CN113937318B - Process method of electrolyte supported solid oxide fuel unit cell - Google Patents

Process method of electrolyte supported solid oxide fuel unit cell Download PDF

Info

Publication number
CN113937318B
CN113937318B CN202111199199.1A CN202111199199A CN113937318B CN 113937318 B CN113937318 B CN 113937318B CN 202111199199 A CN202111199199 A CN 202111199199A CN 113937318 B CN113937318 B CN 113937318B
Authority
CN
China
Prior art keywords
electrolyte
support structure
cathode
anode
ceramic green
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202111199199.1A
Other languages
Chinese (zh)
Other versions
CN113937318A (en
Inventor
温良成
张宪隆
梁咏芯
马泽荣
余思亭
何欣悦
梁晓贤
严日峰
柯旭阳
莫泳康
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dongguan Huachuang Education Technology Co ltd
Original Assignee
Dongguan Huachuang Education Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dongguan Huachuang Education Technology Co ltd filed Critical Dongguan Huachuang Education Technology Co ltd
Priority to CN202111199199.1A priority Critical patent/CN113937318B/en
Publication of CN113937318A publication Critical patent/CN113937318A/en
Application granted granted Critical
Publication of CN113937318B publication Critical patent/CN113937318B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0289—Means for holding the electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M2008/1293—Fuel cells with solid oxide electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inert Electrodes (AREA)
  • Fuel Cell (AREA)

Abstract

The invention belongs to the technical field of fuel cells, and provides a manufacturing method of an electrolyte supported solid oxide fuel cell, which comprises the following steps: respectively molding and cutting the cathode support structure electrolyte slurry, the anode support structure electrolyte slurry and the electrolyte layer electrolyte slurry to obtain a cathode support structure ceramic green compact film, an anode support structure ceramic green compact film and an electrolyte layer ceramic green compact film; drying and sintering the three ceramic green films after hot-press molding to obtain a cathode support structure, an electrolyte layer and an anode support structure; and adding the cathode and anode catalytic material slurry into a cathode and anode support structure, and sequentially drying and sintering to obtain a cathode layer and an anode layer. The manufacturing method reduces the thickness of the electrolyte layer to 3-5 mu m to improve the output power of the unit cell and can provide the mechanical strength of the SOFC unit cell.

