CN114512697A - Preparation method of laser melting solid oxide fuel cell electrolyte layer - Google Patents
Preparation method of laser melting solid oxide fuel cell electrolyte layer Download PDFInfo
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- CN114512697A CN114512697A CN202210162348.5A CN202210162348A CN114512697A CN 114512697 A CN114512697 A CN 114512697A CN 202210162348 A CN202210162348 A CN 202210162348A CN 114512697 A CN114512697 A CN 114512697A
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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
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
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Abstract
The invention provides a preparation method of a laser melting solid oxide fuel cell electrolyte layer, which relates to the technical field of solid oxide fuel cell preparation.A porous zirconia plate is taken as a substrate, a laser is taken as an energy source, slurry prepared from electrolyte powder is soaked on the surface of the substrate, and the surface of the electrolyte is firstly scanned in a crossed manner under low energy density to be heated, preheated and dried, so that ceramic is prevented from cracking due to rapid thermal shrinkage; then gradually increasing the energy density until the electrolyte layer powder is completely sintered and fused; finally, gradually reducing the energy density to scan the surface of the electrolyte until the surface is completely cooled; and repeating the steps to prepare the compact electrolyte layer with the corresponding thickness. The invention has the beneficial effects that: the compact electrolyte layer can be obtained on the basis of not damaging the anode structure, the battery performance is improved, the production cost is reduced, and the preparation time is shortened.
Description
Technical Field
The invention belongs to the technical field of solid oxide fuel cell preparation, and particularly relates to a preparation method of a laser melting solid oxide fuel cell electrolyte layer.
Background
Energy and environmental problems are key restriction factors of sustainable development of human society all the time, and the strategic importance of energy development in the world is that an energy system which is green, low-carbon, safe and efficient is constructed. As a new energy technology, the solid oxide fuel cell is an all-solid-state chemical power generation device which can directly convert the chemical energy of fuel into electric energy under the medium-high temperature environment, the power generation efficiency reaches 45-60 percent, and the cogeneration efficiency reaches more than 80 percent. The fuel has the advantages of wide fuel adaptability, high energy conversion efficiency, all solid state, modular assembly, zero pollution and the like, can directly use various hydrocarbon fuels such as hydrogen, carbon monoxide, natural gas, liquefied gas, coal gas, biomass gas and the like, is used as a stationary power station in civil fields such as large-scale centralized power supply, medium-sized power distribution, small-sized household combined heat and power supply and the like, and has wide application prospect as a power source for ships, vehicles and other mobile power sources. Currently, solid oxide fuel cells are widely used as a strategic reserve technology in many developed countries of the world.
The solid oxide fuel cell is composed of a porous anode support, a dense electrolyte and a porous cathode, wherein the preparation of the dense electrolyte layer mainly comprises the steps of adopting a complex tape casting method (tape casting method refers to a method of adding a proper amount of additives such as a solvent, a dispersant, a binder and the like into ceramic powder, fully ball-milling and mixing to obtain uniform and stable slurry, scraping the slurry at a certain speed by a scraper of a tape casting machine to form a flaky blank with a certain thickness on a substrate), a die pressing method (a simple molding method of metal powder or ceramic powder, namely adding a certain amount of pre-processed powder into a customized metal die, applying pressure to make the blank with a certain strength), a screen printing method (screen printing is to print slurry/ceramic ink on the surface of the substrate through meshes, and repeatedly operating for a plurality of times to obtain a coating with a certain thickness), a porous anode support, a dense electrolyte and a porous cathode, wherein the preparation of the dense electrolyte layer mainly comprises the steps of adopting a complex tape casting method (tape casting method is a method of adding a proper amount of additives such as adding a solvent, a dispersant, a binder and the like into ceramic powder, adding a certain amount of a certain, The preparation method comprises the steps of carrying out vacuum evaporation (vacuum evaporation is carried out through vacuum coating equipment, and specially-made zirconium oxide powder is deposited on a substrate by adopting an electron beam to form a ceramic film), carrying out magnetron sputtering (the magnetron sputtering is carried out by forming a conductive material after certain treatment on the powder and sputtering the conductive ceramic powder on a specific target to form the ceramic film), and finally carrying out long-time high-temperature sintering process to prepare the solid oxide fuel cell with the sandwich structure.
Among the above electrolyte layer preparation methods, the tape casting method, the die pressing method, the screen printing method usually require a long time of binder removal and high temperature co-firing, the preparation period is long, the preparation cost is high, and the anode, the electrolyte, and the cathode are difficult to obtain a porous anode structure with an ideal structure after high temperature co-firing, so that a desired three-phase interface cannot be obtained, while the vacuum evaporation method and the magnetron sputtering method usually have high requirements on equipment and materials, and the above methods are usually only suitable for the preparation of flat-plate batteries, and the above reasons cause that the solid oxide fuel batteries are difficult to be commercially applied in a large scale, and the development of the solid oxide fuel battery technology is severely restricted, so that a more efficient, rapid, and simple preparation method must be sought.
