CN113067005A - Preparation method of metal support plate for fuel cell - Google Patents

Preparation method of metal support plate for fuel cell Download PDF

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Publication number
CN113067005A
CN113067005A CN202110297132.5A CN202110297132A CN113067005A CN 113067005 A CN113067005 A CN 113067005A CN 202110297132 A CN202110297132 A CN 202110297132A CN 113067005 A CN113067005 A CN 113067005A
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sintering
metal
powder
percent
metal substrate
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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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Publication of CN113067005A publication Critical patent/CN113067005A/en
Priority to PCT/CN2021/108851 priority patent/WO2022193524A1/en
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/10Fuel cells with solid electrolytes
    • H01M8/1004Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/02Details
    • H01M8/0202Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023Porous and characterised by the material
    • H01M8/0232Metals or alloys
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/02Details
    • H01M8/0202Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023Porous and characterised by the material
    • H01M8/0241Composites
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells

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  • Life Sciences & Earth Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Fuel Cell (AREA)
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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) mixing the powder obtained in the step 2) with a forming agent to obtain powder of semi-solid metal fluid; 4) putting the powder obtained in the step 3) into a rolling mill for rolling to form a metal substrate; 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

Preparation method of metal support plate for fuel cell
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 compared to support SOFCs (as shown in fig. 1) where metals or alloys are used as fuel cells, MS-SOFCs have their 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) 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 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 alloy and Ni-based alloyAs the MS-SOFC metal support body, the difference between the thermal expansion coefficient of the Ni-based alloy and the thermal expansion coefficient of the electrolyte material is large, so that cracks are easy to appear and even the electrolyte layer is peeled off due to overlarge internal thermal stress in the operation process of the battery; 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 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) mixing the powder obtained in the step 2) with a forming agent, wherein the powder accounts for 92-95% and the forming agent accounts for 5-8% by mass percent, and uniformly mixing to obtain solid metal fluid powder;
4) putting the powder obtained in the step 3) into a rolling mill for rolling so as to form a metal substrate;
5) 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;
6) 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;
7) 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;
the sintering process is carried out between step 4) and step 5) or, alternatively, after step 7).
Preferably, the sintering treatment is to place the metal substrate or the metal support plate with the required size on a sintering bearing plate for sintering, wherein the sintering temperature is 1000-1350 ℃, the sintering time is 5-240 min, and the vacuum degree is 10-3Pa~102Pa. The sintered metal support has high strength, and the anode and the metal support are tightly combined. The anode, the electrolyte and the cathode are sintered together, so that the production efficiency can be improved, the production cost can be reduced, and the bonding state of three interfaces of the metal support plate-the anode-the electrolyte-the cathode can be improved.
Preferably, when the sintering treatment is performed between the step 4) and the step 5), flattening the sintered metal substrate, and then performing wax dipping treatment on the flattened metal substrate, namely, putting the metal substrate with the required size into the wax melt for 1-30 min, and taking out the metal substrate and cooling after the wax melt permeates into the pores in the metal substrate. So obtain comparatively level and smooth metal support plate, and through the wax dipping processing, reduce the hole of metal support plate.
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: < 0.03%, 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.
The components of the forming agent have various forms, but preferably, the components of the forming agent in the step 2) comprise the following components in percentage by mass: paraffin wax: 40-60%; microcrystalline wax: 20-30%; castor oil: 0.5-20%; polyethylene wax: 5-15%; EVA wax: 5-15%; stearic acid: 1 to 2 percent. This combined former is easy to remove during dewaxing of the sinter and the green strength of the support plate is high.
Specifically, sintering is carried out after drying in the step 5), the step 6) and the step 7), sintering temperature adopted in the sintering in the step 5) and the sintering in the step 6) is 1050-1400 ℃, sintering time is 10-300 min, sintering temperature adopted in the sintering in the step 7) is 800-1200 ℃, sintering time is 5-300 min, and vacuum degree is 10-3Pa~102Pa。
Preferably, in step 4), the metal fiber felt with the porosity of more than 50% is also added into the rolling mill, and the metal fiber felt and the powder are rolled into the metal substrate. The porosity of the metal fiber felt is large, part of metal powder particles can enter pores of the fibers during rolling, the structure of the fibers can be changed, meanwhile, the strength of the sintered fiber felt is high, and the strength of the metal support plate can be improved.
