High-stability direct methanol / ethanol solid oxide fuel cell material and structural design

Abstract

The invention belongs to the technical field of battery materials and devices, and particularly relates to a high-stability direct methanol / ethanol solid oxide fuel cell material and structural design. The solid oxide fuel cell disclosed by the invention adopts a structure taking the electrolyte as a support body, and the barrier layers are respectively arranged on two sides of the electrolyte and are used for preventing interaction between an electrode and the electrolyte; a corresponding electrode is printed on the barrier layer; and the anode is formed by compounding an inner perovskite anode and an outer metal reforming catalyst layer. By regulating and controlling the defects of the A site of the perovskite material and assisting in reducing atmosphere treatment, reducible metal elements at the B site in perovskite crystals are induced to separate out metal nanoparticles on the surface, so that the catalytic activity of the anode is remarkably improved. And meanwhile, the metal reforming catalyst layer on the outer layer forms a porous metal structure through reduction treatment, so that the reforming efficiency of the metal reforming catalyst layer on methanol / ethanol is enhanced. The structural design effectively improves the stability and catalytic activity of the direct methanol / ethanol solid oxide fuel cell.

Description

Technical Field

[0001] This invention belongs to the field of battery materials and devices technology, specifically relating to a high-stability direct methanol / ethanol solid oxide fuel cell material and structural design. Background Technology

[0002] Solid oxide fuel cells (SOFCs), employing an all-solid-state structure, are environmentally friendly and highly efficient power generation devices with broad application prospects. Current research mainly focuses on systems using hydrogen as fuel, and good electrochemical performance has been achieved. However, the high costs of hydrogen production, storage, and transportation limit its large-scale application. Methanol and ethanol, as important liquid hydrogen carriers, are considered ideal alternative fuels for SOFCs. These alcohol fuels are not only widely available and easy to store and transport, but also have high volumetric energy density and can be obtained from biomass or waste conversion, aligning with the development direction of renewable energy. Therefore, developing solid oxide fuel cells that directly use methanol / ethanol as fuel has significant research value.

[0003] However, direct alcohol SOFCs still face key technological challenges in practical applications. Traditional nickel-based anodes are prone to carbon deposition when using hydrocarbon fuels directly, leading to rapid performance degradation. This is mainly attributed to nickel's high catalytic activity in breaking carbon-hydrogen bonds, which promotes the deposition of carbon species on the anode surface. Therefore, effectively suppressing carbon deposition and improving the long-term stability of the battery while ensuring high electrochemical performance has become a key research focus in this field.

[0004] In recent years, electrolyte-supported perovskite-based anodes have attracted widespread attention in direct alcohol SOFCs due to their excellent anti-carbon deposition properties. To further improve the reforming efficiency of alcohol fuels, a reforming catalyst layer is typically introduced on the anode surface to promote the catalytic conversion of the fuel. Therefore, developing a battery structure that combines high electrochemical activity, excellent anti-carbon deposition properties, and efficient reforming capability is of great significance for promoting the practical application of direct methanol / ethanol solid oxide fuel cells. Summary of the Invention

[0005] To address the problems existing in the prior art, this invention provides a high-stability direct methanol / ethanol solid oxide fuel cell material and structural design. This design aims to significantly improve the carbon deposition resistance of the battery material, enabling the battery to maintain good electrochemical performance even under long-term methanol or ethanol fuel atmospheres, thereby extending its service life.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows: The first aspect of this invention provides a structural design method for a direct methanol / ethanol solid oxide fuel cell, comprising the following steps: (1) Electrolyte ceramic powder is used as electrolyte raw material, and electrolyte sheets are made by pressing and sintering the powder; (2) The barrier layer material is coated on both sides of the electrolyte sheet, dried and then sintered; (3) The perovskite anode material and cathode material containing A-site defects are coated on the surface of the barrier layer on both sides of the electrolyte and then dried. (4) The metal reforming catalyst material is coated on the surface of the perovskite anode, dried, and then co-sintered. It is then treated under a reducing atmosphere to allow the B-site reducible metal to precipitate as nanoparticles on the perovskite crystal surface, forming a porous metal structure in the outer metal reforming catalyst layer. This results in a composite anode structure with the perovskite anode as the inner layer and the porous metal reforming catalyst layer as the outer layer. The overall cross-sectional view of the battery is shown below. Figure 1 As shown.

[0007] Furthermore, the electrolyte ceramic powder is either zirconia-based ceramic powder or Sr / Mg-doped LaGaO3-based ceramic powder.