Description

Process method of electrolyte supported solid oxide fuel unit cell
Technical Field
The invention relates to the technical field of fuel cells, in particular to a manufacturing method of an electrolyte supported solid oxide fuel cell.
Background
In recent years, the consumption ratio of clean energy in energy sources is continuously rising, and Solid Oxide Fuel Cells (SOFCs) are the most efficient energy storage systems for conversion in the field of renewable energy sources. Although SOFCs have the potential to develop into clean alternative energy sources, some parts still need further improvement and enhancement in order to make the utilization of SOFCs more popular. For example, (Y 0.08Zr0.92)O1.96 (8 mol% of ytria-stabilized zirconia,8 YSZ) is an electrolyte ceramic material commercialized at present, and has conductivity of 0.1S cm -1 at the operation temperature of 1000 ℃, but the SOFC has the following defects that (1) the composition interface is easy to react, (2) the thermal stability is easy to be reduced when the SOFC is used at high temperature, (3) the interface jointing degree is influenced by the expansion coefficient to be increased, the cracking of the cell is easy to be caused due to the action of high-temperature thermal stress, and (4) the material selection of the electrode and the bipolar plate part is limited in order to ensure the stable use at high temperature, and the material cost of the electrode and the bipolar plate part of the type is high, so that the manufacturing cost of the SOFC is directly influenced.
The root of the above problems is basically because the electrolyte part must have good conductivity at high temperature, the first generation SOFC is an electrolyte supporting type (electrolyte support cell, ESC) with an electrolyte thickness of about 140 to 200 μm, and the impedance is large because the electrolyte is thick and the distance the ions need to move is long, although the mechanical strength is good. One of the solutions is to reduce the thickness of the electrolyte to reduce the impedance caused by the electrolyte portion, but if the electrolyte material used in the SOFC is too thin, the mechanical stability of the unit cell is reduced, and the unit cell is easily brittle, so that the stack assembly is difficult and the shock resistance is weak.
To overcome the problem of reduced mechanical strength due to the reduced thickness of the electrolyte, a second generation SOFC (anode or cathode support cell, ascor CSC) was developed in which the thickness of the electrolyte was greatly reduced to 3-10 μm, while the thickness of one of the anode or cathode was increased to 500-600 μm, while the thickness of the other electrode was 30-60 μm, by transferring the task of maintaining mechanical strength to the anode or cathode. Although this method is effective in lowering the resistance value of the electrolyte portion, the porous electrode portion is not strong enough in mechanical strength even if the thickness is increased. If the improvement can be made directly from the electrolyte portion, the SOFC can be operated at a lower temperature while maintaining a high mechanical strength of the electrolyte layer, not only can the power of the cell operation be increased, but also the material selectivity of the electrode and bipolar plate portions can be increased and the manufacturing cost of the SOFC can be reduced if the operating temperature of the SOFC is reduced.
Therefore, research and development of an electrolyte supported solid oxide fuel cell with good conductivity, high mechanical strength, low impedance and low cost at low temperature will have important economic value and significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a manufacturing method of an electrolyte supported solid oxide fuel cell. The present invention starts from structural aspects and improves electrochemical reaction sites of electrode portions while improving mechanical strength and electrochemical conversion efficiency of electrolyte-supported solid oxide fuel cell cells.
In order to achieve the above object, the present invention provides the following technical solutions:
The invention provides a manufacturing method of an electrolyte supported solid oxide fuel cell, which comprises the following steps:
1) Respectively molding and cutting the cathode support structure electrolyte slurry, the anode support structure electrolyte slurry and the electrolyte layer electrolyte slurry to obtain a cathode support structure ceramic green compact film, an anode support structure ceramic green compact film and an electrolyte layer ceramic green compact film;
2) Drying and sintering the three ceramic green film obtained in the step 1) after hot press molding to obtain a cathode support structure, an electrolyte layer and an anode support structure;
3) Adding cathode catalytic material slurry into a cathode supporting structure, and sequentially drying and sintering to obtain a cathode layer;
And adding anode catalytic material slurry into the anode support structure, and sequentially drying and sintering to obtain an anode layer.
Preferably, the cathode support structure electrolyte slurry and the anode support structure electrolyte slurry in the step 1) comprise electrolyte powder, pore-forming agent, fluxing agent and thin film preparation Cheng Jiangliao additive; the mass ratio of the electrolyte powder to the pore-forming agent to the fluxing agent to the thin film Cheng Jiangliao additive is 0.5-10.5:0.5-2.5:5-10;
The electrolyte slurry of the electrolyte layer comprises electrolyte powder, a fluxing agent and a Cheng Jiangliao thin film additive; the mass ratio of the electrolyte powder to the fluxing agent to the thin film Cheng Jiangliao additive is 85-95:0.5-2.5:5-12.
Preferably, the electrolyte powder comprises (Sm0.2Ce0.8)O1.9、(Sr0.2Ce0.8)(Ga0.8Mg0.2)O3-δ、Bi2O3、(Gd0.2Ce0.8)O1.9、(Gd0.15Y0.05Ce0.8)O1.9 or 8YSZ; the 8YSZ contains Y 2O3 and ZrO 2 with the mol ratio of 7-9:90-94;
The pore-forming agent comprises one or more of activated carbon powder, starch and ethyl cellulose;
The fluxing agent comprises Li 2CO3、B2O3、Al2O3 or Bi 2O3;
The film-making Cheng Jiangliao additive comprises polyvinyl butyral, polyethylene glycol, dibutyl phthalate, glycerol, corn oil, lauryl sulfate and a solvent; the mass ratio of the polyvinyl butyral to the polyethylene glycol to the dibutyl phthalate to the glycerol to the corn oil to the lauryl sulfate is 5-8:0.1-1.2: 0.1 to 1.2:0.1 to 0.7:0 to 0.7:0.1 to 0.7; the mass volume ratio of the polyvinyl butyral to the solvent is 5-8 g: 65-120 mL; the solvent comprises butanone, ethanol solution, acetone and water in a volume ratio of 30-55:20-45:10-15:5-10; in the ethanol solution, the volume fraction of ethanol is 92-97%.
Preferably, the molding process in step 1) is a doctor blade molding process;
In the scraper forming treatment, the scraper gaps of the cathode support structure electrolyte slurry and the anode support structure electrolyte slurry are 300-500 mu m, the rolling speed is 300-500 mm/min, and the heating and drying area comprises 68-72 ℃/50cm and 88-92 ℃/50cm;
The gap of the scraper of the electrolyte slurry of the electrolyte layer is 30-50 mu m, the rolling speed is 1000-1500 mm/min, and the heating and drying area comprises 68-72 ℃/50cm and 88-92 ℃/50cm.
Preferably, in the hot press molding process in step 2), the electrolyte layer ceramic green film is disposed between the anode support structure ceramic green film and the cathode support structure ceramic green film; the thickness ratio of the anode support structure ceramic green film to the electrolyte layer ceramic green film is 180-240:3-10:180-240; the temperature of the hot press molding is 45-85 ℃, and the rate is 110-130 kg/cm 2.
Preferably, the sintering in step 2) is performed by: sintering the integrated ceramic green body at 1300-1500 ℃ for 4-6 hours and then cooling to 900-1100 ℃;
The temperature rising rate of the mixture is 0.8 to 1.2 ℃/min when the temperature rises to 1300 to 1500 ℃; the cooling rate of cooling to 900-1100 ℃ is 0.8-1.2 ℃/min.
