CN113054215A - Method for manufacturing metal support plate for fuel cell - Google Patents

Method for manufacturing metal support plate for fuel cell Download PDF

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Publication number
CN113054215A
CN113054215A CN202110297120.2A CN202110297120A CN113054215A CN 113054215 A CN113054215 A CN 113054215A CN 202110297120 A CN202110297120 A CN 202110297120A CN 113054215 A CN113054215 A CN 113054215A
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powder
sintering
metal substrate
layer
metal
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包崇玺
陈志东
颜巍巍
童璐佳
朱志荣
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Mbtm New Materials Group Co ltd
NBTM New Materials Group Co Ltd
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Mbtm New Materials Group Co ltd
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Priority to PCT/CN2021/108858 priority patent/WO2022193525A1/en
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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
    • H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • 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
    • H01M8/023—Porous and characterised by the material
    • H01M8/0232—Metals or alloys
    • 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
    • H01M8/023—Porous and characterised by the material
    • H01M8/0241—Composites
    • 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
    • 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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  • Chemical Kinetics & Catalysis (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Fuel Cell (AREA)

Abstract

The invention relates to a manufacturing method of a metal support plate for a fuel cell, which sequentially comprises the following steps: 1) adopting one of sintered stainless steel, heat-resistant steel, nickel-based alloy, cobalt-based alloy, titanium alloy and chromium-based alloy; 2) screening the powder in the step 1), and selecting the powder with the granularity of 13-250 um; 3) placing the powder in an inner hole of a measuring device, removing excessive powder, and placing on a burning bearing plate; 4) sintering the setter plate with the measuring device; 5) coating the anode slurry on the upper surface of the metal substrate to form an anode layer on the upper surface of the metal substrate; 6) coating an electrolyte slurry on an upper surface of the anode layer to form an electrolyte coating on a surface of the anode layer; 7) the cathode slurry is coated on the upper surface of the electrolyte coating layer to form a cathode layer on the upper surface of the electrolyte coating layer, thereby manufacturing a metal support plate. Eliminate sintering deformation and raise the combining tightness between the anode layer and the metal base plate.

Description

Method for manufacturing metal support plate for fuel cell
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to a manufacturing method of a metal support plate for a fuel cell.
Background
The solid oxide fuel cell is an ideal fuel cell, and not only has the advantages of high efficiency and environmental protection of the fuel cell, but also has the following outstanding advantages:
(1) the solid oxide fuel cell has an all-solid structure, does not have the corrosion problem and the electrolyte loss problem caused by using a liquid electrolyte, and is expected to realize long-life operation. (2) The working temperature of the solid oxide fuel cell is 800-1000 ℃, the electrocatalyst does not need to adopt noble metal, and natural gas, coal gas and hydrocarbon can be directly adopted as fuel, so that the fuel cell system is simplified. (3) The high-temperature waste heat discharged by the solid oxide fuel cell can form combined circulation with a gas turbine or a steam turbine, so that the total power generation efficiency is greatly improved.
At present, the traditional solid oxide fuel cell mostly adopts ceramic materials or metal ceramic composite materials as a support body. Ceramic materials are not easily machined, have poor thermal shock resistance and welding performance, and are not favorable for the assembly of fuel cell (SOFC) stacks. Metal supported solid oxide fuel cells (MS-SOFCs) (as shown in fig. 1) have unique advantages over support SOFCs that use metals or alloys as fuel cells: (1) the cost is low: the cost of the metal material is far lower than that of the metal ceramic composite material; (2) and (3) quick start: the good heat-conducting property of the metal can reduce the temperature gradient in the battery, and the quick start is realized, so that the battery can be applied to the mobile field; (3) workability: compared with ceramics, the metal material has better processability, which greatly reduces the processing difficulty of the SOFC; (4) sealing is facilitated: by utilizing the welding sealing technology of the metal material, the problem that the SOFC is difficult to seal can be avoided. The metal support serves primarily to transport gas, conduct current, and provide stable structural support for the cell. When the MS-SOFC uses the hydrocarbon fuel, the metal support body can be used as an in-situ reforming layer, the hydrocarbon fuel is firstly subjected to chemical reforming in the metal support body, and the generated synthesis gas is subjected to electrochemical oxidation in the anode functional layer. The MS-SOFC is not only suitable for the application field of the traditional Solid Oxide Fuel Cell (SOFC), such as a fixed power station, a backup power supply, a charging pile and the like, but also can be used as a range extender of mobile equipment such as a heavy truck or an electric vehicle and the like.
The current metal-supported solid oxide fuel cell, such as the preparation method of the porous metal-supported low-temperature solid oxide fuel cell in the invention patent application of China, the patent application number of which is CN200610118649.9 (application publication number of CN1960047A), discloses a preparation method of the porous metal-supported low-temperature solid oxide fuel cell, NiO-ScSZ (or CGO) is selected as a support raw material to prepare the support, and the preparation method has the disadvantages of complex process and high manufacturing difficulty.
In addition, at present, a Fe-Cr alloy support prepared by tape casting, an anode and an electrolyte blank body are laminated and then placed in a reducing atmosphere for high-temperature sintering, an anode catalyst is injected into the side of a metal support of a half cell, a cathode layer is printed on the surface of an electrolyte through screen printing, and the anode and the cathode are sintered in situ in the cell testing process. The process effectively avoids the diffusion of metal elements at high temperature, but the in-situ sintering temperature is too low, the bonding strength of the cathode and the electrolyte interface is low, and the battery performance attenuation is low. The porous metal body with the anode and the electrolyte is prepared by adopting a co-casting method, and the sintering deformation, the anode or electrolyte layer peeling and the like of the material are easily caused due to different sintering temperatures of the metal and the electrolyte. And a dry pressing forming method is adopted to prepare the metal support body and the micro-tube type metal support body. Because the metal supporting layer is thin, the metal supporting plate is easy to have uneven thickness after dry pressing, so that the sintering deformation is inconsistent, and the combination between the anode, the electrolyte and the matrix is influenced; the metal thickness of the micro-tube type metal support body is not easy to realize uniform control, and the combination with an anode and the like is influenced.
Using Fe-based alloysAnd Ni-based alloy is used as a metal support body of the MS-SOFC, and because the thermal expansion coefficient of the Ni-based alloy is greatly different from that of an electrolyte material, the internal thermal stress is overlarge in the operation process of the battery, so that cracks are easy to appear, and even an electrolyte layer is peeled off; the pure Ni support body has poor oxidation resistance and is easy to agglomerate and coarsen, so that the performance of the SOFC is rapidly attenuated. These disadvantages of Ni-based alloys severely hamper their application in SOFC supports; while Fe-based alloy, particularly ferritic stainless steel, is used as the support, although ferritic stainless steel has a high-temperature coefficient of thermal expansion CTE (11X 10)-6～13×10-6K-1) With YSZ (yttria stabilized zirconia) and GDC (Gd)2O3Doped CeO2)(13×10-6～14×10-6K-1) The electrolytes are very close, but long-term operation in a medium-high temperature, humid atmosphere is likely to result in oxidation of the metallic material and interdiffusion of Fe and Cr elements in the stainless steel support with the Ni-based anode. In the preparation or operation process of the MS-SOFC, Fe and Cr elements in the support body diffuse into the anode to form oxides in the operation process of the cell, so that the performance of the cell is rapidly attenuated; meanwhile, Ni element in the anode diffuses into the stainless steel support body, so that the thermal expansion coefficient of the support body is changed, the internal stress of the battery is increased, and the structural stability is reduced.
