layer by adopting a dipping-pulling method to obtain a zirconia electrolyte layer; then Ce is mixed_0.8Sm_0.2O_1.9Mixing the powder and the organic slurry B in a mass ratio of 20:80, and thenThen coating the slurry on the surface of a zirconia electrolyte layer by adopting a dipping-pulling method to form Ce_0.8Sm_0.2O_1.9An electrolyte layer, thereby forming a dual electrolyte layer;

(6) and (3) placing the structure in a muffle furnace, and sintering at 1400 ℃ for 4h to obtain the half cell.

S3, preparing a mixed solution A of cerium nitrate, calcium nitrate and citric acid, wherein the concentration of the cerium nitrate in the mixed solution A is 0.70mol/L, the concentration of the calcium nitrate is 0.078mol/L, and the concentration of the citric acid is 2.0 mol/L. Soaking the half cell in the S2 in the mixed solution A (wherein the mass ratio of the zirconium oxide with the tubular structure to the mixed solution A is 10:100) to form a pretreated sample A, wherein the vacuum degree of soaking is 50 kPa; the soaking time is 0.5 h;

s4, calcining the pretreated sample A in an air atmosphere at 500 ℃ for 0.5h to obtain an intermediate;

s5, repeating the operations S3-S4 until the Ce in the intermediate_0.95Ca_0.10O_2-δThe content of (A) reaches 12.9 wt%;

s6, preparing a mixed solution B of nickel nitrate, ammonium paramolybdate and citric acid, wherein the concentration of the nickel nitrate in the mixed solution B is 1.3mol/L, the concentration of the ammonium paramolybdate is 0.031mol/L, and the concentration of the citric acid is 2.0 mol/L. Soaking the intermediate in S5 in a mixed solution B (wherein the mass ratio of the intermediate to the mixed solution B is 10:100) to form a pretreated sample B, wherein the vacuum degree of soaking is 50 kPa; the soaking time is 0.5 h;

s7, calcining the pretreated sample B in an air atmosphere at 500 ℃ for 0.5h to obtain a crude product;

s8, repeating the operations S6-S7 on the crude product until the content of NiMo in the crude product reaches 2.1 wt%, and obtaining the half cell comprising the anode catalytic layer support, wherein NiMo-Ce_0.95Ca_0.10O_2-δThe catalyst content was 15.0 wt%.

S9, preparing a cathode on the half-cell comprising the anode catalyst layer support body, and specifically comprising the following steps: la_0.6Sr_0.4Co_0.2Fe_0.8O_3-δMixing cathode powder with organic slurry AWherein La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δThe content of the cerium oxide is 15 wt%, and a dipping-pulling method is adopted to carry out on Ce_0.8Sm_0.2O_1.9Preparation of La on electrolyte surface_0.6Sr_0.4Co_0.2Fe_0.8O_3-δAnd a cathode layer, wherein the battery cathode is sintered at 1000 ℃ to obtain the SOFC.

Example 6

SOFC, comprising an anode catalytic layer support comprising the structure:

(1) a flat-plate-structured zirconia support having a porous structure; wherein the thickness of the flat plate is 0.5mm, and the average pore diameter of pores of the porous structure is 2.0 μm; the porosity of the flat plate-type structure zirconia is 30%;

(2)NiMo/Ce_0.85Ca_0.15O_2-δcatalyst of said NiMo/Ce_0.85Ca_0.15O_2-δThe catalyst is filled in the pores of the porous structure,

the preparation method of the SOFC comprises the following steps:

s1, mixing (ZrO)₂)_0.92(Y₂O₃)_0.08The powder and the PMMA powder are mixed in a mass ratio of 85:15, and a ceramic body is prepared by a powder tabletting method (the powder tabletting method is shown in the prior art: Panthi, D., Hedayat, N.,&du, Y. (2018), a degradation behavor of a yttria-stabilized zirconia powder for a solid oxide fuel cell electrolytes, 7(4), 325-335), and calcining for 2h at 900 ℃ to obtain a porous zirconia support with a flat plate structure;

s2, preparing a half cell on the basis of the zirconium oxide support body with the flat plate type structure. The method comprises the following specific steps:

(1) dissolving ethyl cellulose in terpineol to prepare an ethyl cellulose-terpineol solution with the ethyl cellulose concentration of 5 wt%; then, adding 10 wt% of dibutyl phthalate and 10 wt% of n-butyl alcohol into the solution to prepare organic slurry C;

(2) mixing NiO and zirconia powder according to a mass ratio of 80:20, performing ball milling and crushing to obtain NiO-zirconia powder, mixing the NiO-zirconia powder and organic slurry C according to a mass ratio of 60:40, and preparing a NiO-zirconia anode current collection layer on the surface of a porous zirconia ceramic support body by adopting a screen printing process;

(3) mixing NiO and zirconia powder according to the mass ratio of 50:50, performing ball milling and crushing to obtain NiO-zirconia powder, mixing the NiO-zirconia powder and organic slurry C according to the mass ratio of 60:40, and preparing a NiO-zirconia anode functional layer on the surface of a NiO-zirconia anode current collecting layer by adopting a screen printing process;

(4) mixing zirconia powder and organic slurry C according to the mass ratio of 50:50, and preparing a zirconia electrolyte layer on the surface of the NiO-zirconia anode functional layer by adopting a screen printing process;

(5) adding Ce_0.8Sm_0.2O_1.9Mixing the powder and the organic slurry C in a mass ratio of 50:50, and preparing Ce on the surface of the zirconia electrolyte layer by adopting a screen printing process_0.8Sm_0.2O_1.9An electrolyte layer, thereby forming a dual electrolyte layer;

(6) and (3) placing the structure in a muffle furnace, and sintering at 1400 ℃ for 4h to obtain the half cell.