Disclosure of Invention
The invention provides a preparation method of a laser melting solid oxide fuel cell electrolyte layer, which solves the technical problems of the preparation of the solid oxide fuel cell electrolyte layer in the prior art.
The invention provides a preparation method of a laser melting solid oxide fuel cell electrolyte layer, which adopts a mode of gradually increasing laser energy to melt electrolyte powder on the surface of a substrate and then gradually reducing the laser energy to prepare the electrolyte layer.
The invention relates to a preparation method of a laser melting solid oxide fuel cell electrolyte layer, which comprises the following steps: (1) a laser is used as an energy source, slurry prepared from electrolyte powder is soaked on the surface of a substrate, and the surface of the electrolyte is firstly scanned in a crossed mode under low energy density to be heated, preheated and dried, so that ceramic is prevented from cracking due to rapid thermal shrinkage; (2) then gradually increasing the energy density until the electrolyte layer powder is completely sintered and melted; (3) finally, gradually reducing the energy density to scan the surface of the electrolyte until the electrolyte is completely cooled; (4) and repeating the steps to prepare the compact electrolyte layer with the corresponding thickness.
The substrate is a porous zirconia plate.
The electrolyte powder of the invention includes, but is not limited to yttria-stabilized zirconia nanopowder and cerium oxide powder.
The heating power range of the energy source is 30-150W.
The laser of the present invention includes, but is not limited to, a fiber laser, a CO2 laser.
It should be understood that the statements herein reciting aspects are not intended to limit the critical or essential features of any embodiment of the invention, nor are they intended to limit the scope of the invention. Other features of the present invention will become apparent from the following description.
The invention has the beneficial effects that: the preparation method of the electrolyte layer can prepare the compact electrolyte layer on the basis of not damaging the anode structure, thereby maintaining the original structure, improving the performance of the battery, simultaneously preparing the battery structures with different shapes and types, and greatly expanding the application field of the fuel battery.
Drawings
FIG. 1 is a process flow diagram of a laser melting solid oxide fuel cell dielectric layer preparation method of the present invention;
FIG. 2 is a sectional view of an electrolyte for a solid oxide fuel cell prepared in example 1 of the present invention;
fig. 3 is a cross-sectional view of an electrolyte of a solid oxide fuel cell prepared in example 2 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, 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 some, but not all, embodiments of the present invention. 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.
Example 1
Firstly, mixing absolute ethyl alcohol: the method comprises the following steps of preparing zirconia nano powder according to a mass ratio of 6:4, adding a small amount of dispersing agent, performing ball milling for 8 hours at 280r/min to obtain zirconia slurry, enabling a zirconia ceramic substrate to be fully distributed with the powder slurry in a surface impregnation mode, adopting a continuous optical fiber laser as an energy source, positioning a zirconia substrate, setting a laser scanning model to be a circle with the diameter of 10mm, dividing scanning process parameters into three stages according to the energy density, and firstly performing cross scanning on the surface of the substrate from low to high by using the energy density to perform drying and preheating, wherein the drying and preheating stage is a drying and preheating stage; then sintering and melting the ceramic layer under the maximum energy density to form a laser melting stage; finally, the energy density is gradually reduced from high to low for cross scanning to prevent the ceramic from rapid cooling and cracking, and the cooling stage is adopted; repeating the steps for 5 times to finish the preparation of the compact electrolyte layer to obtain the electrolyte layer with a certain thickness, wherein specific scanning process parameters are shown in table 1; the electrolyte preparation method does not need further sintering.
Table 1 example 1 laser scanning process parameters
Example 2
Adding absolute ethyl alcohol: the method comprises the following steps of preparing zirconia nano powder according to a mass ratio of 6:4, adding a small amount of dispersing agent, performing ball milling for 8 hours at 280r/min to obtain zirconia slurry, enabling a zirconia ceramic substrate to be fully distributed with the powder slurry in a surface impregnation mode, adopting a continuous optical fiber laser as an energy source, positioning a zirconia substrate, setting a laser scanning model to be a circle with the diameter of 10mm, dividing scanning process parameters into three stages according to the energy density, and firstly performing cross scanning on the surface of the substrate from low to high by using the energy density to perform drying and preheating, wherein the drying and preheating stage is a drying and preheating stage; then sintering and melting the ceramic layer under the maximum energy density to form a laser melting stage; finally, the energy density is gradually reduced from high to low to perform cross scanning so as to prevent rapid cooling and cracking of the ceramic, the steps are repeated for 5 times as a cooling and cooling stage, the preparation of a compact electrolyte layer is completed, and the electrolyte layer with a certain thickness is obtained, wherein specific scanning process parameters are shown in a table 2; the electrolyte preparation method does not need further sintering.