[0008] Furthermore, the barrier layer material is Ce. 1-x Gd x O 2-x / 2 (GDC) or Ce 1-x La x O 2-x / 2 (LDC), where x is 0.05-0.30.

[0009] Furthermore, an LDC barrier layer slurry was prepared using the sol-gel method, the preparation method including the following steps: Calculate according to the stoichiometric ratio in the chemical formula, weigh out citric acid dissolved in deionized water as solution A, weigh out the required La and Ce nitrates dissolved in deionized water as solution B, mix solution A and solution B and add ethylene glycol, heat and stir to obtain dry coagulation effect, dry, calcine and ball mill to obtain LDC powder, mix the powder with electrode slurry to obtain LDC barrier layer slurry.

[0010] Furthermore, the perovskite anode material is at least one of A, B, and C: A: Sr 1-a Ti x (Fe 1-β Ru β ) 1-x O 3-δ (STFR), where 0 ≤ a < 1, 0 <x,y≤1, 0<β<1; B:Sr2Mo y (Fe 1-β Ru β ) 2-y O 6-δ(SFMR), where 0 ≤ a < 1, 0 <x,y≤1, 0<β<1; C:Sr2Fe 1+ xMo 1-x O 6-δ (SFM), where -0.20≤x≤+0.20.

[0011] Furthermore, the STFR anode functional layer slurry and the STFR-SMFR anode functional layer slurry are prepared using the sol-gel method. The preparation method includes the following steps: Calculations were performed based on the stoichiometric ratio of the metal ions at sites A and B in the chemical formula. Citric acid was dissolved in deionized water as solution A, the required metal Sr and Fe nitrates were dissolved in deionized water as solution B, the required amount of ruthenium chloride was dissolved in deionized water as solution C, and the required amount of Bu-Ti was dissolved in ethanol as solution D. The above liquids were mixed and then ethylene glycol was added. After heating and stirring, a dry coagulation effect was obtained. After drying, calcination, and ball milling, STFR powder was obtained. The powder was mixed with electrode slurry to obtain STFR anode functional layer slurry. Calculations were performed based on the stoichiometric ratio of the metal ions at sites A and B in the chemical formula. Citric acid was dissolved in deionized water as solution A, the required metal Sr and Fe nitrates were dissolved in deionized water as solution B, the required amount of ruthenium chloride was dissolved in deionized water as solution C, and the required amount of ammonium molybdate tetrahydrate was dissolved in deionized water as solution D. The above liquids were mixed and then ethylene glycol was added. After heating and stirring, a dry coagulation effect was obtained. After drying, calcination, and ball milling, SFMR powder was obtained. STFR powder and SFMR powder were mixed and then added to electrode slurry to obtain STFR-SMFR anode functional layer slurry.

[0012] Furthermore, in the STFR-SMFR anode functional layer slurry, the mass ratio of STFR powder to SFMR powder is 7:3.

[0013] Furthermore, the cathode material is any one of D, E, and F: D:SrTi 1-x-y Fe x Co y O 3-δ (STFC), where 0.1≤x≤0.8, 0≤y≤0.5, and x + y<1; E:La 1-x Sr x MnO 3-δ (LSM), where 0.10 ≤ x ≤ 0.50; F:La 1-x Sr x Co 1-y Fe y O3-δ (LSCF), where 0.20≤x≤0.60, 0.20≤y≤0.80.

[0014] Furthermore, the STFC cathode functional layer slurry was prepared using the sol-gel method, and the preparation method includes the following steps: Calculations were performed based on the stoichiometric ratio of metal ions at sites A and B in the chemical formula. Citric acid was dissolved in deionized water as solution A, the required metal nitrates Sr, Fe, and Co were dissolved in deionized water as solution B, and the required amount of Bu-Ti was dissolved in ethanol as solution C. Solution A and solution C were mixed and added to solution B, followed by the addition of ethylene glycol. After heating and stirring, a dry coagulation effect was obtained. After drying, calcination, and ball milling, STFC powder was obtained. The powder was then mixed with electrode slurry to obtain STFC cathode functional layer slurry.

[0015] Furthermore, the metal reforming catalyst layer is at least one of Fe, Co, Ni, and Cu.

[0016] Furthermore, the preparation method of Fe reforming catalyst slurry is as follows: after mixing commercial Fe2O3 powder with electrode slurry, Fe reforming catalyst slurry is obtained.

