CN108123158B - Low-temperature ceramic electrolyte membrane for solid oxide fuel cell and preparation method thereof - Google Patents
Low-temperature ceramic electrolyte membrane for solid oxide fuel cell and preparation method thereof Download PDFInfo
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- 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
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
- H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
- H01M8/126—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing cerium oxide
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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention provides a low-temperature ceramic electrolyte membrane for a solid oxide fuel cell and a preparation method thereof, which adopts Ce (NO)3)3·6H2O as main raw material, BaCO3And TiO2Mixing the raw materials by slurrying and ball milling, and then adding α -MnO2And aluminum phosphate screen printing to form a film, and placing the film in a box furnace for heat preservation and sintering at the temperature of 1130-2、BaTiO3Doped CeO2The electrolyte membrane is formed of α -MnO2Phase transition induced BaTiO at 200 deg.C3Polarization is generated, so that the electrolyte has obvious conductivity at the temperature of 450-500 ℃, the working temperature of the battery is reduced, and BaTiO3The invention can overcome the defects of high working temperature and long starting time of the existing solid oxide fuel cell, can effectively relieve the problem that the ionic conductance of an electrolyte membrane is obviously reduced due to the reduction of the working temperature of the cell, and is beneficial to realizing the medium-low temperature and the practicability of the solid oxide fuel cell.
Description
Technical Field
The invention relates to the field of fuel cell materials, in particular to a low-temperature ceramic electrolyte membrane for a solid oxide fuel cell and a preparation method thereof.
Background
Because the traditional fossil fuel is not renewable and the environmental pollution caused in the using process is serious, the search for environment-friendly renewable energy is a serious task for people in the 21 st century. The Fuel cell (Fuel cell) is a novel energy technology, which directly converts chemical energy of Fuel into electric energy through electrochemical reaction, and the used Fuel is hydrogen-rich substances such as hydrogen, methanol and hydrocarbons, and has no pollution to the environment, high energy efficiency and high power density, so the Fuel cell has wide application prospect.
Solid Oxide Fuel Cells (SOFC), belonging to the third generation Fuel cells, are all-Solid-state chemical power generation devices that directly convert chemical energy stored in Fuel and oxidant into electrical energy at medium and high temperatures, with high efficiency and excellent long-term performance stability, without the need for catalysts, and with a large reduction in system costs. Because the solid oxide is adopted as the electrolyte, the problems of electrolyte corrosion and the like do not exist; the fuel has wide adaptability and can be made of edible hydrogen, CO, natural gas (methane), coal gasified gas, hydrocarbon and the like. The traditional SOFC has the working temperature of over 750 ℃, is difficult to control, has long starting time and the like, the higher operating temperature can cause the problems of narrow selection range of battery materials, interface reaction between electrodes and electrolyte, difficult battery sealing and the like, the cost of the battery is high, and therefore the development of the market of the battery is limited, the working temperature of the solid fuel battery is reduced, particularly the reduction of the working temperature of the electrolyte, and the solid fuel battery has extremely high practical value for popularizing the application of the solid fuel battery in new energy vehicles.
The electrolyte is the most central component of the SOFC, and the charge transport characteristics and the thermal expansion properties of the electrolyte not only directly influence the working temperature and the electric energy conversion efficiency of the cell, but also determine the selection of cathode and anode materials matched with the electrolyte and the corresponding preparation technology. Generally, SOFC electrolyte materials need to have the following conditions: 1) high ionic conductivity: the ohmic resistance of the electrolyte membrane can be reduced; 2) negligible electron conductivity: the short-circuit current in the battery can be reduced; 3) The stability is better under the oxidizing atmosphere and the reducing atmosphere; 4) the mechanical strength is high: electrolyte cracking and the like are not easy to occur under the working condition of the fuel cell.
The cerium oxide-based electrolyte has a face-centered cubic fluorite structure, cerium ions are located at the central position of a simple cubic lattice composed of oxygen ions, the coordination number is 8, and oxygen ions occupy the central position of a tetrahedron formed by the cerium ions, and the coordination number is 4. The pure cerium oxide has a very low conductivity, and the oxygen ion conductivity at 600 ℃ is about 1X 10-5S/cm, but when CeO is partially substituted by aliovalent ions, e.g. ions of a divalent alkaline earth metal or a trivalent rare earth metal2Ce in (1)4+In order to keep the charge balance, certain oxygen vacancies are generated in the crystal lattice, and the oxygen ion conductivity can be greatly improved by doping cerium oxide.