S3, preparing a mixed solution A of cerium nitrate, calcium nitrate and citric acid, wherein the concentration of the cerium nitrate in the mixed solution A is 0.3mol/L, the concentration of the calcium nitrate is 0.033mol/L, and the concentration of the citric acid is 1.50 mol/L. Soaking the half cell in the S2 in the mixed solution A (wherein the mass ratio of the zirconium oxide with the flat plate structure to the mixed solution A is 1:100) to form a pretreated sample A, wherein the vacuum degree of soaking is 50 kPa; the soaking time is 0.5 h;

s4, calcining the pretreated sample A in an air atmosphere at 500 ℃ for 0.5h to obtain an intermediate;

s5, repeating the operations S3-S4 until the Ce in the intermediate_0.85Ca_0.15O_2-δThe content of (A) reaches 4.3 wt%;

s6, preparing a mixed solution B of nickel nitrate, ammonium paramolybdate and citric acid, wherein the concentration of nickel nitrate in the mixed solution B is 0.4mol/L, the concentration of ammonium paramolybdate is 0.0095mol/L, and the concentration of citric acid is 1.0 mol/L. Soaking the intermediate in S5 in a mixed solution B (wherein the mass ratio of the intermediate to the mixed solution B is 1:100) to form a pretreated sample B, wherein the vacuum degree of soaking is 50 kPa; the soaking time is 0.5 h;

s7, calcining the pretreated sample B in an air atmosphere at 500 ℃ for 0.5h to obtain a crude product;

s8, repeating the operations S6-S7 on the crude product until the content of NiMo in the crude product reaches 0.7 wt%, and obtaining the half cell comprising the anode catalytic layer support, wherein NiMo-Ce_0.95Ca_0.10O_2-δThe catalyst content was 5.0 wt%.

S9, preparing a cathode on the half-cell comprising the anode catalyst layer support body, and specifically comprising the following steps: la_0.6Sr_0.4Co_0.2Fe_0.8O_3-δMixing the cathode powder with an organic slurry C, wherein La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δThe content of (B) is 60 wt%, and the silk-screen printing process is adopted to process Ce_0.8Sm_0.2O_1.9Preparation of La on electrolyte surface_0.6Sr_0.4Co_0.2Fe_0.8O_3-δAnd a cathode layer, wherein the battery cathode is sintered at 1000 ℃ to obtain the SOFC.

Example 7

SOFC, comprising an anode catalytic layer support comprising the structure:

(1) a flat-plate-structured zirconia support having a porous structure; wherein the thickness of the flat plate is 1.0mm, and the average pore diameter of pores of the porous structure is 2.5 μm; the porosity of the flat plate structure zirconia was 35%;

(2)NiMo/Ce_0.85Ca_0.15O_2-δcatalyst of said NiMo/Ce_0.85Ca_0.15O_2-δThe catalyst is filled in the pores of the porous structure,

the preparation method of the SOFC comprises the following steps:

s1, mixing (ZrO)₂)_0.92(Y₂O₃)_0.08Mixing the powder and PMMA powder according to a mass ratio of 80:20, preparing a ceramic blank by adopting a powder tabletting method, and calcining for 2 hours at 900 ℃ to obtain a porous zirconia support body with a flat plate type structure;

s2, preparing a half cell on the basis of the zirconium oxide support body with the flat plate type structure. The method comprises the following specific steps:

(1) dissolving ethyl cellulose in terpineol to prepare an ethyl cellulose-terpineol solution with the ethyl cellulose concentration of 5 wt%; then, 10 wt% of dibutyl phthalate and 10 wt% of n-butanol were added to the solution to prepare an organic slurry C

(2) Mixing NiO and zirconia powder according to a mass ratio of 80:20, performing ball milling and crushing to obtain NiO-zirconia powder, mixing the NiO-zirconia powder and organic slurry C according to a mass ratio of 60:40, and preparing a NiO-zirconia anode current collection layer on the surface of a porous zirconia ceramic support body by adopting a screen printing process;

(3) mixing NiO and zirconia powder according to the mass ratio of 50:50, performing ball milling and crushing to obtain NiO-zirconia powder, mixing the NiO-zirconia powder and organic slurry C according to the mass ratio of 60:40, and preparing a NiO-zirconia anode functional layer on the surface of a NiO-zirconia anode current collecting layer by adopting a screen printing process;

(4) mixing zirconia powder and organic slurry C according to the mass ratio of 50:50, and preparing a zirconia electrolyte layer on the surface of the NiO-zirconia anode functional layer by adopting a screen printing process;

(5) adding Ce_0.8Sm_0.2O_1.9Mixing the powder and the organic slurry C in a mass ratio of 50:50, and preparing Ce on the surface of the zirconia electrolyte layer by adopting a screen printing process_0.8Sm_0.2O_1.9Electrolyte layer to form a dual electrolyte layer

(6) And (3) placing the structure in a muffle furnace, and sintering at 1400 ℃ for 4h to obtain the half cell.