[0017] Furthermore, in the barrier layer slurry, anode functional layer slurry, cathode functional layer slurry, and metal reforming catalyst layer slurry, the molar ratio of metal ions, ethylene glycol, and citric acid is 1:1.5:2.

[0018] Furthermore, the electrode slurry is Heraeus binder, and the mass ratio of powder to electrode slurry in the barrier layer slurry, anode functional layer slurry, cathode functional layer slurry and metal reforming catalyst layer slurry is 1:1 to 1:1.2.

[0019] Furthermore, during the preparation of the barrier layer slurry, anode functional layer slurry, cathode functional layer slurry, and metal reforming catalyst layer slurry, the gel drying temperature is 80-150℃, the calcination temperature is 900-1200℃, and the ball milling time is 10-30 hours.

[0020] Furthermore, the sintering temperature in steps (1), (2) and (4) is 900-1400 ℃.

[0021] Furthermore, the coating described in steps (2), (3) and (4) can be any one of screen printing, blade coating, inkjet printing, or slot coating.

[0022] Furthermore, the reducing atmosphere is a humidified hydrogen atmosphere, and the balancing gas is high-purity nitrogen or argon. This atmosphere is used to simulate the operating environment of the anode side of a solid oxide fuel cell.

[0023] A second aspect of the present invention provides a direct methanol / ethanol solid oxide fuel cell obtained by the above-described design method. The battery adopts a structure with an electrolyte as the support. The battery structure comprises, in sequence, a cathode functional layer, a barrier layer, an electrolyte layer, another barrier layer, an anode functional layer, and a metal reforming catalyst layer. The electrolyte layer has a thickness of 150-200 micrometers, the barrier layer has a thickness of 5-10 micrometers, the anode and cathode functional layers each have a thickness of 10-15 micrometers, and the metal reforming catalyst layer has a thickness of 10-15 micrometers.

[0024] Compared with the prior art, the beneficial effects of the present invention are: This invention provides a high-stability direct methanol / ethanol solid oxide fuel cell material and structural design. The solid oxide fuel cell of this invention employs an electrolyte-supported structure, with barrier layers on both sides of the electrolyte to prevent interaction between the electrodes and the electrolyte; corresponding electrodes are printed on the barrier layers; the anode is composed of an inner perovskite anode and an outer metal reforming catalyst layer. By controlling the defects at the A-sites of the perovskite material and applying a reducing atmosphere, reducible metal elements at the B-sites of the perovskite crystal are induced to precipitate as metal nanoparticles on the surface, thereby significantly improving the catalytic activity of the anode. Simultaneously, the reduction treatment causes the outer metal reforming catalyst layer to form a porous metal structure, enhancing its reforming efficiency for methanol / ethanol. This effectively improves the stability and catalytic activity of the direct methanol / ethanol solid oxide fuel cell. Specifically, this invention has the following advantages: (1) Experimental verification shows that the battery constructed according to the present invention has a dense electrolyte layer and a barrier layer. The dense electrolyte layer ensures that the battery system has good ion conduction capability; while the introduction of the barrier layer effectively suppresses the mutual diffusion and side reactions between the electrode and electrolyte materials at high temperatures. By controlling the A-site defects of the perovskite anode material and treating it in a reducing atmosphere, the reducible metal ions doped at the B-site are precipitated in situ on the surface of the perovskite matrix, forming highly dispersed metal nanoparticles, thereby significantly improving the electrocatalytic activity of the anode.

[0025] (2) The composite anode designed in this invention, which is tightly bonded to the metal reforming catalyst layer and the perovskite anode functional layer, exhibits excellent electrochemical performance in battery performance testing. In long-term stability testing, the battery output performance remained stable without significant degradation, indicating that the structure has good catalytic activity and anti-carbon deposition ability.

[0026] In summary, the high-stability direct methanol / ethanol solid oxide fuel cell material and structural design method provided by this invention offer an effective and reliable solution to the carbon deposition problem faced by direct alcohol SOFCs in practical applications. Attached Figure Description

[0027] Figure 1 This is a cross-sectional view of the overall structure of a single cell in a direct methanol / ethanol solid oxide fuel cell.

[0028] Figure 2 This is a schematic diagram of the microstructure of STFR-SFMR as the anode material.

[0029] Figure 3 This is a schematic diagram of the microstructure of Fe as a metal reforming catalyst layer material.

[0030] Figure 4 This is a comparison curve of battery performance under methanol atmosphere.

[0031] Figure 5 This is a comparison curve of battery performance under an ethanol atmosphere. Detailed Implementation

[0032] 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.

[0033] 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.