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 fiber felt of the material is similar to the stainless steel powder material, and is beneficial to improving the strength of the metal support body, especially the high-temperature strength.
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. Is beneficial to the generation of battery generalization.
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; 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, so that the sintering deformation is eliminated, and the bonding tightness between the anode layer and the metal substrate is improved. The powder of the forming agent is adopted for rolling, so that the green strength is higher, the sintering shrinkage is controllable, 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. 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 a metal-backed plate fuel cell construction;
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;
FIG. 6 is the pore morphology after sintering in example 13;
FIG. 7 is the pore morphology after sintering in example 14.
Detailed Description
The invention is described in further detail below with reference to the accompanying examples.
Example 1:
the method for manufacturing a metal support plate for a fuel cell of the present embodiment sequentially includes the steps of:
1) 434L stainless steel powder is selected, and the 434L stainless steel powder 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 powder, wherein the granularity is 325-500 meshes, and the loose density of the powder is 2.25g/cm3(ii) a Wherein the granularity range of 60 meshes to 1000 meshes is 13 to 250 mu m;
3) mixing materials: mixing the powder obtained in the step 2) with a forming agent, wherein the forming agent comprises the following components in percentage by mass: 50 percent; microcrystalline wax: 25 percent; castor oil: 10 percent; polyethylene wax: 5 percent; EVA wax: 8 percent; stearic acid: 2%, mixing ratio: the metal powder accounts for 92 percent, the forming agent accounts for 8 percent, the mixing temperature is over 82 ℃, the semi-solid metal fluid is obtained after uniform mixing, and the temperature of the semi-solid metal fluid is required to be maintained at 60-80 ℃;
4) rolling a green body: placing the material obtained in the step 3) into a hopper for powder rolling, rolling a green strip, wherein the green strip is a metal substrate, the thickness of the strip is 0.55mm, the width of the strip is 130mm, cutting the green strip into metal substrates 4 with the thickness of 110mm multiplied by 0.55mm, and placing the metal substrates on a setter plate;
5) and (3) sintering: placing the sintering bearing plate with the rolled green body into a vacuum furnace for sintering, wherein the sintering temperature is 1250 ℃, the sintering time is 50 minutes, and the vacuum degree in the vacuum sintering furnace is 10-3Pa, 4X 10 of backflushing for preventing chromium and other elements from evaporating4Pa argon gas;
6) flattening: and placing the sintered blank of the metal support plate between two flat templates, applying pressure, and pressing the height of the sintered blank to 0.55mm to form the metal support plate.
7) Wax dipping: melting polyethylene wax at 110 deg.C, at 119 deg.C, putting the metal support plate into the wax melt for 10min, and taking out the metal plate for cooling after the pores are infiltrated with wax.
As can be seen from fig. 2, the metal support plate has a large number of pores, which ensures good air permeability.
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 raw materials: 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 of 325 mesh and apparent density of 2.25g/cm3
3) Mixing materials: mixing the powder obtained in the step 2) with a forming agent, wherein the forming agent comprises the following components in percentage by mass: 45 percent; microcrystalline wax: 30 percent; castor oil: 8 percent; polyethylene wax: 7 percent; EVA wax: 8 percent; stearic acid: 2%, mixing ratio: the metal powder accounts for 94 percent, the forming agent accounts for 6 percent, the mixing temperature is more than 85 ℃, the semi-solid metal fluid is obtained after uniform mixing, and the temperature of the semi-solid metal fluid is required to be maintained at 60-80 ℃.
4) Rolling a green body: placing the material obtained in the step 3) in a hopper for powder rolling, and rolling a green strip with the thickness of 0.9mm and the width of 130 mm. The green strip was cut into 110X 0.9mm metal substrates 4 and placed on a setter plate.