Preferably, the sintering in the step 3) is that the temperature is reduced to 900-1100 ℃ after the sintering is carried out for 4-6 hours at 1050-1250 ℃;
the temperature rising rate of the mixture is 0.8 to 1.2 ℃/min when the temperature rises to 1050 to 1250 ℃; the cooling rate of cooling to 900-1100 ℃ is 0.8-1.2 ℃/min.
Preferably, the cathode catalytic material slurry and the anode catalytic material slurry in the step 3) comprise nano powder, nano electrolyte oxide, pore-forming agent, leveling agent, polyvinyl butyral, polyethylene glycol, dibutyl phthalate, glycerol, corn oil, lauryl sulfate and solvent; wherein, in the cathode catalytic material slurry, the nano powder is (La 0.8Sr0.2)MnO3-δ, in the anode catalytic material slurry, the nano powder is nano nickel oxide powder;
The mass ratio of the nano powder to the nano electrolyte oxide to the pore-forming agent to the leveling agent to the polyvinyl butyral to the polyethylene glycol to the dibutyl phthalate to the glycerol to the corn oil to the lauryl sulfate is 80-90:1-5:0.3-1:0.3-1:5-6:0.1-0.5:0.1-0.5:0.05-0.5:0.1-0.5;
the mass volume ratio of the nano electrolyte oxide to the solvent is 1-5 g: 110-145 mL;
the solvent comprises butanone, ethanol solution, acetone and water in a volume ratio of 50-60:40-50:10-20:10-15; in the ethanol solution, the volume fraction of ethanol is 92-97%.
The beneficial effects of the invention include the following points:
1) The present invention starts from structural aspects and improves electrochemical reaction sites of electrode portions while improving mechanical strength and electrochemical conversion efficiency of electrolyte-supported solid oxide fuel cell cells.
2) The invention utilizes electrolyte materials to build the basic structure of an electrolyte supported Solid Oxide Fuel (SOFC) unit cell, and then places cathode and anode catalytic materials into the cathode and anode structural layers. The manufacturing method of the invention enables the electrolytes of the cathode and the anode and the electrolyte layer to form an integrated structure, reduces the thickness of the electrolyte layer to 3-5 mu m to improve the output power of the unit cell and simultaneously can provide the mechanical strength of the SOFC unit cell.
Drawings
Fig. 1 is a microstructure diagram of an electrolyte supported solid oxide fuel cell of example 1;
Fig. 2 is a view showing the structure of an electrolyte support structure including a cathode support structure, an electrolyte layer and an anode support structure, which is completed by sintering in example 1.
Detailed Description
The invention provides a manufacturing method of an electrolyte supported solid oxide fuel cell, which comprises the following steps:
1) Respectively molding and cutting the cathode support structure electrolyte slurry, the anode support structure electrolyte slurry and the electrolyte layer electrolyte slurry to obtain a cathode support structure ceramic green compact film, an anode support structure ceramic green compact film and an electrolyte layer ceramic green compact film;
2) Drying and sintering the three ceramic green film obtained in the step 1) after hot press molding to obtain a cathode support structure, an electrolyte layer and an anode support structure;
3) Adding cathode catalytic material slurry into a cathode supporting structure, and sequentially drying and sintering to obtain a cathode layer;
And adding anode catalytic material slurry into the anode support structure, and sequentially drying and sintering to obtain an anode layer.
The cathode support structure electrolyte slurry and the anode support structure electrolyte slurry in the step 1) preferably comprise electrolyte powder, pore-forming agent, fluxing agent and film-making Cheng Jiangliao additive; the mass ratio of the electrolyte powder to the pore-forming agent to the fluxing agent to the thin film Cheng Jiangliao additive is preferably 80-92:0.5-10.5:0.5-2.5:5-10, more preferably 83-90:2-8:1-2:7-9, and even more preferably 85-88:3-7:1.5:8.
The electrolyte slurry of the electrolyte layer in the step 1) preferably comprises electrolyte powder, fluxing agent and Cheng Jiangliao additives in a film preparation; the mass ratio of the electrolyte powder, the fluxing agent and the thin film Cheng Jiangliao additive is preferably 85-95:0.5-2.5:5-12, more preferably 88-92:1-2:7-10, and even more preferably 90:1.5:8-9.
The electrolyte powder of the present invention preferably contains (Sm0.2Ce0.8)O1.9、(Sr0.2Ce0.8)(Ga0.8Mg0.2)O3-δ、Bi2O3、(Gd0.2Ce0.8)O1.9、(Gd0.15Y0.05Ce0.8)O1.9 or 8YSZ; the 8YSZ preferably contains Y 2O3 and ZrO 2, and the molar ratio of the Y 2O3 and the ZrO 2 is preferably 7-9:90-94, and more preferably 8:92; the δ in (Sr 0.2Ce0.8)(Ga0.8Mg0.2)O3-δ) is preferably 0.2 to 0.3, more preferably 0.23 to 0.27, and still more preferably 0.25.
The pore-forming agent preferably comprises one or more of activated carbon powder, starch and ethylcellulose; when the pore-forming agent comprises several components at the same time, the components are preferably mixed in equal mass ratios;
The fluxing agent preferably comprises Li 2CO3、B2O3、Al2O3 or Bi 2O3;
The film process slurry additive preferably comprises polyvinyl butyral, polyethylene glycol, dibutyl phthalate, glycerol, corn oil, lauryl sulfate, and a solvent; the mass ratio of the polyvinyl butyral to the polyethylene glycol to the dibutyl phthalate to the glycerol to the corn oil to the lauryl sulfate is preferably 5-8:0.1-1.2: 0.1 to 1.2:0.1 to 0.7:0 to 0.7:0.1 to 0.7, more preferably 6 to 7:0.5 to 1:0.2 to 0.8:0.2 to 0.6:0.2 to 0.6:0.2 to 0.6, more preferably 6.5:0.6 to 0.8:0.3 to 0.5:0.3 to 0.5:0.3 to 0.5:0.3 to 0.5; the mass volume ratio of the polyvinyl butyral to the solvent is preferably 5-8 g:65 to 120mL, more preferably 6 to 7g:70 to 110mL, more preferably 6.5g: 80-100 mL; the solvent preferably comprises butanone, an ethanol solution, acetone and water, wherein the volume ratio of the butanone to the ethanol solution to the acetone to the water is preferably 30-55:20-45:10-15:5-10, more preferably 35-50:25-40:11-14:6-9, and even more preferably 40-45:30-35: 7-8; the water is preferably ultrapure water; in the ethanol solution, the volume fraction of ethanol is preferably 92 to 97%, more preferably 93 to 96%, and even more preferably 94 to 95%.
The molding treatment in step 1) is preferably a doctor blade molding treatment;
In the doctor blade forming treatment, the doctor blade gap of the cathode support structure electrolyte slurry and the anode support structure electrolyte slurry is preferably 300-500 mu m, more preferably 350-450 mu m, more preferably 400 mu m, and the winding speed is preferably 300-500 mm/min, more preferably 350-450 mm/min, more preferably 400mm/min; the heated drying zone preferably comprises 68 to 72℃/50cm and 88 to 92℃/50cm, more preferably 70℃/50cm and 90℃/50cm;
the doctor blade gap of the electrolyte slurry of the electrolyte layer is preferably 30 to 50 μm, more preferably 35 to 45 μm, and still more preferably 40 μm; the winding speed is preferably 1000-1500 mm/min, more preferably 1100-1400 mm/min, and even more preferably 1200-1300 mm/min; the heated drying zone preferably comprises 68 to 72℃/50cm and 88 to 92℃/50cm, more preferably 70℃/50cm and 90℃/50cm.
The cutting in the step 1) is preferably that the sizes of the cathode support structure ceramic green film and the anode support structure ceramic green film are the same as those of the electrolyte layer ceramic green film.
In the hot press molding process in the step 2), the electrolyte layer ceramic green film is preferably arranged between the anode support structure ceramic green film and the cathode support structure ceramic green film; the thickness ratio of the anode support structure ceramic green film to the electrolyte layer ceramic green film to the cathode support structure ceramic green film is preferably 180-240:3-10:180-240, more preferably 200-220:4-8:200-220, and even more preferably 210:5-6:210; the temperature of the hot press molding is preferably 45 to 85 ℃, more preferably 50 to 80 ℃, and even more preferably 60 to 70 ℃; the rate is preferably 110 to 130kg/cm 2, more preferably 115 to 125kg/cm 2, still more preferably 120kg/cm 2.