S3, preparing a mixed solution A of cerium nitrate, calcium nitrate and citric acid, wherein the concentration of the cerium nitrate in the mixed solution A is 0.60mol/L, the concentration of the calcium nitrate is 0.066mol/L, and the concentration of the citric acid is 1.32 mol/L. Soaking the half cell in the S2 in the mixed solution A (wherein the mass ratio of the zirconium oxide with the flat plate structure to the mixed solution A is 5:100) to form a pretreated sample A, wherein the vacuum degree of soaking is 50 kPa; the soaking time is 0.5 h;

s4, calcining the pretreated sample A in an air atmosphere at 500 ℃ for 0.5h to obtain an intermediate;

s5, repeating the operations S3-S4 until the Ce in the intermediate_0.85Ca_0.15O_2-δThe content of (A) reaches 8.6 wt%;

s6, preparing a mixed solution B of nickel nitrate, ammonium paramolybdate and citric acid, wherein the concentration of nickel nitrate in the mixed solution B is 0.8mol/L, the concentration of ammonium paramolybdate is 0.019mol/L, and the concentration of citric acid is 1.5 mol/L. Soaking the intermediate in S5 in a mixed solution B (wherein the mass ratio of the intermediate to the mixed solution B is 5:100) to form a pretreated sample B, wherein the vacuum degree of soaking is 50 kPa; the soaking time is 0.5 h;

s7, calcining the pretreated sample B in an air atmosphere at 500 ℃ for 0.5h to obtain a crude product;

s8, repeating the operations S6-S7 on the crude product until the content of NiMo in the crude product reaches 1.4 wt%, and obtaining the half cell comprising the anode catalytic layer support, wherein NiMo-Ce_0.95Ca_0.10O_2-δThe catalyst content was 10.0 wt%.

S9, preparing a cathode on the half-cell comprising the anode catalyst layer support body, and specifically comprising the following steps: la_0.6Sr_0.4Co_0.2Fe_0.8O_3-δMixing the cathode powder with an organic slurry C, wherein La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δThe content of (B) is 60 wt%, and the silk-screen printing process is adopted to process Ce_0.8Sm_0.2O_1.9Preparation of La on electrolyte surface_0.6Sr_0.4Co_0.2Fe_0.8O_3-δAnd a cathode layer, wherein the battery cathode is sintered at 1000 ℃ to obtain the SOFC.

Example 8

SOFC, comprising an anode catalytic layer support comprising the structure:

(1) a flat-plate-structured zirconia support having a porous structure; wherein the thickness of the flat plate is 1.5mm, and the average pore diameter of pores of the porous structure is 3.0 μm; the porosity of the flat plate-structured zirconia was 43%;

(2)NiMo/Ce_0.85Ca_0.15O_2-δcatalyst of said NiMo/Ce_0.85Ca_0.15O_2-δThe catalyst is filled in the pores of the porous structure,

the preparation method of the SOFC comprises the following steps:

s1, mixing (ZrO)₂)_0.92(Y₂O₃)_0.08Mixing the powder and PMMA powder according to a mass ratio of 75:25, preparing a ceramic blank by adopting a powder tabletting method, and calcining for 2 hours at 900 ℃ to obtain a porous zirconia support body with a flat plate type structure;

s2, preparing a half cell on the basis of the zirconium oxide support body with the flat plate type structure. The method comprises the following specific steps:

(1) dissolving ethyl cellulose in terpineol to prepare an ethyl cellulose-terpineol solution with the ethyl cellulose concentration of 5 wt%; then, 10 wt% of dibutyl phthalate and 10 wt% of n-butanol were added to the solution to prepare an organic slurry C

(2) Mixing NiO and zirconia powder according to a mass ratio of 80:20, performing ball milling and crushing to obtain NiO-zirconia powder, mixing the NiO-zirconia powder and organic slurry C according to a mass ratio of 60:40, and preparing a NiO-zirconia anode current collection layer on the surface of a porous zirconia ceramic support body by adopting a screen printing process;

(3) mixing NiO and zirconia powder according to the mass ratio of 50:50, performing ball milling and crushing to obtain NiO-zirconia powder, mixing the NiO-zirconia powder and organic slurry C according to the mass ratio of 60:40, and preparing a NiO-zirconia anode functional layer on the surface of a NiO-zirconia anode current collecting layer by adopting a screen printing process;

(4) mixing zirconia powder and organic slurry C according to the mass ratio of 50:50, and preparing a zirconia electrolyte layer on the surface of the NiO-zirconia anode functional layer by adopting a screen printing process;

(5) adding Ce_0.8Sm_0.2O_1.9Mixing the powder and the organic slurry C in a mass ratio of 50:50, and preparing Ce on the surface of the zirconia electrolyte layer by adopting a screen printing process_0.8Sm_0.2O_1.9Electrolyte layer to form a dual electrolyte layer

(6) And (3) placing the structure in a muffle furnace, and sintering at 1400 ℃ for 4h to obtain the half cell.