5) And (3) sintering: and placing the setter plate with the powder rolling green body into a push rod furnace for sintering. The sintering temperature is 1200 ℃, 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%.
6) Flattening: and placing the sintered blank of the metal support plate between two flat templates, applying pressure, and pressing the height of the sintered blank to 0.55mm to form the metal support plate.
7) 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.
As can be seen from fig. 3, the metal support plate has a large number of pores, which ensures good air permeability.
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 the raw materials are 430L stainless steel powder: c: 0.025%, Cr: 17.1%, Mn: 0.8%, Si: 0.6%, iron: the balance;
2) sieving the powder, wherein the granularity range is 200-325 meshes, and the loose density of the powder is 2.30g/cm3
3) Mixing materials: mixing the powder obtained in the step 2) with a forming agent, wherein the forming agent comprises the following components in percentage by mass: 45 percent; microcrystalline wax: 30 percent; castor oil: 8 percent; polyethylene wax: 7 percent; EVA wax: 8 percent; stearic acid: 2%, mixing ratio: the metal powder accounts for 94 percent, the forming agent accounts for 6 percent, the mixing temperature is more than 85 ℃, the semi-solid metal fluid is obtained after uniform mixing, and the temperature of the semi-solid metal fluid is required to be maintained at 60-80 ℃.
4) Rolling a green body: placing the material obtained in the step 3) in a hopper for powder rolling, rolling a green strip with the thickness of 0.9mm and the width of 130mm, cutting the green strip into metal substrates 4 with the thickness of 110X 0.9mm, and placing the metal substrates on a setter plate.
5) And (3) sintering: and (3) placing the sintering bearing plate with the powder rolling green body into a push rod furnace for sintering, wherein the sintering temperature is 1250 ℃, the sintering time is 30 minutes, and the sintering atmosphere adopted in the sintering process is a mixed gas of high-purity hydrogen and argon, wherein the volume ratio of the argon is 30%.
6) Flattening: and placing the sintered blank of the metal support plate between two flat templates, applying pressure, and pressing the height of the sintered blank to 0.55mm to obtain the metal support plate.
7) 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.
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, wherein the granularity range is 200-325 meshes, and the loose density of the powder is 2.30g/cm3
3) Mixing materials: mixing the powder obtained in the step 2) with a forming agent, wherein the forming agent comprises the following components in percentage by mass: 45 percent; microcrystalline wax: 30 percent; castor oil: 8 percent; polyethylene wax: 7 percent; EVA wax: 9 percent; stearic acid: 1% and mixing ratio: the metal powder accounts for 94 percent, the forming agent accounts for 6 percent, the mixing temperature is more than 85 ℃, the semi-solid metal fluid is obtained after uniform mixing, and the temperature of the semi-solid metal fluid is required to be maintained at 60-80 ℃.
4) Rolling a green body: placing the material obtained in the step 3) in a hopper for powder rolling, rolling a green strip with the thickness of 0.9mm and the width of 130mm, cutting the green strip into metal substrates 4 with the thickness of 110X 0.9mm, and placing the metal substrates on a setter plate.
5) And (3) sintering: and (3) placing the sintering bearing plate with the powder rolling green body into a push rod furnace for sintering, wherein the sintering temperature is 1300 ℃, the sintering time is 30 minutes, and the sintering atmosphere is a mixed gas of high-purity hydrogen and argon, wherein the volume ratio of the argon is 30%.
6) Flattening: and placing the sintered blank of the metal support plate between two flat templates, applying pressure, and pressing the height of the sintered blank to 0.55mm to obtain the metal support plate.
7) 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.
