CN110845232A - Solid electrolyte supported oxide fuel cell with three-dimensional topological structure and preparation method thereof - Google Patents

Solid electrolyte supported oxide fuel cell with three-dimensional topological structure and preparation method thereof Download PDF

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CN110845232A
CN110845232A CN201911127121.1A CN201911127121A CN110845232A CN 110845232 A CN110845232 A CN 110845232A CN 201911127121 A CN201911127121 A CN 201911127121A CN 110845232 A CN110845232 A CN 110845232A
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electrolyte
photocuring
printing
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topological structure
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CN110845232B (en
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赵喆
孟翔
王操
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Shanghai Institute of Technology
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Abstract

The invention discloses an electrolyte supported solid oxide fuel cell with a three-dimensional topological structure based on a photocuring 3D printing and forming technology. The invention mainly comprises the following five steps: preparing ceramic light-cured resin slurry; designing a three-dimensional model with a three-dimensional topological structure by utilizing a three-cycle minimized surface method (TPMS); photocuring the 3D printing ceramic blank; degreasing and sintering the ceramic blank; and (5) filling an electrode material. The electrolyte supporting and solidifying fuel cell with the three-dimensional topological structure greatly increases the area of an effective contact surface of an electrolyte-electrode and improves the power density of unit volume; and the reaction gas is conveniently discharged due to the mutually independent high-connectivity pore channel structures. By combining the advantages of the two aspects, the product of the invention can greatly improve the power generation efficiency of the solid oxide fuel cell.

Description

Solid electrolyte supported oxide fuel cell with three-dimensional topological structure and preparation method thereof
Technical Field
The invention belongs to the technical field of solid fuel cells, and particularly relates to a solid electrolyte supported oxide fuel cell with a three-dimensional topological structure and a preparation method thereof.
Background
In China, the main energy source for generating electricity for a long time is coal. Nowadays, the proportion of coal electricity in China in the total amount of electricity generated is about 75%. With the further development and utilization of other various resources and the development of nuclear power, although the proportion of the generated energy of coal electricity is reduced, the generated energy of coal electricity still occupies more than 70% of the total amount of generated energy in China within five to ten years. A large amount of coal is used for generating electricity and supplying heat, and a heavy burden of environmental protection can be brought. Dust particles, ash and smoke generated in the coal thermal power generation process can pollute air, and the generated waste water and waste liquid pose great threat to water resources. And the energy conversion rate of thermal power generation is low, and the energy waste is serious.
A fuel cell is a chemical device that directly converts chemical energy of fuel into electrical energy, and is also called an electrochemical generator. It is a fourth power generation technology following hydroelectric power generation, thermal power generation and atomic power generation. The fuel cell converts the Gibbs free energy in the chemical energy of the fuel into electric energy through electrochemical reaction, and is not limited by the Carnot cycle effect, so the efficiency is high; in addition, fuel cells use fuel and oxygen as raw materials; meanwhile, no mechanical transmission part is arranged, so that no noise pollution is caused, and the discharged harmful gas is less. It follows that fuel cells are the most promising power generation technology from the viewpoint of energy conservation and ecological environment conservation.
Solid oxide fuel cells, known as third generation fuel cells, have an electrolyte that is a solid, void-free metal oxide with ions shuttled in the crystal by oxygen ions. The electromotive force of a solid oxide fuel cell is derived from the different oxygen partial pressures on the two sides of the cell. The single battery is composed of a positive electrode and a negative electrode (the negative electrode is a fuel electrode, and the positive electrode is an oxidant electrode) and an electrolyte. The main functions of the anode and the cathode are to conduct electrons and provide diffusion channels for reaction gas and product gas. The solid electrolyte separates the gases at two sides, and oxygen chemical potential gradient is generated due to the difference of oxygen partial pressure at two sides, under the action of the chemical potential gradient, oxygen ions which obtain electrons at the cathode move to the anode through the solid electrolyte, and the electrons are released at the anode, so that voltage is formed at the two electrodes.
Although the solid oxide fuel cell has many attractive advantages, the traditional manufacturing process is complex and generally requires hundreds of steps, wherein the complex packaging process is a technical key for restricting the large-scale application of the SOFC power generation system. The introduction of 3D printing technology can reduce the packaging process, and is of great benefit to the application of the solid oxide fuel cell. In addition, low power density is one of the important limitations. Although the power of fuel cells has been developed over the past several decades, the power density needs to be further increased if it is desired to be competitive in the portable electronic and automotive fields.
The solid electrolyte with the three-dimensional topological structure greatly improves the area of a three-phase reaction zone, is beneficial to improving the quantity of oxygen ions which jump in unit time and improves the power density of a fuel cell. And the light porous structure designed by the topological optimization has the characteristics of high specific strength, high strength, rigidity and the like, and has wide application prospect in solid fuel cells.
The 3D printing technology, also known as additive manufacturing, has the advantages of simple operation, high forming speed, high precision and the like. With the continuous development of 3D printing technology, it has been gradually applied to various fields of manufacturing industry. The 3D printing ceramic material is combined with a relatively advanced sintering technology to prepare the ceramic part with high precision and high strength, compared with the traditional preparation process, the processing cost can be obviously reduced, the production period can be shortened, raw materials can be saved, and a product with a very complex internal structure can be manufactured. The advent of 3D printing technology offers the possibility of manufacturing complex shaped components.
Disclosure of Invention
The invention aims to provide an electrolyte-supported solid fuel cell with a three-dimensional topological structure and a preparation method thereof, aiming at the defect that the electrolyte three-phase reaction area of the existing solid fuel cell is small.
In order to achieve the above object, the present invention provides a method for preparing 8 mol yttria-stabilized zirconia photosensitive resin paste for photocuring 3D printing, comprising: uniformly stirring photosensitive resin, adding 1-6% by mass of a dispersing agent, adding 40-65% by volume of zirconia ceramic powder (8YSZ) into the mixed solution, finally adding 1-5% by mass of a photoinitiator, using zirconia grinding balls with the diameter of 3-5 mm, wherein the ball-to-material ratio is 1:2, the rotating speed is 100r/min, and carrying out ball milling for 3-9 h to obtain 8-mole yttria-stabilized zirconia photosensitive resin slurry for photocuring 3D printing.
Preferably, the photosensitive resin is a mixture prepared by HEA, HDDA, TMPTA and TPGDA according to a volume ratio of 2:2:3:4, the dispersant is PAA, and the photoinitiator is TPO.
The invention also provides 8-mol yttria-stabilized zirconia photosensitive resin paste for photocuring 3D printing prepared by the method.
The invention also provides a preparation method of the 8YSZ electrolyte with the three-dimensional topological junction, which is characterized by comprising the following steps:
1) pouring the 8 mol of yttria-stabilized zirconia photosensitive resin slurry for photocuring 3D printing into a charging basket of photocuring printing equipment for printing;
2) using three-dimensional modeling software to create a TPMS topological structure, adjusting the model structure to obtain a TPMS topological optimization structure model which is 3-10 times larger than the surface area of the traditional solid electrolyte, and storing the TPMS topological optimization structure model in an STL format;
3) importing the STL format model with the topological structure designed in the step 2) into a photocuring 3D printer;
4) setting specific parameters of photocuring printing, and starting printing after all the parameters are set, so that the ceramic slurry is printed and formed layer by layer;
5) taking the printed green body off the forming platform, and cleaning the green body with alcohol;
6) putting the ceramic green body obtained in the step 5) into an ultraviolet curing box for secondary curing;
7) and then placing the electrolyte in a muffle sintering furnace for green body degreasing and sintering to obtain the high-density 8YSZ electrolyte with a three-dimensional topological structure.
Preferably, the three-dimensional modeling software in the step 2) is one of Magics, Solidworks, UG or AUTO CAD.
Preferably, the specific parameters of the curing printing in the step 4) are as follows: the thickness of the photocuring printing layer is 0.01-0.1 mm, the wavelength of the photocuring light source is 350-450 nm, and the photocuring light intensity is 1000-20000 mu w/cm2The exposure time of the photocuring single layer is 3-8 s, the exposure time of the photocuring first layer is 5-10 s, and the secondary photocuring time is 30-120 s.
Preferably, the step 7) of setting the parameters of degreasing and sintering of the green body comprises: and (3) keeping the temperature for 1-2 h at the temperature rising rate of 1-3 ℃/min at 0-600 ℃, keeping the temperature for 2-3 h at the temperature rising rate of 5-8 ℃/min at 600-1500 ℃, and naturally cooling at 1500-room temperature.
The invention also provides the 8YSZ electrolyte with the three-dimensional topological junction prepared by the method.
The invention also provides a preparation method of the electrolyte supported solid oxide fuel cell with the three-dimensional topological structure, which is characterized by comprising the following steps of:
1) preparing anode slurry: adding nickel oxide powder and 8YSZ powder into water according to the proportion of 6:4, and then adding a dispersing agent, a binder and a wetting agent to prepare slurry with the solid phase content of 20-45 vol%;
2) injecting the slurry obtained in the step 1) into one surface of the 8YSZ electrolyte with the three-dimensional topological structure, and sintering at 1200-1450 ℃ after freeze drying;
3) preparing a cathode slurry: adding Lanthanum Strontium Manganate (LSM) powder and 8YSZ powder into water according to the proportion of 6:4, and then adding a dispersing agent, a binder and a wetting agent to prepare slurry with the solid phase content of 20-45 vol%;
4) injecting the slurry obtained in the step 3) into the other side of the 8YSZ electrolyte with the three-dimensional topological structure in the step 2), freezing, drying and sintering at 900-1150 ℃ to obtain the electrolyte-supported solid oxide fuel cell with the three-dimensional topological structure.
Preferably, the dispersing agent in step 1) and step 3) is PAA, the binder is PVA, and the wetting agent is PEG.
The invention also provides the electrolyte supported solid oxide fuel cell with the three-dimensional topological structure prepared by the method.
Compared with the prior art, the invention has the beneficial effects that:
1) according to the invention, the solid electrolyte supporting structure with high specific surface area, high strength and good surface quality is designed by topological optimization of the solid electrolyte structure and shape.
2) The invention uses the high-precision photocuring 3D printing technology to perform printing molding, and obtains the ideal electrolyte supporting mechanism with the three-dimensional topological structure.
3) The topological structure electrolyte supporting structure prepared by the invention has a mutually-communicated pore channel structure, and is convenient for gas to pass through and escape.
4) The invention can prepare the electrolyte supported solid oxide fuel cell with an internal through hole structure, accurately controllable shape, size and macroscopic morphology and supporting strength by a photocuring printing technology and subsequent degreasing sintering.
Drawings
Fig. 1 is a schematic diagram of a DLP printing apparatus for manufacturing electrolyte-supported solid oxide fuel cells having a topology.
Fig. 2 is a structural model of a high specific surface area electrolyte supported solid oxide fuel cell with a topological structure designed using three-dimensional mapping software: a and B are P-cell structures of two different unit cell sizes.
Fig. 3 is a 3D printing technique to form an electrolyte supported solid oxide fuel cell shaped sample with three-dimensional topology: A. b, C and D, E, F are two different cell sizes of P-cell structures.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
The embodiment provides a preparation method of an electrolyte supported solid oxide fuel cell with a three-dimensional topological structure, which comprises the following specific preparation steps:
step 1: preparation of 8YSZ electrolyte with three-dimensional topological junction:
step a: 8 molar yttria stabilized zirconia photosensitive resin syrup for photocured 3D printing:
photosensitive resins HEA, HDDA, TMPTA, TPGDA (shanghai alatin biochemicals ltd.) were mixed in the following ratio of 2:2:3:4, uniformly stirring, adding 1-6% by mass of a dispersing agent (PAA, Toyo chemical Co., Ltd., Japan) into the mixture, adding 40-65% by mass of zirconia ceramic powder (8YSZ, Toyo chemical Co., Ltd., Japan) into the mixture, and finally adding 1-5% by mass of a photoinitiator (TPO, national drug group industry Co., Ltd.), using zirconia grinding balls with the diameter of 3-5 mm, the ball-to-material ratio of 1:2, the rotating speed of 100r/min, and the ball-milling for 3-9 h to obtain 8 mol of yttria-stabilized zirconia photosensitive resin slurry for photocuring 3D printing;
step b: as shown in fig. 2A, a TPMS structure with a high specific surface area is drawn by using Magics three-dimensional mapping software, and the theoretical specific surface area is 3-5 times of the surface area of the conventional electrolyte;
step c: as shown in fig. 1, placing 8 mol of yttria-stabilized zirconia photosensitive resin slurry for photocuring 3D printing obtained in step a under a DLP photocuring machine for printing, wherein the wavelength is 405nm, the light intensity is 10000 μ w/cm2, the printing layer is 50 μm thick, the first layer exposure time is 3s, the single-layer exposure time is 1s, printing layer by layer, accumulating and forming, and performing secondary curing for 1min after alcohol cleaning to obtain a ceramic green body;
step d: c, putting the 4-step ceramic green body obtained in the step c into a common non-pressure muffle furnace for degreasing and sintering, keeping the temperature for 1 hour at the temperature rising rate of 1 ℃/min between 0 and 600 ℃, keeping the temperature for 2 hours at the temperature rising rate of 5 ℃/min between 600 and 1500 ℃, and naturally cooling to the room temperature; finally, an electrolyte model with a topological structure and a high specific surface area is obtained, and as shown in fig. 3A, 3B and 3C, the electrolyte model has a pore channel structure with high mutual connectivity, so that gas can flow through and escape easily;
step 2: preparation of electrolyte-supported solid oxide fuel cells with three-dimensional topology:
step e: preparing anode slurry: adding NiO powder (Alfa Elisa chemical Co., Ltd.) and 8YSZ powder (Nippon Tosoh Co., Ltd.) into water at a ratio of 6:4, and adding a dispersant (PAA, Toya Japan synthetic Co., Ltd.), a binder (PVA, national drug group industries Co., Ltd.) and a wetting agent (PEG, national drug group industries Co., Ltd.) in an amount of 0.5 to 5%, 0.5 to 5% and 0.5 to 5% by mass respectively to prepare a slurry having a solid phase content of 20 to 45 vol%;
step f: injecting the slurry obtained in step e into one side of the 8YSZ electrolyte with the three-dimensional topological structure obtained in step d, and sintering at 1200-1450 ℃ after freeze drying;
step g: preparing a cathode slurry: adding an LSM powder (national drug group industry Co., Ltd.) and an 8YSZ powder (Japan eastern Cao Co., Ltd.) into water at a ratio of 6:4, and adding a dispersant (PAA, Japan east Asia synthetic Co., Ltd.), a binder (PVA, national drug group industry Co., Ltd.) and a wetting agent (PEG, national drug group industry Co., Ltd.) in an amount of 0.5-5%, 0.5-5% and 0.5-5% by mass respectively to prepare a slurry having a solid phase content of 20-45 vol%;
step h: and (e) injecting the slurry obtained in the step (g) into the other side of the 8YSZ electrolyte with the three-dimensional topological structure in the step (f), freezing, drying and sintering at 900-1150 ℃ to obtain the electrolyte-supported solid oxide fuel cell with the three-dimensional topological structure.
Example 2
The embodiment provides a preparation method of an electrolyte supported solid oxide fuel cell with a three-dimensional topological structure, which comprises the following specific preparation steps:
step 1: preparation of 8YSZ electrolyte with three-dimensional topological junction:
step a: 8 molar yttria stabilized zirconia photosensitive resin syrup for photocured 3D printing:
photosensitive resins HEA, HDDA, TMPTA, TPGDA (shanghai alatin biochemicals ltd.) were mixed in the following ratio of 2:2:3:4, uniformly stirring, adding 1-6% by mass of a dispersing agent (PAA, Toyo chemical Co., Ltd., Japan) into the mixture, adding 40-65% by mass of zirconia ceramic powder (8YSZ, Toyo chemical Co., Ltd., Japan) into the mixture, and finally adding 1-5% by mass of a photoinitiator (TPO, national drug group industry Co., Ltd.), using zirconia grinding balls with the diameter of 3-5 mm, the ball-to-material ratio of 1:2, the rotating speed of 100r/min, and the ball-milling for 3-9 h to obtain 8 mol of yttria-stabilized zirconia photosensitive resin slurry for photocuring 3D printing;
step b: as shown in fig. 2B, a TPMS structure with a high specific surface area is drawn by using Magics three-dimensional mapping software, and the theoretical specific surface area is 6-10 times of the surface area of the conventional electrolyte;
step c: as shown in fig. 1, 8 mol of yttria-stabilized zirconia photosensitive resin paste for photocuring 3D printing obtained in step a is placed under a DLP photocuring machine for printing, the wavelength is 405nm, and the light intensity is 10000 μ w/cm2Printing layer thickness is 50 μm, first layer exposure time is 3s, single layer exposure time is 1s, layer-by-layer printing accumulation molding is carried out, secondary curing is carried out for 1min after alcohol cleaning, and ceramic green body is obtained;
step d: c, putting the 4-step ceramic green body obtained in the step c into a common non-pressure muffle furnace for degreasing and sintering, keeping the temperature for 1 hour at the temperature rising rate of 1 ℃/min between 0 and 600 ℃, keeping the temperature for 2 hours at the temperature rising rate of 5 ℃/min between 600 and 1500 ℃, and naturally cooling to the room temperature; finally, an electrolyte model with a topological structure and a high specific surface area is obtained, and as shown in fig. 3D, 3E and 3F, the electrolyte model has a pore structure with high mutual connectivity, so that gas circulation and escape are facilitated;
step 2: preparation of electrolyte-supported solid oxide fuel cells with three-dimensional topology:
step e: preparing anode slurry: adding NiO nickel powder (Alfa Angsa chemical Co., Ltd.) and 8YSZ powder (Nippon Cao Co., Ltd.) into water at a ratio of 6:4, and adding a dispersant (PAA, Nippon east Asia synthetic Co., Ltd.), a binder (PVA, national drug group industry Co., Ltd.) and a wetting agent (PEG, national drug group industry Co., Ltd.) in an amount of 0.5-5%, 0.5-5% and 0.5-5% by mass respectively to prepare a slurry having a solid phase content of 20-45 vol%;
step f: injecting the slurry obtained in step e into one side of the 8YSZ electrolyte with the three-dimensional topological structure obtained in step d, and sintering at 1200-1450 ℃ after freeze drying;
step g: preparing a cathode slurry: adding an LSM powder (national drug group industry Co., Ltd.) and an 8YSZ powder (Japan eastern Cao Co., Ltd.) into water at a ratio of 6:4, and adding a dispersant (PAA, Japan east Asia synthetic Co., Ltd.), a binder (PVA, national drug group industry Co., Ltd.) and a wetting agent (PEG, national drug group industry Co., Ltd.) in an amount of 0.5-5%, 0.5-5% and 0.5-5% by mass respectively to prepare a slurry having a solid phase content of 20-45 vol%;
step h: and (e) injecting the slurry obtained in the step (g) into the other side of the 8YSZ electrolyte with the three-dimensional topological structure in the step (f), freezing, drying and sintering at 900-1150 ℃ to obtain the electrolyte-supported solid oxide fuel cell with the three-dimensional topological structure.

Claims (10)

1. A method of preparing an 8 molar yttria stabilized zirconia photosensitive resin paste for photocured 3D printing, comprising: uniformly stirring photosensitive resin, adding 1-6% by mass of a dispersing agent, adding 40-65% by volume of zirconia ceramic powder into the mixed solution, finally adding 1-5% by mass of a photoinitiator, using zirconia grinding balls with the diameter of 3-5 mm, wherein the ball-to-material ratio is 1:2, the rotating speed is 100r/min, and ball-milling is carried out for 3-9 h to obtain 8-mol yttria-stabilized zirconia photosensitive resin slurry for photocuring 3D printing.
2. The method of preparing an 8 molar yttria stabilized zirconia photosensitive resin paste for photocuring 3D printing according to claim 1, wherein the photosensitive resin is a mixture of HEA, HDDA, TMPTA, TPGDA formulated in a volume ratio of 2:2:3:4, the dispersant is PAA, and the photoinitiator is TPO.
3. An 8 molar yttria stabilized zirconia photosensitive resin paste for photocuring 3D printing prepared by the method of claim 1 or 2.
4. A preparation method of 8YSZ electrolyte with a three-dimensional topological structure is characterized by comprising the following steps:
1) pouring the 8 molar yttria stabilized zirconia photosensitive resin slurry for photocuring 3D printing of claim 3 into a barrel of a photocuring printing apparatus for printing;
2) using three-dimensional modeling software to create a TPMS topological structure, adjusting the model structure to obtain a TPMS topological optimization structure model which is 3-10 times larger than the surface area of the traditional solid electrolyte, and storing the TPMS topological optimization structure model in an STL format;
3) importing the STL format model with the topological structure designed in the step 2) into a photocuring 3D printer;
4) setting specific parameters of photocuring printing, and starting printing after all the parameters are set, so that the ceramic slurry is printed and formed layer by layer;
5) taking the printed green blank off the forming platform, and cleaning the green blank with alcohol;
6) putting the ceramic green body obtained in the step 5) into an ultraviolet curing box for secondary curing;
7) and then placing the electrolyte in a muffle sintering furnace for green body degreasing and sintering to obtain the high-density 8YSZ electrolyte with a three-dimensional topological structure.
5. The method for preparing 8YSZ electrolyte with three-dimensional topological structure according to claim 4, wherein the three-dimensional modeling software in the step 2) is one of Magics, Solidworks, UG or AUTO CAD.
6. The device of claim 4 having a three-dimensional topologyThe preparation method of the 8YSZ electrolyte with the stamp structure is characterized in that the specific parameters of the curing and printing in the step 4) are as follows: the thickness of the photocuring printing layer is 0.01-0.1 mm, the wavelength of the photocuring light source is 350-450 nm, and the photocuring light intensity is 1000-20000 mu w/cm2The exposure time of the photocuring single layer is 3-8 s, the exposure time of the photocuring first layer is 5-10 s, and the secondary photocuring time is 30-120 s.
7. The method of claim 4, wherein the step 7) of setting parameters for degreasing and sintering the green body comprises: and (3) keeping the temperature for 1-2 h at the temperature rising rate of 1-3 ℃/min at 0-600 ℃, keeping the temperature for 2-3 h at the temperature rising rate of 5-8 ℃/min at 600-1500 ℃, and naturally cooling at 1500-room temperature.
8. An 8YSZ electrolyte with a three-dimensional topological junction prepared by the method of any one of claims 4 to 7.
9. A method of making an electrolyte supported solid oxide fuel cell having a three-dimensional topology, comprising the steps of:
1) preparing anode slurry: adding nickel oxide powder and 8YSZ powder into water according to the proportion of 6:4, and then adding a dispersing agent, a binder and a wetting agent to prepare slurry with the solid phase content of 20-45 vol%;
2) injecting the slurry obtained in the step 1) into one side of the 8YSZ electrolyte with a three-dimensional topological structure according to claim 8, and sintering at 1200-1450 ℃ after freeze drying;
3) preparing a cathode slurry: adding lanthanum strontium manganate powder and 8YSZ powder into water according to the proportion of 6:4, and then adding a dispersing agent, a binder and a wetting agent to prepare slurry with the solid phase content of 20-45 vol%;
4) injecting the slurry obtained in the step 3) into the other side of the 8YSZ electrolyte with the three-dimensional topological structure in the step 2), freezing, drying and sintering at 900-1150 ℃ to obtain the electrolyte-supported solid oxide fuel cell with the three-dimensional topological structure.
10. An electrolyte-supported solid oxide fuel cell having a three-dimensional topology made by the method of claim 9.
CN201911127121.1A 2019-11-18 2019-11-18 Solid electrolyte supported oxide fuel cell with three-dimensional topological structure and preparation method thereof Active CN110845232B (en)

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