Table 2 example 2 laser scanning process parameters at various stages
Example 3
Adding absolute ethyl alcohol: the method comprises the following steps of (1) preparing zirconia nano powder in a mass ratio of 1:1, adding a small amount of dispersing agent, performing ball milling for 16 hours at 280r/min to obtain zirconia slurry, enabling a zirconia ceramic substrate to be fully distributed with the powder slurry in a surface impregnation mode, adopting a continuous optical fiber laser as an energy source, positioning a zirconia substrate, setting a laser scanning model to be a circle with the diameter of 10mm, dividing scanning process parameters into three stages according to the energy density, and firstly performing cross scanning on the surface of the substrate from low to high by using the energy density to perform drying and preheating, wherein the drying and preheating stage is a drying and preheating stage; then sintering and melting the ceramic layer under the maximum energy density to form a laser melting stage; finally, the energy density is gradually reduced from high to low to perform cross scanning so as to prevent rapid cooling and cracking of the ceramic, the steps are repeated for 5 times as a cooling and cooling stage, the preparation of a compact electrolyte layer is completed, and the electrolyte layer with a certain thickness is obtained, wherein specific scanning process parameters are shown in a table 3; the electrolyte preparation method does not need further sintering.
Table 3 example 3 laser scanning process parameters at various stages
Example 4
Adding absolute ethyl alcohol: the method comprises the following steps of (1) preparing zirconia nano powder according to a mass ratio of 5:5, adding a small amount of dispersing agent, performing ball milling for 8 hours at 280r/min to obtain zirconia slurry, enabling a zirconia ceramic substrate to be fully distributed with the powder slurry in a surface impregnation mode, adopting a continuous optical fiber laser as an energy source, positioning a zirconia substrate, setting a laser scanning model to be a circle with the diameter of 10mm, dividing scanning process parameters into three stages according to the energy density, and firstly performing cross scanning on the surface of the substrate from low to high by using the energy density to perform drying and preheating, wherein the drying and preheating stage is a drying and preheating stage; then sintering and melting the ceramic layer under the maximum energy density to form a laser melting stage; finally, the energy density is gradually reduced from high to low to perform cross scanning so as to prevent rapid cooling and cracking of the ceramic, the steps are repeated for 5 times as a cooling and cooling stage, the preparation of a compact electrolyte layer is completed, and the electrolyte layer with a certain thickness is obtained, wherein specific scanning process parameters are shown in a table 4; the electrolyte preparation method does not need further sintering.
Table 4 example 4 laser scanning process parameters at various stages
The invention provides a novel preparation method of an electrolyte layer of a solid oxide fuel cell, which adopts laser melting to prepare the electrolyte, and can obtain a compact electrolyte layer on the basis of not damaging an anode structure by adjusting various process parameters, thereby improving the performance of the cell, reducing the production cost and shortening the preparation time.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made or substituted in a similar manner to the specific embodiments described herein by those skilled in the art without departing from the spirit or exceeding the scope of the invention as defined in the appended claims, the invention being expressed as directly or indirectly connected.
Claims (6)
1. A method for preparing a laser melting solid oxide fuel cell electrolyte layer is characterized in that the electrolyte layer is prepared by gradually increasing laser energy to melt electrolyte powder on the surface of a substrate and then gradually reducing the laser energy.
2. The method for preparing the electrolyte layer of the laser melting solid oxide fuel cell according to claim 1, which is characterized by comprising the following steps: (1) a laser is used as an energy source, slurry prepared from electrolyte powder is soaked on the surface of a substrate, and the surface of the electrolyte is firstly scanned in a crossed mode under low energy density to be heated, preheated and dried, so that ceramic is prevented from cracking due to rapid thermal shrinkage; (2) then gradually increasing the energy density until the electrolyte layer powder is completely sintered and melted; (3) finally, gradually reducing the energy density to scan the surface of the electrolyte until the electrolyte is completely cooled; (4) and repeating the steps to prepare the compact electrolyte layer with the corresponding thickness.
3. The method of claim 2, wherein the substrate is a porous zirconia plate.
4. The method of claim 2, wherein the electrolyte powder includes, but is not limited to yttria stabilized zirconia nanopowder, cerium oxide powder.
5. The method for preparing the electrolyte layer of the laser melting solid oxide fuel cell according to claim 2, wherein the heating power of the energy source is in a range of 30-150W.
6. The method of claim 2, wherein the laser comprises but is not limited to a fiber laser, a CO2 laser.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115064709A (en) * | 2022-06-24 | 2022-09-16 | 中国科学院长春应用化学研究所 | Method for constructing ordered electrode of high-temperature solid oxide fuel cell/electrolytic cell |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115064709A (en) * | 2022-06-24 | 2022-09-16 | 中国科学院长春应用化学研究所 | Method for constructing ordered electrode of high-temperature solid oxide fuel cell/electrolytic cell |
| CN115064709B (en) * | 2022-06-24 | 2024-02-13 | 中国科学院长春应用化学研究所 | Method for constructing ordered electrode of high-temperature solid oxide fuel cell/electrolytic cell |
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