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: 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 range is 200-325 meshes, and the loose density of the powder is 2.30g/cm3
3) Mixing materials: mixing the powder obtained in the step 2) with a forming agent, wherein the forming agent comprises the following components in percentage by mass: 45 percent; microcrystalline wax: 30 percent; castor oil: 8 percent; polyethylene wax: 7 percent; EVA wax: 9 percent; stearic acid: 1% and mixing ratio: the metal powder accounts for 94 percent, the forming agent accounts for 6 percent, the mixing temperature is more than 85 ℃, the semi-solid metal fluid is obtained after uniform mixing, and the temperature of the semi-solid metal fluid is required to be maintained at 60-80 ℃.
4) Rolling a green body: placing the material obtained in the step 3) in a hopper for powder rolling, rolling a green strip with the thickness of 0.9mm and the width of 130mm, cutting the green strip into metal substrates 4 with the thickness of 110X 0.9mm, and placing the metal substrates on a setter plate.
5) And (3) sintering: and placing the setter plate with the powder rolling green body into a push rod furnace for sintering. 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%.
6) Flattening: and placing the sintered blank of the metal support plate between two flat templates, applying pressure, and pressing the height of the sintered blank to 0.55mm to obtain the metal support plate.
7) Wax dipping: the polyethylene wax was melted at a melting temperature of 120 ℃. And (3) 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 the wax.
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 310 stainless steel, C: less than or equal to 0.25 percent, Si: less than or equal to 1.50 percent, Mn: less than or equal to 2.00 percent, P: less than or equal to 0.045%, S: 0.0.03% or less, Cr: 24.0-26.0%, Ni: 19.0-22.0%, iron: and (4) the balance.
2) Sieving the powder, wherein the granularity range is 200-325 meshes, and the loose density of the powder is 2.30g/cm3
3) Mixing materials: mixing the powder obtained in the step 2) with a forming agent, wherein the forming agent comprises the following components in percentage by mass: 45 percent; microcrystalline wax: 30 percent; castor oil: 8 percent; polyethylene wax: 7 percent; EVA wax: 9 percent; stearic acid: 1% and mixing ratio: the metal powder accounts for 94 percent, the forming agent accounts for 6 percent, the mixing temperature is more than 85 ℃, the semi-solid metal fluid is obtained after uniform mixing, and the temperature of the semi-solid metal fluid is required to be maintained at 60-80 ℃.
4) Rolling a green body: placing the material obtained in the step 3) in a hopper for powder rolling, and rolling a green strip with the thickness of 0.9mm and the width of 130 mm. The green strip was cut into 110X 0.9mm metal substrates 4 and placed on a setter plate.
5) And (3) sintering: and placing the setter plate with the powder rolling green body into a push rod furnace for sintering. 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%.
6) Flattening: and placing the sintered blank of the metal support plate between two flat templates, applying pressure, and pressing the height of the sintered blank to 0.55mm to obtain the metal support plate.
7) Wax dipping: the polyethylene wax was melted at a melting temperature of 120 ℃. And (3) 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 the wax. One of paraffin wax, EVA wax or PP wax may also be used.
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 stainless steel powder 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 powder, selecting the powder with the granularity of 100-200 meshes and the loose packing density of 2.35g/cm3
3) Mixing materials: mixing the powder obtained in the step 2) with a forming agent, wherein the forming agent comprises the following components in percentage by mass: 50 percent; microcrystalline wax: 25 percent; castor oil: 10 percent; polyethylene wax: 5 percent; EVA wax: 8 percent; stearic acid: 2%, mixing ratio: the metal powder accounts for 92 percent, the forming agent accounts for 8 percent, the mixing temperature is over 82 ℃, the semi-solid metal fluid is obtained after uniform mixing, and the temperature is required to be maintained at 60-80 ℃.
4) Rolling a green body: placing the material obtained in the step 3) in a hopper for powder rolling, rolling a green strip with the thickness of 0.9mm and the width of 130mm, cutting the green strip into metal substrates 4 with the thickness of 110X 0.9mm, and placing the metal substrates on a setter plate.
5) 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.
6) 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).
7) 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.