The hot press molding is preferably carried out by firstly carrying out hot press molding on the ceramic green film of the anode support structure, then adding the ceramic green film of the electrolyte layer to the surface of the ceramic green film of the anode support structure for hot press molding, and finally adding the ceramic green film of the cathode support structure to the surface of the ceramic green film of the electrolyte layer for hot press molding.
The cathode support structure and the anode support structure are porous, and the electrolyte layer has high compactness.
The sintering process in step 2) of the invention is preferably as follows: the integrated ceramic green body is sintered for 4 to 6 hours at 1300 to 1500 ℃ and then cooled to 900 to 1100 ℃, more preferably sintered for 4.5 to 5.5 hours at 1350 to 1450 ℃ and then cooled to 950 to 1050 ℃, more preferably sintered for 5 hours at 1380 to 1420 ℃ and then cooled to 980 to 1000 ℃; after the temperature is reduced to 980-1000 ℃, the sintering process is finished, and the natural furnace is preferably cooled to room temperature.
The heating rate of the step 2) to 1300-1500 ℃ is preferably 0.8-1.2 ℃/min, and more preferably 1 ℃/min; the cooling rate of cooling to 900 to 1100 ℃ is preferably 0.8 to 1.2 ℃/min, more preferably 1 ℃/min.
The sintering in the step 3) is preferably to cool to 900-1100 ℃ after 4-6 hours of sintering at 1050-1250 ℃, more preferably to cool to 950-1050 ℃ after 4.5-5.5 hours of sintering at 1100-1200 ℃, more preferably to cool to 980-1000 ℃ after 5 hours of sintering at 1130-1150 ℃; after the temperature is reduced to 980-1000 ℃, the sintering process is finished, and the natural furnace is preferably cooled to room temperature.
The temperature rising rate of the step 3) to 1050-1250 ℃ is preferably 0.8-1.2 ℃/min, and more preferably 1 ℃/min; the cooling rate of cooling to 900 to 1100 ℃ is preferably 0.8 to 1.2 ℃/min, more preferably 1 ℃/min.
The sintering in step 2) and step 3) of the invention is preferably performed by using a high-temperature furnace.
The cathode catalytic material slurry in the step 3) of the invention permeates into the pores of the cathode support structure, and the anode catalytic material slurry permeates into the pores of the anode support structure.
The cathode catalytic material slurry and the anode catalytic material slurry in the step 3) of the invention preferably comprise nano powder, nano electrolyte oxide, pore-forming agent, leveling agent, polyvinyl butyral, polyethylene glycol, dibutyl phthalate, glycerol, corn oil, lauryl sulfate and solvent; wherein, in the cathode catalytic material slurry, the nano powder is preferably (La 0.8Sr0.2)MnO3-δ, wherein the delta is preferably 0.05-0.15, more preferably 0.08-0.12, more preferably 0.1;
The mass ratio of the nano powder to the nano electrolyte oxide to the pore-forming agent to the leveling agent to the polyvinyl butyral to the polyethylene glycol to the dibutyl phthalate to the glycerol to the corn oil to the lauryl sulfate is preferably 80-90:1-5:0.3-1:0.3-1:5-6:0.1-0.5:0.1-0.5:0.05-0.5:0.1-0.5, more preferably 82-88:2-4:0.5-0.8:0.5-0.8:5.5:0.2-0.4:0.2-0.4:0.1-0.4:0.2-0.4, and even more preferably 85-86:3:0.6-0.7:0.6-0.7:5:0.3:0.3:0.2-0.3:0.3:0.3-0.3:0.3:0.1-0.3:0.4;
The nanoelectrolyte oxide preferably comprises (Sm0.2Ce0.8)O1.9、(Sr0.2Ce0.8)(Ga0.8Mg0.2)O3-δ、Bi2O3、(Gd0.2Ce0.8)O1.9、(Gd0.15Y0.05Ce0.8)O1.9 or 8YSZ; the 8YSZ preferably contains Y 2O3 and ZrO 2, and the molar ratio of the Y 2O3 and the ZrO 2 is preferably 7-9:90-94, and more preferably 8:92; δ in (Sr 0.2Ce0.8)(Ga0.8Mg0.2)O3-δ) is preferably 0.2 to 0.3, more preferably 0.23 to 0.27, and still more preferably 0.25;
the mass volume ratio of the nano electrolyte oxide to the solvent is preferably 1-5 g:110 to 145mL, more preferably 2 to 4g:120 to 140mL, more preferably 3g: 125-135 mL;
The solvent preferably comprises butanone, an ethanol solution, acetone and water, wherein the volume ratio of the butanone to the ethanol solution to the acetone to the water is preferably 50-60:40-50:10-20:10-15, more preferably 52-58:42-48:12-17:11-14, and even more preferably 54-56:44-45:14-15:12-13; the water is preferably ultrapure water; in the ethanol solution, the volume fraction of ethanol is preferably 92 to 97%, more preferably 94 to 96%, and even more preferably 95%;
The pore-forming agent is preferably activated carbon powder, starch or ethylcellulose; the leveling agent is preferably polydimethylsiloxane, aqueous polyurethane, high molecular weight acrylic acid or fluorine modified acrylic acid.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Grinding 0.2mole Sm 2O3(69.74364g),1.6mole CeO2 (275.39008 g) and mixing uniformly, calcining at 1600 ℃ to synthesize SDC (Sm 0.2Ce0.8O1.9) electrolyte oxide, and grinding the calcined SDC into sample powder by a crushing device to obtain electrolyte powder.
Grinding and mixing electrolyte powder, fluxing agent, pore-forming agent and film preparation Cheng Jiangliao additive in a mass ratio of 80:2:9.5:8.5 to obtain 100g of cathode support structure electrolyte slurry and 100g of anode support structure electrolyte slurry respectively, wherein the fluxing agent is Li 2CO3, the pore-forming agent comprises activated carbon powder, starch and ethylcellulose in a mass ratio of 6:1.5:2, the film preparation slurry additive comprises polyvinyl butyral, polyethylene glycol, dibutyl phthalate, glycerol, corn oil and lauryl sulfate in a mass ratio of 6:0.5:0.5:0.5:0.5:0.5, and the film preparation Cheng Jiangliao additive further comprises a solvent in a ratio of 80mL:6g, solvent comprising volume ratio 40:20:10: butanone of 10, ethanol solution (volume fraction of ethanol 95%), acetone and ultrapure water. And carrying out scraper forming treatment on the cathode support structure electrolyte slurry and the anode support structure electrolyte slurry, wherein a scraper gap is 400 mu m, the rolling speed is 400mm/min, the heating and drying areas are 70 ℃/50cm and 90 ℃/50cm sections, and the cathode support structure electrolyte ceramic green embryo film and the anode support structure electrolyte ceramic green embryo film are manufactured, and the thickness of each film is 50 mu m after the two films are dried.
The electrolyte powder with the mass ratio of 90:2:8, a fluxing agent and a film preparation Cheng Jiangliao additive are ground and mixed to obtain 100g electrolyte slurry with an electrolyte layer, wherein the fluxing agent is Li 2CO3, the film preparation Cheng Jiangliao additive comprises polyvinyl butyral, polyethylene glycol, dibutyl phthalate, glycerol and lauryl sulfate with the mass ratio of 5:0.5:0.5:0.5:0.5, the film preparation Cheng Jiangliao additive further comprises a solvent, and the ratio of the solvent to the polyvinyl butyral is 105mL:6g, solvent comprising butanone, ethanol solution (volume fraction of ethanol 95%), acetone and ultrapure water in a volume ratio of 50:40:10:5. And carrying out scraper forming treatment on the electrolyte slurry of the electrolyte layer, wherein the scraper gap is 40 mu m, the rolling speed is 1200mm/min, the heating and drying area is 70 ℃/50cm and 90 ℃/50cm, and the electrolyte ceramic green film with the thickness of 5 mu m is prepared by drying.