Chinese patent application No. 200510011957.7 discloses a zinc-doped cerium oxide-inorganic salt composite electrolyte for low-temperature solid oxide fuel cells, which is a two-phase or multi-phase composite material formed by mixing zinc-doped cerium oxide directly synthesized at low temperature with inorganic salt and carrying out heat treatment, wherein the open-circuit voltage of the cell reaches 1.02V at 600 DEG CThe output power reaches 600mWcm-2The above. However, the battery has higher performance at 600 ℃, and when the working temperature is continuously reduced to the temperature range of 450 ℃ and 500 ℃, the performance of the battery cannot be ensured.
Chinese invention patent application No. 200980131358.5 discloses a method for depositing ceramic films, especially submicron thickness ceramic films, such as films of stabilized zirconia and doped ceria such as CGO (cerium gadolinium oxide), on ceramic or metal surfaces. The invention deposits at least two layers of metal oxide crystalline ceramics on the substrate surface for the manufacture of fuel cells operating at high and medium temperatures, and also metal supported medium temperature SOFCs operating in the range of 450 ℃ to 650 ℃. However, at least two layers of metal oxide crystalline ceramics need to be deposited in the scheme, the interface between the film layers is not favorable for ion transmission, and the preparation process is complex and is not favorable for large-scale production and application.
Therefore, the electrolyte membrane and the preparation process scheme which are simple and controllable in process scheme and effectively overcome the defects of high working temperature and long starting time of the conventional solid oxide fuel cell have high practical value for promoting the reduction of the working temperature of the electrolyte.
Disclosure of Invention
Aiming at the defects of high working temperature and long starting time of the existing solid oxide fuel cell, the invention provides the low-temperature ceramic electrolyte membrane for the solid oxide fuel cell and the preparation method thereof, which can effectively relieve the problem that the ionic conductance of the electrolyte membrane is obviously reduced due to the reduction of the working temperature of the cell, and are favorable for realizing the medium-low temperature and the practicability of the solid oxide fuel cell.
In order to solve the problems, the invention adopts the following technical scheme:
(1) weighing 10-50 parts by mass of Ce (NO)3)3·6H2O powder, 8-15 parts by mass of BaCO3Powder and 10-12 parts by mass of TiO2Uniformly mixing powder, adding 1-3 parts by mass of a cross-linking agent and sufficient organic solvent, and performing ball milling by using a high-energy ball mill to obtain precursor slurry;
(2) adding 10-1 parts into the precursor slurry4 parts by mass of α -MnO2And 2-5 parts by mass of aluminum phosphate, stirring to obtain uniform slurry, and forming a film on the surfaces of the two sides of the electrode by adopting screen printing for at least three times;
(3) placing the printed electrode in a high-temperature box furnace, heating at the speed of 2-5 ℃/min, respectively carrying out heat preservation sintering at the temperature of 1130-2、BaTiO3Doped CeO2The electrolyte membrane of (1).
Preferably, the organic solvent is a mixed solution of one or more of N, N-dimethylacetamide, N-dimethylformamide, dimethyl sulfoxide and tetrahydrofuran.
Preferably, the crosslinking agent is one of acrylic acid, acrylamide, ethylene glycol dimethacrylate and ethylene glycol acrylate.
Preferably, the rotating speed of the high-energy ball mill is controlled at 800-1200rpm, and the ball milling time is controlled at 2-5 hours.
Preferably, the viscosity of the precursor slurry is 5000-.
Preferably, the screen is made of metal, the aperture of the screen is 40-300 μm, and the scraping speed of the scraper in the screen printing is controlled to be 1-2 mm/s.
Preferably, the screen-printing film thickness is 50 to 300 μm.
Preferably, in the step (3), inert gas is introduced into the electrolyte membrane in a high-temperature sintering process to protect the electrolyte membrane, the inert gas is one of argon, nitrogen and carbon dioxide, and acid-base neutralization treatment is performed on tail gas in the high-temperature sintering process to avoid Ce (NO)3)3The acid gas produced by decomposition pollutes the atmosphere.