8) And (3) sintering: placing a metal support plate with an anode layer, a cathode layer and an electrolyte coating on a sintering plate, and then placing the metal support plate in a vacuum furnace for sintering to prepare the metal support plate, wherein the sintering temperature is 1300 ℃, the sintering time is 50 minutes, and the vacuum degree in the vacuum sintering furnace is 10-3Pa, 4X 10 for preventing chromium from evaporating4Pa of argon gas.
Fig. 4 shows the pores of the metal support plate, and it can be seen that there are many interconnected pores in the support plate, the density is low, and the porosity is greater than 50%. The supporting plate of the embodiment is about 50% of the weight of the existing metal supporting plate with the same thickness, and the purpose of light weight is achieved.
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 raw materials: c: 0.025%, Cr: 17.5%, Mn: 0.8%, Si: 0.6%, Mo: 1.05%, iron: the balance;
2) sieving the above powder to obtain powder with particle size less than 325 meshes and apparent density of 2.25g/cm3
3) Mixing materials: mixing the powder obtained in the step 2) with a forming agent, wherein the forming agent comprises the following components: 45 percent; microcrystalline wax: 30 percent; castor oil: 8 percent; polyethylene wax: 7 percent; EVA wax: 8 percent; stearic acid: 2%, mixing ratio: the metal powder accounts for 94 percent, the forming agent accounts for 6 percent, the mixing temperature is more than 85 ℃, and after uniform mixing, semi-solid metal fluid is obtained, and the temperature is required to be maintained at 60-80 ℃.
4) Rolling a green body: placing the material obtained in the step 3) in a hopper for powder rolling, and rolling a green strip with the thickness of 0.9mm and the width of 130 mm. The green strip was cut into 110X 0.9mm metal substrates 4 and placed on a setter plate.
5) 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.
6) 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.
7) 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.
8) And (3) sintering: and placing the setter plate with the powder rolling green body into a push rod furnace for sintering. The sintering temperature was 1200 ℃ and the sintering time was 30 minutes. The sintering atmosphere is a mixed gas of high-purity hydrogen and argon, wherein the volume ratio of the argon is 30%.
Fig. 5 shows the pores of the metal support plate, and it can be seen that there are many interconnected pores in the support plate, the density is low, and the porosity is greater than 50%. The support plate of the present invention is about 50% by weight of the conventional metal support plate having the same thickness, and is lightweight.
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 the raw materials are 430L stainless steel powder: c: 0.025%, Cr: 17.1%, Mn: 0.8%, Si: 0.6%, iron: the balance;
2) sieving the powder, wherein the granularity range is 200-325 meshes, and the loose density of the powder is 2.30g/cm3
3) Mixing materials: mixing the powder obtained in the step 2) with a forming agent, wherein the forming agent comprises the following components: 45 percent; microcrystalline wax: 30 percent; castor oil: 8 percent; polyethylene wax: 7 percent; EVA wax: 8 percent; stearic acid: 2%, mixing ratio: the metal powder accounts for 94 percent, the forming agent accounts for 6 percent, the mixing temperature is more than 85 ℃, and after uniform mixing, semi-solid metal fluid is obtained, and the temperature is required to be maintained at 60-80 ℃.
4) Rolling a green body: placing the material obtained in the step 3) in a hopper for powder rolling, and rolling a green strip with the thickness of 0.9mm and the width of 130 mm. The green strip was cut into 110X 0.9mm metal substrates 4 and placed on a setter plate.
5) 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 ═ 0.1), NiO, methyl ethyl ketone, ethanol, triethanolamine, starch, polyvinyl butyral PVB, polyethylene glycol PEG, and glutamic acid PHT.
6) Preparing an electrolyte coating: the prepared electrolyte slurry is processed by screen printingOr a dip coating method, is uniformly applied on the anode layer 2, and the uncoated lower surface is placed on a setter plate to be dried and sintered, thereby forming the 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.
7) 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.
8) And (3) sintering: and placing the setter plate with the powder rolling green body into a push rod furnace for sintering. The sintering temperature is 1250 ℃, 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%.