The dried anode support structure ceramic green film of 50 μm/sheet is laminated to a thickness of 200 μm, hot press molding is performed at 50 ℃ and 120kg/cm 2, the dried 1-sheet electrolyte layer ceramic green film (5 μm/sheet) is laminated to the anode support structure ceramic green film of 200 μm thickness, and hot press molding is performed at 60 ℃ and 120kg/cm 2 to form a composite green structure of the anode support structure ceramic green and the electrolyte layer ceramic green. And superposing the dried 4 ceramic green films (50 mu m/piece) with the cathode support structure on the ceramic green film with the electrolyte layer of the composite green structure, and performing hot press molding at 80 ℃ and 120kg/cm 2 to obtain the composite green structure with the thickness of 405 mu m. Drying the composite green body structure in a baking oven, and sintering in a high-temperature sintering furnace, wherein the sintering process comprises the following steps: heating to 1400 ℃ at the room temperature at the speed of 1 ℃/min, sintering for 5 hours at 1400 ℃, then cooling to 1000 ℃ at the speed of 1 ℃/min, ending the sintering procedure, and naturally cooling to the room temperature in a furnace to obtain the cathode support structure, the electrolyte layer and the anode support structure.
The mass ratio is 85:2:0.5:0.5:5.5:0.2:0.3:0.2:0.2:0.3, nano nickel oxide powder, bi 2O3, activated carbon powder, polydimethylsiloxane, polyvinyl butyral, polyethylene glycol, dibutyl phthalate, glycerol, corn oil and lauryl sulfate are ground and mixed to obtain anode catalytic material slurry, the anode catalytic material slurry further comprises a solvent, and the ratio of the solvent to Bi 2O3 is 125mL:3g, solvent comprising butanone, ethanol solution (95% by volume), acetone and water in a volume ratio of 55:45:15:12. The anode catalytic material slurry is fully infiltrated into all pores of the anode support structure to form a semi-coagulated viscous polymer colloid. The mass ratio is 85:2:0.5: 0.5:5.5:0.2:0.3:0.2:0.2:0.2:0.3 (La 0.8Sr0.2)MnO3-δ (delta is 0.08)), bi 2O3, activated carbon powder, polydimethylsiloxane, polyvinyl butyral, polyethylene glycol, dibutyl phthalate, glycerol, corn oil and lauryl sulfate are ground and mixed to obtain a cathode catalytic material slurry, the anode catalytic material slurry further comprises a solvent, the ratio of the solvent to Bi 2O3 is 125mL:3g, the solvent comprises butanone, an ethanol solution (volume fraction is 95%) and acetone in a volume ratio of 55:45:15:12, and water.
Sintering an anode support structure and a cathode support structure respectively containing anode catalytic material slurry and cathode catalytic material slurry in a high-temperature furnace, wherein the sintering process comprises the following steps: heating to 1150 ℃ at the speed of 1 ℃/min at room temperature, sintering for 5h at 1150 ℃, then cooling to 1000 ℃ at the speed of 1 ℃/min, ending the sintering procedure, and naturally cooling to room temperature in a furnace to obtain the anode layer and the cathode layer.
The microstructure of the electrolyte-supported solid oxide fuel cell of example 1 is shown in fig. 1. In the prior art, cathode and anode catalytic materials and electrolyte powder are uniformly mixed according to a proper proportion and then used as electrode materials of SOFC, and in the cell microstructure manufactured by the method, the electrolytes of the cathode and anode do not form an integrated structure with the electrolyte layer. If the thickness of the electrolyte layer is reduced to increase the output of the unit cell, mechanical strength is sacrificed, and even if the cathode and anode layers are thickened, the mechanical strength that can be increased is still quite limited. In addition, the thickening of the cathode layer and the anode layer can enlarge the volume of the cell stack assembled by the rear end, which is not beneficial to the temperature maintenance of the cell stack and the development of products. The invention utilizes electrolyte materials to build the basic structure of the SOFC unit cell, and then places cathode and anode catalytic materials into the cathode and anode structural layers. As can be seen from fig. 1, in the microstructure of the unit cell manufactured by the method of the present invention, the electrolytes of the cathode and anode and the electrolyte layer form an integrated structure, and the thickness of the electrolyte layer is reduced to 5 μm to increase the output power of the unit cell, while still providing the mechanical strength of the SOFC unit cell.
The sintered electrolyte-supported structure comprising the cathode support structure, electrolyte layer, and anode support structure of example 1 is shown in fig. 2. As can be seen from fig. 2, in the electrolyte-supported structure formed by the electrolyte, the pores of the electrode layer have been completely filled with the catalytic materials of the cathode and anode. The electrolyte layer has a high compact structure, the electrode layer has a porous structure, activated carbon powder forms micropores, starch forms mesopores, and ethyl cellulose forms macropores, and is used for placing catalytic materials of a cathode and an anode.
Example 2
Grinding 0.2mole Sm 2O3(69.74364g)、1.6mole CeO2 (275.39008 g) and mixing uniformly, calcining at 1600 ℃ to synthesize SDC (Sm 0.2Ce0.8O1.9) electrolyte oxide, and grinding the calcined SDC into sample powder by a crushing device to obtain electrolyte powder.
Grinding and mixing electrolyte powder, fluxing agent, pore-forming agent and film preparation Cheng Jiangliao additive in a mass ratio of 85:2:6:7 to obtain 100g of cathode support structure electrolyte slurry and 100g of anode support structure electrolyte slurry respectively, wherein the fluxing agent is Li 2CO3, the pore-forming agent comprises active carbon powder, starch and ethylcellulose in a mass ratio of 3:2:1, the film preparation slurry additive comprises polyvinyl butyral, polyethylene glycol, dibutyl phthalate, glycerol, corn oil and lauryl sulfate in a mass ratio of 5:0.7:0.8:0.5:0.5:0.5, the film preparation Cheng Jiangliao additive further comprises a solvent, and the ratio of the solvent to the polyvinyl butyral is 90mL:5g, solvent comprising volume ratio 45:25:10: butanone of 10, ethanol solution (volume fraction of ethanol 95%), acetone and ultrapure water. And carrying out scraper forming treatment on the cathode support structure electrolyte slurry and the anode support structure electrolyte slurry, wherein a scraper gap is 300 mu m, the rolling speed is 300mm/min, the heating and drying areas are 68 ℃/50cm and 88 ℃/50cm sections, and the cathode support structure electrolyte ceramic green embryo film and the anode support structure electrolyte ceramic green embryo film are manufactured, and the thickness of each film is 40 mu m after the two films are dried.
The electrolyte powder with the mass ratio of 86:2:12, a fluxing agent and a film preparation Cheng Jiangliao additive are ground and mixed to obtain 100g electrolyte slurry with an electrolyte layer, wherein the fluxing agent is Li 2CO3, the film preparation Cheng Jiangliao additive comprises polyvinyl butyral, polyethylene glycol, dibutyl phthalate, glycerol and lauryl sulfate with the mass ratio of 7:0.5:0.3:0.3:0.5, the film preparation Cheng Jiangliao additive further comprises a solvent, and the ratio of the solvent to the polyvinyl butyral is 95mL:7g, solvent comprising butanone, ethanol solution (volume fraction of ethanol 95%), acetone and ultrapure water in a volume ratio of 45:35:10:5. And carrying out scraper forming treatment on the electrolyte slurry of the electrolyte layer, wherein the scraper gap is 30 mu m, the winding speed is 1100mm/min, the heating and drying area is 68 ℃/50cm and 88 ℃/50cm, and the electrolyte ceramic green film with the thickness of 3 mu m is prepared by drying. Cutting the electrolyte ceramic green film of the anode support structure, the electrolyte ceramic green film of the cathode support structure and the electrolyte ceramic green film of the electrolyte layer into ceramic green films with the same length and width.