Therefore, further improvements in the existing methods of manufacturing metal support plates for fuel cells are needed.
Disclosure of Invention
The present invention is directed to a method for manufacturing a metal support plate for a fuel cell, which can improve the bonding between an anode and a substrate by eliminating the sintering deformation, in view of the above-mentioned current state of the art.
The technical scheme adopted by the invention for solving the technical problems is as follows: a method for manufacturing a metal support plate for a fuel cell, comprising the following steps in sequence:
1) adopting one of sintered stainless steel, heat-resistant steel, nickel-based alloy, cobalt-based alloy, titanium alloy and chromium-based alloy;
2) screening the powder in the step 1), and selecting the powder with the granularity of 13-250 um;
3) placing the powder in an inner hole of a measuring device, removing excessive powder, and placing on a burning bearing plate;
4) sintering the burning bearing plate with the measuring device, forming a metal substrate by the powder in the measuring device, and flattening the metal substrate;
5) coating the anode slurry on the upper surface of the metal substrate, then placing the uncoated lower surface of the metal substrate on a burning bearing plate, and sintering after drying, thereby forming an anode layer on the upper surface of the metal substrate;
6) coating electrolyte slurry on the upper surface of the anode layer, then placing the uncoated lower surface of the metal substrate on a setter plate, and sintering after drying, thereby forming an electrolyte coating on the upper surface of the anode layer;
7) the cathode slurry is coated on the upper surface of the electrolyte coating layer, and then the uncoated lower surface of the metal substrate is laid on a setter plate, dried and then sintered to form a cathode layer on the upper surface of the electrolyte coating layer, thereby manufacturing a metal support plate.
In order to reduce the pores of the metal support plate, wax dipping treatment is carried out between the step 4) and the step 5), namely, the metal substrate with the required size is placed into wax melt for 1-30 min, and the metal substrate is taken out and cooled after the wax melt permeates into the pores in the metal substrate.
Preferably, in step 3), a metal fiber felt cutting piece with porosity greater than 50% is laid on the upper surface of the setter plate, a gauge for placing the powder is placed above the metal fiber felt cutting piece, and a metal substrate with a double-layer structure is formed after sintering, wherein the double-layer structure comprises a fiber felt layer and a sintering powder layer which are arranged up and down.Lower partThe metal fiber felt is paved, so that the sintering deformation can be reduced, and meanwhile, the porosity and the strength of the metal fiber are higher, so that the gas can enter the anode and support the anode.
The component content of the metal fiber felt can be various forms, and preferably, the metal fiber felt comprises the following components in percentage by mass: carbon: less than or equal to 0.06 percent, nickel: 0-25%, molybdenum: 0-4%, chromium: 10-30%, niobium: 0-3%, aluminum: 0-10%, titanium: 0-3%, silicon: 0-1%, manganese: 0-2%, not more than 2% of unavoidable impurities, iron: and (4) the balance. The metal felt is better combined with the powder, and the strength of the supporting plate can be improved.
Preferably, the sintered stainless steel is selected in the step 1), and the components of the sintered stainless steel comprise the following components in percentage by mass: carbon: less than or equal to 0.06 percent, nickel: 0-25%, molybdenum: 0-4%, chromium: 10-30%, niobium: 0-3%, aluminum: 0-10%, titanium: 0-3%, silicon: 0-1%, manganese: 0-2%, not more than 2% of unavoidable impurities, iron: and (4) the balance. The metal powder is well combined with the anode after sintering, and the thermal expansion coefficients are matched.
Preferably, in the step 4), the sintering temperature is 1000-1350 ℃, the sintering time is 5-240 min, and the vacuum degree is 10-3Pa～102Pa。
Specifically, the sintering temperature in the step 5) is 1050-1400 ℃, the sintering time is 10-300 min, the sintering temperature in the step 6) is 1000-1400 ℃, the sintering time is 10-300 min, the sintering temperature adopted in the sintering in the step 7) is 800-1200 ℃, the sintering time is 5-300 min, and the vacuum degree is 10-3Pa～102Pa。
Preferably, the anode slurry contains NiO, butanone, ethanol, triethanolamine, starch, polyvinyl butyral (PVB), polyethylene glycol (PEG), glutamic acid (PHT), yttria-stabilized zirconia and Sr2-xCaxFe1.5Mo0.5O6-δ(x is 0, 0.1, 0.3, 0.5). The battery reaction is facilitated.
Preferably, the electrolyte slurry comprises butanone, ethanol, triethanolamine, polyvinyl butyral (PVB), polyethylene glycol (PEG), glutamic acid (PHT), yttria-stabilized zirconia and LaGaO3A base electrolyte, Ba (Sr) Ce (Ln) O3And CeO2Based on one of the solid electrolytes. The thermal expansion coefficient of the electrolyte slurry is close to that of the anode and the cathode, and the electrolyte slurry is well combined after sintering.
Preferably, the cathode slurry is Sr2-xCaxFe1.5Mo0.5O6-δ、LSM(La1-xSrxMn03)、LSCF((La，Sr)(Co，Fe)O3) A of pyrochlore structure2Ru2O7－x(a ═ Pb, Bi) ceramic, Ag-YDB composite ceramic, and perovskite-structured L-type ceramic, wherein x is 0, 0.1, 0.3, or 0.5. This cathode material is tightly bound to the electrolyte layer.
Compared with the prior art, the invention has the advantages that: the preparation method of the metal support plate for the fuel cell has simple process, can realize mass production of the metal support plate without a die, reduces the production cost and improves the production efficiency; through the drawing of the metal fibers, the sintering deformation of the metal support plate is effectively reduced, and meanwhile, the deformation can also be effectively reduced by matching with the thermal expansion coefficients among the anode, the electrolyte and the cathode. Eliminate sintering deformation and improve the bonding tightness between the anode layer and the metal substrate. The metal fiber felt and the powder are loosely packed and sintered, so that the strength is high, and the sintering deformation is controllable. Compared with a supporting plate using a metal plate, the density is low, the weight is light, and the light weight is favorably realized. The support plate prepared from the metal plate needs to be subjected to multiple coating treatments, so that the cost is high, and the cost is low. In addition, through the wax dipping treatment, the pore of the metal substrate can be controlled, and the gas can conveniently pass through the metal substrate.
Drawings
FIG. 1 is a cross-sectional view of a metal-backed plate fuel cell construction of an embodiment;
FIG. 2 is a scanning electron micrograph of a fracture after sintering according to example 1;
FIG. 3 is a cross-sectional metallographic image of example 1 after sintering;
FIG. 4 is a topographical view of the sintered metal fiber mat side of example 1;
FIG. 5 is a graph of the pore morphology after sintering for example 5;
FIG. 6 is a graph of the pore morphology after flattening in example 5;
FIG. 7 is a graph of the pore morphology after sintering for example 6;
FIG. 8 is a graph of the pore morphology after flattening in example 6.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments
Example 1:
the method for manufacturing a metal support plate for a fuel cell of the present embodiment sequentially includes the steps of:
1) preparing raw materials: 434L stainless steel powder is selected as a material, and the 434L stainless steel comprises the following components in percentage by mass: 0.025%, Cr: 17.5%, Mn: 0.8%, Si: 0.6%, Mo: 1.05%, iron: the balance;
2) sieving the powder, wherein the granularity range is 150-200 meshes, and the loose packed density of the powder is 2.35g/cm3。
3) The burning bearing plate is ceramic containing 95% of alumina;
4) powder spreading: the other part of the material is selected from a metal fiber felt, and the metal fiber felt comprises the following components in percentage by mass: 0.015%, Cr: 18.5%, Mn: 0.6%, Si: 0.3%, Ni: 10.1%, iron: the balance; the porosity is 80%, and the thickness is 0.1 mm; cutting the metal fiber felt into 125 x 125mm, placing the cut metal fiber felt on a setter plate, then pouring the powder obtained in the step 2) into an inner hole of a measuring device, removing redundant powder, and placing the measuring device with the powder on the metal fiber felt of the setter plate; the inner hole of the gauge has a size of 120 × 120mm and a thickness of 0.15mm, and the gauge is an existing gauge and is not described in detail in this embodiment; namely, when the area of the metal fiber felt is S1, the inner hole area of the gauge is S2, and S1 is (1.01-1.5) S2.
5) And (3) sintering: sintering the setter plate with the measuring device at 1250 ℃ for 120 minutes in a vacuum recoil of 3X 104Pa argon gas, metal powder particles and metal fiber felt in the measuring device are sintered to form a metal substrate, the metal substrate is of a double-layer structure, the double-layer structure comprises a fiber felt layer and a sintered powder layer which are arranged up and down, and then the metal substrate is taken out.
6) Flattening: placing the sintered metal substrate material on two flatBetween the templates, pressure was applied to a height of 0.65mm and a density of 4.7g/cm after pressing3。
7) Preparing an anode layer: the anode slurry is uniformly applied to the upper surface of the cut metal substrate 4 by screen printing or dip coating, and the uncoated lower surface of the metal substrate 4 is placed on a setter plate and dried, thereby forming the anode layer 2 on the upper surface of the metal substrate 4. The anode slurry comprises Sr2-xCaxFe1.5Mo0.5O6-δ(x ═ 0), NiO, butanone, ethanol, triethanolamine, starch, polyvinyl butyral PVB, polyethylene glycol PEG, and glutamic acid PHT.
8) Preparing an electrolyte coating: the prepared electrolyte slurry is uniformly coated on the anode layer 2 by a screen printing or dip coating method, and the uncoated lower surface is placed on a setter plate to be dried and sintered, thereby forming an electrolyte coating 3 on the upper surface of the anode layer 2. The electrolyte slurry comprises yttria-stabilized zirconia electrolyte, butanone, ethanol, triethanolamine, polyvinyl butyral (PVB), polyethylene glycol (PEG) and glutamic acid (PHT).
9) Preparing a cathode layer: sr is2-xCaxFe1.5Mo0.5O6-δ(x ═ 0) cathode paste made of a cathode material was uniformly applied on the upper surface of the electrolyte coating layer by screen printing or dip coating method, and after the uncoated lower surface was placed on a setter plate and dried, a cathode layer 1 was formed on the upper surface of the electrolyte coating layer 3, as shown in fig. 1.
The scanning electron microscope photograph of the flattened fracture is shown in fig. 2, the pore metallographic phase after sintering is shown in fig. 3, and the morphology of the metal fiber felt surface after sintering is shown in fig. 4. As can be seen from fig. 2 to 4, the metal powder particles are tightly bonded to the metal fiber mat.
Example 2:
the method for manufacturing a metal support plate for a fuel cell of the present embodiment sequentially includes the steps of:
1) preparing raw materials, wherein 430L of stainless steel powder is selected as the material, and the 430L of stainless steel comprises the following components in percentage by mass: c: 0.025%, Cr: 17.2%, Mn: 0.9%, Si: 0.5%, iron: the balance;
2) sieving the powder to obtain powder with a granularity of 200-320 meshes and a loose powder packing density of 2.25g/cm3。
3) The burning bearing plate is a ceramic plate containing 95% of alumina;
4) powder spreading: the other part of the material is selected from a metal fiber felt, and the metal fiber felt comprises the following components in percentage by mass: 0.015%, Cr: 17.5%, Mn: 0.6%, Si: 0.3%, Ni: 13.4%, Mo: 2.46%, iron: the balance; the porosity of the metal fiber felt is 60%, and the thickness of the metal fiber felt is 1.1 mm; cutting the metal fiber felt into 125 x 125mm, placing the cut metal fiber felt on a burning board, then pouring the powder in the step 2) into an inner hole of a measuring device, removing the redundant powder, and placing the measuring device with the powder on the metal fiber felt of the burning board; the size of the inner hole of the measuring device is 120 multiplied by 120mm, and the thickness is 1.0 mm; when the area of the metal fiber felt is S1, the inner hole area of the gauge is S2, and S1 is (1.01-1.5) S2;
5) and (3) sintering: and (2) sintering the setter plate with the measuring device at the sintering temperature of 1200 ℃ for 120 minutes in a sintering atmosphere of 10 vol% argon gas + 90% hydrogen gas, sintering the metal powder particles and the metal fiber felt in the measuring device to form a metal substrate 4, wherein the metal substrate 4 is of a double-layer structure, the double-layer structure comprises a fiber felt layer and a sintered powder layer which are arranged up and down, and then taking out the metal substrate 4.
6) Flattening: placing the sintered metal substrate 4 between two flat templates, applying pressure until the height is 1.45mm, and the density is 5.0g/cm after pressing3。
7) Preparing an anode layer: the anode slurry is uniformly applied to the upper surface of the cut metal substrate 4 by screen printing or dip coating, and the uncoated lower surface of the metal substrate 4 is placed on a setter plate and dried, thereby forming the anode layer 2 on the upper surface of the metal substrate 4. The anode slurry comprises yttria-stabilized zirconia YSZ, NiO, butanone, ethanol, triethanolamine, starch, polyvinyl butyral PVB, polyethylene glycol PEG and glutamic acid PHT.
8) Preparing an electrolyte coating: the prepared electrolyte slurry is uniformly coated on the anode layer 2 by a screen printing or dip coating method, and the uncoated lower surface is placed on a setter plate to be dried and sintered, thereby forming an electrolyte coating 3 on the upper surface of the anode layer 2. The electrolyte slurry comprises yttria-stabilized zirconia electrolyte, butanone, ethanol, triethanolamine, polyvinyl butyral (PVB), polyethylene glycol (PEG) and glutamic acid (PHT).
9) Preparing a cathode layer: sr is2-xCaxFe1.5Mo0.5O6-δ(x ═ 0) cathode paste made of a cathode material was uniformly applied on the upper surface of the electrolyte coating layer by screen printing or dip coating method, and after the uncoated lower surface was placed on a setter plate and dried, a cathode layer 1 was formed on the upper surface of the electrolyte coating layer 3, thereby forming a metal support plate.
Example 3:
the method for manufacturing a metal support plate for a fuel cell of the present embodiment sequentially includes the steps of:
1) preparing raw materials, wherein 434L stainless steel powder is selected as the material, and the 434L stainless steel comprises the following components in percentage by mass: c: 0.025%, Cr: 17.5%, Mn: 0.8%, Si: 0.6%, Mo: 1.05%, iron: the balance;
2) screening the stainless steel powder, wherein the granularity is 100-150 meshes, and the loose density of the powder is 2.55g/cm3。
3) The burning bearing plate is a ceramic plate containing 95% of alumina;
4) powder spreading: the other part of the material is a metal fiber felt which comprises the following components in percentage by mass: 0.015%, Cr: 17.2%, Mn: 0.9%, Si: 0.5%, porosity 60%, iron: the balance; the thickness of the metal fiber felt is 0.4 mm; cutting the metal fiber felt into 125 x 125mm, placing the cut metal fiber felt on a setter plate, pouring the powder obtained in the step 2) into an inner hole of a measuring device, removing redundant powder, and then placing the measuring device with the powder on the metal fiber felt of the setter plate; the size of the inner hole of the measuring device is 120 multiplied by 120mm, and the thickness is 0.7 mm;
5) and (3) sintering: sintering the setter plate with the measuring device at the sintering temperature of 1300 ℃ for 60 minutes, wherein the sintering atmosphere is 10 vol% argon + 90% hydrogen, sintering the metal powder particles and the metal fiber felt in the measuring device to form a metal substrate 4, wherein the metal substrate 4 is of a double-layer structure, the double-layer structure comprises a fiber felt layer and a sintering powder layer which are arranged up and down, and then taking out the metal substrate.
6) Flattening: placing the sintered metal substrate 4 between two flat templates, applying pressure until the height is 1.0mm, and the density is 4.5g/cm after pressing3。
7) Preparing an anode layer: the anode slurry is uniformly applied to the upper surface of the cut metal substrate 4 by screen printing or dip coating, and the uncoated lower surface of the metal substrate 4 is placed on a setter plate and dried, thereby forming the anode layer 2 on the upper surface of the metal substrate 4. The anode slurry comprises Sr2-xCaxFe1.5Mo0.5O6-δ(x ═ 0.5), NiO, methyl ethyl ketone, ethanol, triethanolamine, starch, polyvinyl butyral PVB, polyethylene glycol PEG, and glutamic acid PHT.
8) Preparing an electrolyte coating: the prepared electrolyte slurry is uniformly coated on the anode layer 2 by a screen printing or dip coating method, and the uncoated lower surface is placed on a setter plate to be dried and sintered, thereby forming an electrolyte coating 3 on the upper surface of the anode layer 2. The electrolyte slurry comprises CeO2Solid electrolyte, butanone, ethanol, triethanolamine, polyvinyl butyral PVB, polyethylene glycol PEG and glutamic acid PHT.
9) Preparing a cathode layer: sr is2-xCaxFe1.5Mo0.5O6-δ(x ═ 0.5) cathode paste made of a cathode material was uniformly applied on the upper surface of the electrolyte coating layer by screen printing or dip coating method, and the uncoated lower surface was placed on a setter plate and dried, thereby forming a cathode layer 1 on the upper surface of the electrolyte coating layer 3.
Example 4:
the method for manufacturing a metal support plate for a fuel cell of the present embodiment sequentially includes the steps of:
1) preparing raw materials, wherein 434L stainless steel powder is selected as the material, and the 434L stainless steel powder comprises the following components in percentage by mass: 0.025%, Cr: 17.5%, Mn: 0.8%, Si: 0.6%, Mo: 1.05%, iron: the balance;
2) screening the powder, wherein the granularity is 325-500 meshes, and the loose density of the powder is 2.15g/cm3。
3) The burning bearing plate is a ceramic plate containing 95% of alumina;
4) powder spreading: the other part is a metal fiber felt, and the metal fiber felt comprises the following components in percentage by mass: 0.06%, Cr: 21.1%, Mn: 0.9%, Si: 0.3%, Al: 4.79%, iron: the balance; the porosity of the metal fiber felt is 65%, and the thickness of the metal fiber felt is 0.2 mm; then cutting the metal fiber felt into 125 x 125mm, and placing the cut metal fiber felt on a setter plate; then pouring the powder in the step 2 into an inner hole of a measuring device, removing the redundant powder, and then placing the measuring device with the powder on the metal fiber felt of the setter plate; the size of the inner hole of the measuring device is 120 multiplied by 120mm, and the thickness is 0.3 mm;
5) and (3) sintering: the setter plate with the gauge placed therein was sintered at a sintering temperature of 1200 ℃ for 60 minutes. The sintering atmosphere is 10 vol% argon gas + 90% hydrogen gas, the metal powder particles and the metal fiber felt in the measuring device are sintered to form the metal substrate 4, the metal substrate 4 is of a double-layer structure, the double-layer structure comprises a fiber felt layer and a sintered powder layer which are arranged up and down, and then the metal substrate 4 is taken out.
6) Flattening: placing the sintered metal substrate 4 between two flat templates, applying pressure, pressing to a height of 0.6mm, and making the pressed metal substrate have a density of 4.8g/cm3；
7) Preparing an anode layer: the anode slurry is uniformly applied to the upper surface of the cut metal substrate 4 by screen printing or dip coating, and the uncoated lower surface of the metal substrate 4 is placed on a setter plate and dried, thereby forming the anode layer 2 on the upper surface of the metal substrate 4. The anode slurry bagIs composed of Sr2-xCaxFe1.5Mo0.5O6-δ(x ═ 0.1), NiO, methyl ethyl ketone, ethanol, triethanolamine, starch, polyvinyl butyral PVB, polyethylene glycol PEG, and glutamic acid PHT.
8) Preparing an electrolyte coating: the prepared electrolyte slurry is uniformly coated on the anode layer 2 by a screen printing or dip coating method, and the uncoated lower surface is placed on a setter plate to be dried and sintered, thereby forming an electrolyte coating 3 on the upper surface of the anode layer 2. The electrolyte slurry comprises Ba (Sr) Ce (Ln) O3Electrolyte, butanone, ethanol, triethanolamine, polyvinyl butyral PVB, polyethylene glycol PEG and glutamic acid PHT.