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: 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, wherein the granularity range is 200-325 meshes, and the loose density of the powder is 2.30g/cm3
3) Mixing materials: mixing the powder obtained in the step 2) with a forming agent, wherein the forming agent comprises the following components: 45 percent; microcrystalline wax: 30 percent; castor oil: 8 percent; polyethylene wax: 7 percent; EVA wax: 9 percent; stearic acid: 1% and mixing ratio: the metal powder accounts for 94 percent, the forming agent accounts for 6 percent, the mixing temperature is more than 85 ℃, and after uniform mixing, semi-solid metal fluid is obtained, and the temperature is required to be maintained at 60-80 ℃.
4) Rolling a green body: placing the material obtained in the step 3) in a hopper for powder rolling, and rolling a green strip with the thickness of 0.9mm and the width of 130 mm. The green strip was cut into 110X 0.9mm metal substrates 4 and placed on a setter plate.
5) 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.
6) 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.
7) 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.
8) And (3) sintering: and placing the setter plate with the powder rolling green body into a push rod furnace for sintering. The sintering temperature is 1250 ℃, 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%.
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: c: 0.06%, Cr: 21.1%, Mn: 0.9%, Si: 0.3%, Al: 4.79%, iron: the balance;
2) sieving the above powder to obtain powder with particle size range of-200 +325 mesh and apparent density of 2.30g/cm3
3) Mixing materials: mixing the powder obtained in the step 2) with a forming agent, wherein the forming agent comprises the following components: 45 percent; microcrystalline wax: 30 percent; castor oil: 8 percent; polyethylene wax: 7 percent; EVA wax: 9 percent; stearic acid: 1% and mixing ratio: the metal powder accounts for 94 percent, the forming agent accounts for 6 percent, the mixing temperature is more than 85 ℃, and after uniform mixing, semi-solid metal fluid is obtained, and the temperature is required to be maintained at 60-80 ℃.
4) Rolling a green body: placing the material obtained in the step 3) in a hopper for powder rolling, and rolling a green strip with the thickness of 0.9mm and the width of 130 mm. The green strip was cut into 110X 0.9mm metal substrates 4 and placed on a setter plate.
5) Preparing an anode layer: yttria Stabilized Zirconia (YSZ) was made into a slurry. The electrolyte slurry comprises YSZ, NiO, butanone, ethanol, triethanolamine, starch, polyvinyl butyral (PVB), polyethylene glycol (PEG), glutamic acid (PHT) and the like. The prepared slurry is uniformly applied to one surface of the cut metal substrate 4 by screen printing, dip coating, or the like, and the uncoated surface is placed on a setter plate and dried.
6) Preparing an electrolyte coating: 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.
7) Preparing a cathode layer: sr is2-xCaxFe1.5Mo0.5O6-δ(x ═ 0.5) cathode paste made of cathode material was uniformly applied on the upper surface of electrolyte coating layer by screen printing or dip coating method, and after the uncoated lower surface was placed on a setter plate and dried, thereby forming a layer of electrolyte on the electrolyteThe upper surface of the coating layer 3 is formed with a cathode layer 1.
8) And (3) sintering: and placing the setter plate with the powder rolling green body into a push rod furnace for sintering. The sintering temperature is 1330 ℃, 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 20%.
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 310 stainless steel, C: less than or equal to 0.25 percent; si: less than or equal to 1.50 percent; mn: less than or equal to 2.00 percent; p: less than or equal to 0.045%; s: less than or equal to 0.0.03 percent; cr: 24.0 to 26.0 percent; ni: 19.0-22.0%, iron: and (4) the balance.
2) Sieving the powder, wherein the granularity range is 200-325 meshes, and the loose density of the powder is 2.30g/cm3
3) Mixing materials: mixing the powder obtained in the step 2) with a forming agent, wherein the forming agent comprises the following components: 45 percent; microcrystalline wax: 30 percent; castor oil: 8 percent; polyethylene wax: 7 percent; EVA wax: 9 percent; stearic acid: 1% and mixing ratio: the metal powder accounts for 94 percent, the forming agent accounts for 6 percent, the mixing temperature is more than 85 ℃, and after uniform mixing, semi-solid metal fluid is obtained, and the temperature is required to be maintained at 60-80 ℃.