S3, preparing a mixed solution A of cerium nitrate, calcium nitrate and citric acid, wherein the concentration of the cerium nitrate in the mixed solution A is 0.70mol/L, the concentration of the calcium nitrate is 0.078mol/L, and the concentration of the citric acid is 2.0 mol/L. Soaking the half cell in the S2 in the mixed solution A (wherein the mass ratio of the zirconium oxide with the flat plate structure to the mixed solution A is 10:100) to form a pretreated sample A, wherein the vacuum degree of soaking is 50 kPa; the soaking time is 0.5 h;

s4, calcining the pretreated sample A in an air atmosphere at 500 ℃ for 0.5h to obtain an intermediate;

s5, repeating the operations S3-S4 until the Ce in the intermediate_0.85Ca_0.15O_2-δThe content of (A) reaches 12.9 wt%;

s6, preparing a mixed solution B of nickel nitrate, ammonium paramolybdate and citric acid, wherein the concentration of the nickel nitrate in the mixed solution B is 1.3mol/L, the concentration of the ammonium paramolybdate is 0.031mol/L, and the concentration of the citric acid is 2.0 mol/L. Soaking the intermediate in S5 in a mixed solution B (wherein the mass ratio of the intermediate to the mixed solution B is 10:100) to form a pretreated sample B, wherein the vacuum degree of soaking is 50 kPa; the soaking time is 0.5 h;

s7, calcining the pretreated sample B in an air atmosphere at 500 ℃ for 0.5h to obtain a crude product;

s8, repeating the operations S6-S7 on the crude product until the content of NiMo in the crude product reaches 2.1 wt%, and obtaining the half cell comprising the anode catalytic layer support, wherein NiMo-Ce_0.95Ca_0.10O_2-δThe catalyst content was 15.0 wt%.

S9. in the above-mentioned formulaPreparing a cathode on a half cell of the polar catalytic layer support body, and specifically comprising the following steps: la_0.6Sr_0.4Co_0.2Fe_0.8O_3-δMixing the cathode powder with an organic slurry C, wherein La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δThe content of (B) is 60 wt%, and the silk-screen printing process is adopted to process Ce_0.8Sm_0.2O_1.9Preparation of La on electrolyte surface_0.6Sr_0.4Co_0.2Fe_0.8O_3-δAnd a cathode layer, wherein the battery cathode is sintered at 1000 ℃ to obtain the SOFC.

Example 9

SOFC, comprising an anode catalytic layer support comprising the structure:

(1) a flat-plate-structured zirconia support having a porous structure; wherein the thickness of the flat plate is 0.5mm, and the average pore diameter of pores of the porous structure is 2.0 μm; the porosity of the flat plate-type structure zirconia is 30%;

(2)NiMo/Ce_0.85Ca_0.15O_2-δcatalyst of said NiMo/Ce_0.85Ca_0.15O_2-δThe catalyst is filled in the pores of the porous structure,

the preparation method of the SOFC comprises the following steps:

s1, mixing (ZrO)₂)_0.92(Y₂O₃)_0.08Mixing the powder and PMMA powder according to a mass ratio of 90:10, preparing a ceramic blank by adopting a powder tabletting method, and calcining for 2 hours at 900 ℃ to obtain a porous zirconia support body with a flat plate type structure;

s2, preparing a half cell on the basis of the zirconium oxide support body with the flat plate type structure. The method comprises the following specific steps:

(1) dissolving ethyl cellulose in terpineol to prepare an ethyl cellulose-terpineol solution with the ethyl cellulose concentration of 5 wt%; then, adding 10 wt% of dibutyl phthalate and 10 wt% of n-butyl alcohol into the solution to prepare organic slurry C;

(2) mixing NiO and zirconia powder according to a mass ratio of 80:20, performing ball milling and crushing to obtain NiO-zirconia powder, mixing the NiO-zirconia powder and organic slurry C according to a mass ratio of 60:40, and preparing a NiO-zirconia anode current collection layer on the surface of a porous zirconia ceramic support body by adopting a screen printing process;

(3) mixing NiO and zirconia powder according to the mass ratio of 50:50, performing ball milling and crushing to obtain NiO-zirconia powder, mixing the NiO-zirconia powder and organic slurry C according to the mass ratio of 60:40, and preparing a NiO-zirconia anode functional layer on the surface of a NiO-zirconia anode current collecting layer by adopting a screen printing process;

(4) mixing zirconia powder and organic slurry C according to the mass ratio of 50:50, and preparing a zirconia electrolyte layer on the surface of the NiO-zirconia anode functional layer by adopting a screen printing process;

(5) adding Ce_0.8Sm_0.2O_1.9Mixing the powder and the organic slurry C in a mass ratio of 50:50, and preparing Ce on the surface of the zirconia electrolyte layer by adopting a screen printing process_0.8Sm_0.2O_1.9An electrolyte layer, thereby forming a dual electrolyte layer;

(6) and (3) placing the structure in a muffle furnace, and sintering at 1400 ℃ for 4h to obtain the half cell.

