CN113571750B - Wide bandgap semiconductor electrolyte and preparation method thereof, wide bandgap semiconductor electrolyte fuel cell and assembly method thereof - Google Patents
Wide bandgap semiconductor electrolyte and preparation method thereof, wide bandgap semiconductor electrolyte fuel cell and assembly method thereof Download PDFInfo
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- CN113571750B CN113571750B CN202110796106.7A CN202110796106A CN113571750B CN 113571750 B CN113571750 B CN 113571750B CN 202110796106 A CN202110796106 A CN 202110796106A CN 113571750 B CN113571750 B CN 113571750B
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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
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
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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
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- 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
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- 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
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Abstract
The invention relates to a wide bandgap semiconductor electrolyte and a preparation method thereof, a wide bandgap semiconductor electrolyte fuel cell and an assembly method thereof, wherein the electrolyte is magnesium oxide nano powder prepared by a coprecipitation method, the magnesium oxide nano powder has a wide bandgap value of 6.29eV, and also has considerable ionic conductivity at 420-500 ℃, and the fuel cell formed by assembling the magnesium oxide nano powder shows excellent output power, better repeatability and stability for more than 100 hours at a low temperature interval.
Description
Technical Field
The invention relates to the technical field of solid oxide fuel cells, in particular to a wide bandgap semiconductor electrolyte and a preparation method thereof, and a wide bandgap semiconductor electrolyte fuel cell and an assembly method thereof.
Background
A Solid Oxide Fuel Cell (SOFC) is a power generation device that directly converts chemical energy of fuel into electrical energy, and has attracted a lot of attention due to its advantages such as high energy conversion efficiency, low pollution, and fuel diversity, and has become an important point and a hot spot in the field of new energy in recent years.
Conventional SOFCs typically employ doped zirconia and doped ceria as the electrolyte layers of their core components. However, such electrolyte materials need to be operated at a high temperature of 800 to 1000 ℃ to obtain a sufficiently high ionic conductivity for the battery to operate properly, which causes problems of high cost, technical complexity, and life decay of the battery, thereby further leading to commercialization of the SOFC.
In order to solve this problem, it is necessary to develop a novel electrolyte having high ionic conductivity at a low temperature, thereby reducing the operating temperature of the battery.
Disclosure of Invention
In view of the above problems, a wide bandgap semiconductor electrolyte and a method for preparing the same, a wide bandgap semiconductor electrolyte fuel cell and a method for assembling the wide bandgap semiconductor electrolyte fuel cell are provided, which are intended to effectively solve the problems in the SOFC cell.
The specific technical scheme is as follows:
a first aspect of the present invention is to provide a method for preparing a wide bandgap semiconductor electrolyte (MgO), having such characteristics as including the steps of
1) Weighing hydrolyzable magnesium salt, preparing into 500ml magnesium salt solution with concentration of 0.5mol/L, and continuously stirring the magnesium salt solution by adopting a magnetic stirrer;
2) Weighing hydrolyzable sodium salt according to the molar ratio of the hydrolyzable sodium salt to magnesium salt, preparing 200ml of sodium salt solution, dropwise adding the sodium salt solution into the magnesium salt solution, stirring for 5 hours, stopping stirring, standing the feed liquid at room temperature for 12 hours, filtering, and cleaning to obtain a precursor;
3) And (3) drying the precursor in an oven at 130 ℃ for 24 hours, calcining the dried material in a muffle furnace at 850 ℃ for 5 hours, and then fully grinding to obtain the nano powder of the wide bandgap semiconductor electrolyte.
The above production method is also characterized in that the magnesium salt in the step 1) is magnesium nitrate.
The above production method is also characterized in that the sodium salt in the step 2) is sodium carbonate.
A second aspect of the present invention is to provide a wide bandgap semiconductor electrolyte having such characteristics as being produced by the production method according to any one of claims 1 to 3.
A third aspect of the invention is to provide a fuel cell based on the above wide bandgap semiconductor electrolyte, having the features comprising the wide bandgap semiconductor electrolyte of claim 4.
A fourth aspect of the present invention is to provide a method for assembling a fuel cell based on the above wide bandgap semiconductor electrolyte, having such features that it comprises the steps of:
1) Weighing a proper amount of NCAL powder, taking terpineol according to 3 times of the volume of the NCAL powder, fully mixing the NCAL powder with the terpineol, grinding, uniformly coating the material on foamed nickel, and drying to prepare an NCAL-Ni electrode slice;
2) Weighing 0.25g of wide bandgap semiconductor electrolyte powder, fully grinding, putting a piece of NCAL-Ni electrode in a battery grinding tool, then scattering the wide bandgap semiconductor electrolyte powder, flattening, covering a piece of NCAL-Ni electrode, and pressing and forming the material in a die by a tablet press under 10MPa to form a battery piece.
