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CN-122000395-A - High-stability direct methanol/ethanol solid oxide fuel cell material and structural design

CN122000395ACN 122000395 ACN122000395 ACN 122000395ACN-122000395-A

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 a structural design. The solid oxide fuel cell adopts a structure taking electrolyte as a supporting body, wherein barrier layers are respectively arranged on two sides of the electrolyte and used for preventing interaction between the electrode and the electrolyte, corresponding electrodes are printed on the barrier layers, and an anode is formed by compositing a perovskite anode of an inner layer and a metal reforming catalytic layer of an outer layer. The defect of the A site of the perovskite material is regulated and controlled, and the reduction atmosphere treatment is assisted, so that the reducible metal element of the B site in the perovskite crystal is induced to precipitate metal nano particles on the surface, and the catalytic activity of the anode is obviously improved. Meanwhile, the metal reforming catalytic layer on the outer layer forms a porous metal structure by reduction treatment, so that the reforming efficiency of the metal reforming catalytic layer on methanol/ethanol is enhanced. The structural design effectively improves the stability and the catalytic activity of the direct methanol/ethanol solid oxide fuel cell.

Inventors

  • ZHANG SHANLIN
  • WANG ZIXU

Assignees

  • 中山大学

Dates

Publication Date
20260508
Application Date
20260129

Claims (10)

  1. 1. The structural design method of the direct methanol/ethanol solid oxide fuel cell is characterized by comprising the following steps of: (1) Electrolyte ceramic powder is adopted as electrolyte raw material, and the electrolyte sheet is manufactured by pressurizing and sintering the powder; (2) Coating a barrier layer material on two sides of an electrolyte sheet, and sintering after drying; (3) Respectively coating perovskite anode materials and cathode materials containing A-site defects on the surfaces of barrier layers on two sides of an electrolyte, and drying; (4) The method comprises the steps of coating a metal reforming catalytic layer material on the surface of a perovskite anode, drying, performing co-sintering, and then treating in a reducing atmosphere to enable B-site reducible metal to be separated out on the surface of perovskite crystals in a nano particle form, enabling an outer metal reforming catalytic layer to form a porous metal structure, and forming a composite anode structure with the perovskite anode as an inner layer and the porous metal reforming catalytic layer as an outer layer.
  2. 2. The structural design method of a direct methanol/ethanol solid oxide fuel cell according to claim 1, wherein the electrolyte ceramic powder is any one of zirconia-based ceramic powder or Sr/Mg doped LaGaO 3 -based ceramic powder.
  3. 3. The method of claim 1, wherein the barrier layer is Ce 1-x Gd x O 2-x/2 or Ce 1-x La x O 2-x/2 , and x is 0.05-0.30.
  4. 4. The structural design method of a direct methanol/ethanol solid oxide fuel cell according to claim 1, wherein the perovskite anode material is at least one of A, B, C: a: sr 1-a Ti x (Fe 1-β Ru β ) 1-x O 3-δ , wherein 0≤a <1, 0< x, y is less than or equal to 1, 0< beta <1; b: sr 2 Mo y (Fe 1-β Ru β ) 2-y O 6-δ , wherein 0≤a <1, 0< x, y is less than or equal to 1, 0< beta <1; sr 2 Fe 1+ xMo 1-x O 6-δ , wherein x is more than or equal to-0.20 and less than or equal to +0.20.
  5. 5. The structural design method of a direct methanol/ethanol solid oxide fuel cell according to claim 1, wherein the cathode material is any one of D, E, F: SrTi 1-x-y Fe x Co y O 3-δ , wherein x is more than or equal to 0.1 and less than or equal to 0.8, y is more than or equal to 0 and less than or equal to 0.5, and x+y is less than 1; La 1-x Sr x MnO 3-δ , wherein x is more than or equal to 0.10 and less than or equal to 0.50; La 1-x Sr x Co 1-y Fe y O 3-δ , wherein x is more than or equal to 0.20 and less than or equal to 0.60,0.20 and y is more than or equal to 0.80.
  6. 6. The method for designing a structure of a direct methanol/ethanol solid oxide fuel cell according to claim 1, the metal reforming catalyst layer is characterized in that the metal reforming catalyst layer is at least one of Fe, co, ni, cu.
  7. 7. The method according to claim 1, wherein the sintering temperatures in step (1), step (2) and step (4) are 900-1400 ℃.
  8. 8. The structural design method of a direct methanol/ethanol solid oxide fuel cell according to claim 1, wherein the coating in step (2), step (3) and step (4) is any one of screen printing, doctor blade coating, inkjet printing and slit coating.
  9. 9. The method according to claim 1, wherein the reducing atmosphere is a humidified hydrogen atmosphere, and the balance gas is high-purity nitrogen or argon, and the atmosphere is used for simulating the operation environment of the anode side of the solid oxide fuel cell.
  10. 10. A direct methanol/ethanol solid oxide fuel cell obtained by the design method as claimed in any one of claims 1 to 9, wherein the cell adopts a structure using an electrolyte as a support, the cell structure is sequentially a cathode functional layer, a barrier layer, an electrolyte layer, a barrier layer, an anode functional layer and a metal reforming catalytic layer, the thickness of the electrolyte layer is 150 to 200 micrometers, the thickness of the barrier layer is 5 to 10 micrometers, the thicknesses of the anode functional layer and the cathode functional layer are 10 to 15 micrometers, and the thickness of the metal reforming catalytic layer is 10 to 15 micrometers.