9) Preparing a cathode layer: sr is2-xCaxFe1.5Mo0.5O6-δ(x ═ 0.3) cathode paste made of a cathode material was uniformly applied on the upper surface of the electrolyte coating layer by screen printing or dip coating method, and after the uncoated lower surface was placed on a setter plate and dried, a cathode layer 1 was formed on the upper surface of the electrolyte coating layer 3, thereby forming a metal support plate.
Example 5:
the method for manufacturing a metal support plate for a fuel cell of the present embodiment sequentially includes the steps of:
1) preparing raw materials, wherein 434L stainless steel powder is selected as the material, and the 434L stainless steel powder comprises the following components in percentage by mass: 0.025%, Cr: 17.5%, Mn: 0.8%, Si: 0.6%, Mo: 1.05%, iron: the balance;
2) sieving the powder, wherein the granularity range is 150-200 meshes, and the loose density of the powder is 2.35g/cm 3.
3) The burning bearing plate is a ceramic plate containing 95% of alumina;
4) and (3) sintering: sintering the setter plate with the measuring device at the sintering temperature of 1200 ℃ for 120 minutes in the atmosphere of vacuum recoil of 3 x 104Pa argon gas, putting the powder in the step 2) into an inner hole of a measuring device, and removing redundant powder, wherein the size of the inner hole of the measuring device is 120 x 120mm, and the thickness of the inner hole is 1.2 mm; sintering of the powder in the gauge to form a metal matrixA plate 4, followed by taking out the metal substrate 4;
5) flattening: placing the sintered metal substrate 4 between two flat templates, applying pressure, pressing to a height of 0.65mm, and making the pressed metal substrate have a density of 4.5g/cm3。
6) Wax dipping: and melting polyethylene wax at 120 ℃, putting the metal support plate into the wax melt for 5 minutes, and taking out the metal plate for cooling after the pores are infiltrated with wax. Melted paraffin wax, EVA wax or PP wax may also be used.
7) Preparing an anode layer: the anode slurry is uniformly applied to the upper surface of the cut metal substrate 4 by screen printing or dip coating, and the uncoated lower surface of the metal substrate 4 is placed on a setter plate and dried, thereby forming the anode layer 2 on the upper surface of the metal substrate 4. The anode slurry comprises Sr2-xCaxFe1.5Mo0.5O6-δ(x ═ 0.3), NiO, methyl ethyl ketone, ethanol, triethanolamine, starch, polyvinyl butyral PVB, polyethylene glycol PEG, and glutamic acid PHT.
8) Preparing an electrolyte coating: the prepared electrolyte slurry is uniformly coated on the anode layer 2 by a screen printing or dip coating method, and the uncoated lower surface is placed on a setter plate to be dried and sintered, thereby forming an electrolyte coating 3 on the upper surface of the anode layer 2. The electrolyte slurry comprises Ba (Sr) Ce (Ln) O3Electrolyte, butanone, ethanol, triethanolamine, polyvinyl butyral PVB, polyethylene glycol PEG and glutamic acid PHT.
9) Preparing a cathode layer: sr is2-xCaxFe1.5Mo0.5O6-δ(x ═ 0.3) cathode paste made of a cathode material was uniformly applied on the upper surface of the electrolyte coating layer by screen printing or dip coating method, and after the uncoated lower surface was placed on a setter plate and dried, a cathode layer 1 was formed on the upper surface of the electrolyte coating layer 3, thereby forming a metal support plate.
As can be seen from fig. 5 and 6, the metal support plate has a large number of pores, which ensures good air permeability. The support plate of the present embodiment is about 50% by weight of the conventional metal support plate having the same thickness, and the purpose of weight reduction is achieved.
Example 6:
the method for manufacturing a metal support plate for a fuel cell of the present embodiment sequentially includes the steps of:
1) preparing raw materials, wherein 434L stainless steel powder is selected as the material, and the 434L stainless steel powder comprises the following components in percentage by mass: 0.025%, Cr: 17.5%, Mn: 0.8%, Si: 0.6%, Mo: 1.05%, iron: the balance;
2) sieving the powder, wherein the granularity is 100-150 meshes, and the loose density of the powder is 2.60g/cm3。
3) The burning bearing plate is ceramic containing 95% of alumina, the powder in the step 2) is poured into an inner hole of the measuring device, and redundant powder is removed, wherein the size of the inner hole of the measuring device is 120 x 120mm, and the thickness of the inner hole of the measuring device is 1.2 mm;
4) and (3) sintering: sintering the setter plate with the measuring device at 1250 ℃ for 80 minutes in a vacuum recoil of 1 × 103Pa argon gas, sintering the powder in the measuring device to form a metal substrate 4, and then taking out the metal substrate 4;
5) flattening: placing the sintered metal substrate 4 between rollers of a rolling mill for rolling until the height is 0.68mm and the density after pressing is 4.59g/cm3。
6) Preparing an anode layer: the anode slurry is uniformly applied to the upper surface of the cut metal substrate 4 by screen printing or dip coating, and the uncoated lower surface of the metal substrate 4 is placed on a setter plate and dried, thereby forming the anode layer 2 on the upper surface of the metal substrate 4. The anode slurry comprises Sr2-xCaxFe1.5Mo0.5O6-δ(x ═ 0.3), NiO, methyl ethyl ketone, ethanol, triethanolamine, starch, polyvinyl butyral PVB, polyethylene glycol PEG, and glutamic acid PHT.
7) Preparing an electrolyte coating: the prepared electrolyte slurry is uniformly coated on the anode layer 2 by screen printing or dip coating, and the uncoated lower surface is placed on a setter plate to be dried and sintered, thereby forming an anode layer 2The upper surface is formed with an electrolyte coating 3. The electrolyte slurry comprises Ba (Sr) Ce (Ln) O3Electrolyte, butanone, ethanol, triethanolamine, polyvinyl butyral PVB, polyethylene glycol PEG and glutamic acid PHT.
8) Preparing a cathode layer: sr is2-xCaxFe1.5Mo0.5O6-δ(x ═ 0.3) cathode paste made of a cathode material was uniformly applied on the upper surface of the electrolyte coating layer by screen printing or dip coating method, and after the uncoated lower surface was placed on a setter plate and dried, a cathode layer 1 was formed on the upper surface of the electrolyte coating layer 3, thereby forming a metal support plate.
As can be seen from fig. 7 and 8, the metal support plate has a large number of pores and a low density, and thus can ensure good air permeability. The support plate of the present embodiment is about 50% by weight of the conventional metal support plate having the same thickness, and the purpose of weight reduction is achieved.
Example 7:
the method for manufacturing a metal support plate for a fuel cell of the present embodiment sequentially includes the steps of:
1) preparing raw materials, wherein 434L stainless steel powder is selected as the material, and the 434L stainless steel powder comprises the following components in percentage by mass: 0.025%, Cr: 17.5%, Mn: 0.8%, Si: 0.6%, Mo: 1.05%, iron: the balance;
2) screening the powder, wherein the granularity is 200-325 meshes, and the loose packing density of the powder is 2.42g/cm 3.
3) The burning bearing plate is a ceramic plate containing 95% of alumina, the powder in the step 2) is poured into an inner hole of the measuring device, and redundant powder is removed, wherein the size of the inner hole of the measuring device is 120 x 120mm, and the thickness of the inner hole of the measuring device is 1.2 mm;
4) and (3) sintering: the setter plate with the gauge placed therein was placed in a pusher furnace, sintered at a sintering temperature of 1250 ℃ for 30 minutes in a sintering atmosphere of 80 vol% nitrogen and 20 vol% hydrogen, and the powder in the gauge was sintered to form a metal substrate 4, which was then taken out.
5) Flattening: placing the sintered metal substrate between rollers of a rolling mill for rolling until the height is 0.68mm and the density after pressingIs 4.59g/cm3And cutting the metal substrate 4 material into the required size by laser, a shearing machine or a punch press.
6) Preparing an anode layer: the anode slurry is uniformly applied to the upper surface of the cut metal substrate 4 by screen printing or dip coating, and the uncoated lower surface of the metal substrate 4 is placed on a setter plate and dried, thereby forming the anode layer 2 on the upper surface of the metal substrate 4. The anode slurry comprises Sr2-xCaxFe1.5Mo0.5O6-δ(x ═ 0.3), NiO, methyl ethyl ketone, ethanol, triethanolamine, starch, polyvinyl butyral PVB, polyethylene glycol PEG, and glutamic acid PHT.
7) Preparing an electrolyte coating: the prepared electrolyte slurry is uniformly coated on the anode layer 2 by a screen printing or dip coating method, and the uncoated lower surface is placed on a setter plate to be dried and sintered, thereby forming an electrolyte coating 3 on the upper surface of the anode layer 2. The electrolyte slurry comprises Ba (Sr) Ce (Ln) O3Electrolyte, butanone, ethanol, triethanolamine, polyvinyl butyral PVB, polyethylene glycol PEG and glutamic acid PHT.
8) Preparing a cathode layer: sr is2-xCaxFe1.5Mo0.5O6-δ(x ═ 0.3) cathode paste made of a cathode material was uniformly applied on the upper surface of the electrolyte coating layer by screen printing or dip coating method, and after the uncoated lower surface was placed on a setter plate and dried, a cathode layer 1 was formed on the upper surface of the electrolyte coating layer 3, thereby forming a metal support plate.
Example 8:
the method for manufacturing a metal support plate for a fuel cell of the present embodiment sequentially includes the steps of:
1) preparing raw materials, wherein 430L of stainless steel powder is selected as the material, and the 430L of stainless steel powder comprises the following components in percentage by mass: 0.025%, Cr: 16.8%, Mn: 0.6%, Si: 0.5%, iron: the balance;
2) sieving the powder, wherein the granularity is 100-150 meshes, and the loose density of the powder is 2.45g/cm3。
3) The burning bearing plate is a ceramic plate containing 95% of alumina, the powder in the step 2) is poured into an inner hole of the measuring device, and redundant powder is removed, wherein the size of the inner hole of the measuring device is 120 x 120mm, and the thickness of the inner hole of the measuring device is 1.2 mm;
4) and (3) sintering: and placing the burning bearing plate with the measuring device in a push rod furnace, sintering for 30 minutes at the sintering temperature of 1250 ℃ under the sintering atmosphere of 80 vol% nitrogen and 20 vol% hydrogen, sintering the powder in the measuring device to form the metal substrate 4, and taking out the metal substrate material.
5) Flattening: placing the sintered metal substrate material between rollers of a rolling mill for rolling until the height is 0.68mm and the density after pressing is 4.59g/cm3。
6) Preparing an anode layer: the anode slurry is uniformly applied to the upper surface of the cut metal substrate by screen printing or dip coating, and the uncoated lower surface of the metal substrate is placed on a setter plate and dried, thereby forming the anode layer 2 on the upper surface of the metal substrate. The anode slurry comprises Sr2-xCaxFe1.5Mo0.5O6-δ(x ═ 0.3), NiO, methyl ethyl ketone, ethanol, triethanolamine, starch, polyvinyl butyral PVB, polyethylene glycol PEG, and glutamic acid PHT.
7) Preparing an electrolyte coating: the prepared electrolyte slurry is uniformly coated on the anode layer 2 by a screen printing or dip coating method, and the uncoated lower surface is placed on a setter plate to be dried and sintered, thereby forming an electrolyte coating 3 on the upper surface of the anode layer 2. The electrolyte slurry comprises Ba (Sr) Ce (Ln) O3Electrolyte, butanone, ethanol, triethanolamine, polyvinyl butyral PVB, polyethylene glycol PEG and glutamic acid PHT.
8) Preparing a cathode layer: sr is2-xCaxFe1.5Mo0.5O6-δ(x ═ 0.3) cathode paste made of a cathode material was uniformly applied on the upper surface of the electrolyte coating layer by screen printing or dip coating method, and the uncoated lower surface was placed on a setter plate and dried, thereby forming a cathode layer 1 on the upper surface of the electrolyte coating layer 3, thereby forming a cathode layerTo form a metal support plate.
Example 9:
the method for manufacturing a metal support plate for a fuel cell of the present embodiment sequentially includes the steps of:
1) preparing raw materials, wherein 316L stainless steel powder is selected as the material, and comprises the following components in percentage by mass: 0.03%, Cr: 17.8%, Ni: 12.5%, Mn: 1.2%, Si: 0.8%, Mo: 2.48%, iron: the balance;
2) sieving the powder, wherein the granularity is 200-325 meshes, and the loose density of the powder is 2.45g/cm3。
3) The burning bearing plate is a ceramic plate containing 95% of alumina, the powder in the step 2) is poured into an inner hole of the measuring device, and redundant powder is removed, wherein the size of the inner hole of the measuring device is 120 x 120mm, and the thickness of the inner hole of the measuring device is 1.2 mm;
4) and (3) sintering: placing the burning bearing plate with the measuring device in a vacuum furnace, sintering for 180 minutes at 1180 ℃ in the vacuum back-flushing 1 multiplied by 10 in the sintering atmosphere4Pa argon gas, powder in the measuring device is sintered to form a metal substrate, and then the metal substrate material is taken out;
5) flattening: placing the sintered metal substrate material between rollers of a rolling mill for rolling until the height is 0.68mm and the density after pressing is 4.59g/cm3。
6) Preparing an anode layer: the anode slurry is uniformly applied to the upper surface of the cut metal substrate by screen printing or dip coating, and the uncoated lower surface of the metal substrate is placed on a setter plate and dried, thereby forming the anode layer 2 on the upper surface of the metal substrate. The anode slurry comprises yttria-stabilized zirconia YSZ, NiO, butanone, ethanol, triethanolamine, starch, polyvinyl butyral PVB, polyethylene glycol PEG and glutamic acid PHT.
7) Preparing an electrolyte coating: the prepared electrolyte slurry is uniformly coated on the anode layer 2 by a screen printing or dip coating method, and the uncoated lower surface is placed on a setter plate to be dried and sintered, thereby forming an electrolyte coating 3 on the upper surface of the anode layer 2. The electrolyte slurry comprises yttria-stabilized zirconia electrolyte, butanone, ethanol, triethanolamine, polyvinyl butyral (PVB), polyethylene glycol (PEG) and glutamic acid (PHT).
8) Preparing a cathode layer: sr is2-xCaxFe1.5Mo0.5O6-δ(x ═ 0.1) cathode paste made of a cathode material was uniformly applied on the upper surface of the electrolyte coating layer by screen printing or dip coating method, and the uncoated lower surface was placed on a setter plate and dried, thereby forming a cathode layer 1 on the upper surface of the electrolyte coating layer 3.
Example 10:
the method for manufacturing a metal support plate for a fuel cell of the present embodiment sequentially includes the steps of:
1) preparing raw materials, wherein 316L stainless steel powder is selected as the material, and comprises the following components in percentage by mass: 0.03%, Cr: 17.8%, Ni: 12.5%, Mn: 1.2%, Si: 0.8%, Mo: 2.48%, iron: the balance;
2) sieving the powder, wherein the granularity is 325-1000 meshes, the size is 13-250 um, and the loose density of the powder is 2.25g/cm3。
3) The burning bearing plate is a ceramic plate containing 95% of alumina, the powder in the step 2) is poured into an inner hole of the measuring device, and redundant powder is removed, wherein the size of the inner hole of the measuring device is 120 x 120mm, and the thickness of the inner hole of the measuring device is 1.2 mm;
4) and (3) sintering: placing the burning bearing plate with the measuring device in a vacuum furnace, sintering for 200 minutes at the sintering temperature of 1120 ℃, wherein the sintering atmosphere is vacuum back flushing 1X 103Pa argon gas, powder in the measuring device is sintered to form a metal substrate, and then the metal substrate is taken out.
5) Flattening: placing the sintered metal substrate material between rollers of a rolling mill for rolling until the height is 0.68mm and the density after pressing is 4.59g/cm3。
6) Preparing an anode layer: uniformly coating the anode slurry on the upper surface of the cut metal substrate by screen printing or dip coating method, placing the uncoated lower surface of the metal substrate on a burning plate, and drying to obtain the final productAn anode layer 2 is formed on the surface. The anode slurry comprises Sr2-xCaxFe1.5Mo0.5O6-δ(x ═ 0.3), NiO, methyl ethyl ketone, ethanol, triethanolamine, starch, polyvinyl butyral PVB, polyethylene glycol PEG, and glutamic acid PHT.
7) Preparing an electrolyte coating: the prepared electrolyte slurry is uniformly coated on the anode layer 2 by a screen printing or dip coating method, and the uncoated lower surface is placed on a setter plate to be dried and sintered, thereby forming an electrolyte coating 3 on the upper surface of the anode layer 2. The electrolyte slurry comprises Ba (Sr) Ce (Ln) O3Electrolyte, butanone, ethanol, triethanolamine, polyvinyl butyral PVB, polyethylene glycol PEG and glutamic acid PHT.
8) Preparing a cathode layer: sr is2-xCaxFe1.5Mo0.5O6-δ(x ═ 0.3) cathode paste made of a cathode material was uniformly applied on the upper surface of the electrolyte coating layer by screen printing or dip coating method, and after the uncoated lower surface was placed on a setter plate and dried, a cathode layer 1 was formed on the upper surface of the electrolyte coating layer 3, thereby forming a metal support plate.
Example 11:
the method for manufacturing a metal support plate for a fuel cell of the present embodiment sequentially includes the steps of:
1) preparing raw materials, wherein the raw materials are iron-chromium-aluminum powder, and the iron-chromium-aluminum powder comprises the following components in percentage by mass: c: 0.06%, Cr: 21.1%, Mn: 0.9%, Si: 0.3%, Al: 4.79%, iron: the balance;
2) sieving the powder, wherein the granularity is 325-1000 meshes, the size is 13-250 um, and the loose density of the powder is 2.25g/cm3。
3) The burning bearing plate is ceramic containing 95% of alumina, the powder in the step 2) is poured into an inner hole of the measuring device, and redundant powder is removed, wherein the size of the inner hole of the measuring device is 120 x 120mm, and the thickness of the inner hole of the measuring device is 1.2 mm;
4) and (3) sintering: placing the setter plate with the measuring device in a vacuum furnace, and sintering at 1150 deg.C for 20 deg.CThe sintering atmosphere is vacuum recoil 1X 10 in 0 minute3Pa argon gas, powder in the measuring device is sintered to form a metal substrate, and then the metal substrate is taken out.
5) Flattening: placing the sintered metal substrate material between rollers of a rolling mill for rolling until the height is 0.68mm and the density after pressing is 4.59g/cm3。
6) Preparing an anode layer: the anode slurry is uniformly applied to the upper surface of the cut metal substrate by screen printing or dip coating, and the uncoated lower surface of the metal substrate is placed on a setter plate and dried, thereby forming the anode layer 2 on the upper surface of the metal substrate. The anode slurry comprises Sr2-xCaxFe1.5Mo0.5O6-δ(x ═ 0.3), NiO, methyl ethyl ketone, ethanol, triethanolamine, starch, polyvinyl butyral PVB, polyethylene glycol PEG, and glutamic acid PHT.
7) Preparing an electrolyte coating: the prepared electrolyte slurry is uniformly coated on the anode layer 2 by a screen printing or dip coating method, and the uncoated lower surface is placed on a setter plate to be dried and sintered, thereby forming an electrolyte coating 3 on the upper surface of the anode layer 2. The electrolyte slurry comprises Ba (Sr) Ce (Ln) O3Electrolyte, butanone, ethanol, triethanolamine, polyvinyl butyral PVB, polyethylene glycol PEG and glutamic acid PHT.
8) Preparing a cathode layer: sr is2-xCaxFe1.5Mo0.5O6-δ(x ═ 0.3) cathode paste made of a cathode material was uniformly applied on the upper surface of the electrolyte coating layer by screen printing or dip coating method, and after the uncoated lower surface was placed on a setter plate and dried, a cathode layer 1 was formed on the upper surface of the electrolyte coating layer 3, thereby forming a metal support plate.
Example 12:
this embodiment differs from embodiment 3 described above only in that: 1. the metal fiber felt is different, and specifically comprises the following components in percentage by mass: c: 0.006%, Cr: 10%, Mn: 2%, Si: 1%, Al: 10%, Nb: 2%, Ti: 2%, Ni: 25%, iron: and (4) the balance.
2. The stainless steel is different, specifically, heat-resistant steel is adopted, and comprises the following components in percentage by mass: c: 0.025%, Cr: 30%, Mn: 2%, Mo: 4%, iron: and (4) the balance.
3. The sintering parameters in the step 5) are different, specifically, the sintering temperature is 1050 ℃, and the sintering time is 300 min.
4. The cathode slurry is different, specifically, LSCF ((La, Sr) (Co, Fe) O is adopted3) And (3) preparing cathode slurry.
Example 13:
this embodiment differs from embodiment 3 described above only in that: 1. the metal fiber felt is different, and specifically comprises the following components in percentage by mass: c: 0.006%, Ni: 25%, Cr: 30%, Mo: 4%, Nb: 3%, Al: 5%, Ti: 3%, iron: and (4) the balance.
2. The raw materials in the step 1) are different, and specifically, the sintered stainless steel comprises the following components in percentage by mass: c: 0.025%, Cr: 10%, Si: 1%, Ni: 25%, Nb: 3%, Al: 10%, Ti: 3%, iron: and (4) the balance.
3. The sintering parameters in the step 5) are different, specifically, the sintering temperature is 1400 ℃, and the sintering time is 10 min.
Furthermore, the sintered stainless steel may be replaced with one of a nickel-based alloy, a cobalt-based alloy, a titanium alloy, and a chromium-based alloy.
4. The cathode slurry is different, and specifically, the cathode slurry is prepared from one of composite ceramic and L-shaped ceramic with a perovskite structure.
In addition, the cathode slurry can also adopt LSM (La)1-xSrxMn03) And pyrochlore-structured A2Ru2O 7-x (a ═ Pb, Bi) ceramics, wherein x is 0, 0.1, 0.3, 0.5.
The setter plates of the above embodiments are not easily deformed or cracked when being sintered, heated and cooled. The measuring device in the above embodiment may also be a conventional measuring device with a bottom, the powder in step 2) is poured into the measuring device, the powder higher than the measuring device is removed by a scraper, then the setter plate is covered on the powder measuring device containing the powder, the setter plate, the metal fiber mat and the measuring device are turned over by 180 °, and the powder measuring device is taken out.

Claims (10)

1. A method for manufacturing a metal support plate for a fuel cell, comprising the following steps in sequence:
1) adopting one of sintered stainless steel, heat-resistant steel, nickel-based alloy, cobalt-based alloy, titanium alloy and chromium-based alloy;
2) screening the powder in the step 1), and selecting the powder with the granularity of 13-250 um;
3) placing the powder in an inner hole of a measuring device, removing excessive powder, and placing on a burning bearing plate;
4) sintering the burning bearing plate with the measuring device, forming a metal substrate by the powder in the measuring device, and flattening the metal substrate;
5) coating the anode slurry on the upper surface of the metal substrate, then placing the uncoated lower surface of the metal substrate on a burning bearing plate, and sintering after drying, thereby forming an anode layer on the upper surface of the metal substrate;
6) coating electrolyte slurry on the upper surface of the anode layer, then placing the uncoated lower surface of the metal substrate on a setter plate, and sintering after drying, thereby forming an electrolyte coating on the upper surface of the anode layer;
7) the cathode slurry is coated on the upper surface of the electrolyte coating layer, and then the uncoated lower surface of the metal substrate is laid on a setter plate, dried and then sintered to form a cathode layer on the upper surface of the electrolyte coating layer, thereby manufacturing a metal support plate.
2. The manufacturing method according to claim 1, characterized in that: and (5) performing wax dipping treatment between the step 4) and the step 5), namely putting the metal substrate with the required size into the wax melt for 1-30 min, taking out the metal substrate after the wax melt permeates into the pores in the metal substrate, and cooling.
3. The manufacturing method according to claim 1, characterized in that: in the step 4), a metal fiber felt cutting piece with porosity of more than 50% is laid on the upper surface of the burning bearing plate, a measuring device for placing powder is placed above the metal fiber felt cutting piece, a metal substrate with a double-layer structure is formed after sintering, and the double-layer structure comprises a fiber felt layer and a sintering powder layer which are arranged up and down.
4. The manufacturing method according to claim 3, characterized in that: the metal fiber felt comprises the following components in percentage by mass: carbon: less than or equal to 0.06 percent, nickel: 0-25%, molybdenum: 0-4%, chromium: 10-30%, niobium: 0-3%, aluminum: 0-10%, titanium: 0-3%, silicon: 0-1%, manganese: 0-2%, not more than 2% of unavoidable impurities, iron: and (4) the balance.
5. The manufacturing method according to claim 1, characterized in that: selecting sintered stainless steel in the step 1), wherein the sintered stainless steel comprises the following components in percentage by mass: carbon: less than or equal to 0.06 percent, nickel: 0-25%, molybdenum: 0-4%, chromium: 10-30%, niobium: 0-3%, aluminum: 0-10%, titanium: 0-3%, silicon: 0-1%, manganese: 0-2%, not more than 2% of unavoidable impurities, iron: and (4) the balance.
6. The manufacturing method according to claim 1, characterized in that: in the step 4), the sintering temperature is 1000-1350 ℃, the sintering time is 5-240 min, and the vacuum degree is 10-3Pa～102Pa。
7. The manufacturing method according to claim 1, characterized in that: the sintering temperature in the step 5) is 1050-1400 ℃, the sintering time is 10-300 min, the sintering temperature in the step 6) is 1000-1400 ℃, the sintering time is 10-300 min, the sintering temperature adopted in the sintering in the step 7) is 800-1200 ℃, the sintering time is 5-300 min, and the vacuum degree is 10-3Pa～102Pa。
8. The manufacturing method according to any one of claims 1 to 7, characterized in that: the anode slurry comprises NiO, butanone, ethanol, triethanolamine, starch, polyvinyl butyral (PVB), polyethylene glycol (PEG), glutamic acid (PHT), yttria-stabilized zirconia and Sr2-xCaxFe1.5Mo0.5O6-δ(x is 0, 0.1, 0.3, 0.5).
9. The manufacturing method according to claim 8, characterized in that: the electrolyte slurry comprises butanone, ethanol, triethanolamine, polyvinyl butyral (PVB), polyethylene glycol (PEG), glutamic acid PHT, yttria-stabilized zirconia and LaGaO3A base electrolyte, Ba (Sr) Ce (Ln) O3And CeO2Based on one of the solid electrolytes.
10. The manufacturing method according to claim 9, characterized in that: the cathode slurry is Sr2- xCaxFe1.5Mo0.5O6-δ、LSM(La1-xSrxMn03)、LSCF((La，Sr)(Co，Fe)O3) A of pyrochlore structure2Ru2O7－x(a ═ Pb, Bi) ceramic, Ag-YDB composite ceramic, and perovskite-structured L-type ceramic, wherein x is 0, 0.1, 0.3, or 0.5.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114142046A (en) * 2021-11-22 2022-03-04 东睦新材料集团股份有限公司 Method for manufacturing metal support plate for fuel cell
CN114188561A (en) * 2021-11-22 2022-03-15 东睦新材料集团股份有限公司 Preparation method of metal support plate for fuel cell
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