S3, preparing a mixed solution A of cerium nitrate, calcium nitrate and citric acid, wherein the concentration of the cerium nitrate in the mixed solution A is 0.3mol/L, the concentration of the calcium nitrate is 0.033mol/L, and the concentration of the citric acid is 1.80 mol/L. Soaking the half cell in the S2 in the mixed solution A (wherein the mass ratio of the zirconium oxide with the flat plate structure to the mixed solution A is 1:100) to form a pretreated sample A, wherein the vacuum degree of soaking is 50 kPa; the soaking time is 0.5 h;

s4, calcining the pretreated sample A in an air atmosphere at 500 ℃ for 0.5h to obtain an intermediate;

s5, repeating the operations S3-S4 until the Ce in the intermediate_0.85Ca_0.15O_2-δThe content of (A) reaches 4.3 wt%;

s6, preparing a mixed solution B of nickel nitrate, ammonium paramolybdate and citric acid, wherein the concentration of nickel nitrate in the mixed solution B is 0.4mol/L, the concentration of ammonium paramolybdate is 0.0095mol/L, and the concentration of citric acid is 1.0 mol/L. Soaking the intermediate in S5 in a mixed solution B (wherein the mass ratio of the intermediate to the mixed solution B is 1:100) to form a pretreated sample B, wherein the vacuum degree of soaking is 50 kPa; the soaking time is 0.5 h;

s7, calcining the pretreated sample B in an air atmosphere at 500 ℃ for 0.5h to obtain a crude product;

s8, repeating the operations S6-S7 on the crude product until the content of NiMo in the crude product reaches 0.7 wt%, and obtaining the half cell comprising the anode catalytic layer support, wherein NiMo-Ce_0.95Ca_0.10O_2-δThe catalyst content was 5.0 wt%.

S9, preparing a cathode on the half-cell comprising the anode catalyst layer support body, and specifically comprising the following steps: la_0.6Sr_0.4Co_0.2Fe_0.8O_3-δMixing the cathode powder with an organic slurry C, wherein La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δThe content of (B) is 60 wt%, and the silk-screen printing process is adopted to process Ce_0.8Sm_0.2O_1.9Preparation of La on electrolyte surface_0.6Sr_0.4Co_0.2Fe_0.8O_3-δAnd a cathode layer, wherein the battery cathode is sintered at 1000 ℃ to obtain the SOFC.

Example 10

SOFC, comprising an anode catalytic layer support comprising the structure:

(1) a flat-plate-structured zirconia support having a porous structure; wherein the thickness of the flat plate is 1.5mm, and the average pore diameter of pores of the porous structure is 3.0 μm; the porosity of the flat plate-structured zirconia was 43%;

(2)NiMo/Ce_0.85Ca_0.15O_2-δcatalyst of said NiMo/Ce_0.85Ca_0.15O_2-δThe catalyst is filled in the pores of the porous structure,

the preparation method of the SOFC comprises the following steps:

s1, mixing (ZrO)₂)_0.92(Y₂O₃)_0.08Mixing the powder and PMMA powder according to a mass ratio of 70:30, preparing a ceramic blank by adopting a powder tabletting method, and calcining for 2 hours at 900 ℃ to obtain a porous zirconia support body with a flat plate type structure;

s2, preparing a half cell on the basis of the zirconium oxide support body with the flat plate type structure. The method comprises the following specific steps:

(1) dissolving ethyl cellulose in terpineol to prepare an ethyl cellulose-terpineol solution with the ethyl cellulose concentration of 5 wt%; then, 10 wt% of dibutyl phthalate and 10 wt% of n-butanol were added to the solution to prepare an organic slurry C

(2) Mixing NiO and zirconia powder according to a mass ratio of 80:20, performing ball milling and crushing to obtain NiO-zirconia powder, mixing the NiO-zirconia powder and organic slurry C according to a mass ratio of 60:40, and preparing a NiO-zirconia anode current collection layer on the surface of a porous zirconia ceramic support body by adopting a screen printing process;

(3) mixing NiO and zirconia powder according to the mass ratio of 50:50, performing ball milling and crushing to obtain NiO-zirconia powder, mixing the NiO-zirconia powder and organic slurry C according to the mass ratio of 60:40, and preparing a NiO-zirconia anode functional layer on the surface of a NiO-zirconia anode current collecting layer by adopting a screen printing process;

(4) mixing zirconia powder and organic slurry C according to the mass ratio of 50:50, and preparing a zirconia electrolyte layer on the surface of the NiO-zirconia anode functional layer by adopting a screen printing process;

(5) adding Ce_0.8Sm_0.2O_1.9Mixing the powder and the organic slurry C in a mass ratio of 50:50, and preparing Ce on the surface of the zirconia electrolyte layer by adopting a screen printing process_0.8Sm_0.2O_1.9Electrolyte layer to form a dual electrolyte layer

(6) And (3) placing the structure in a muffle furnace, and sintering at 1400 ℃ for 4h to obtain the half cell.