The dried electrolyte ceramic green film of the anode support structure of 40 mu m/sheet is added to 240 mu m thickness, hot press molding is carried out at 47 ℃ and 120kg/cm 2, the dried ceramic green film of the electrolyte layer of 1 sheet (3 mu m/sheet) is added to the ceramic green film of the anode support structure of 240 mu m thickness, and hot press molding is carried out at 58 ℃ and 120kg/cm 2 to form the composite green structure of the anode support structure and the ceramic green of the electrolyte layer. And superposing the dried 5 ceramic green films (40 mu m/piece) with the cathode support structure on the ceramic green film with the electrolyte layer of the composite green structure, and performing hot press molding at 75 ℃ and 120kg/cm 2 to obtain the composite green structure with the thickness of 443 mu m. Drying the composite green body structure in a baking oven, and sintering in a high-temperature sintering furnace, wherein the sintering process comprises the following steps: heating to 1350 ℃ at the room temperature at the speed of 0.9 ℃/min, sintering at 1350 ℃ for 6 hours, then cooling to 950 ℃ at the speed of 0.9 ℃/min, ending the sintering procedure, and naturally cooling to room temperature in a furnace to obtain the cathode support structure, the electrolyte layer and the anode support structure.
The anode catalytic material slurry is prepared by grinding and mixing nano nickel oxide powder (Gd 0.2Ce0.8)O1.9, starch, aqueous polyurethane, polyvinyl butyral, polyethylene glycol, dibutyl phthalate, glycerol, corn oil and lauryl sulfate with the mass ratio of 82:4:0.7:0.5:5:0.2:0.3:0.3:0.3:0.2 to obtain anode catalytic material slurry, the anode catalytic material slurry further comprises a solvent, the ratio of the solvent to (Gd 3836 is 115mL:4 g), the solvent comprises butanone and ethanol solution with the volume ratio of 50:40:12:12 (volume fraction is 95%), the acetone and water.
Sintering an anode support structure and a cathode support structure respectively containing anode catalytic material slurry and cathode catalytic material slurry in a high-temperature furnace, wherein the sintering process comprises the following steps: heating to 1100 ℃ at the room temperature at the speed of 0.9 ℃/min, sintering at 1100 ℃ for 6 hours, then cooling to 970 ℃ at the speed of 0.9 ℃/min, ending the sintering procedure, and naturally cooling to the room temperature in a furnace to obtain the anode layer and the cathode layer.
Example 3
Grinding 0.2mole Sm 2O3(69.74364g)、1.6mole CeO2 (275.39008 g) and mixing uniformly, calcining at 1600 ℃ to synthesize SDC (Sm 0.2Ce0.8O1.9) electrolyte oxide, and grinding the calcined SDC into sample powder by a crushing device to obtain electrolyte powder.
Grinding and mixing electrolyte powder, a fluxing agent, a pore-forming agent and a film preparation Cheng Jiangliao additive in a mass ratio of 88:1:5:6 to obtain 100g of cathode support structure electrolyte slurry and 100g of anode support structure electrolyte slurry respectively, wherein the fluxing agent is Li 2CO3, the pore-forming agent comprises active carbon powder, starch and ethylcellulose in a mass ratio of 3:1:1, the film preparation slurry additive comprises polyvinyl butyral, polyethylene glycol, dibutyl phthalate, glycerol, corn oil and lauryl sulfate in a mass ratio of 7:0.9:0.9:0.4:0.4:0.5, the film preparation Cheng Jiangliao additive further comprises a solvent, and the ratio of the solvent to the polyvinyl butyral is 100mL:7g, solvent comprising butanone, ethanol solution (volume fraction of ethanol 95%), acetone and ultrapure water in a volume ratio of 50:35:12:8. And carrying out scraper forming treatment on the cathode support structure electrolyte slurry and the anode support structure electrolyte slurry, wherein a scraper gap is 500 mu m, the rolling speed is 500mm/min, the heating and drying areas are 72 ℃/50cm and 92 ℃/50cm sections, and the cathode support structure electrolyte ceramic green embryo film and the anode support structure electrolyte ceramic green embryo film are manufactured, and the thickness of each film is 45 mu m after the two films are dried.
The electrolyte powder, the fluxing agent and the film preparation Cheng Jiangliao additive with the mass ratio of 92:1:7 are ground and mixed to obtain 100g electrolyte slurry with an electrolyte layer, wherein the fluxing agent is Li 2CO3, the film preparation Cheng Jiangliao additive comprises polyvinyl butyral, polyethylene glycol, dibutyl phthalate, glycerol and lauryl sulfate with the mass ratio of 7:0.5:0.3:0.3:0.5, the film preparation Cheng Jiangliao additive further comprises a solvent, and the ratio of the solvent to the polyvinyl butyral is 115mL:7g, solvent comprising butanone, ethanol solution (volume fraction of ethanol 95%), acetone and ultrapure water in a volume ratio of 50:40:12:8. And carrying out scraper forming treatment on the electrolyte slurry of the electrolyte layer, wherein the scraper gap is 50 mu m, the winding speed is 1400mm/min, the heating and drying area is 72 ℃/50cm and 92 ℃/50cm, and the electrolyte ceramic green film with the thickness of 5 mu m is prepared by drying.
45 Μm/sheet of dried anode support structure electrolyte ceramic green film was laminated to 225 μm thickness, hot press molding was performed at 52℃at 120kg/cm 2, and 1 sheet of dried electrolyte layer ceramic green film (5 μm/sheet) was laminated to 225 μm thick anode support structure electrolyte layer ceramic green film, hot press molding was performed at 64℃at 120kg/cm 2 to form a composite green structure of anode support structure and electrolyte layer ceramic green. And superposing 5 dried ceramic green films (45 mu m/piece) with the cathode support structure on the ceramic green film with the electrolyte layer of the composite green structure, and performing hot press molding at 82 ℃ and 120kg/cm 2 to obtain the composite green structure with the thickness of 455 mu m. Drying the composite green body structure in a baking oven, and sintering in a high-temperature sintering furnace, wherein the sintering process comprises the following steps: heating to 1450 ℃ at the speed of 1.1 ℃/min, sintering for 4 hours at 1450 ℃, then cooling to 1050 ℃ at the speed of 1.1 ℃/min, ending the sintering procedure, and naturally cooling to room temperature in a furnace to obtain the cathode support structure, the electrolyte layer and the anode support structure.
The anode catalytic material slurry was prepared by grinding and mixing nano nickel oxide powder (Gd 0.15Y0.05Ce0.8)O1.9, ethylcellulose, fluorine modified acrylic acid, polyvinyl butyral, polyethylene glycol, dibutyl phthalate, glycerol, corn oil and lauryl sulfate in a mass ratio of 88:2:0.4:0.7:5.8:0.4:0.2:0.2:0.2:0.4:0.2:0.2 to obtain an anode catalytic material slurry, the anode catalytic material slurry further comprising a solvent, the solvent comprising butanone in a volume ratio of 58:47:18:13 (volume fraction of 95%), an ethanol solution (acetone and water. The anode catalytic material slurry was completely infiltrated into all pores of the anode support structure to form a semi-coagulated viscous polymer colloid, and the cathode catalytic material slurry was prepared by grinding and mixing La 0.8Sr0.2)MnO3-δ (delta 0.1), (Gd 0.15Y0.05Ce0.8)O1.9, ethylcellulose, vinyl alcohol, fluorine modified acrylic acid, butyraldehyde, lauryl sulfate in a volume ratio of 135ml:2 g), the cathode catalytic material slurry comprising butanone in a volume ratio of 58:47:18:13, (volume fraction of 95%), acetone and water. The cathode catalytic material slurry was prepared by grinding and mixing the cathode catalytic material slurry in a mass ratio of 88:2:0.4:0.4:0.7:0.8:0.2:0.2:0.2 (volume fraction of Gd, 3).
Sintering an anode support structure and a cathode support structure respectively containing anode catalytic material slurry and cathode catalytic material slurry in a high-temperature furnace, wherein the sintering process comprises the following steps: heating to 1200 ℃ at the room temperature at the speed of 1.1 ℃/min, sintering for 4.5h at the temperature of 1200 ℃, then cooling to 1070 ℃ at the speed of 1.1 ℃/min, ending the sintering procedure, and naturally cooling to the room temperature in a furnace to obtain the anode layer and the cathode layer.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (7)

