CN113067004B - Preparation method of metal support plate for fuel cell - Google Patents
Preparation method of metal support plate for fuel cell Download PDFInfo
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- CN113067004B CN113067004B CN202110297131.0A CN202110297131A CN113067004B CN 113067004 B CN113067004 B CN 113067004B CN 202110297131 A CN202110297131 A CN 202110297131A CN 113067004 B CN113067004 B CN 113067004B
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 255
- 239000002184 metal Substances 0.000 title claims abstract description 254
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- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 205
- 239000000758 substrate Substances 0.000 claims abstract description 186
- 239000003792 electrolyte Substances 0.000 claims abstract description 122
- 238000005245 sintering Methods 0.000 claims abstract description 108
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- 239000011651 chromium Substances 0.000 claims abstract description 31
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 52
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- 239000012298 atmosphere Substances 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
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- 229910017060 Fe Cr Inorganic materials 0.000 description 1
- 229910002544 Fe-Cr Inorganic materials 0.000 description 1
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- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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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
- 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 & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Fuel Cell (AREA)
Abstract
The invention relates to a preparation 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 obtained in the step 1); 3) laying powder on the upper surface of a burning board, then spraying a bonding agent onto the powder layer to bond the powder layer, and then continuously and sequentially laying the powder layer and the bonding agent to obtain a metal substrate with the required thickness; 4) 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; 5) coating an electrolyte slurry on an upper surface of the anode layer to form an electrolyte coating on a surface of the anode layer; 6) 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
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to a preparation 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) are support SOFCs that use metals or alloys as fuel cells, which have unique advantages: (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) processability: compared with ceramics, the metal material has better processability, which greatly reduces the processing difficulty of the SOFC; (4) sealing is facilitated: by using the welding sealing technology of the metal material, the problem that the SOFC is difficult to seal can be avoided. The metal support is primarily responsible for gas transport, current conduction, and provides stable structural support for the cell. When the MS-SOFC uses the hydrocarbon fuel, the metal support can be used as an in-situ reforming layer, the hydrocarbon fuel is firstly chemically reformed in the metal support, and the generated synthetic gas is electrochemically oxidized at the anode 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 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 metal support side of a half cell, a cathode layer is printed on the surface of the 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.
The Fe-based alloy and the Ni-based alloy are adopted as the MS-SOFC metal support body, and because the difference between the thermal expansion coefficient of the Ni-based alloy and the thermal expansion coefficient of the electrolyte material is large, the internal thermal stress is overlarge in the operation process of the battery, so that cracks are easy to appear, and even the 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. Fe and Cr element diffusion in support body during MS-SOFC preparation or operationTo the anode, oxides are formed during cell operation, resulting in rapid degradation of cell performance; 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 eliminate sintering deformation to improve bonding tightness between an anode layer and a substrate.
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 particle size of 13-250 μm;
3) placing a sintering plate in a chamber of additive manufacturing equipment, placing the powder sieved in the step 2) in a powder container in the additive manufacturing equipment, then laying the powder in the powder container on the upper surface of the sintering plate, wherein the thickness of the laid powder layer is 0.005-0.3 mm, then spraying a bonding agent on the powder layer so as to bond the powder layers together, then continuously laying the powder layer and the bonding agent on the upper surface of the bonded powder layer in sequence until a metal substrate with the required thickness is obtained, and taking out the metal substrate and the sintering plate;
4) coating the anode slurry on the upper surface of the metal substrate, and then laying the uncoated lower surface of the metal substrate on a setter plate and drying to form an anode layer on the upper surface of the metal substrate;
5) coating an electrolyte slurry on an upper surface of the anode layer, subsequently laying an uncoated lower surface of the metal substrate on a setter plate, and drying to form an electrolyte coating on the upper surface of the anode layer;
6) coating the cathode slurry on the upper surface of the electrolyte coating, and then laying the uncoated lower surface of the metal substrate on a setter plate and drying to form a cathode layer on the upper surface of the electrolyte coating, thereby manufacturing a metal support plate;
step S1 is performed between the above steps 3) and 4) or after step 6), step S1 is to place a metal substrate or a metal support plate of a desired size on a setter plate, then perform a heating process to remove the binder in the metal substrate, and perform sintering after the heating process.
Preferably, the heating treatment is to heat the mixture to 300-700 ℃ and keep the temperature for 5-240 min, or to heat the mixture to 1000 ℃ at a heating rate of 0.5-20 ℃/min. In this way, the adhesive in the metal substrate is released.
Preferably, the sintering temperature in the sintering is 1000-1350 ℃, the sintering time is 5-240 min, and the vacuum degree in the sintering is 10-3Pa～102Pa。
Preferably, when the step S1 is located between the step 3) and the step 4), the sintered metal substrate in the step S1 is subjected to a flattening process. Thus, a relatively flat metal support plate is obtained.
Preferably, the flattened metal substrate is subjected to wax dipping treatment, that is, the metal substrate with the required size is placed in a wax melt for 1-30 min, and the metal substrate is taken out and cooled after the wax melt permeates into pores in the metal substrate. The pores of the metal support plate are reduced by the wax dipping treatment.
There are various ways to realize the metal substrate curing, but preferably, in step 3), the metal substrate and the setter plate are taken out after the metal substrate is cured, wherein the metal substrate is cured by placing the metal substrate for 10-500 min, or by heating the metal substrate to 40-200 ℃.
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 thermal expansion coefficient of the sintered stainless steel is matched with that of the anode, the electrolyte and the like.
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-δWherein x is 0, 0.1, 0.3, 0.5. The material is tightly combined with the metal support plate.
Preferably, the electrolyte slurry comprises butanone, ethanol, triethanolamine, polyvinyl butyral (PVB), polyethylene glycol (PEG), glutamic acid (PHT), yttria-stabilized zirconia and LaGaO3Base 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; during sintering, due to the supporting effect of the sintering bearing plate, the sintering shrinkage of the metal supporting plate is basically close to that of the anode material, the sintering deformation is eliminated, the combination tightness between the anode layer and the metal substrate is improved, and the green body of the supporting plate adopting the additive manufacturing technology has the advantages of higher green body strength, controllable sintering shrinkage and controllable sintering deformation. Compared with a supporting plate using a metal plate, the density is low, the weight is light, and the light weight is favorably realized. In addition, the support plate made of the metal plate needs to be subjected to multiple coating treatments, and the cost is high. 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 the metal-backed plate fuel cell structure of the present embodiment;
FIG. 2 is the pore morphology after sintering in example 1;
FIG. 3 is the pore morphology after sintering in example 2;
FIG. 4 is the pore morphology after sintering in example 7;
FIG. 5 is the pore morphology after sintering in example 8.
Detailed Description
The invention is described in further detail below with reference to the following examples of the drawings.
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: c: 0.025%, Cr: 17.5%, Mn: 0.8%, Si: 0.6%, Mo: 1.05%, iron: the balance;
2) sieving the powder, and selecting the powder with the granularity range of 150-200 meshes, wherein the apparent density of the powder is 2.35g/cm3；
3) The burning board is a ceramic board containing 95% of alumina, the size of the burning board is 140 multiplied by 140mm, and the burning board is not easy to deform and crack during sintering, heating and cooling;
4) placing the setter plate in the step 3) in a chamber of an additive manufacturing device, placing the powder sieved in the step 2) in a powder container in the additive manufacturing device, then laying the powder in the powder container on the upper surface of the setter plate by a powder laying system of the additive manufacturing device, wherein the thickness of the laid powder layer is 0.1mm, then spraying an adhesive onto the powder layer by an adhesive spraying system of the additive manufacturing device, wherein the adhesive is epoxy resin, so that the powder layers are bonded together, and then continuously laying the powder layer and the adhesive on the upper surface of the bonded powder layer in sequence until a metal substrate with a required thickness is obtained, namely forming the metal substrate in a layer-by-layer manner, wherein the size of the metal substrate is 120 x 120mm, the thickness of the metal substrate is 1.0mm, the initial size of the laid powder layer is L1, and the final size of the metal substrate is L2, (L1-L2)/L2 is 1-20%;
5) and (3) curing: placing the metal substrate in the step 4) in a cavity of additive manufacturing equipment for 120min so as to completely cure the metal substrate, and taking out the setter plate and the metal substrate after curing;
6) preparing an anode layer:
uniformly coating the anode slurry on the upper surface of the cut metal substrate 4 by a screen printing or dip coating method, and then laying the uncoated lower surface of the metal substrate 4 on a setter plate, and drying to form an 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;
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 YSZ electrolyte, butanone, ethanol, triethanolamine, polyvinyl butyral (PVB), polyethylene glycol (PEG) and glutamic acid (PHT);
8) preparing a cathode layer: sr is2-xCaxFe1.5Mo0.5O6-δAnd x is 0.1, a cathode paste made of a cathode material is uniformly coated on the upper surface of the electrolyte coating layer by a screen printing or dip coating method, and the uncoated lower surface is dried by being placed on a setter plate, and then dried from the topAnd a cathode layer 1 is formed on the upper surface of the electrolyte coating layer 3, as shown in fig. 1;
9) and (3) sintering: placing a metal support plate with an anode layer, an electrolyte coating and a cathode layer on a sintering plate, and then placing the metal support plate and the cathode layer in a push rod furnace for sintering, wherein the sintering temperature is 1300 ℃, the sintering time is 50min, and the vacuum degree in the push rod furnace is 10-3Pa, recharging 4X 10 to prevent chromium and other elements from evaporating4Pa of argon gas.
The pores of the sintered metal substrate are shown in fig. 2, and as can be seen from fig. 2, the plate manufactured by the additive remains a large number of connected pores and can completely become a support plate. In the embodiment, the metal support plate is prepared by using an additive manufacturing technology, the pores are controllable, the green strength is high, the sintering deformation is similar to that of a powder metallurgy process, the operation is simple, no mold is used, and the manufacturing cost of the support plate is low.
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 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) sieving the above powder, selecting powder with particle size range of-100 mesh +150 mesh, and bulk density of 2.60g/cm3；
3) The setter plate is a ceramic plate containing 95% of alumina, the size of the setter plate is 140 x 140mm, and the setter plate is not easy to deform and crack during sintering, heating and cooling;
4) placing the setter plate in the step 3) in a chamber of an additive manufacturing device, placing the powder sieved in the step 2) in a powder container in the additive manufacturing device, then laying the powder in the powder container on the upper surface of the setter plate through a powder laying system of the additive manufacturing device, wherein the thickness of the laid powder layer is 0.2mm, then spraying an adhesive onto the powder layer by using an adhesive spraying system of the additive manufacturing device, wherein the adhesive is polyvinylpyrrolidone (PVP), so that the powder layers are bonded together, and then continuously laying the powder layer and the adhesive on the upper surface of the bonded powder layer in sequence until a metal substrate with the required thickness is obtained, namely forming the metal substrate in a layer-by-layer mode, wherein the size of the metal substrate is 120 x 120mm, and the thickness of the metal substrate is 0.9 mm;
5) and (3) curing: curing the formed metal substrate and the powder at a heating temperature of 100 ℃ for 30min, and taking out the setter plate and the metal substrate after curing;
6) preparing an anode layer: uniformly coating the anode slurry on the upper surface of the cut metal substrate 4 by a screen printing or dip coating method, and then laying the uncoated lower surface of the metal substrate 4 on a setter plate, and drying to form an 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;
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 YSZ electrolyte, butanone, ethanol, triethanolamine, polyvinyl butyral (PVB), polyethylene glycol (PEG) and glutamic acid (PHT);
8) preparing a cathode layer: sr is2-xCaxFe1.5Mo0.5O6-δAnd x is 0.3, a cathode slurry made of a cathode material is uniformly coated on the upper surface of the electrolyte coating layer by a screen printing or dip coating method, and after the uncoated lower surface is placed on a setter plate and dried, a cathode layer 1 is formed on the upper surface of the electrolyte coating layer 3;
9) and (3) sintering: placing a metal support plate with an anode layer, an electrolyte coating and a cathode layer on a sintering plate, and then placing the metal support plate and the cathode layer in a push rod furnace for sintering, wherein the sintering temperature is 1300 ℃, the sintering time is 50min, and the vacuum degree in the push rod furnace is 10-3Pa, sintering atmosphere is mixed gas of high-purity hydrogen and argon, wherein the volume ratio of argon is 30%, and 4 × 10 is added for preventing chromium and other elements from evaporating4Pa of argon gas.
Referring to fig. 3, it can be seen from fig. 3 that the pores of the sintered metal substrate are still partially connected and can be used as channels for fuel cell gases.
In the embodiment, the metal support plate is prepared by using an additive manufacturing technology, the pores are controllable, the green strength is high, the sintering deformation is similar to that of a powder metallurgy process, the operation is simple, no mold is used, and the manufacturing cost of the support plate is low.
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 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: 17.1%, Mn: 0.8%, Si: 0.6%, iron: the balance;
2) screening the powder, selecting the powder with the granularity range of 325-500 meshes and the loose packing density of 2.20g/cm3；
3) The burning board is a ceramic board containing 95% of alumina, and the size of the burning board is 140 multiplied by 140 mm;
4) placing the sintering plate in the step 3) in a chamber of an additive manufacturing device, placing the powder sieved in the step 2) in a powder container in the additive manufacturing device, then laying the powder in the powder container on the upper surface of the sintering plate by a powder laying system of the additive manufacturing device, wherein the thickness of the laid powder layer is 0.05mm, then spraying a bonding agent onto the powder layer by using a bonding agent spraying system of the additive manufacturing device, wherein the bonding agent is polyacrylamide, so that the powder layers are bonded together, and then continuously laying the powder layer and the bonding agent on the upper surface of the bonded powder layer in sequence until a metal substrate with the required thickness is obtained, namely forming the metal substrate in a layer-by-layer mode, wherein the size of the metal substrate is 120 x 120mm, and the thickness of the metal substrate is 0.7 mm;
5) and (3) curing: curing the formed metal substrate and the powder at a heating temperature of 100 ℃ for 30min, and taking out the setter plate and the metal substrate after curing;
6) preparing an anode layer: uniformly coating the anode slurry on the upper surface of the cut metal substrate 4 by a screen printing or dip coating method, and then laying the uncoated lower surface of the metal substrate 4 on a setter plate, and drying to form an 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;
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 YSZ electrolyte, butanone, ethanol, triethanolamine, polyvinyl butyral (PVB), polyethylene glycol (PEG) and glutamic acid (PHT);
8) preparing a cathode layer: sr2-xCaxFe1.5Mo0.5O6-δAnd x is 0.1, a cathode paste made of a cathode material is uniformly coated on the upper surface of the electrolyte coating layer by a screen printing or dip coating method, and the uncoated lower surface is placed on a setter plate and dried, thereby forming a cathode layer 1 on the upper surface of the electrolyte coating layer 3;
9) and (3) sintering: placing a metal support plate with an anode layer, an electrolyte coating and a cathode layer on a burning bearing plate, and then placing the metal support plate and the burning bearing plate together in a push rod furnace for sintering, wherein the sintering temperature is 1220 ℃, the sintering time is 30min, and the vacuum degree in the push rod furnace is 10-3Pa, the sintering atmosphere is a mixed gas of high-purity hydrogen and argon, wherein the volume ratio of the argon is 30%. Recharging by 4X 10 to prevent chromium and other elements from evaporating4Pa of argon gas.
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 the materials are 316L stainless steel powder: c: 0.03%, Cr: 17.8%, Ni: 12.5%, Mn: 1.2%, Si: 0.8%, Mo: 2.48%, iron: the balance;
2) sieving the powder, and selecting the powder with the granularity range of 200-325 meshes and the loose packed density of 2.30g/cm3。
3) The setter plate is a ceramic plate containing 95% of alumina, and the size of the setter plate is 140X 140 mm.
4) Placing the sintering plate in the step 3) in a chamber of an additive manufacturing device, placing the powder sieved in the step 2) in a powder container in the additive manufacturing device, then laying the powder in the powder container on the upper surface of the sintering plate by a powder laying system of the additive manufacturing device, wherein the thickness of the laid powder layer is 0.05mm, then spraying a bonding agent onto the powder layer by using a bonding agent spraying system of the additive manufacturing device, wherein the bonding agent is polyacrylamide, so that the powder layers are bonded together, and then continuously laying the powder layer and the bonding agent on the upper surface of the bonded powder layer in sequence until a metal substrate with the required thickness is obtained, namely forming the metal substrate in a layer-by-layer mode, wherein the size of the metal substrate is 120 x 120mm, and the thickness of the metal substrate is 1.0 mm;
5) curing the formed metal substrate and the powder at a heating temperature of 70 ℃ for 30min, and taking out the setter plate and the metal substrate after curing;
6) preparing an anode layer: uniformly coating the anode slurry on the upper surface of the cut metal substrate 4 by a screen printing or dip coating method, and then, placing the uncoated lower surface of the metal substrate 4 on a setter plate and drying to form 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;
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 YSZ electrolyte, butanone, ethanol, triethanolamine, polyvinyl butyral (PVB), polyethylene glycol (PEG) and glutamic acid (PHT);
8) preparing a cathode layer: sr is2-xCaxFe1.5Mo0.5O6-δAnd x is 0.5, a cathode paste made of a cathode material is uniformly coated on the upper surface of the electrolyte coating layer by a screen printing or dip coating method, and the uncoated lower surface is placed on a setter plate and dried, thereby forming a cathode layer 1 on the upper surface of the electrolyte coating layer 3;
9) and (3) sintering: placing a metal support plate with an anode layer, an electrolyte coating and a cathode layer on a firing plate, placing the metal support plate and the firing plate together in a push rod furnace for sintering, wherein the sintering temperature is 1220 ℃, the sintering time is 30min, and the vacuum degree in the push rod furnace is 10-3Pa, sintering atmosphere is mixed gas of high-purity hydrogen and argon, wherein the volume ratio of argon is 30%, and in order to prevent elements such as chromium from evaporating, back filling is carried out for 4 multiplied by 104Pa of argon gas.
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 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, selecting the powder with the granularity range of 400 meshes to 1000 meshes and the loose packing density of the powder of 2.05g/cm3；
3) The burning board is a ceramic board containing 95% of alumina, and the size of the burning board is 140 multiplied by 140 mm;
4) placing the setter plate in the step 3) in a chamber of an additive manufacturing device, placing the powder sieved in the step 2) in a powder container in the additive manufacturing device, then laying the powder in the powder container on the upper surface of the setter plate through a powder laying system of the additive manufacturing device, wherein the thickness of the laid powder layer is 0.08mm, then spraying a bonding agent onto the powder layer by using a bonding agent spraying system of the additive manufacturing device so as to bond the powder layers together, and then continuously laying the powder layer and the bonding agent on the upper surface of the bonded powder layer in sequence until a metal substrate with the required thickness is obtained, namely forming the metal substrate in a layer-by-layer mode, wherein the size of the metal substrate is 120 x 120mm, and the thickness of the metal substrate is 1.0 mm;
5) and (3) curing: placing the metal substrate obtained in the step 4) in a cavity of additive manufacturing equipment for 120min so as to completely cure the metal substrate, and taking out the setter plate and the metal substrate after curing is finished; in addition, in order to improve the manufacturing efficiency, the metal substrate may be separately removed for curing.
6) Preparing an anode layer: uniformly coating the anode slurry on the upper surface of the cut metal substrate 4 by a screen printing or dip coating method, and then, placing the uncoated lower surface of the metal substrate 4 on a setter plate and drying to form 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;
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 YSZ electrolyte, butanone, ethanol, triethanolamine, polyvinyl butyral (PVB), polyethylene glycol (PEG) and glutamic acid (PHT);
8) preparing a cathode layer: sr is2-xCaxFe1.5Mo0.5O6-δAnd x is 0.1, a cathode paste made of a cathode material is uniformly coated on the upper surface of the electrolyte coating layer by a screen printing or dip coating method, and the uncoated lower surface is dried by being placed on a setter plate so as to be on the upper surface of the electrolyte coating layer 3A cathode layer 1 is formed on the surface;
9) and (3) sintering: placing a metal support plate with an anode layer, an electrolyte coating and a cathode layer on a sintering plate, and then placing the metal support plate and the cathode layer in a push rod furnace for sintering, wherein the sintering temperature is 1250 ℃, the sintering time is 50min, and the vacuum degree in the push rod furnace is 10-3Pa, recharging 4X 10 to prevent chromium and other elements from evaporating4Pa of argon gas.
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 the raw materials are iron-chromium-aluminum powder, and the iron-chromium-aluminum 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) screening the powder, selecting the powder with the granularity range of 200-325 meshes and the loose packing density of 2.35g/cm3；
3) The setter plate is a ceramic plate containing 95% of alumina, and the size of the setter plate is 140 multiplied by 140 mm;
4) placing the setter plate in the step 3) in a chamber of an additive manufacturing device, placing the powder sieved in the step 2) in a powder container in the additive manufacturing device, then laying the powder in the powder container on the upper surface of the setter plate through a powder laying system of the additive manufacturing device, wherein the thickness of the laid powder layer is 0.15mm, then spraying a bonding agent onto the powder layer by using a bonding agent spraying system of the additive manufacturing device so as to bond the powder layers together, and then continuously laying the powder layer and the bonding agent on the upper surface of the bonded powder layer in sequence until a metal substrate with the required thickness is obtained, namely forming the metal substrate in a layer-by-layer mode, wherein the size of the metal substrate is 120 x 120mm, and the thickness of the metal substrate is 1.2 mm;
5) and (3) curing: curing the formed metal substrate and the powder at a heating temperature of 100 ℃ for 30min, and taking out the setter plate and the metal substrate after curing;
6) preparing an anode layer: the anode slurry is prepared by screen printing or dippingThe coating method is uniformly applied on the upper surface of the cut metal substrate 4, and then the uncoated lower surface of the metal substrate 4 is laid 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;
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 YSZ electrolyte, butanone, ethanol, triethanolamine, polyvinyl butyral (PVB), polyethylene glycol (PEG) and glutamic acid (PHT);
8) preparing a cathode layer: LSCF ((La, Sr) (Co, Fe) O3) The prepared cathode slurry is uniformly coated on the upper surface of the electrolyte coating by a screen printing or dip coating method, and the uncoated lower surface is placed on a burning board for drying, so that a cathode layer 1 is formed on the upper surface of the electrolyte coating 3;
9) and (3) sintering: placing a metal support plate with an anode layer, an electrolyte coating and a cathode layer on a sintering plate, and then placing the metal support plate and the cathode layer in a push rod furnace for sintering, wherein the sintering temperature is 1300 ℃, the sintering time is 50min, and the vacuum degree in the push rod furnace is 10-3Pa, recharging 4X 10 to prevent chromium and other elements from evaporating4Pa of argon gas.
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 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) sieving the above powder, and selectingTaking powder with the granularity range of 150 meshes to 200 meshes and the loose packing density of the powder of 2.35g/cm3。
3) The setter plate is a ceramic plate containing 95% of alumina, and the size of the setter plate is 140 multiplied by 140 mm;
4) placing the burning board in the step 3) in a chamber of an additive manufacturing device, placing the powder sieved in the step 2) in a powder container in the additive manufacturing device, then laying the powder in the powder container on the upper surface of the burning board through a powder laying system of the additive manufacturing device, wherein the thickness of the laid powder layer is 0.1mm, then spraying a bonding agent onto the powder layer by using a bonding agent spraying system of the additive manufacturing device, wherein the bonding agent is polyvinyl alcohol, so that the powder layers are bonded together, and then continuously laying the powder layer and the bonding agent on the upper surface of the bonded powder layer in sequence until a metal substrate with the required thickness is obtained, namely forming the metal substrate in a layer-by-layer mode, wherein the size of the metal substrate is 120 x 120mm, and the thickness of the metal substrate is 1.0 mm;
5) placing the metal substrate obtained in the step 4) in a cavity of additive manufacturing equipment for 120min so as to completely cure the metal substrate, and taking out the setter plate and the metal substrate after curing is finished;
6) and (3) sintering: placing a metal support plate with an anode layer, an electrolyte coating and a cathode layer on a sintering plate, and then placing the metal support plate and the cathode layer together in a push rod furnace for sintering, wherein the sintering temperature is 1250 ℃, the sintering time is 50min, and the vacuum degree in the push rod furnace is 10-3Pa, recharging 4X 10 to prevent chromium and other elements from evaporating4Pa of argon gas. In addition, in order to remove the binder from the metal substrate, a heat treatment, specifically, heating to a temperature of 500 ℃ for 100min, was performed before sintering.
The sintered pores are shown in fig. 4, and the porosity is about 30%, which can meet the requirement of the electrochemical reaction of the gas through the support plate.
7) Preparing an anode layer:
the anode slurry is uniformly applied on the upper surface of the cut metal substrate 4 by screen printing or dip coating, and then the uncoated lower surface of the metal substrate 4 is laid on a setter plateDrying is performed to form the anode layer 2 on the upper surface of the metal substrate 4; the anode slurry comprises Sr2-xCaxFe1.5Mo0.5O6-δ(x ═ 0.1), 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 YSZ electrolyte, butanone, ethanol, triethanolamine, polyvinyl butyral (PVB), polyethylene glycol (PEG) and glutamic acid (PHT);
9) preparing a cathode layer: a cathode paste made of Ag-YDB composite ceramic is uniformly applied on the upper surface of the electrolyte coating layer by screen printing or dip coating, and the uncoated lower surface is placed on a setter plate and dried, thereby forming a cathode layer 1 on the upper surface of the electrolyte coating layer 3.
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 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) sieving the powder, selecting the powder with the granularity range of 100 meshes-150 meshes and the loose packing density of 2.60g/cm3。
3) The setter plate is a ceramic plate containing 95% of alumina, and the size of the setter plate is 140 multiplied by 140 mm;
4) placing the burning board in the step 3) in a chamber of an additive manufacturing device, placing the powder sieved in the step 2) in a powder container in the additive manufacturing device, then laying the powder in the powder container on the upper surface of the burning board through a powder laying system of the additive manufacturing device, wherein the thickness of the laid powder layer is 0.2mm, then spraying a bonding agent onto the powder layer by using a bonding agent spraying system of the additive manufacturing device, wherein the bonding agent is furan resin, so that the powder layers are bonded together, and then continuously laying the powder layer and the bonding agent on the upper surface of the bonded powder layer in sequence until a metal substrate with the required thickness is obtained, namely forming the metal substrate in a layer-by-layer mode, wherein the size of the metal substrate is 120 x 120mm, and the thickness of the metal substrate is 0.9 mm;
5) curing the formed metal substrate and the powder at a heating temperature of 100 ℃ for 30min, and taking out the setter plate and the metal substrate after curing;
6) and (3) sintering: the setter plate with the powder rolled green compact placed therein is placed in a pusher furnace to be sintered. The sintering temperature is 1300 ℃, and the sintering time is 30 minutes. The sintering atmosphere is a mixed gas of high-purity hydrogen and argon, wherein the volume ratio of the argon is 30%. The sintered pores have a porosity of about 40% as shown in fig. 5, and can fully satisfy the requirement of the electrochemical reaction of the gas passing through the support plate.
7) Preparing an anode layer:
uniformly coating the anode slurry on the upper surface of the cut metal substrate 4 by a screen printing or dip coating method, and then laying the uncoated lower surface of the metal substrate 4 on a setter plate, and drying to form an anode layer 2 on the upper surface of the metal substrate 4; the anode slurry comprises Sr2-xCaxFe1.5Mo0.5O6-δ(x ═ 0.3) Z, 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 YSZ electrolyte, butanone, ethanol, triethanolamine, polyvinyl butyral (PVB), polyethylene glycol (PEG) and glutamic acid (PHT);
9) preparing a cathode layer: a cathode paste made of L-type ceramic having a perovskite structure is uniformly applied on the upper surface of the electrolyte coating layer by screen printing or dip coating, and the uncoated lower surface is placed on a setter plate and dried, thereby forming a cathode layer 1 on the upper surface of the electrolyte coating layer 3.
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 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: 17.1%, Mn: 0.8%, Si: 0.6%, iron: the balance;
2) screening the powder, selecting the powder with the granularity range of 325-500 meshes and the loose packing density of 2.20g/cm3。
3) The setter plate is a ceramic plate containing 95% of alumina, and the size of the setter plate is 140 multiplied by 140 mm;
4) placing the sintering plate in the step 3) in a chamber of an additive manufacturing device, placing the powder sieved in the step 2) in a powder container in the additive manufacturing device, then laying the powder in the powder container on the upper surface of the sintering plate by a powder laying system of the additive manufacturing device, wherein the thickness of the laid powder layer is 0.05mm, then spraying a bonding agent onto the powder layer by using a bonding agent spraying system of the additive manufacturing device, wherein the bonding agent is furan resin, so that the powder layers are bonded together, and then continuously laying the powder layer and the bonding agent on the upper surface of the bonded powder layer in sequence until a metal substrate with the required thickness is obtained, namely forming the metal substrate in a layer-by-layer mode, wherein the size of the metal substrate is 120 x 120mm, and the thickness of the metal substrate is 0.7 mm;
5) curing the formed metal substrate and the powder at a heating temperature of 100 ℃ for 30min, and taking out the setter plate and the metal substrate after curing;
6) and (3) sintering: the setter plate with the powder rolled green compact placed therein is placed in a pusher furnace to be sintered. The sintering temperature is 1300 ℃, and the sintering time is 30 minutes. The sintering protective atmosphere is a mixed gas of high-purity hydrogen and argon, wherein the volume ratio of the argon is 30%;
7) preparing an anode layer:
uniformly coating the anode slurry on the upper surface of the cut metal substrate 4 by a screen printing or dip coating method, and then laying the uncoated lower surface of the metal substrate 4 on a setter plate, and drying to form an 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, 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 YSZ electrolyte, butanone, ethanol, triethanolamine, polyvinyl butyral (PVB), polyethylene glycol (PEG) and glutamic acid (PHT);
9) preparing a cathode layer: a is to be2Ru2O7－xA cathode paste made of (a ═ Pb, Bi) (x ═ 0) was uniformly applied on the upper surface of the electrolyte coating layer by screen printing or dip coating, 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 the materials are 316L stainless steel powder, and the 316L stainless steel comprises the following components in percentage by mass: c: 0.03%, Cr: 17.8%, Ni: 12.5%, Mn: 1.2%, Si: 0.8%, Mo: 2.48%, iron: the balance;
2) screening the powder, and selecting the powder with the granularity range of 200-325 meshesBulk density of powder 2.30g/cm3；
3) The setter plate is a ceramic plate containing 95% of alumina, and the size of the setter plate is 140 multiplied by 140 mm;
4) placing the burning board in the step 3) into a chamber of an additive manufacturing device, placing the powder sieved in the step 2) into a powder container in the additive manufacturing device, then laying the powder in the powder container on the upper surface of the burning board through a powder laying system of the additive manufacturing device, wherein the thickness of the laid powder layer is 0.05mm, then spraying a bonding agent onto the powder layer by using a bonding agent spraying system of the additive manufacturing device so as to bond the powder layers together, and then continuously and sequentially laying the powder layer and the bonding agent on the upper surface of the bonded powder layer until a metal substrate with the required thickness is obtained, namely forming the metal substrate in a layer-by-layer mode, wherein the size of the metal substrate is 120 x 120mm, and the thickness of the metal substrate is 1.0 mm;
5) curing the formed metal substrate and the powder at a heating temperature of 70 ℃ for 30min, and taking out the setter plate and the metal substrate after curing;
6) and (3) sintering: placing the burning bearing plate with the metal substrate into a push rod furnace for sintering, wherein the sintering temperature is 1220 ℃, the sintering time is 30 minutes, and the vacuum degree is 10-3Pa, sintering atmosphere is mixed gas of high-purity hydrogen and argon, wherein the volume ratio of the argon is 30%;
7) preparing an anode layer:
uniformly coating the anode slurry on the upper surface of the cut metal substrate 4 by a screen printing or dip coating method, and then laying the uncoated lower surface of the metal substrate 4 on a setter plate, and drying to form an 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 paste is uniformly coated on the anode layer 2 by screen printing or dip coating, and the uncoated lower surface is coatedAnd 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 LaGaO3Base electrolyte, butanone, ethanol, triethanolamine, polyvinyl butyral (PVB), polyethylene glycol (PEG) and glutamic acid (PHT);
9) preparing a cathode layer: a is to be2Ru2O7－xA cathode paste made of a cathode material (a ═ Pb, Bi) (x ═ 0.5) was uniformly applied to the upper surface of the electrolyte coating layer by screen printing or dip coating, 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 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, selecting the powder with the granularity range of 400 meshes to 1000 meshes and the loose packing density of the powder of 2.05g/cm3；
3) The setter plate is a ceramic plate containing 95% of alumina, and the size of the setter plate is 140 multiplied by 140 mm;
4) placing the setter plate in the step 3) in a chamber of an additive manufacturing device, placing the powder sieved in the step 2) in a powder container in the additive manufacturing device, then laying the powder in the powder container on the upper surface of the setter plate through a powder laying system of the additive manufacturing device, wherein the thickness of the laid powder layer is 0.08mm, then spraying a bonding agent onto the powder layer by using a bonding agent spraying system of the additive manufacturing device so as to bond the powder layers together, and then continuously laying the powder layer and the bonding agent on the upper surface of the bonded powder layer in sequence until a metal substrate with the required thickness is obtained, namely forming the metal substrate in a layer-by-layer mode, wherein the size of the metal substrate is 120 x 120mm, and the thickness of the metal substrate is 1.0 mm;
5) placing the metal substrate obtained in the step 4) in a cavity of additive manufacturing equipment for 120min so as to completely cure the metal substrate, and taking out the setter plate and the metal substrate after curing is finished;
6) and (3) sintering: placing the burning bearing plate with the metal substrate in a push rod furnace, heating to 1000 ℃ at a heating rate of 10 ℃/min, removing the adhesive in the metal substrate, and then sintering at 1250 ℃ for 50 minutes at a vacuum degree of 10-3Pa, sintering atmosphere is a mixed gas of high-purity hydrogen and argon, wherein the volume ratio of the argon is 30%;
7) preparing an anode layer:
uniformly coating the anode slurry on the upper surface of the cut metal substrate 4 by a screen printing or dip coating method, and then laying the uncoated lower surface of the metal substrate 4 on a setter plate, and drying to form an anode layer 2 on the upper surface of the metal substrate 4; the anode slurry comprises CeO2The electrolyte comprises a base solid electrolyte, 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 Ba (Sr) Ce (Ln) O3Electrolyte, butanone, ethanol, triethanolamine, polyvinyl butyral PVB, polyethylene glycol PEG and glutamic acid PHT;
9) preparing a cathode layer: a is to be2Ru2O7－xA cathode paste made of (a ═ Pb, Bi) (x ═ 0.3) was uniformly applied on the upper surface of the electrolyte coating layer by screen printing or dip coating, 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 12:
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, selecting the powder with the granularity range of 200 meshes to 325 meshes, wherein the loose density of the powder is 2.35g/cm3；
3) The setter plates were ceramic plates containing 95% alumina, and the size of the setter plates was 140X 140 mm.
4) Placing the burning board in the step 3) into a chamber of an additive manufacturing device, placing the powder sieved in the step 2) into a powder container in the additive manufacturing device, then laying the powder in the powder container on the upper surface of the burning board through a powder laying system of the additive manufacturing device, wherein the thickness of the laid powder layer is 0.15mm, then spraying a bonding agent onto the powder layer by using a bonding agent spraying system of the additive manufacturing device so as to bond the powder layers together, and then continuously and sequentially laying the powder layer and the bonding agent on the upper surface of the bonded powder layer until a metal substrate with the required thickness is obtained, namely forming the metal substrate in a layer-by-layer mode, wherein the size of the metal substrate is 120 x 120mm, and the thickness of the metal substrate is 1.2 mm;
5) placing the metal substrate in the step 4) in a cavity of additive manufacturing equipment for 120min so as to completely cure the metal substrate, and taking out the setter plate and the metal substrate after curing;
6) placing the burning bearing plate with the metal substrate in a push rod furnace, heating to 1000 ℃ at a heating rate of 0.5 ℃/min, and then sintering at 1300 ℃ for 50 minutes under a vacuum degree of 10-3Pa, sintering atmosphere is a mixed gas of high-purity hydrogen and argon, wherein the volume ratio of the argon is 30%;
7) preparing an anode layer:
uniformly coating the anode slurry on the upper surface of the cut metal substrate 4 by a screen printing or dip coating method, and then laying the uncoated lower surface of the metal substrate 4 on a setter plate, and drying to form an 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 LaGaO3Base electrolyte, butanone, ethanol, triethanolamine, polyvinyl butyral (PVB), polyethylene glycol (PEG) and glutamic acid (PHT);
9) preparing a cathode layer: a is to be2Ru2O7－xA cathode paste made of (a ═ Pb, Bi) (x ═ 0.1) ceramic was uniformly applied on the upper surface of the electrolyte coating layer by screen printing or dip coating, 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 13:
this embodiment differs from embodiment 7 described above only in that: 1. the raw materials adopted in the step 1) are different, and specifically, the sintered stainless steel comprises the following components in percentage by mass: c: 0.025%, Ni: 25%, Cr: 10%, Si: 1%, Nb: 3%, Al: 10%, Ti: 3%, iron: and (4) the balance.
2. The thickness of the powder layer laid in the step 3) is 0.005 mm; the standing time in the step 5) is 500 min; 3. And step 6) differently, specifically, placing the metal substrate on a burning bearing plate, then carrying out heating treatment for removing the adhesive in the metal substrate, carrying out heat preservation for 120min when the temperature is increased to 300 ℃, sintering after the heating treatment, wherein the sintering temperature is 1050 ℃, the sintering time is 300min, then carrying out flattening treatment on the sintered metal substrate, carrying out wax dipping treatment on the flattened metal substrate, namely placing the metal substrate with the required size into wax melt for 1-30 min, and taking out the metal substrate after the wax melt permeates into pores in the metal substrate and cooling.
Example 14:
this embodiment differs from embodiment 13 described above only in that:
step 6) is different, specifically, the metal substrate is placed on a burning bearing plate, then heating treatment for removing the adhesive in the metal substrate is carried out, the temperature is kept for 5min after the metal substrate is heated to 700 ℃, sintering is carried out after the heating treatment, the sintering temperature is 1050 ℃, the sintering time is 300min, and the vacuum degree is 10.
Example 15:
this embodiment differs from embodiment 13 described above only in that:
step 6) is different, specifically, the metal substrate is placed on a burning bearing plate, then heating treatment for removing the adhesive in the metal substrate is carried out, the temperature is kept for 240min after the metal substrate is heated to 500 ℃, and sintering is carried out after the heating treatment, wherein the sintering temperature is 1050 ℃, the sintering time is 300min, and the vacuum degree is 102Pa, recharging 10 to prevent chromium and other elements from evaporating2Pa of argon gas.
Example 16:
this embodiment differs from embodiment 7 described above only in that: 1. the raw materials adopted in the step 1) are different, and specifically, the heat-resistant steel is adopted and comprises the following components in percentage by mass: c: 0.025%, Mo: 4%, Cr: 30%, Nb: 1%, Ti: 2%, Mn: 2%, Al: 2%, iron: and the balance.
2. The thickness of the powder layer laid in the step 3) is 0.3 mm; the standing time in the step 5) is 10 min;
3. and 6) differently, specifically, placing the setter plate with the metal substrate in a push rod furnace, heating to 1000 ℃ at the heating rate of 20 ℃/min in the step 6), and then sintering, wherein the sintering temperature is 1400 ℃ and the sintering time is 10 min. For preventing chromium and other elements from evaporating, recharging by 5X 104Argon gas at Pa.
Example 17:
this embodiment differs from embodiment 6 described above only in that: the heating temperature in the step 5) is 200 ℃; a heating temperature of 40 c may also be used.
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. In the above embodiment, the 100-1000 mesh is equivalent to 13-150 μm, and the protective atmosphere for sintering in the above embodiment may be a mixed gas containing 1-90 vol% of hydrogen based on nitrogen, or a mixed gas containing 1-90 vol% of hydrogen based on argon.
Claims (8)
1. A method for manufacturing a metal support plate for a fuel cell, comprising the following steps in sequence:
1) one powder of sintered stainless steel, heat-resistant steel, nickel-based alloy, cobalt-based alloy, titanium alloy and chromium-based alloy is used as a raw material;
2) screening the powder in the step 1), and selecting the powder with the particle size of 13-250 μm;
3) placing a burning board in a cavity of the additive manufacturing equipment, placing the powder sieved in the step 2) in a powder container in the additive manufacturing equipment, then paving the powder in the powder container on the upper surface of the burning board, wherein the thickness of the paved powder layer is 0.005-0.3 mm, then spraying a binder on the powder layer so as to bond the powder layers together, then continuously paving the powder layer and the binder on the upper surface of the bonded powder layer in sequence until a metal substrate with the required thickness is obtained, and taking out the metal substrate and the burning board;
in the step 3), after the metal substrate is solidified, taking out the metal substrate and the burning plate, wherein the metal substrate is solidified by placing the metal substrate for 10-500 min, or the metal substrate is solidified by heating the metal substrate to 40-200 ℃;
4) coating the anode slurry on the upper surface of the metal substrate, and then placing the uncoated lower surface of the metal substrate on a setter plate and drying to form an anode layer on the upper surface of the metal substrate;
5) coating an electrolyte slurry on an upper surface of the anode layer, and subsequently laying an uncoated lower surface of the metal substrate on a setter plate and drying to form an electrolyte coating on the upper surface of the anode layer;
6) coating the cathode slurry on the upper surface of the electrolyte coating, and then laying the uncoated lower surface of the metal substrate on a setter plate and drying to form a cathode layer on the upper surface of the electrolyte coating, thereby manufacturing a metal support plate;
and step S1 is carried out between the step 3) and the step 4) or after the step 6), wherein the step S1 is to place the metal substrate or the metal support plate with the required size on the setter plate, and then carry out heating treatment for removing the binder in the metal substrate, wherein the heating treatment is to heat the metal substrate to 300-700 ℃ for 5-240 min or raise the temperature to 1000 ℃ at the temperature raising speed of 0.5-20 ℃/min and then sinter the metal substrate or the metal support plate after the heating treatment.
2. The production method according to claim 1, characterized in that: the sintering temperature in the sintering is 1000-1350 ℃, the sintering time is 5-240 min, and the vacuum degree in the sintering is 10-3Pa～102Pa。
3. The production method according to claim 2, characterized in that: when step S1 is located between step 3) and step 4), the sintered metal substrate in step S1 is subjected to a flattening process.
4. The production method according to claim 3, characterized in that: and (3) carrying out wax dipping treatment on the flattened metal substrate, namely putting the metal substrate with the required size into a wax melt for 1-30 min, taking out the metal substrate after the wax melt permeates into pores in the metal substrate, and cooling.
5. The method of claim 1, wherein: 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 to 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 the balance.
6. The production method according to any one of claims 1 to 5, 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−δWherein x =0, 0.1, 0.3, 0.5.
7. The method of manufacturing according to claim 6, 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 CeO2A base solid electrolyte.
8. The method of claim 7, wherein: the cathode slurry is Sr2-xCaxFe1.5Mo0.5O6−δ、LSM（La1-xSrxMn03）、LSCF（(La，Sr)(Co，Fe)O3) A of pyrochlore structure2Ru2O7－xOne of (a = Pb, Bi) ceramic, Ag-YDB composite ceramic, and perovskite-structured L-type ceramic, the aforementioned x =0, 0.1, 0.3, 0.5.
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| US10236528B2 (en) * | 2016-07-18 | 2019-03-19 | Northwestern University | Three dimensional extrusion printed electrochemical devices |
| CN112242546B (en) * | 2020-10-16 | 2021-10-01 | 广东省科学院新材料研究所 | Metal-supported self-sealing solid oxide fuel cells/electrolyzers and stacks based on additive manufacturing |
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| JPH0835287A (en) * | 1994-07-21 | 1996-02-06 | Inax Corp | Panel and manufacturing thereof |
| CN105355947A (en) * | 2015-11-25 | 2016-02-24 | 山东理工大学 | Method for three-dimensionally printing honeycomb-type solid oxide fuel cell with three-dimensional channel |
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