4) Rolling a green body: placing the material obtained in the step 3) in a hopper for powder rolling, and rolling a green strip with the thickness of 0.9mm and the width of 130 mm. The green strip was cut into 110X 0.9mm metal substrates 4 and placed on a setter plate.
5) 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.
6) 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).
7) 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.
8) And (3) sintering: and placing the setter plate with the powder rolling green body into a push rod furnace for sintering. 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 40%.
Example 13:
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) screening the powder, wherein the granularity is 100-200 meshes, and the loose density of the powder is 2.35g/cm3
3) Mixing materials: mixing the powder obtained in the step 2) with a forming agent, wherein the forming agent comprises the following components: 50 percent; microcrystalline wax: 25 percent; castor oil: 10 percent; polyethylene wax: 5 percent; EVA wax: 8 percent; stearic acid: 2%, mixing ratio: the metal powder accounts for 92 percent, the forming agent accounts for 8 percent, the mixing temperature is over 82 ℃, the semi-solid metal fluid is obtained after uniform mixing, and the temperature is required to be maintained at 60-80 ℃.
4) Rolling a green body: the other part of the material is a metal fiber felt which 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 of the metal fiber felt is 80%, and the thickness of the metal fiber felt is 0.1 mm; placing the material of the step 3) and the metal fiber felt in a hopper of powder rolling, rolling a green strip together, wherein the thickness of the strip is 0.7mm, the width of the strip is 120mm, cutting the green strip into a metal substrate 4 with the thickness of 110 multiplied by 0.9mm, and placing the metal substrate on a setter plate.
5) 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.
6) 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).
7) 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, 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.
8) And (3) sintering: and placing the setter plate with the powder rolling green compact into a vacuum furnace for sintering. The sintering temperature was 1300 ℃ and the sintering time was 50 minutes. The vacuum degree in the vacuum sintering furnace is 10-3Pa, and 4X 10 of elements such as chromium can be back-flushed to prevent evaporation4Pa of argon gas.
Fig. 6 shows the pores of the metal support plate, and it can be seen that there are many interconnected pores in the support plate, the density is low, and the porosity is greater than 50%. The support plate of the present invention is about 50% by weight of the conventional metal support plate having the same thickness, and is lightweight.
Example 14:
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 above powder to obtain powder with particle size less than 325 mesh and apparent density of 2.25g/cm3
3) Mixing materials: mixing the powder obtained in the step 2) with a forming agent, wherein the forming agent comprises the following components: 45 percent; microcrystalline wax: 30 percent; castor oil: 8 percent; polyethylene wax: 7 percent; EVA wax: 8 percent; stearic acid: 2%, mixing ratio: the metal powder accounts for 94 percent, the forming agent accounts for 6 percent, the mixing temperature is more than 85 ℃, and after uniform mixing, semi-solid metal fluid is obtained, and the temperature is required to be maintained at 60-80 ℃.
4) Rolling a green body: the other part of the material is a metal fiber felt which 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: and (4) the balance. The porosity of the metal fiber felt is 60%, and the thickness of the metal fiber felt is 1.1 mm; placing the material of step 3) and the metal fiber felt in a hopper of powder rolling, and rolling a green strip together, wherein the thickness of the strip is 1.6mm, and the width of the strip is 130 mm. The green strip was cut into 110X 0.9mm metal substrates 4 and placed on a setter plate.
5) Preparing an anode layer: yttria Stabilized Zirconia (YSZ) was made into a slurry. The electrolyte slurry comprises YSZ, NiO, butanone, ethanol, triethanolamine, starch, polyvinyl butyral (PVB), polyethylene glycol (PEG) and glutamic acid (PHT). The prepared slurry is uniformly applied to one surface of the cut metal substrate 4 by screen printing, dip coating, or the like, and the uncoated surface is placed on a setter plate and dried.