The beneficial effect of above-mentioned scheme is:
1) The wide bandgap semiconductor electrolyte (MgO) provided by the invention has considerable ionic conductivity at 420-500 ℃, and can effectively reduce electronic conductivity due to the wide bandgap value of 6.29eV, so that the MgO can be used as an electrolyte to be applied to SOFC;
2) The wide bandgap semiconductor electrolyte provided by the invention can effectively reduce the operating temperature of the fuel cell;
3) The semiconductor electrolyte fuel cell provided by the invention can show excellent output power, better repeatability and stability of more than 100 hours in a low-temperature interval;
4) The invention adopts the dry pressing method to prepare the fuel cell, omits the high-temperature presintering step of the traditional cell and simplifies the cell manufacturing process.
Drawings
FIG. 1 is an XRD pattern of MgO provided in an embodiment of the present invention;
FIG. 2 is an SEM image of MgO provided in an embodiment of the present invention;
FIG. 3 is a diagram illustrating the forbidden bandwidth values of MgO provided in an embodiment of the present invention;
fig. 4 is a sectional view of a fuel cell provided in an embodiment of the invention;
FIG. 5 is an I-V, I-P curve of a fuel cell provided in an embodiment of the present invention;
FIG. 6 is an EIS map of a fuel cell provided in an embodiment of the invention;
FIG. 7 is a graph comparing I-V and I-P curves of five fuel cells provided in an example of the present invention;
fig. 8 is a stability chart of a fuel cell provided in an embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
It should be noted that the embodiments and features of the embodiments of the present invention may be combined with each other without conflict.
The invention is further described with reference to the following drawings and specific examples, which are not intended to be limiting.
Example 1
A wide bandgap semiconductor electrolyte is prepared from
1) Weighing magnesium nitrate, preparing into 500ml of magnesium salt solution with the concentration of 0.5mol/L, and then continuously stirring the magnesium salt solution by adopting a magnetic stirrer;
2) Weighing sodium carbonate according to the molar ratio of the sodium carbonate to the magnesium salt, preparing the sodium carbonate solution into 200ml of sodium salt solution, then dropwise adding the sodium salt solution into the magnesium salt solution, stirring for 5 hours, stopping stirring, standing the feed liquid at room temperature for 12 hours, filtering, and cleaning to obtain a precursor;
3) And (3) drying the precursor in an oven at 130 ℃ for 24 hours, finally calcining the dried material in a muffle furnace at 850 ℃ for 5 hours, and fully grinding to obtain the nano powder of the wide-bandgap semiconductor electrolyte.
As shown in FIGS. 1 and 2, the wide bandgap semiconductor electrolyte provided in the embodiment of the present invention has a periclase structure in accordance with MgO standard PDF card (JCPDS: 00-026958), and has uniform particle distribution and size of 200-500nm.
As shown in fig. 3, the wide bandgap semiconductor electrolyte provided in the embodiment of the present invention has a wide bandgap value of 6.29eV (converted from the light absorption result measured by an ultraviolet-visible spectrophotometer).
Example 2
The assembly method of the fuel cell based on the wide bandgap semiconductor electrolyte comprises the following steps:
1) Weighing appropriate amount of NCAL powder (Ni) 0.8 Co 0.15 Al 0.05 LiO 2-δ Purchased from tianjinbamo technologies), taking terpineol according to 3 times of the powder volume, fully mixing NCAL powder with terpineol, grinding, uniformly coating the material on foamed nickel, and drying to prepare the NCAL-Ni electrode plate;
2) Weighing 0.25g of wide bandgap semiconductor electrolyte powder, fully grinding, putting a piece of NCAL-Ni electrode in a battery grinding tool, then scattering the wide bandgap semiconductor electrolyte powder, flattening, covering a piece of NCAL-Ni electrode, and pressing and forming the material in a die by a tablet press under 10MPa to form a battery piece.
As shown in fig. 4, the MgO electrolyte layer and the porous NCAL-Ni electrode were clearly seen in the cross section of the fuel cell provided by the example of the present invention, and the middle electrolyte layer was superior in airtightness.
As shown in FIG. 5, the open-circuit voltage of the fuel cell provided in the embodiment of the present invention is above 1V at a low temperature range of 420-500 ℃, no short circuit occurs, and the power density of the fuel cell reaches 810mW cm when tested at 500 ℃ -2 And considerable output performance is shown.