In another aspect, a low temperature ceramic electrolyte membrane for a solid oxide fuel cell is provided, which is prepared by the above method.
Aiming at the defects of high working temperature and long starting time of the existing solid oxide fuel cell, the oxygen ion conductivity can be greatly improved by doping cerium oxide, and the preparation conditions of the existing doping process scheme are harshIn view of the fact that the operation temperature range is high, the invention provides a low-temperature ceramic electrolyte membrane for a solid oxide fuel cell and a preparation method thereof, wherein Ce (NO) is adopted3)3·6H2O as main raw material, BaCO3And TiO2Mixing the raw materials by slurrying and ball milling, and then adding α -MnO2And aluminum phosphate screen printing to form a film, and placing the film in a box furnace for heat preservation and sintering at the temperature of 1130-2、BaTiO3Doped CeO2Barium titanate is a typical ferroelectric, has a tetragonal structure at room temperature, and shows strong ferroelectricity with spontaneous polarization along the c-axis, the invention has the obvious advantage of utilizing α -MnO2Phase transition induced BaTiO at 200 deg.C3Polarization is generated so that the electrolyte has significant conductivity at approximately 450 ℃ - & 500 ℃, reducing the cell operating temperature. And BaTiO3The introduction of the oxygen ion provides a conduction channel for oxygen ions, can effectively relieve the problem that the ionic conductance of an electrolyte membrane is obviously reduced due to the reduction of the working temperature of the cell, and is favorable for realizing the medium-low temperature and the practicability of the solid oxide fuel cell.
The performance of the battery material obtained by the composite membrane electrode of the fuel cell prepared by the invention and the gadolinium-doped cerium oxide electrolyte is tested at the test temperature of 400-550 ℃, as shown in table 1.
Table 1:
| item | conductivity/S.cm-1（450℃） | Maximum output power/W |
| The electrolyte of the present invention | 0.95 | 18.4-28.5 |
| Gadolinium doped cerium oxide electrolyte | 0.08 | 6.55-10.35 |
Compared with the prior art, the invention provides a preparation method of a composite membrane electrode of a fuel cell, which has the outstanding characteristics and excellent effects that:
1. the electrolyte membrane of the invention is α -MnO2Phase transition induced BaTiO at 200 deg.C3Polarization is generated so that the electrolyte has significant conductivity at 450-500 ℃, and the all-solid-oxide electrolyte material for the fuel cell reduces the cell operating temperature.
2、BaTiO3The introduction of the oxygen ion provides a conduction channel for oxygen ions, can effectively relieve the problem that the ionic conductance of an electrolyte membrane is obviously reduced due to the reduction of the working temperature of the cell, and is favorable for realizing the medium-low temperature and the practicability of the solid oxide fuel cell.
3. The invention has simple process, reduces the manufacturing cost and promotes the development of the solid oxide fuel cell to low temperature and commercialization.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
(1) Weighing 10 parts by mass of Ce (NO)3)3·6H2O powder, 15 parts by mass of BaCO3Powder and 12 parts by mass of TiO2Uniformly mixing powder, adding 1 part by mass of acrylic acid and 30 parts by mass of N, N-dimethylacetamide, adjusting the rotating speed of a high-energy ball mill to 1200rpm, controlling the ball milling time to 2 hours, and mixing the powderBall milling by a high-energy ball mill to obtain precursor slurry with the viscosity of 5000mPa & s;
(2) adding α -MnO 10 weight portions into the precursor slurry2And 2 parts by mass of aluminum phosphate, stirring to obtain uniform slurry, and forming a film on the surfaces of the two sides of the electrode by adopting screen printing, wherein the screen is a metal screen, the aperture of the screen is 300 mu m, the scraping speed of a scraper in the screen printing is controlled to be 1 mm/s, the printing is carried out at least three times, and the thickness of the formed film by the screen printing is 50 mu m;
(3) placing the printed electrode in a high-temperature box furnace, introducing argon gas in the high-temperature sintering process, heating at the speed of 2 ℃/min, respectively carrying out heat preservation sintering at the temperature of 1130 ℃ for 20 hours, and then cooling to room temperature at the speed of 5 ℃/min to obtain α -MnO2、BaTiO3Doped CeO2The electrolyte membrane performs acid-base neutralization treatment on tail gas in the high-temperature sintering process to avoid Ce (NO)3)3The acid gas produced by decomposition pollutes the atmosphere.