1. A method of fabricating an electrolyte supported solid oxide fuel cell comprising the steps of:
1) Respectively molding and cutting the cathode support structure electrolyte slurry, the anode support structure electrolyte slurry and the electrolyte layer electrolyte slurry to obtain a cathode support structure ceramic green compact film, an anode support structure ceramic green compact film and an electrolyte layer ceramic green compact film;
2) Drying and sintering the three ceramic green film obtained in the step 1) after hot press molding to obtain a cathode support structure, an electrolyte layer and an anode support structure;
3) Adding cathode catalytic material slurry into a cathode supporting structure, and sequentially drying and sintering to obtain a cathode layer;
adding anode catalytic material slurry into an anode supporting structure, and sequentially drying and sintering to obtain an anode layer;
Step 3) the cathode catalytic material slurry and the anode catalytic material slurry both comprise nano powder, nano electrolyte oxide, pore-forming agent, leveling agent, polyvinyl butyral, polyethylene glycol, dibutyl phthalate, glycerol, corn oil, lauryl sulfate and solvent; wherein, in the cathode catalytic material slurry, the nano powder is (La 0.8Sr0.2)MnO3-δ, in the anode catalytic material slurry, the nano powder is nano nickel oxide powder;
The mass ratio of the nano powder to the nano electrolyte oxide to the pore-forming agent to the leveling agent to the polyvinyl butyral to the polyethylene glycol to the dibutyl phthalate to the glycerol to the corn oil to the lauryl sulfate is 80-90: 1 to 5:0.3 to 1:0.3 to 1:5 to 6:0.1 to 0.5:0.1 to 0.5:0.05 to 0.5:0.05 to 0.5:0.1 to 0.5;
Step 1), the molding treatment is a scraper molding treatment;
In the scraper forming treatment, the scraper gaps of the cathode support structure electrolyte slurry and the anode support structure electrolyte slurry are 300-500 mu m, the rolling speed is 300-500 mm/min, and the heating and drying area comprises 68-72 ℃/50cm and 88-92 ℃/50cm;
the gap of the scraper of the electrolyte slurry of the electrolyte layer is 30-50 mu m, the rolling speed is 1000-1500 mm/min, and the heating and drying area comprises 68-72 ℃/50cm and 88-92 ℃/50cm;
Step 1), the cathode support structure electrolyte slurry and the anode support structure electrolyte slurry both comprise electrolyte powder, pore-forming agent, fluxing agent and film making Cheng Jiangliao additive;
The electrolyte slurry of the electrolyte layer comprises electrolyte powder, a fluxing agent and a Cheng Jiangliao thin film additive;
The pore-forming agent comprises one or more of activated carbon powder, starch and ethyl cellulose;
The fluxing agent comprises Li 2CO3、B2O3、Al2O3 or Bi 2O3;
the mass ratio of the electrolyte powder, the pore-forming agent, the fluxing agent and the film-forming Cheng Jiangliao additive in the step 1) is 0.5-10.5: 0.5 to 2.5:5 to 10;
The film-making Cheng Jiangliao additive comprises polyvinyl butyral, polyethylene glycol, dibutyl phthalate, glycerol, corn oil, lauryl sulfate and a solvent; the mass ratio of the polyvinyl butyral to the polyethylene glycol to the dibutyl phthalate to the glycerol to the corn oil to the lauryl sulfate is 5-8: 0.1 to 1.2:0.1 to 1.2:0.1 to 0.7:0 to 0.7:0.1 to 0.7; the mass volume ratio of the polyvinyl butyral to the solvent is 5-8 g: 65-120 mL; the solvent comprises the following components in percentage by volume: 20-45: 10 to 15: butanone 5-10, ethanol solution, acetone and water; in the ethanol solution, the volume fraction of ethanol is 92-97%;
in the hot press molding process of the step 2), the electrolyte layer ceramic green film is arranged between the anode support structure ceramic green film and the cathode support structure ceramic green film; the thickness ratio of the anode support structure ceramic green film to the electrolyte layer ceramic green film is 180-240: 3-10: 180-240.
2. The process method according to claim 1, wherein the mass ratio of the electrolyte powder, the fluxing agent and the thin film Cheng Jiangliao additive is 85-95: 0.5 to 2.5:5 to 12.
3. The process of claim 2, wherein the electrolyte powder comprises (Sm0.2Ce0.8)O1.9、(Sr0.2Ce0.8)(Ga0.8Mg0.2)O3-δ、Bi2O3(Gd0.2Ce0.8)O1.9、(Gd0.15Y0.05Ce0.8)O1.9 or 8YSZ; the 8YSZ comprises the components with the molar ratio of 7 to 9: y 2O3 and ZrO 2 of 90 to 94.
4. A process according to claim 3, wherein the hot press molding in step 2) is carried out at a temperature of 45-85 ℃ and a rate of 110-130 kg/cm 2.
5. The method according to claim 4, wherein the sintering in step 2) is performed by: sintering the integrated ceramic green body at 1300-1500 ℃ for 4-6 hours and then cooling to 900-1100 ℃;
The temperature rising rate of the mixture is 0.8 to 1.2 ℃/min when the temperature rises to 1300 to 1500 ℃; the cooling rate of cooling to 900-1100 ℃ is 0.8-1.2 ℃/min.
6. The method according to claim 4 or 5, wherein the sintering in step 3) is performed at 1050-1250 ℃ for 4-6 hours, and then cooling to 900-1100 ℃;
the temperature rising rate of the mixture is 0.8 to 1.2 ℃/min when the temperature rises to 1050 to 1250 ℃; the cooling rate of cooling to 900-1100 ℃ is 0.8-1.2 ℃/min.
7. The process according to claim 6, wherein the mass to volume ratio of the nano-electrolyte oxide to the solvent is 1-5 g: 110-145 mL;
The solvent comprises 50-60 volume percent: 40-50: 10-20: 10 to 15 butanone, ethanol solution, acetone and water;
In the ethanol solution, the volume fraction of ethanol is 92-97%.
CN202111199199.1A 2021-10-14 2021-10-14 Process method of electrolyte supported solid oxide fuel unit cell Active CN113937318B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111199199.1A CN113937318B (en) 2021-10-14 2021-10-14 Process method of electrolyte supported solid oxide fuel unit cell