As shown in fig. 6, the polarization resistance of the electrode in the fuel cell provided in the example of the present invention significantly increased with a decrease in temperature, which indicates that the catalytic activity of the electrode was greatly decreased with a decrease in temperature, resulting in a decrease in cell performance; meanwhile, the ohmic resistance of the battery is gradually increased, but the increase range is small, which shows that the MgO electrolyte can still maintain high ionic conductivity in a low-temperature range.
In the invention, the steps are repeated, and 5 battery pieces are prepared. As shown in fig. 7, the performance fluctuation amplitude of each cell was small, indicating that the performance of the fuel cell has good repeatability.
As shown in FIG. 8, the fuel cell provided in the example of the present invention was operated at 500 ℃ and 100mA cm -2 Can continuously and stably operate under the constant current density, and the stability is considerable when the operating voltage is maintained at about 0.9V for more than 100 hours.
As described above, it is demonstrated that the wide bandgap semiconductor electrolyte provided by the present invention can effectively reduce the operating temperature of the solid oxide fuel cell.
While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention.
Claims (4)
1. A wide-gap semiconductor electrolyte fuel cell is characterized in that an electrolyte of the wide-gap semiconductor electrolyte fuel cell is wide-gap semiconductor electrolyte MgO, and the preparation of the wide-gap semiconductor electrolyte MgO comprises the following steps:
1) Weighing hydrolyzable magnesium salt, preparing to form 500ml of magnesium salt solution with the concentration of 0.5mol/L, and then continuously stirring the magnesium salt solution by adopting a magnetic stirrer;
2) Weighing hydrolyzable sodium salt according to the molar ratio of the hydrolyzable sodium salt to magnesium salt, preparing 200ml of sodium salt solution, dropwise adding the sodium salt solution into the magnesium salt solution, stirring for 5 hours, stopping stirring, standing the feed liquid at room temperature for 12 hours, filtering, and cleaning to obtain a precursor;
3) And (3) drying the precursor in an oven at 130 ℃ for 24 hours, finally calcining the dried material in a muffle furnace at 850 ℃ for 5 hours, and fully grinding to obtain the nano powder of the wide bandgap semiconductor electrolyte.
2. The wide bandgap semiconductor electrolyte fuel cell according to claim 1, wherein the magnesium salt in step 1) is magnesium nitrate.
3. The wide bandgap semiconductor electrolyte fuel cell according to claim 1, wherein the sodium salt in step 2) is sodium carbonate.
4. A method of assembling the wide bandgap semiconductor electrolyte fuel cell of claim 1, comprising the steps of:
1) Weighing a proper amount of NCAL powder, taking terpineol according to 3 times of the volume of the NCAL powder, fully mixing the NCAL powder with the terpineol, grinding, uniformly coating the material on foamed nickel, and drying to prepare an NCAL-Ni electrode slice;
2) Weighing 0.25g of wide bandgap semiconductor electrolyte powder, fully grinding, putting a piece of NCAL-Ni electrode in a battery grinding tool, then scattering the wide bandgap semiconductor electrolyte powder, flattening, covering a piece of NCAL-Ni electrode, and pressing and forming the material in the die by a tablet press under 10MPa to form a battery piece.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2004362913A (en) * | 2003-06-04 | 2004-12-24 | Nissan Motor Co Ltd | Electrolyte for solid oxide fuel cell, and manufacturing method of the same |
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| JP2988673B2 (en) * | 1989-09-19 | 1999-12-13 | 株式会社東芝 | Molten carbonate fuel cell |
| US20070054170A1 (en) * | 2005-09-02 | 2007-03-08 | Isenberg Arnold O | Oxygen ion conductors for electrochemical cells |
| JP6016147B2 (en) * | 2011-04-12 | 2016-10-26 | Toto株式会社 | Solid oxide fuel cell |
| CN103054128B (en) * | 2012-12-31 | 2014-12-10 | 杭州师范大学 | Application of nanometer magnesium oxide as antimicrobial |
| KR101748989B1 (en) * | 2016-03-14 | 2017-06-20 | 부산대학교 산학협력단 | MgO partially stabilized zirconia doped with Mn or Co |
| CN109802161A (en) * | 2018-12-28 | 2019-05-24 | 南京晓庄学院 | A kind of low-temperature solid oxide fuel cell |
| CN110021771B (en) * | 2019-04-23 | 2020-07-28 | 湖北大学 | Based on SnO2Preparation method of Schottky junction fuel cell of-SDC semiconductor-ion conductor |
| CN112687929A (en) * | 2020-12-29 | 2021-04-20 | 东北大学 | Lithium oxide electrode micro-molten salt ceramic fuel cell and preparation method thereof |
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