The conductivity was measured using a conductivity meter model DDSJ-308F, and the electrolyte membranes of the examples were assembled into flat plates of 5X 5cm2The fuel cell, hydrogen is fuel, air is oxidizing agent, test the performance under the test temperature 400-.
Example 2
(1) 50 parts by mass of Ce (NO)3)3·6H2O powder, 8 parts by mass of BaCO3Powder and 12 parts by mass of TiO2Uniformly mixing powder, adding 3 parts by mass of acrylamide and 35 parts by mass of N, N-dimethylformamide, and carrying out ball milling by using a high-energy ball mill, wherein the rotating speed of the high-energy ball mill is controlled at 800rpm, and the ball milling time is controlled at 5 hours, so as to obtain precursor slurry with the viscosity of 15000mPa & s;
(2) adding α -MnO in 4 weight portions into the precursor slurry2And 5 parts by mass of aluminum phosphate, stirring to obtain uniform slurry, forming films on the surfaces of the two sides of the electrode by adopting screen printing, wherein the screen is made of metal and has the aperture of 40 mu m, and the screen printing is carried outThe scraping speed of the middle scraper is controlled to be 2mm./s, at least three times of printing are carried out, and the thickness of a silk-screen printing film is 100 mu m;
(3) placing the printed electrode in a high-temperature box-type furnace, introducing inert gas in the high-temperature sintering process to protect the condition, wherein the inert gas is one of argon, nitrogen and carbon dioxide, and performing acid-base neutralization treatment on tail gas in the high-temperature sintering process to avoid Ce (NO)3)3The acid gas generated by decomposition pollutes the atmosphere, the temperature is raised at the speed of 2 ℃/min, the temperature is respectively kept at 1150 ℃, sintered and kept for 12 hours, and then the temperature is lowered to the room temperature at the speed of 5 ℃/min to obtain α -MnO2、BaTiO3Doped CeO2The electrolyte membrane of (1).
The conductivity was measured using a conductivity meter model DDSJ-308F, and the electrolyte membranes of the examples were assembled into flat plates of 5X 5cm2The fuel cell, hydrogen is fuel, air is oxidizing agent, test the performance under the test temperature 400-.
Example 3
(1) Weighing 18 parts by mass of Ce (NO)3)3·6H2O powder, 12 parts by mass of BaCO3Powder and 11 parts by mass of TiO2Uniformly mixing powder, adding 1.5 parts by mass of mixed solution consisting of ethylene glycol dimethacrylate, dimethyl sulfoxide and tetrahydrofuran, and carrying out ball milling by using a high-energy ball mill, wherein the rotating speed of the high-energy ball mill is controlled at 1000rpm, and the ball milling time is controlled at 3 hours, so as to obtain precursor slurry with the viscosity of 10000mPa & s;
(2) adding α -MnO of 12 parts by mass into the precursor slurry2And 4 parts by mass of aluminum phosphate, stirring to obtain uniform slurry, forming a film on the surfaces of the two sides of the electrode by adopting screen printing, wherein the screen is made of metal, the aperture of the screen is 120 mu m, the scraping speed of a scraper in the screen printing is controlled to be 1.2 mm/s, the printing is carried out at least three times, and the thickness of the formed film by the screen printing is 150 mu m;
(3) placing the printed electrode in a high-temperature box furnace, introducing nitrogen in the high-temperature sintering process, and performing sintering at the speed of 4 ℃/minHeating, respectively keeping the temperature of 1140 ℃, sintering and keeping the temperature for 16 hours, and then cooling to room temperature at the speed of 5 ℃/min to obtain α -MnO2、BaTiO3Doped CeO2The tail gas is subjected to acid-base neutralization treatment in the high-temperature sintering process, so that Ce (NO) is avoided3)3The acid gas produced by decomposition pollutes the atmosphere.
The conductivity was measured using a conductivity meter model DDSJ-308F, and the electrolyte membranes of the examples were assembled into flat plates of 5X 5cm2The fuel cell, hydrogen as fuel, air as oxidant, tests the performance under the test temperature of 400-.
Example 4
(1) Weighing 23 parts by mass of Ce (NO)3)3·6H2O powder, 10 parts by mass of BaCO3Powder and 11 parts by mass of TiO2Uniformly mixing powder, adding 1-3 parts by mass of acrylic glycol esters and 42 parts by mass of N, N-dimethylformamide, controlling the rotating speed of a high-energy ball mill at 900rpm, controlling the ball milling time at 3.5 hours, and performing ball milling by the high-energy ball mill to obtain precursor slurry with the viscosity of 12000mPa & s;
(2) adding 11 parts by mass of α -MnO into the precursor slurry2And 4 parts by mass of aluminum phosphate, stirring to obtain uniform slurry, forming a film on the surfaces of the two sides of the electrode by adopting screen printing, wherein the screen is made of metal, the aperture of the screen is 240 mu m, the scraping speed of a scraper in the screen printing is controlled to be 1 mm/s, the printing is carried out at least three times, and the thickness of the formed film by the screen printing is 120 mu m;
(3) placing the printed electrode in a high-temperature box-type furnace, introducing inert gas in the high-temperature sintering process to protect the condition, wherein the inert gas is one of argon, nitrogen and carbon dioxide, and performing acid-base neutralization treatment on tail gas in the high-temperature sintering process to avoid Ce (NO)3)3The acid gas generated by decomposition pollutes the atmosphere, the temperature is raised at the speed of 2 ℃/min, the temperature is respectively kept at 1160 ℃, sintered and preserved for 16 hours, and then the temperature is kept at the speed of 5 ℃/minCooling to room temperature to obtain α -MnO2、BaTiO3Doped CeO2The electrolyte membrane of (1).
The conductivity was measured using a conductivity meter model DDSJ-308F, and the electrolyte membranes of the examples were assembled into flat plates of 5X 5cm2The fuel cell, hydrogen is fuel, air is oxidizing agent, test the performance under the test temperature 400-.
Example 5
(1) Weighing 24 parts by mass of Ce (NO)3)3·6H2O powder, 14.5 parts by mass of BaCO3Powder and 10 parts by mass of TiO2Uniformly mixing powder, adding 3 parts by mass of acrylic acid and 30 parts by mass of dimethyl sulfoxide, and carrying out ball milling by using a high-energy ball mill, wherein the rotating speed of the high-energy ball mill is controlled at 1050rpm, and the ball milling time is controlled at 3.5 hours, so as to obtain precursor slurry with the viscosity of 12000mPa & s;
(2) adding α -MnO of 10-14 parts by mass into the precursor slurry2And 2-5 parts by mass of aluminum phosphate, stirring to obtain uniform slurry, and forming a film on the surfaces of the two sides of the electrode by adopting screen printing, wherein the screen is a metal screen, the aperture of the screen is 230 mu m, the scraping speed of a scraper in the screen printing is controlled to be 1.6 mm/s, the printing is carried out at least three times, and the thickness of the formed film by the screen printing is 270 mu m;
(3) placing the printed electrode in a high-temperature box-type furnace, introducing inert gas in the high-temperature sintering process to protect the condition, wherein the inert gas is one of argon, nitrogen and carbon dioxide, and performing acid-base neutralization treatment on tail gas in the high-temperature sintering process to avoid Ce (NO)3)3The acid gas generated by decomposition pollutes the atmosphere, the temperature is raised at the rate of 3 ℃/min, the temperature is respectively maintained at 1160 ℃, sintered and maintained for 16 hours, and then the temperature is lowered to the room temperature at the rate of 5 ℃/min to obtain α -MnO2、BaTiO3Doped CeO2The electrolyte membrane of (1).
The conductivity was measured using a conductivity meter model DDSJ-308F, and the electrolyte membranes of the examples were assembled into flat plates of 5X 5cm2Fuel cell with hydrogen as fuel and airThe gas is an oxidant, the performance is tested under the condition that the test temperature is 400-550 ℃, the maximum output current is measured to reach 20 amperes, and the maximum output power reaches 18.4 watts.