[0034] Example 1: Material and structural design of a direct methanol / ethanol solid oxide fuel cell (STFR-SMFR-Fe anode) (1) Using electrolyte ceramic powder La 0.8 Sr 0.2 Ga 0.8 Mg 0.2 O3 was used as the electrolyte raw material, and the powder was pressed and sintered at 1400 °C to form an electrolyte sheet with a thickness of 200 micrometers. (2) According to Ce 0.4 La 0.6 O 2-δThe stoichiometric ratios in the chemical formulas were calculated. Citric acid was dissolved in deionized water as solution A, and the required La and Ce nitrates were dissolved in deionized water as solution B. Solutions A and B were mixed, and ethylene glycol was added. The molar ratio of metal ions, ethylene glycol, and citric acid was 1:1.5:2. The mixture was sealed and stirred at 60 °C for 2 hours. It was then heated to 80 °C and stirred until the mixture became concentrated and bubbly. The resulting gel-like solution was transferred to a 150 °C oven for drying. The dried sample was then pre-calcined in a muffle furnace at 400 °C and 600 °C for 30 minutes each. After grinding, the pre-calcined sample was calcined in a muffle furnace at 1050 °C for 5 hours. The calcined powder was ball-milled for 24 hours to obtain La. 0.4 Ce 0.6 O 2-δ The powder was mixed with Heraeus binder at a mass ratio of 1:1.2 to obtain LDC barrier layer slurry. The barrier layer was printed onto both sides of the electrolyte using screen printing. After drying at 120 °C, it was calcined at 1250 °C to form a dense barrier layer with a thickness of 5 micrometers. (3) According to the chemical formula Sr 0.95 Ti 0.3 (Fe 0.9 Ru 0.1 ) 0.7 The stoichiometric ratio of metal ions at the A and B sites in O3 was calculated. Citric acid was dissolved in deionized water as solution A; the required amounts of Sr and Fe nitrates were dissolved in deionized water as solution B; the required amount of ruthenium chloride was dissolved in deionized water as solution C; and the required amount of Bu-Ti was dissolved in ethanol as solution D. These liquids were mixed, and ethylene glycol was added. The molar ratio of metal ions, ethylene glycol, and citric acid was 1:1.5:2. The mixture was sealed and stirred at 60 °C for 2 hours. It was then heated to 80 °C and stirred until the mixture concentrated and bubbled. The resulting gel-like solution was transferred to a 150 °C oven for drying. The dried sample was then pre-calcined in a muffle furnace at 400 °C and 600 °C for 30 minutes each. After grinding, the pre-calcined sample was calcined in a muffle furnace at 1050 °C for 5 hours. The calcined powder was ball-milled for 24 hours to obtain Sr. 0.95 Ti 0.3 (Fe 0.9 Ru 0.1 ) 0.7 O3 powder; according to the chemical formula Sr 1.9 Mo 0.6 (Fe 0.9 Ru 0.1 ) 1.4The stoichiometric ratio of metal ions at sites A and B in O6 was calculated. Citric acid was dissolved in deionized water as solution A; the required amounts of Sr and Fe nitrates were dissolved in deionized water as solution B; the required amount of ruthenium chloride was dissolved in deionized water as solution C; and the required amount of ammonium molybdate tetrahydrate was dissolved in deionized water as solution D. These liquids were mixed, and ethylene glycol was added. The molar ratio of metal ions, ethylene glycol, and citric acid was 1:1.5:2. The mixture was sealed and stirred at 60 °C for 2 hours. It was then heated to 80 °C and stirred until the mixture concentrated and bubbled. The resulting gel-like solution was transferred to a 150 °C oven for drying. The dried sample was then pre-calcined in a muffle furnace at 400 °C and 600 °C for 30 minutes each. After grinding, the pre-calcined sample was calcined in a muffle furnace at 1050 °C for 5 hours. The calcined powder was ball-milled for 24 hours to obtain Sr. 1.9 Mo 0.6 (Fe 0.9 Ru 0.1 ) 1.4 O6 powder, Sr 0.95 Ti 0.3 (Fe 0.9 Ru 0.1 ) 0.7 O3 powder and Sr 1.9 Mo 0.6 (Fe 0.9 Ru 0.1 ) 1.4 O6 powder was mixed at a mass ratio of 7:3 and then mixed with Heraeus binder at a mass ratio of 1:1.2 to obtain STFR-SMFR anode functional layer slurry. According to the chemical formula Sr 0.95 Ti 0.3 (Fe 0.9 Co 0.1 ) 0.7 The stoichiometric ratio of metal ions at the A and B sites in O3 was calculated. Citric acid was dissolved in deionized water as solution A, the required metal nitrates (Sr, Fe, and Co) were dissolved in deionized water as solution B, and the required amount of Bu-Ti was dissolved in ethanol as solution C. Solutions A and C were mixed and added to solution B, followed by ethylene glycol. The molar ratio of metal ions, ethylene glycol, and citric acid was 1:1.5:2. The mixture was sealed and stirred at 60 °C for 2 hours. It was then heated to 80 °C and stirred until the mixture was concentrated and bubbly. The resulting gel-like solution was transferred to an oven at 150 °C and dried. The dried sample was then pre-calcined in a muffle furnace at 400 °C and 600 °C for 30 minutes each. After grinding, the pre-calcined sample was calcined in a muffle furnace at 1050 °C for 5 hours. The calcined powder was ball-milled for 24 hours to obtain Sr. 0.95 Ti 0.3 (Fe 0.9 Co 0.1 )0.7 O3 powder, Sr 0.95 Ti 0.3 (Fe 0.9 Co 0.1 ) 0.7 O3 powder and Heraeus binder are mixed at a mass ratio of 1:1.2 to obtain STFC cathode functional layer paste; STFR-SMFR anode functional layer paste and STFC cathode functional layer paste were printed onto the surface of the barrier layers on both sides of the electrolyte using screen printing. After drying at 120 °C, the thickness of the STFR-SMFR anode functional layer and the STFC cathode functional layer were 15 micrometers. (4) Commercial Fe2O3 powder and Heraeus binder were mixed at a mass ratio of 1:1.2 to obtain Fe reforming catalyst slurry. The Fe reforming catalyst slurry was printed onto the surface of the STFR-SMFR anode functional layer. After drying at 120 °C, the functional layer and the metal reforming catalyst layer were co-fired at 1050 °C. The thickness of the Fe reforming catalyst layer was 10 micrometers, resulting in an electrolyte-supported battery with a composite anode structure. The battery prepared above was treated at 800 °C in a reducing atmosphere (humidified hydrogen atmosphere, with high-purity nitrogen as the balance gas) for 2 hours, causing nano-metal particles to precipitate on the surface of the perovskite anode substrate. The metal in the reforming layer was reduced to form a porous metal catalyst layer structure. The microstructure diagram of the STFR-SMFR-Fe anode in this embodiment is shown below. Figure 3 As shown in the image, electron microscopy reveals images of the sample surface before and after the reduction of the Fe layer. It can be seen that the Fe catalyst layer forms a porous structure after treatment with a reducing atmosphere, which can improve the reforming efficiency of methanol / ethanol.