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111199199.1A CN113937318B (en) 2021-10-14 2021-10-14 Process method of electrolyte supported solid oxide fuel unit cell

Publications (2)

Publication Number Publication Date
CN113937318A CN113937318A (en) 2022-01-14
CN113937318B true CN113937318B (en) 2024-04-19

Family

ID=79279359

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111199199.1A Active CN113937318B (en) 2021-10-14 2021-10-14 Process method of electrolyte supported solid oxide fuel unit cell

Country Status (1)

Country Link
CN (1) CN113937318B (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101563805A (en) * 2006-11-23 2009-10-21 丹麦科技大学 Thin solid oxide cell
CN101978537A (en) * 2008-03-18 2011-02-16 丹麦科技大学 An all ceramics solid oxide fuel cell
CN103811789A (en) * 2012-11-07 2014-05-21 中国科学院上海硅酸盐研究所 Solid oxide fuel cell with symmetrical electrodes, and preparation method and application thereof
TW201817068A (en) * 2016-10-26 2018-05-01 行政院原子能委員會核能研究所 Method of processing SOFC cell powder and fabricating thin-film cell
CN112448010A (en) * 2020-11-25 2021-03-05 广东石油化工学院 Preparation method of multi-layer structure composite block with porous sub-millimeter layer connected with high-compactness composite micron layer

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101563805A (en) * 2006-11-23 2009-10-21 丹麦科技大学 Thin solid oxide cell
CN101978537A (en) * 2008-03-18 2011-02-16 丹麦科技大学 An all ceramics solid oxide fuel cell
CN103811789A (en) * 2012-11-07 2014-05-21 中国科学院上海硅酸盐研究所 Solid oxide fuel cell with symmetrical electrodes, and preparation method and application thereof
TW201817068A (en) * 2016-10-26 2018-05-01 行政院原子能委員會核能研究所 Method of processing SOFC cell powder and fabricating thin-film cell
CN112448010A (en) * 2020-11-25 2021-03-05 广东石油化工学院 Preparation method of multi-layer structure composite block with porous sub-millimeter layer connected with high-compactness composite micron layer

Also Published As

Publication number Publication date
CN113937318A (en) 2022-01-14

Similar Documents

Publication Publication Date Title
AU2004252862B2 (en) Stack supported solid oxide fuel cell
CN101577340B (en) Method for preparing cathode-supported tubular solid oxide fuel cells
CN100399611C (en) Method for preparing solid oxide fuel cell cathode load type half-cell
CN1323459C (en) Fuel battery structure and process for preparing same
KR20140085431A (en) Composite anode for a solid oxide fuel cell with improved mechanical integrity and increased efficiency
CN100589271C (en) Preparation method of hollow fiber type solid oxide fuel cell
CN107785598B (en) Half-cell symmetrical solid oxide fuel cell
CN101359746A (en) Large size tubular solid oxide fuel cell and preparation thereof
CN100448088C (en) A making method for self-supported solid oxide fuel battery
CN111384421A (en) Five-layer structure single cell, preparation method thereof and prepared product
CN112436171B (en) Solid electrolyte support body and preparation method and application thereof
CN116722189B (en) Preparation method of anode-supported tubular proton conductor ceramic fuel cell
CN114171769B (en) Method for preparing solid oxide fuel cell stack by adopting 3D printing technology
CN104037425A (en) Medium-temperature SOFC (solid oxide fuel cell) flat-plate anode-supported monocell anode structure and preparation method thereof
KR100793155B1 (en) Fabrication method for unit cell of solid oxide fuel cell
CN113937318B (en) Process method of electrolyte supported solid oxide fuel unit cell
CN104577142A (en) Preparation method of solid oxide fuel cell gradient structure cathode film
Torres-Garibay et al. Ln0. 6Sr0. 4Co1− yFeyO3− δ (Ln= La and Nd; y= 0 and 0.5) cathodes with thin yttria-stabilized zirconia electrolytes for intermediate temperature solid oxide fuel cells
KR100660218B1 (en) Fabrication method for anode of solid oxide fuel cell
CN109216740A (en) A kind of anode support and preparation method thereof of hollow symmetrical SOFC battery
CN116826130A (en) Preparation method of solid oxide fuel cell
CN101510612B (en) Method for preparing stephanoporate anode support body using paper fabric a pore-forming agent
CN114044673A (en) Method for preparing ceramic composite membrane of proton conduction type solid oxide pool by water-based tape casting
CN107275657A (en) A kind of simple method for preparing of anode of solid oxide fuel cell supporter
CN116960420B (en) Preparation method of reversible solid oxide battery with double-layer straight hole structure

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant