CN115207386A - Preparation method of full-film flat plate membrane band tandem type solid oxide fuel cell pack - Google Patents

Preparation method of full-film flat plate membrane band tandem type solid oxide fuel cell pack Download PDF

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CN115207386A
CN115207386A CN202210769733.6A CN202210769733A CN115207386A CN 115207386 A CN115207386 A CN 115207386A CN 202210769733 A CN202210769733 A CN 202210769733A CN 115207386 A CN115207386 A CN 115207386A
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film
anode
membrane
porous
solid oxide
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刘江
夏美荣
颜晓敏
谭楷
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South China University of Technology SCUT
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0289—Means for holding the electrolyte
    • 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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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
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  • Sustainable Energy (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Fuel Cell (AREA)

Abstract

A method for preparing a full-film flat plate film belt series solid oxide fuel battery pack. And preparing a porous framework support body, a porous anode and a compact electrolyte by using a tape casting method, and preparing the half-cell stack by integrally molding and sintering. The casting method is characterized in that material powder is prepared into slurry with good fluidity, the slurry is cast and scraped off on a flat substrate by a scraper, and a casting film is obtained after drying; the porous support body is made of a high-temperature-resistant electronic insulating ceramic material, and a casting film of the porous support body is cut into a designed shape; the porous anode is made of metal ceramic compounded by metal nickel and yttrium stabilized zirconia, and a casting film of the porous anode is cut into a long strip with a designed size. Compared with the traditional preparation process, the flat-plate membrane-belt series battery pack prepared by the integrated forming method has the advantages that the processes are reduced, the preparation time is shortened, the preparation energy consumption is reduced, and the prepared battery pack has the characteristics of small size and high voltage output and has wide application prospect in the field of portable power supplies.

Description

Preparation method of full-film flat plate membrane band tandem type solid oxide fuel cell pack
Technical Field
The invention relates to a fuel cell, in particular to a solid oxide fuel cell stack, and specifically relates to a preparation method of a full-membrane flat plate membrane strip serial solid oxide fuel cell stack.
Background
At present, the development of clean energy sources such as solar energy and wind energy is not mature, and how to efficiently and cleanly utilize the existing fossil energy sources becomes an important subject. Fuel cell is a new type of power generation device which can convert the chemical energy of fuel into electric energy with high efficiency, has the advantage of cleanness and high efficiency, and is known as one of the most important clean energy technologies in 21 century. Among various fuel cells, a Solid Oxide Fuel Cell (SOFC) technology is a high and new technology developed in recent years, works at a higher temperature, has the advantages of high efficiency, wide fuel use range, high-quality waste heat, capability of driving a gas turbine so as to further improve the power generation efficiency, capability of realizing combined heat and power, and the like, and is expected to be widely applied to power stations, distributed power supplies, and the like.
The flat SOFC electric pile has the advantages of light weight, portability, wide commercialization prospect, and the like, in the current preparation technology, the tape casting method is an important preparation process in preparing large-area ceramic products due to the advantages of convenient operation, simple equipment, high production efficiency, mass production, high product consistency and the like, and the common flat SOFC electric pile adopts a single cell as a unit, namely, a cathode and an anode are respectively prepared on two sides of a single cell support body to form only one single cell, and then the single cells are connected in series through a bipolar plate current collector, or a large support body is directly prepared through the tape casting method, and the rest parts of the cell are prepared through other methods such as silk screen printing and the like. Although it is known that the advantages of casting are so outstanding, it is also only used to produce a certain part of the battery during the production process. In order to fully exert the casting advantages, the method creates innovation for preparing the series battery pack by the casting method. The method can produce the half battery pack with the integration of the porous framework supporting body, the anode and the electrolyte in large batch, and the efficiency of preparing the battery pack is greatly improved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method for preparing a half battery pack with three parts of a porous support, an electrolyte and an anode integrated by a tape casting method, which can be produced in batch. The integrated half-battery pack can generate electricity only by coating the cathode at the later stage, and the preparation method has the remarkable advantages of high efficiency, low cost, large-batch preparation and the like. The method has the advantages that the advantage of high performance of the porous framework support is exerted, the disadvantage of a single battery is overcome, a plurality of batteries are connected into a whole by using a porous support body, the electrolyte and the anode of the plurality of single batteries can be prepared by a preparation process, namely a tape casting method, the advantages of high efficiency and low cost of the traditional tape casting method are ingeniously and innovatively applied, the small single batteries are prepared by simple and ingenious cutting, and a plurality of single batteries work together on one electrolyte. The simple process of preparing the anode and the electrolyte film by the tape casting method can freely cut the sizes of the anode and the electrolyte and design the batteries with different sections. The single batteries of the battery pack are arranged on the same side of the support body, so that the connection between the batteries and the test of the batteries can avoid the difficult problem of sealing the traditional multi-section batteries. The single batteries are arranged on the same surface, and the anode is connected with the cathode of the other battery by silver paste, so that series connection can be realized. The monolithic battery pack prepared by the tape casting method has mature process, can be produced in large batch and has obvious cost advantage.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a full-film flat plate membrane belt series solid oxide fuel cell stack comprises the following steps: preparing a porous framework support body, a porous anode membrane and a compact electrolyte membrane by adopting a tape casting method, and integrally forming the porous framework support body, the porous anode membrane and the compact electrolyte membrane to prepare a half-cell group;
the casting method is characterized in that material powder is prepared into slurry with good fluidity, the slurry is cast and scraped off on a flat substrate by a scraper, and a casting film with the thickness of 10-50um is obtained after drying; the porous support body is made of a high-temperature-resistant electronic insulating ceramic material, and a casting film of the porous support body is cut into a designed shape; the porous anode film is made of metal ceramic (NiO-YSZ) compounded by metal nickel and Yttrium Stabilized Zirconia (YSZ), and a casting film of the porous anode film is cut into a strip shape with a designed size; the compact electrolyte membrane is made of YSZ (yttria stabilized zirconia) material, and a casting film of the compact electrolyte membrane is cut into the same size as the porous substrate and then a slender window is cut on the casting film;
the integrated molding is to stack the multilayer support body casting films together, then cut the porous anode film into a strip shape, arrange the porous anode film on the stacked support body film in parallel according to the design position, finally place the electrolyte casting film with the thin strip window on the support body film on which the anode film is arranged, make the thin strip window of the electrolyte film face to a long edge end of each anode film, expose the anode for subsequent electric connection, and integrally mold the stacked layers of films on a hot press to obtain a half-cell group green body; sintering the green half-cell pack in the air at 1400 ℃ to obtain a half-cell pack; the cathode film is made of a composite material of LSM and YSZ, is coated on the electrolyte layer of the substrate by a coating method, and is fired at 1200 ℃ to form a series battery pack; connecting the cathode of one single cell with the anode of the other single cell by silver paste to form a series connection, and covering the anode by the silver paste to prevent air leakage; sealing one side of a support body of the battery pack with an anode chamber wall made of an insulating ceramic material to form an anode chamber; at the working temperature, the gas-guide tube is used for providing fuel gas for the porous support body of the battery pack and providing oxidant gas for the cathode side, and then electric energy output can be obtained.
In the method, the adopted high-temperature-resistant electronic insulating material is a ceramic material, and the ceramic material is an alumina-based material or a zirconia-based material; the porous structure is obtained by adding pore-forming agent into the slurry.
In the method, the high-temperature-resistant electronic insulating ceramic material is mullite, corundum or zirconia.
In the method, the porous anode film is made of metal ceramic compounded by metal nickel and Yttrium Stabilized Zirconia (YSZ), and the anode film formed by tape casting can be cut into any size and shape; for example, cut into a long strip shape and a ladder shape.
In the method, the full-film flat plate membrane belt tandem type solid oxide fuel cell group comprises the following steps: different shapes and sizes can be designed according to different requirements, for example, a rectangular shape and a circular sheet shape can be designed, and the number of single battery sections is more than 2.
In the method, step pressing or integral pressing is adopted for manufacturing convenience, and finally the half battery pack is formed by one-time firing.
In the method, the cathode film is a porous cathode film and is formed by mixing LSM powder and YSZ powder, wherein the mass fraction of the YSZ powder is 25-50%, and the YSZ powder is prepared on the electrolyte layer of the substrate by adopting a painting method or a screen printing method.
In the method, the gas guide pipe is a pipe made of high-temperature-resistant and oxidation-resistant material.
In the method, the gas guide tube is a quartz tube or a ceramic tube.
In the above process, the fuel gas is hydrogen; the oxidant gas is oxygen or air.
In the invention, the specific steps of preparing the half-cell stack by casting integration are shown in figure 1:
the first step is as follows: a porous support base film ((a) in fig. 1), an anode film ((b) in fig. 1), and an electrolyte film ((c) in fig. 1) were prepared by a casting method.
The second step is that: a porous support is prepared. Casting the slurry into film as shown in (a) of FIG. 1, folding 4 films in half for 2 times, pressing at 5MPa pressure and room temperature for 5min, and pressing to obtain support as shown in (a) of FIG. 1 1 ) Wherein l is s /w s About 9/5 (l) s 、w s >0)。
The third step: and preparing the porous anode film. The anode film obtained by casting was cut into a length of l as shown in FIG. 1 (b) a Width of w a Rectangular anode film (b) 2 ) Setting the anode interval to be l s2 (depending on the specific cell number n), (b) 2 ) At a distance of l from the upper and lower edges of the support s1 At a distance w from the left and right edges of the support s1 . Wherein l is satisfied s ＝nl a +(n-1)l s2 +2l s1 ，w s ＝w a +2w s1 (l s1 、l s2 、w s1 、w s2 )>0. The cut anode sheet (b) 2 ) Are arranged in parallel at equal intervals in (a) 1 ) Fixing the mixture on a support by pressing at room temperature and 10MPa for 5min to obtain (a) 1 +b 2 )。
The fourth step: and preparing an electrolyte. Cutting the electrolyte membrane into n pieces of length l as shown in FIG. 1 (c) e And an anode b 2 W of the same width a The bar hole of (c) in FIG. 1 1 ) Is prepared from (c) 1 ) A film coated on the above (a) 1 +b 2 ) Wherein (c) 1 ) The strip hole of (a) and (b) 2 ) Aligning to expose the strip hole part (b) 2 ) The anode portion of (a). Pressing at 20MPa pressure and room temperature for 20min to form a half-cell stack composed of support, anode and electrolyte as shown in FIG. 1 (a) 1 +b 2 +c 1 ) And then firing the green half-cell substrate at 1400 ℃ for 2h to obtain the half-cell substrate. Wherein 0<l e <l a 。
The preparation of the cathode film is as follows: strontium-doped manganic acid and yttrium stabilized zirconia powder is prepared by mixing the following raw materials in a weight ratio of 6:4, and is coated on the electrolyte layer of the substrate by a coating method, and a certain interval is left between the cathode and the anode 1 Cathode portion and anode b 2 Same width, if length is l 2 Then satisfy l a ＝l e +l 1 +l 2 And after painting, putting the cathode film into an oven for drying, taking out the cathode film after the cathode film is formed, repeating the steps for three times, and finally firing the cathode film at 1200 ℃ for 2 hours to form the cathode film with the thickness of 20-30 um.
Preferably, the connecting body is used for connecting the anode of one section and the cathode of the next section by adopting a brushing method.
Preferably, the porous support matrix is generally square but may be arbitrarily sized and shaped. The porous support matrix is prepared by a tape casting method of yttrium stabilized zirconia powder and pore-forming agent powder.
Preferably, the anode film is a porous anode film made of Ni: the cermet (Ni-YSZ) with YSZ of 1:1 (mass ratio) and the pore-forming agent powder are prepared by a tape casting method, and an anode film is pressed on one side of a porous support body by a hot pressing method, wherein the anode film is in a strip shape.
Preferably, the electrolyte membrane is prepared from yttrium-stabilized zirconia by a casting method. And pressing the electrolyte membrane on the support body by adopting a hot pressing method to completely cover the electrolyte membrane, and cutting out a reserved anode position before pressing.
Preferably, the cathode film is a porous cathode film and is prepared by mixing LSM powder and YSZ powder according to the weight ratio of 6:4, and preparing the electrolyte membrane by a brushing method.
Compared with the prior art, the invention has the following characteristics:
1. the invention provides a preparation method for preparing a monolithic battery pack by a tape casting method. The preparation method has the characteristics of high efficiency, low cost, mass production and the like. The porous support, the anode and the electrolyte integrated half battery pack can be produced in large quantities, the cathode can be simply coated and used for generating electricity in later use, and the battery pack in series connection has higher voltage and output power compared with the traditional single battery.
2. The invention adopts the tape casting method to prepare the half battery pack integrating the porous matrix, the anode and the electrolyte, has higher convenience and economy compared with other methods, and can realize mass production.
The battery pack can be flexibly designed according to the shape and the size of the matrix, the shape and the size of the electrode, the electrode pattern, the pore size and the distribution and the like.
Drawings
FIG. 1 is a flow chart of the casting method for preparing a casting film and the integrated preparation of a porous skeleton matrix, an anode and an electrolyte;
FIG. 2 is a schematic diagram (top view) of a rectangular full-membrane flat-plate membrane strip tandem solid oxide fuel cell stack according to an example;
FIG. 3 is a schematic diagram (left side view) of a rectangular full-membrane flat-plate membrane strip tandem solid oxide fuel cell stack according to an example;
FIG. 4 is a schematic diagram of a testing apparatus for a rectangular full-membrane flat-plate membrane strip tandem solid oxide fuel cell stack in an example;
FIG. 5 is a graph showing the output performance of the tandem solid oxide fuel cell stack having 3 membrane strips connected in series in accordance with example 1;
FIG. 6 is a graph of the output performance of a series of 6 sections of series full membrane flat membrane strips solid oxide fuel cell stack of example 2;
fig. 7 is a graph of the output performance of the series solid oxide fuel cell stack of 10 series full-membrane flat membrane strips in example 3.
The figures show that: porous skeleton 1, anode membrane 2, electrolyte membrane 3, cathode membrane 4, anode chamber 5.
Detailed Description
The invention will be further described with reference to the following examples and the accompanying drawings, but the scope of the invention as claimed is not limited to the examples shown.
Example 1
3 sections of full-film flat plate membrane belt series solid oxide fuel battery packs:
as shown in fig. 3, the rectangular one-piece porous matrix-supported battery is composed of a porous support, an electrolyte membrane 3, a cathode membrane 4, an anode membrane 2, and a connector. The porous support is in the shape of a cuboid (not counting thickness), preferably a rectangular face of dimensions 90mm x 50 mm. The porous skeleton matrix is a mixture formed by mixing YSZ and graphite, the electrolyte membrane material adopts YSZ powder, and the anode film is prepared from Ni: YSZ is 1:1, and is composed of metal ceramic (Ni-YSZ) and graphite, and the three are prepared by adopting a tape casting method. The preparation formula is as follows: (1) porous support formula: 35.0g of YSZ, 5.4g of graphite, 0.7g of TEA and 33.0g of absolute ethanol were put into a ball mill pot and ball-milled for 1 hour by a planetary ball mill. Then 3.0g of PEG-600,3.0g of DOP and 21.0g of PVB-ethanol solution are added, and the mixture is ball-milled for 1.5h to obtain matrix slurry. (2) anode slurry formula: 18.0g of YSZ, 18.0g of NiO,5.4g of graphite, 1.5g of TEA and 26.0g of ethanol are added into a tank for ball milling for 1 hour, and then 21.0g of PVB-ethanol solution, 3.0g of PEG and 3.0g of DOP are added for ball milling for 1.5 hours to obtain anode slurry. (3) electrolyte slurry formula: mixing 35.0g YSZ, 1.4g Al 2 O 3 (sintering aid, ziboXin Hippon chemical Co., ltd., 99.99%), 0.7g TEA and 33.0g ethanol were charged into a ball mill pot and ball milled for 1 hour with a planetary ball mill. Then adding 1.4g of PEG-600,1.05g of DOP and 14.0g of PVB-ethanol solution, and ball-milling for 1.5h to obtain electrolyte slurry.
After the three materials are prepared by a tape casting method, the thin film is processed to obtain the integrated half battery pack. Folding 5 porous support films for 2 times, placing into a hot press, and pressing at 5Mpa at room temperature for 5min. At this time, the size of the substrate is about 90mm x 50mm, the anode film is cut into rectangular sheets (the thickness is not counted) with the size of 40mm x 20mm, each rectangular anode sheet is about 50mm away from the side distance of the substrate, the interval between the rectangular anode sheet and the next anode sheet is about 10mm, 3 anode sheets are placed on the substrate in order, the electrolyte membrane with the area larger than 90mm x 50mm (the area of the substrate) is pressed for 5min at the room temperature at 10MPa, and the anode area with the size of about 40mm x 3mm is reserved on each anode strip part in a cutting mode and is used for connecting the cathode of the next battery. Pressing the cut electrolyte at 20Mpa for 20min at room temperature, firing the substrate at 1400 ℃ for 4h to obtain a semi-cell substrate, brushing LSM cathode slurry with an area of about 40mm x 15mm on a single cell to form a cathode film, wherein the cathode material of the cathode film is prepared from LSM and YSZ powder according to the weight ratio of 6:4 by weight ratio. The cathode is spaced from the anode to prevent short circuit, and fired at 1200 deg.C for 2 hr to obtain a cathode with an area of about 4.5cm 2 And then packaging the battery, sealing the reserved anode area by using silver paste to prevent air leakage, connecting one section of cathode with the next section of anode, brushing silver grids on the cathode for charge collection, sealing the substrate on a quartz test tube by using the silver paste, and testing the open-circuit voltage and the output power of the battery at 800 ℃.
As shown in fig. 4, one side of the support body of the battery pack is sealed by an anode chamber wall made of an insulating ceramic material which is resistant to high temperature and has good stability in both oxidizing and reducing atmospheres to form an anode chamber, and a sealing material is arranged at the joint of the anode chamber wall and the support body and is made of the same material as that of the connecting and sealing body. When the battery pack works, fuel gas is provided for the anode chamber, the fuel gas is hydrogen in the embodiment, and the cathode exposed in the air directly adopts oxygen in the air as an oxidant. The reactions that occur at each electrode and the overall reaction are:
and (3) anode reaction: 2H 2 +2O 2- -4e - →2H 2 O
And (3) cathode reaction: o is 2 -4e - →O 2-
And (3) total reaction: 2H 2 +O 2 →2H 2 O
The output performance curve of the battery is shown in fig. 5. The open-circuit voltage of the 3 batteries in series reaches 2.8V, which is close to the theoretical open-circuit voltage of 3 batteries in series, namely 3V. The porous support can solve the problem of fuel gas transmission and the problem of battery sealing by using the sealing material, and output higher voltage and simultaneously the maximum output power reaches 400mW.
Example 2
6 sections of full-film flat plate membrane belt series solid oxide fuel battery packs:
using the material of example 1, a substrate having an area of 86mm x 50mm was prepared, the anode film was cut into rectangular sheets (thickness not counted) of 40mm x 8mm in size, each rectangular anode sheet was spaced about 50mm from the edge of the substrate, and about 3mm from the next anode sheet, 6 anode sheets were placed in order on the substrate, pressed at room temperature for 5min at 10Mpa, and an electrolyte membrane having an area greater than 86mm x 50mm (substrate area) was taken, and an anode area of about 40mm x 2mm was reserved in each anode strip portion for connection to the cathode of the next cell. Pressing the cut electrolyte at 20MPa at room temperature for 20min, firing the substrate at 1400 deg.C for 4h to obtain a half-cell stack, brushing LSM cathode slurry with an area of about 40mm x 5mm on the single cells to form cathode films, keeping the cathode at a certain distance from the anode to prevent short circuit, firing at 1200 deg.C for 2h to obtain a cathode with an area of about 3cm 2 And then packaging the battery, sealing the reserved anode area by using silver paste to prevent air leakage, connecting one cathode with the next anode, brushing silver grids on the cathodes for charge collection, sealing the substrate on a quartz test tube by using the silver paste, and testing the open-circuit voltage and the output power of the battery at 800 ℃.
As shown in fig. 4, one side of the support body of the battery pack is sealed by an anode chamber wall made of an insulating ceramic material which is resistant to high temperature and has good stability in both oxidizing and reducing atmospheres to form an anode chamber, and a sealing material is arranged at the joint of the anode chamber wall and the support body, and the sealing material is the same as the material of the connecting and sealing body.
The output performance curve of the battery is shown in fig. 6. The open-circuit voltage of the 6 batteries of series batteries reaches 4.5V, and the maximum output power reaches 140mW.
Example 3
10 sections of full-film flat plate membrane belt series solid oxide fuel battery packs:
using the material of example 1, a matrix of 88mm x 50mm area was prepared, the anode film was cut into 40mm x 6mm rectangular sheets (thickness not counted), each rectangular anode sheet was spaced about 50mm from the edge of the substrate, and about 2mm from the next anode sheet, 10 anode sheets were placed in order on the substrate, pressed at room temperature for 5min at 10Mpa, an electrolyte membrane having an area greater than 88mm x 50mm (substrate area) was taken, and an anode area of about 40mm x 2mm was reserved in each anode strip portion cut for connection to the cathode of the next cell. Pressing the cut electrolyte sheet at 20MPa at room temperature for 20min, firing the substrate at 1400 deg.C for 4h to obtain a half-cell stack, brushing LSM cathode slurry with an area of about 40mm x 2.5mm on the single cells to form cathode films, keeping the cathode at a certain distance from the anode to prevent short circuit, firing at 1200 deg.C for 2h and a cathode area of about 2.5cm 2 And then packaging the battery, sealing the reserved anode area by using silver paste to prevent air leakage, connecting one cathode with the next anode, brushing silver grids on the cathodes for charge collection, sealing the substrate on a quartz test tube by using the silver paste, and testing the open-circuit voltage and the output power of the battery at 800 ℃.
As shown in fig. 4, one side of the support body of the battery pack is sealed by an anode chamber wall made of an insulating ceramic material which is resistant to high temperature and has good stability in both oxidizing and reducing atmospheres to form an anode chamber, and a sealing material is arranged at the joint of the anode chamber wall and the support body and is made of the same material as that of the connecting and sealing body.
The output performance curve of the battery is shown in fig. 7. The open-circuit voltage of 10 batteries connected in series reaches 5.4V, and the maximum output power reaches 239mW.