[0035] Comparative Example 1: Material and structural design of a direct methanol / ethanol solid oxide fuel cell (STFR-SMFR anode) Based on Example 1, this comparative example involves directly sintering the dried STFR-SMFR anode functional layer and STFC cathode functional layer from step (3), followed by a reducing atmosphere treatment; that is, no metal reforming catalyst layer is prepared. The rest remains the same as in Example 1. The microstructure diagram of the STFR-SMFR anode in this comparative example is shown below. Figure 2 As shown, treatment in a reducing atmosphere precipitates nano-Fe-Ru particles on the surface of the perovskite matrix, which can effectively improve the catalytic activity of the electrode.

[0036] Comparative Example 2: Material and structural design of a direct methanol / ethanol solid oxide fuel cell (STFR anode) This comparative example is based on Example 1, directly using Sr 0.95 Ti 0.3 (Fe 0.9 Ru0.1 ) 0.7 O3 powder (STFR powder) and Heraeus binder are mixed at a mass ratio of 1:1.2 to obtain STFR anode functional layer slurry, i.e., no SFMR powder is added, and the STFR anode functional layer dried in step (3) is directly sintered with the STFC cathode functional layer, and then subjected to reducing atmosphere treatment, i.e. no metal reforming catalyst layer is prepared. The rest is consistent with Example 1.

[0037] Test case The batteries prepared in Example 1, Comparative Example 1, and Comparative Example 2 were tested at 750°C under no-load conditions. The battery performance comparison curves under methanol atmosphere are shown in the figure below. Figure 4 As shown, the peak power density is 0.77 W / cm². 2 As can be seen, the STFR-SFMR-Fe anode battery equipped with an Fe reforming catalyst layer exhibits the best performance, outperforming both the STFR-SFMR anode and STFR anode batteries, indicating that the composite anode structure can improve the catalytic activity of the electrode; the battery performance comparison curves under ethanol atmosphere are shown in the figure below. Figure 5 As shown, the peak power density is 0.64 W / cm². 2 As can be seen, the performance test results are consistent with those under methanol atmosphere, and the electrochemical performance of the STFR-SFMR-Fe anode battery is still the best, further demonstrating that the battery equipped with the composite anode structure design has better electrochemical performance under methanol / ethanol conditions.

[0038] 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 structural design method for a direct methanol / ethanol solid oxide fuel cell, characterized in that, Includes the following steps: (1) Electrolyte ceramic powder is used as electrolyte raw material, and electrolyte sheets are made by pressing and sintering the powder; (2) The barrier layer material is coated on both sides of the electrolyte sheet, dried and then sintered; (3) The perovskite anode material and cathode material containing A-site defects are coated on the surface of the barrier layer on both sides of the electrolyte and then dried. (4) The metal reforming catalyst material is coated on the surface of the perovskite anode, dried and then co-sintered. Then it is treated in a reducing atmosphere so that the B-site reducible metal precipitates on the surface of the perovskite crystal in the form of nanoparticles, and the outer metal reforming catalyst layer forms a porous metal structure, forming a composite anode structure with the perovskite anode as the inner layer and the porous metal reforming catalyst layer as the outer layer.

2. The structural design method for a direct methanol / ethanol solid oxide fuel cell according to claim 1, characterized in that, The electrolyte ceramic powder is either zirconia-based ceramic powder or Sr / Mg-doped LaGaO3-based ceramic powder.

3. The structural design method for a direct methanol / ethanol solid oxide fuel cell according to claim 1, characterized in that, The barrier layer material is Ce. 1-x Gd x O 2-x / 2 or Ce 1-x La x O 2-x / 2 , where x is 0.05-0.

30.

4. The structural design method for a direct methanol / ethanol solid oxide fuel cell according to claim 1, characterized in that, The perovskite anode material is at least one of A, B, and C: A: Sr 1-a Ti x (Fe 1-β Ru β ) 1-x O 3-δ , where 0 ≤ a < 1, 0 <x,y≤1, 0<β<1; B:Sr2Mo y (Fe 1-β Ru β ) 2-y O 6-δ , where 0 ≤ a < 1, 0 <x,y≤1, 0<β<1; C:Sr2Fe 1+ xMo 1-x O 6-δ , where -0.20≤x≤+0.

20.

5. The structural design method for a direct methanol / ethanol solid oxide fuel cell according to claim 1, characterized in that, The cathode material can be any one of D, E, or F: D:SrTi 1-x-y Fe x Co y O 3-δ Where 0.1≤x≤0.8, 0≤y≤0.5, and x + y<1; E:La 1-x Sr x MnO 3-δ Where 0.10 ≤ x ≤ 0.50; F:La 1-x Sr x Co 1-y Fe y O 3-δ , where 0.20≤x≤0.60, 0.20≤y≤0.

80.

6. The structural design method for a direct methanol / ethanol solid oxide fuel cell according to claim 1, characterized in that, The metal reforming catalyst layer is at least one of Fe, Co, Ni, and Cu.

7. The structural design method for a direct methanol / ethanol solid oxide fuel cell according to claim 1, characterized in that, The sintering temperature in steps (1), (2) and (4) is 900-1400 ℃.

8. The structural design method for a direct methanol / ethanol solid oxide fuel cell according to claim 1, characterized in that, The coating described in steps (2), (3) and (4) is any one of screen printing, blade coating, inkjet printing and slot coating.

9. The structural design method for a direct methanol / ethanol solid oxide fuel cell according to claim 1, characterized in that, The reducing atmosphere is a humidified hydrogen atmosphere, and the balancing gas is high-purity nitrogen or argon. This atmosphere is used to simulate the operating environment of the anode side of a solid oxide fuel cell.

10. A direct methanol / ethanol solid oxide fuel cell obtained by the design method according to any one of claims 1-9, characterized in that, The battery adopts a structure with an electrolyte as the support. The battery structure consists of a cathode functional layer, a barrier layer, an electrolyte layer, a barrier layer, an anode functional layer, and a metal reforming catalyst layer. The electrolyte layer has a thickness of 150-200 micrometers, the barrier layer has a thickness of 5-10 micrometers, the anode and cathode functional layers both have a thickness of 10-15 micrometers, and the metal reforming catalyst layer has a thickness of 10-15 micrometers.

Images