S3, preparing a mixed solution A of cerium nitrate, calcium nitrate and citric acid, wherein the concentration of the cerium nitrate in the mixed solution A is 0.70mol/L, the concentration of the calcium nitrate is 0.078mol/L, and the concentration of the citric acid is 2.0 mol/L. Soaking the half cell in the S2 in the mixed solution A (wherein the mass ratio of the zirconium oxide with the flat plate structure to the mixed solution A is 10:100) to form a pretreated sample A, wherein the vacuum degree of soaking is 50 kPa; the soaking time is 0.5 h;

s4, calcining the pretreated sample A in an air atmosphere at 500 ℃ for 0.5h to obtain an intermediate;

s5, repeating the operations S3-S4 until the Ce in the intermediate_0.85Ca_0.15O_2-δThe content of (A) reaches 12.9 wt%;

s6, preparing a mixed solution B of nickel nitrate, ammonium paramolybdate and citric acid, wherein the concentration of the nickel nitrate in the mixed solution B is 1.3mol/L, the concentration of the ammonium paramolybdate is 0.031mol/L, and the concentration of the citric acid is 2.0 mol/L. Soaking the intermediate in S5 in a mixed solution B (wherein the mass ratio of the intermediate to the mixed solution B is 10:100) to form a pretreated sample B, wherein the vacuum degree of soaking is 50 kPa; the soaking time is 0.5 h;

s7, calcining the pretreated sample B in an air atmosphere at 500 ℃ for 0.5h to obtain a crude product;

s8, repeating the operations S6-S7 on the crude product until the content of NiMo in the crude product reaches 2.1 wt%, and obtaining the half cell comprising the anode catalytic layer support, wherein NiMo-Ce_0.95Ca_0.10O_2-δThe catalyst content was 15.0 wt%.

S9, preparing a cathode on the half-cell comprising the anode catalyst layer support body, and specifically comprising the following steps: la_0.6Sr_0.4Co_0.2Fe_0.8O_3-δMixing the cathode powder with an organic slurry C, wherein La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δThe content of (B) is 60 wt%, and the silk-screen printing process is adopted to process Ce_0.8Sm_0.2O_1.9Preparation of La on electrolyte surface_0.6Sr_0.4Co_0.2Fe_0.8O_3-δAnd a cathode layer, wherein the battery cathode is sintered at 1000 ℃ to obtain the SOFC.

Comparative example

The comparative example adopts a traditional anode-supported SOFC with the structure of Ni-YSZ anode support body/YSZ/Ce_0.8Sm_0.2O_1.9Dual electrolyte layer/La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δAnd a cathode.

Test section

Testing of porosity: the porosity of the anode catalytic layer support of the SOFCs of examples 1-5 was tested according to ISO-18754 using archimedes method;

testing of breaking strength: the anode catalytic layer support of the SOFCs of examples 1-5 were tested for fracture strength by three-point bending according to ISO-23242,

fig. 1 shows the porosity of the tube SOFC anode catalyst layer support in examples 1-5 as a function of the pore former PMMA content. When the pore-forming agent content is 10 wt%, the porosity of the catalyst layer support is only-12%; when the content of the pore-forming agent is increased to 15 wt%, the porosity is obviously increased to 30%; further increasing the pore former content from 15 wt% to 30 wt% showed a slow linear increase in porosity. According to the requirement of SOFC on the porosity of the support body (the porosity range is 30-40%), when the catalyst layer support body is prepared, the content of a proper pore-forming agent PMMA is 15-25 wt%.

Fig. 2 shows the fracture strength of the support of the anode catalytic layer of the tubular SOFC in examples 1-5 as a function of the content of the pore-forming agent PMMA. When the content of the pore-forming agent is 10 wt%, the fracture strength of the catalyst layer support body is 36 MPa; when the content of the pore-forming agent is gradually increased to 30 wt%, the breaking strength is reduced to 12.5 MPa. According to the requirement of SOFC on the strength performance of the support body (the fracture strength is more than 20Mpa), when the catalyst layer support body is prepared, the content of a proper pore-forming agent PMMA is 15-25 wt%.

Figure 3 shows an SEM microstructure photograph of the tube-in-tube SOFC in example 2. The result of SEM image analysis shows that NiO-Ce_0.8Sm_0.2O_1.9The thickness of the anode current collecting layer is 14 mu m, NiO-Ce_0.8Sm_0.2O_1.9The thickness of the anode functional layer is 11 mu m and (ZrO)₂)_0.92(Y2O₃)_0.08/Ce_0.8Sm_0.2O_1.9The thickness of the double electrolyte layer is 10 to 5 μm, respectively, La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δThe thickness of the cathode layer was 11 μm.

Performance testing

Tubular SOFC

The performance of the tubular SOFC of examples 1-5 was investigated using the apparatus shown in FIG. 4, using Al₂O₃And sealing the battery sample by using the ceramic sealant, and carrying out electrochemical performance test at 750 ℃. When hydrogen is used as fuel, the hydrogen is directly input into the anode port of the cell; when isooctane is used as fuel, bubbling method (100 ml min will be used) is used at room temperature^-1Air is passed into the isooctane solution) to mix the isooctane with air and deliver the mixed gas to the anode port of the cell. The invention adopts a standard current-voltage testing technology to research the electrochemical performance of the battery, and adopts a constant current discharging technology to research the working performance stability of the battery.

Fig. 5(a) shows the catalytic performance of the tubular SOFC on isooctane/air of example 2. NiMo-Ce in the catalytic layer at a test temperature of 750 DEG C_0.9Ca_0.1O_2-δThe catalyst can promote the partial oxidation of isooctane fuel, and the conversion rate of isooctane reaches 70 percent, H₂And yields of CO were 30% and 45%, respectively. Fig. 5(b) shows the catalytic performance of the tubular SOFC on isooctane/air as a function of catalyst loading in the catalytic layer support of examples 1-3. When NiMo-Ce_0.9Ca_0.1O_2-δFuel conversion and H at a catalyst content of 0-10 wt%₂And the yield of CO is obviously improved along with the content of the catalyst, which shows that the improvement of the loading capacity of the catalyst is favorable for promoting the conversion of the isooctane fuel in the catalytic layer of the cell. When the catalyst content is further increased from 10 wt% to 15 wt%, the fuel conversion rate and H are increased₂And no significant increase in the yield of CO. Therefore, under the test conditions employed in the present invention, the optimum catalyst content in the SOFC catalytic layer support was-10 wt%.

Figure 6(a) shows the electrochemical performance of SOFC in hydrogen and isooctane fuels with a 10 wt% catalyst loading of example 2. Open circuit of cell when using hydrogen as fuelThe voltage is 1.05V, and the maximum output power density is 458mW/cm²(ii) a When the hydrogen fuel is converted into isooctane/air, the open-circuit voltage of the cell is reduced to 0.98V, and the maximum output power density is reduced to 371mW/cm². Fig. 6(b) shows the maximum output power density of the tubular SOFC in examples 1-5 as a function of the pore-forming agent PMMA content in hydrogen and isooctane fuels. In the range of 10-25 wt% of pore-forming agent, the increase of the content of the pore-forming agent is beneficial to increasing the porosity of the catalyst layer support body, promoting the diffusion of anode reaction gas in the catalyst layer support body and improving the maximum output power density of the cell in hydrogen and isooctane fuel.

Fig. 7 shows the discharge stability curve of the tubular SOFC of example 2 in iso-octane fuel. For a conventional anode-supported SOFC, the cell can be operated for a stable run time of-10 hours (excluding the catalyst deactivation regeneration cycle) by applying a NiMo-based catalyst to the anode surface. However, the conventional anode support has structural stability problems in complex hydrocarbon fuels, which leads to cracking of the cell support after 10 hours, and cell failure. The SOFC provided by the invention is based on the dual functions of structural stability and chemical catalysis of the catalytic support body in complex hydrocarbon fuel, and the single stable operation time of the cell can be increased from 10 hours to 30 hours. This result demonstrates the structural advantages of the disclosed SOFC.

Flat SOFC

The invention was carried out by investigating the properties of the planar SOFCs of examples 6-10 using Al, according to the test apparatus shown in FIG. 8₂O₃And sealing the battery sample by using the ceramic sealant, and carrying out electrochemical performance test at 750 ℃. When hydrogen is used as fuel, the hydrogen is directly input into the anode port of the cell; when isooctane is used as fuel, bubbling method (100 ml min will be used) is used at room temperature^-1Air is passed into the isooctane solution) to mix the isooctane with air and deliver the mixed gas to the anode port of the cell. The invention adopts a standard current-voltage testing technology to research the electrochemical performance of the battery, and adopts a constant current discharging technology to research the working performance stability of the battery.

Figure 9(a) shows the catalytic performance of the planar SOFC of example 7 on isooctane/air at a catalyst loading of 10 wt%. NiMo-Ce in catalytic layer support at test temperature of 750 DEG C_0.9Ca_0.1O_2-δThe catalyst can promote the partial oxidation of isooctane fuel, and the conversion rate of isooctane reaches-60%, H₂And yields of CO were 22% and 35%, respectively. Fig. 9(b) shows the catalytic performance of the planar SOFC on isooctane/air as a function of catalyst loading in the catalytic layer support for examples 6-8. When NiMo-Ce_0.9Ca_0.1O_2-δFuel conversion and H at a catalyst content of 0-10 wt%₂And the yield of CO is obviously improved along with the content of the catalyst, which shows that the improvement of the loading capacity of the catalyst is favorable for promoting the conversion of the isooctane fuel in the catalytic layer of the cell. When the catalyst content is further increased from 10 wt% to 15 wt%, the fuel conversion rate and H are increased₂And no significant increase in the yield of CO. Therefore, under the test conditions employed in the present invention, the optimum content of catalyst in the SOFC catalytic layer is-10 wt%.