Comparative example
(1) Doping cerium oxide with 10 mol% of gadolinium, and dissolving the cerium nitrate and the gadolinium oxide with nitric acid according to the doping concentration of 15 mol% to prepare a mixed solution;
(2) adding citric acid 2-4 times of the total mole number of ions in the mixed solution, heating at 200 deg.C and stirring until the liquid turns into viscous gel, stirring, heating, drying until rapidly burning to obtain fine powder, and sintering at 850 deg.C for 10 hr to obtain the electrolyte material of oxide fuel cell.
Testing the conductivity with DDSJ-308F conductivity meter, sintering with membrane electrode, and assembling into flat plate 5 × 5cm2The fuel cell, hydrogen as fuel, air as oxidant, under the test temperature of 400-.
Table 2 example 1 testing of performance parameters
| Temperature of | Open circuit voltage (V) | Current (A) | Conductivity (S/cm) |
| 550 | 1.60 | 17 | 0.74 |
| 500 | 1.62 | 21 | 0.91 |
| 450 | 1.64 | 22 | 0.95 |
| 400 | 1.61 | 15 | 0.60 |
Table 3 comparative examples test performance parameters
| Temperature of | Open circuit voltage (V) | Current (A) | Conductivity (S/cm) |
| 550 | 1.25 | 15 | 0.48 |
| 500 | 1.01 | 10 | 0.31 |
| 450 | 0.84 | 9 | 0.08 |
| 400 | 0.85 | 6 | 0.002 |
Claims (9)
1. A preparation method of a low-temperature ceramic electrolyte membrane for a solid oxide fuel cell is characterized by comprising the following steps:
(1) weighing 10-50 parts by mass of Ce (NO)3)3·6H2O powder, 8-15 parts by mass of BaCO3Powder and 10-12 parts by mass of TiO2Uniformly mixing powder, adding 1-3 parts by mass of a cross-linking agent and 30-45 parts by mass of an organic solvent, and performing ball milling by using a high-energy ball mill to obtain precursor slurry;
(2) adding α -MnO of 10-14 parts by mass into the precursor slurry2And 2-5 parts by mass of aluminum phosphate, stirring to obtain uniform slurry, and forming a film on the surfaces of the two sides of the electrode by adopting screen printing for at least three times;
(3) placing the printed electrode in a high-temperature box furnace, heating at the speed of 2-5 ℃/min, respectively carrying out heat preservation sintering at the temperature of 1130-2、BaTiO3Doped CeO2The electrolyte membrane of (1).
2. The method of claim 1, wherein the organic solvent is a mixed solution of one or more of N, N-dimethylacetamide, N-dimethylformamide, dimethylsulfoxide, and tetrahydrofuran.
3. The method of claim 1, wherein the cross-linking agent is one of acrylic acid, acrylamide, ethylene glycol dimethacrylate, and ethylene glycol acrylate.
4. The method for preparing a low-temperature ceramic electrolyte membrane for a solid oxide fuel cell as claimed in claim 1, wherein the rotation speed of the high-energy ball mill is controlled at 800-.
5. The method for preparing a low-temperature ceramic electrolyte membrane for a solid oxide fuel cell as claimed in claim 1, wherein the viscosity of the precursor slurry is 5000-.
6. The method according to claim 1, wherein the screen is a metal screen having a hole diameter of 40 to 300 μm, and a scraping speed of the squeegee in the screen printing is controlled to 1 to 2 mm./s.
7. The method of claim 1, wherein the screen printing is performed to a film thickness of 50 to 300 μm.
8. The method for preparing the low-temperature ceramic electrolyte membrane for the solid oxide fuel cell according to claim 1, wherein an inert gas is introduced to protect the temperature during the heat-preservation sintering process in the step (3), the inert gas is one of argon, nitrogen and carbon dioxide, and the acid-base neutralization treatment is performed on tail gas during the heat-preservation sintering process to avoid Ce (NO)3)3The acid gas produced by decomposition pollutes the atmosphere.
9. A low temperature ceramic electrolyte membrane for a solid oxide fuel cell, prepared by the method of any one of claims 1 to 8.
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| MnO2掺杂钛酸钡基PTC陶瓷的电子结构及其电性能研究;周江 等;《广西大学学报（自然科学版）》;20150625;第40卷(第3期);第673-679页 * |
| 固相反应对钆掺杂二氧化铈和钇掺杂铈酸钡电解质电化学性能的影响;王静任 等;《硅酸盐学报》;20150203;第43卷(第2期);第189-194页 * |
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