Claims (10)

1. A preparation method of a full-film flat plate membrane belt series solid oxide fuel cell stack is characterized by comprising the following steps: preparing a porous framework support body, a porous anode membrane and a compact electrolyte membrane by adopting a tape casting method, and integrally forming the porous framework support body, the porous anode membrane and the compact electrolyte membrane to prepare a half-cell group;
the casting method is characterized in that material powder is prepared into slurry with good fluidity, the slurry is cast and scraped off on a flat substrate by a scraper, and a casting film with the thickness of 10-50um is obtained after drying; the porous support body is made of a high-temperature-resistant electronic insulating ceramic material, and a casting film of the porous support body is cut into a designed shape; the porous anode film is made of metal nickel and Yttrium Stabilized Zirconia (YSZ) compounded cermet (NiO-YSZ), and a casting film of the porous anode film is cut into a strip shape with a designed size; the compact electrolyte membrane is made of YSZ (yttria stabilized zirconia) and is cut into the same size as the porous substrate, and then a slender window is cut on the compact electrolyte membrane;
the integrated molding is to stack the multilayer support body casting films together, then cut the porous anode film into a strip shape, arrange the porous anode film on the stacked support body film in parallel according to the design position, finally place the electrolyte casting film with the thin strip window on the support body film on which the anode film is arranged, make the thin strip window of the electrolyte film face to a long edge end of each anode film, expose the anode for subsequent electric connection, and integrally mold the stacked layers of films on a hot press to obtain a half-cell group green body; sintering the half-battery pack green body in the air at 1400 ℃ to obtain a half-battery pack; the cathode film is made of a composite material of LSM and YSZ, is coated on the electrolyte layer of the substrate by a coating method, and is fired at 1200 ℃ to form a series battery pack; connecting the cathode of one monocell with the anode of the other monocell by silver paste to form a series connection, and covering the anode by the silver paste to prevent air leakage; sealing one side of a support body of the battery pack with an anode chamber wall made of insulating ceramic materials to form an anode chamber; at the working temperature, the gas-guide tube is used for providing fuel gas for the porous support body of the battery pack and providing oxidant gas for the cathode side, and then electric energy output can be obtained.
2. The method for preparing the full-film flat membrane strip tandem solid oxide fuel cell stack according to claim 1, wherein the adopted high-temperature-resistant electronic insulating material is a ceramic material, and the ceramic material is an alumina-based material or a zirconia-based material; the porous structure is obtained by adding pore-forming agent into the slurry.
3. The method for preparing the full-film flat membrane strip tandem type solid oxide fuel cell stack according to claim 1 or 2, wherein the high-temperature-resistant electronic insulating ceramic material is mullite, corundum or zirconia.
4. The method for preparing the series solid oxide fuel cell stack with the full-film flat membrane belt according to claim 1, wherein the porous anode membrane is made of a cermet compounded by metallic nickel and yttrium-stabilized zirconia (YSZ), and the anode membrane formed by casting can be cut into any size and shape.
5. The method for preparing the full-membranization flat-plate membrane strip tandem solid oxide fuel cell stack according to claim 1, wherein the number of single cells of the full-membranization flat-plate membrane strip tandem solid oxide fuel cell stack is more than 2.
6. The method according to claim 1, wherein the final half of the stack is fired once for ease of fabrication by step-wise pressing or integral pressing.
7. The method for preparing a series solid oxide fuel cell stack with a full-film flat membrane strip according to claim 1, wherein the cathode membrane is a porous cathode membrane and is formed by mixing LSM powder and YSZ powder, the mass fraction of the YSZ powder is 25% -50%, and the YSZ powder is prepared on an electrolyte layer of a substrate by a painting method or a screen printing method.
8. The method for preparing a full-membrane flat membrane strip tandem type solid oxide fuel cell stack according to claim 1, wherein the gas guide tube is a tube made of high-temperature-resistant and oxidation-resistant material.
9. The method for preparing a full-membrane flat membrane strip tandem type solid oxide fuel cell stack according to claim 8, wherein the gas guide tube is a quartz tube or a ceramic tube.
10. The method for preparing a full-membrane flat-membrane strip tandem solid oxide fuel cell stack according to claim 1, wherein the fuel gas is hydrogen; the oxidant gas is oxygen or air.
CN202210769733.6A 2022-07-01 2022-07-01 Preparation method of full-film flat plate membrane band tandem type solid oxide fuel cell pack Pending CN115207386A (en)

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