Figure 10(a) shows the electrochemical performance of the planar SOFC in hydrogen and isooctane fuels with a 10 wt% catalyst loading of example 7. When hydrogen is used as the fuel, the open-circuit voltage of the cell is 1.05V, and the maximum output power density is 528mW/cm²(ii) a When the hydrogen fuel is converted into isooctane/air, the open-circuit voltage of the cell is reduced to 1.01V, and the maximum output power density is reduced to 437mW/cm². Fig. 10(b) shows the maximum output power density of the SOFCs of examples 6-10 in hydrogen and isooctane fuels as a function of the pore former PMMA content. When the content of the pore-forming agent is 10-25 wt%, the increase of the content of the pore-forming agent is beneficial to increasing the porosity of the catalyst layer support body, promoting the diffusion of anode reaction gas in the catalyst layer support body and improving the maximum output power density of the battery.

Fig. 11 shows the discharge stability curve of the SOFC of example 7 in iso-octane fuel. The NiMo-based catalyst is Applied to the surface of the traditional anode-supported SOFC, and the stable operation time of the cell can reach 8h (excluding the catalyst deactivation and regeneration cycle process, Applied Catalysis B: Environmental 224(2018) 500-507). The single stable running time of the SOFC provided by the invention can be increased from 8 hours to 30 hours. This result demonstrates the structural advantages of the SOFC provided by the present invention.

Claims (7)

1. SOFC, characterized by comprising an anode catalytic layer support comprising the structure:

(1) a zirconia support of tubular or flat structure having a porous structure;

（2）Ni_1-xMo_x/Ce_1-yCa_yO_2-δcatalyst of said Ni_1-xMo_x/Ce_1-yCa_yO_2-δThe catalyst is filled in the pores of the porous structure, wherein x is more than 0 and less than or equal to 0.5, and y is more than or equal to 0.01 and less than or equal to 0.4;

wherein the zirconia is a zirconia previously stabilized with yttria;

in the tubular structure, the inner diameter of the tube is 1.0-5.0mm, and the outer diameter is 2.0-7.0 mm;

in the flat plate type structure, the thickness of the flat plate is 0.5-1.5 mm;

the preparation method of the SOFC comprises the following steps:

s1, (ZrO)₂）_0.92（Y₂O₃）_0.08The powder and polymethyl methacrylate (PMMA) powder are used as raw materials, and are calcined to prepare a zirconium oxide support body with a tubular structure or a flat plate structure;

s2, sequentially preparing an anode current collection layer, an anode functional layer and a double-electrolyte layer on the zirconia support body with the tubular structure or the flat plate structure to form a half cell;

s3, preparing a mixed solution A of cerium nitrate, calcium nitrate and citric acid, and soaking the half cell S2 in the mixed solution A to form a pretreated sample A;

s4, calcining the pretreated sample A in a heated air atmosphere to obtain an intermediate;

s5, repeating the operations S3-S4, namely repeatedly soaking the intermediate in the mixed liquor A and then calcining the intermediate in a heated air atmosphere until the Ce in the intermediate is_1-yCa_yO_2-δThe content of (A) is 4.3-12.9 wt%;

s6, preparing a mixed solution B of nickel nitrate, ammonium paramolybdate and citric acid, and soaking the intermediate prepared in the step S5 in the mixed solution B to form a pretreated sample B;

s7, calcining the pretreated sample B in a heated air atmosphere to obtain a crude product;

s8, repeating the operation S6-S7, namely repeatedly soaking the crude product in the mixed liquid B and calcining the crude product in a heated air atmosphere until Ni in the crude product_1-xMo_xThe content of the anode catalyst layer reaches 0.7 to 2.1 weight percent, and a half cell comprising an anode catalyst layer support body is obtained;

and S9, preparing a cathode on the half cell comprising the anode catalysis layer support to obtain the SOFC.

2. The SOFC of claim 1, wherein the pores have an average pore size of 2.0-3.0 μm.

3. The SOFC of claim 1, wherein the tubular or flat plate zirconia support has a porosity of 30-43%.

4. The SOFC of claim 1, wherein the mixed solution a has a cerium nitrate concentration of 0.3-0.7mol/L, a calcium nitrate concentration of 0.033-0.078mol/L, and a citric acid concentration of 1.0-2.0 mol/L.

5. The SOFC of claim 1, wherein the mixed solution B has a nickel nitrate concentration of 0.4-1.3mol/L, an ammonium paramolybdate concentration of 0.0095-0.031mol/L, and a citric acid concentration of 1.0-2.0 mol/L.

6. The SOFC of claim 1, wherein the tubular or flat plate structure has a mass ratio of zirconia to mixed liquor a of from 1:100 to 10: 100.

7. The SOFC of claim 1, wherein the mass ratio of the intermediate produced in step S5 to mixed liquid B is from 1:100 to 10: 100.

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