Description

High-stability direct methanol/ethanol solid oxide fuel cell material and structural design Technical Field 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 a structural design. Background The Solid Oxide Fuel Cell (SOFC) adopts an all-solid-state structure, is an environment-friendly and efficient power generation device, and has wide application prospect. The current research is mainly focused on a system using hydrogen as fuel, and better electrochemical performance is obtained, but the preparation, storage and transportation costs of hydrogen are higher, so that the large-scale application of hydrogen is limited. Methanol and ethanol are considered as important liquid hydrogen carriers as one of the ideal alternative fuels for SOFCs. The alcohol fuel has the advantages of wide sources, convenient storage and transportation, higher volume energy density, and capability of being obtained by converting biomass or waste, and accords with the development direction of renewable energy sources. Therefore, the development of solid oxide fuel cells directly fuelled with methanol/ethanol has significant research value. However, direct alcohol SOFCs still face key technical challenges in practical applications. The conventional nickel-based anode is susceptible to carbon deposition when the hydrocarbon fuel is directly used, resulting in rapid degradation of battery performance. This is mainly due to the high catalytic cleavage activity of nickel on carbon hydrogen bonds, which promotes the deposition of carbon species on the anode surface. Therefore, how to effectively inhibit carbon deposition and improve long-term stability of the battery while ensuring high electrochemical performance becomes a research focus in the field. In recent years, electrolyte supported perovskite-based anodes have received attention in direct alcohol SOFCs because of their excellent anti-carbon properties. To further increase 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. Based on the above, a battery structure with high electrochemical activity, excellent carbon deposition resistance and high-efficiency reforming capability is developed, and the method has important significance for promoting the practical application of direct methanol/ethanol solid oxide fuel cells. Disclosure of Invention Aiming at the problems in the prior art, the invention provides a high-stability direct methanol/ethanol solid oxide fuel cell material and a structural design. The design aims to remarkably improve the anti-carbon deposition performance of the battery material, so that the battery can still maintain good electrochemical performance in the methanol or ethanol fuel atmosphere for a long time, thereby prolonging the service life of the battery. In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: The first aspect of the present invention provides a structural design method of a direct methanol/ethanol solid oxide fuel cell, comprising the steps of: (1) Electrolyte ceramic powder is adopted as electrolyte raw material, and the electrolyte sheet is manufactured by pressurizing and sintering the powder; (2) Coating a barrier layer material on two sides of an electrolyte sheet, and sintering after drying; (3) Respectively coating perovskite anode materials and cathode materials containing A-site defects on the surfaces of barrier layers on two sides of an electrolyte, and drying; (4) The metal reforming catalytic layer material is coated on the surface of a perovskite anode, is baked and then is subjected to co-sintering, and is treated in a reducing atmosphere, so that B-site reducible metal is precipitated on the surface of perovskite crystals in a nano particle form, and an outer metal reforming catalytic layer is made to form a porous metal structure, so that a composite anode structure taking the perovskite anode as an inner layer and the porous metal reforming catalytic layer as an outer layer is formed, and the overall structure cross section of the battery is shown in figure 1. Further, the electrolyte ceramic powder is any one of zirconia-based ceramic powder or Sr/Mg doped LaGaO 3 -based ceramic powder. Further, the barrier layer material is Ce 1-xGdxO2-x/2 (GDC) or Ce 1-xLaxO2-x/2 (LDC), where x is 0.05-0.30. Further, the LDC barrier layer slurry is prepared by adopting a sol-gel method, and the preparation method comprises the following steps: According to the stoichiometric ratio in the chemical formula, weighing citric acid, dissolving in deionized water to obtain solution A, weighing nitrate of La and Ce, dissolving in deionized water to obtain solution B, mixing solution A and solution B, adding glycol, heating and stirring to obtain dry coagul