6) Preparing an electrolyte coating: yttria Stabilized Zirconia (YSZ) was made into a slurry. The prepared slurry is uniformly coated on the anode layer by screen printing or dip coating, and the uncoated side is placed on a setter plate and dried.
7) 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.
8) And (3) sintering: and placing the setter plate with the powder rolling green body into a push rod furnace for sintering. The sintering temperature is 1200 ℃, 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%.
Fig. 7 shows the pores of the metal support plate, and it can be seen that there are many interconnected pores in the support plate, the density is low, and the porosity is greater than 50%. The support plate of the present invention is about 50% by weight of the conventional metal support plate having the same thickness, and is lightweight.
Example 15:
the method for manufacturing a metal support plate for a fuel cell of the present embodiment 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, wherein the granularity range is 200-325 meshes, and the loose density of the powder is 2.30g/cm3
3) Mixing materials: mixing the powder obtained in the step 2) with a forming agent, wherein the forming agent comprises the following components: 45 percent; microcrystalline wax: 30 percent; castor oil: 8 percent; polyethylene wax: 7 percent; EVA wax: 8 percent; stearic acid: 2%, mixing ratio: the metal powder accounts for 94 percent, the forming agent accounts for 6 percent, the mixing temperature is more than 85 ℃, and after uniform mixing, semi-solid metal fluid is obtained, and the temperature is required to be maintained at 60-80 ℃.
4) Rolling a green body: 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%, iron: and (4) the balance. The porosity of the metal fiber felt is 60%, and the thickness of the metal fiber felt is 0.4 mm; the material of step 3) and the metal fiber mat were placed in a hopper of a powder mill, rolled together into a green tape having a thickness of 0.8mm and a width of 130mm, and the green tape was cut into a metal substrate 4 of 110X 0.9mm and placed on a setter plate.
5) 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.
6) 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).
7) 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.
8) And (3) sintering: and placing the setter plate with the powder rolling green body into a push rod furnace for sintering. The sintering temperature is 1250 ℃, 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%.
Example 16:
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 of 200-325 meshes and the powder apparent density of 2.30g/cm3
3) Mixing materials: mixing the powder obtained in the step 2) with a forming agent, wherein the forming agent comprises the following components: 45 percent; microcrystalline wax: 30 percent; castor oil: 8 percent; polyethylene wax: 7 percent; EVA wax: 9 percent; stearic acid: 1% and mixing ratio: the metal powder accounts for 94 percent, the forming agent accounts for 6 percent, the mixing temperature is more than 85 ℃, and after uniform mixing, semi-solid metal fluid is obtained, and the temperature is required to be maintained at 60-80 ℃.
4) Rolling a green body: the other part of the material is a metal fiber felt which comprises the following components in percentage by mass: 0.006%, Cr: 21.1%, Mn: 0.9%, Si: 0.3%, Al: 4.79%, iron: the balance; the porosity is 65 percent, and the thickness is 0.2 mm; the material of step 3) and the metal fiber mat were placed in a hopper of a powder rolling mill, rolled to a green tape having a thickness of 0.6mm and a width of 130mm, and then the green tape was cut into a metal substrate 4 of 110X 0.9mm and placed on a setter plate.
5) 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.
6) 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).
7) 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.
8) And (3) sintering: and placing the setter plate with the powder rolling green body into a push rod furnace for sintering. The sintering temperature is 1250 ℃, 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%.
Example 17:
this embodiment differs from embodiment 16 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.
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.
The sintering parameters in the step 8) are different, specifically, the sintering temperature is 1050 ℃, and the sintering time is 300 min.
Example 18:
this embodiment differs from embodiment 16 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 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.
The sintering parameters in the step 8) 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. The setter plates of the above embodiments are not easily deformed or cracked when being sintered, heated and cooled.

Claims (11)

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 particle size of 13-250 μm;
3) mixing the powder obtained in the step 2) with a forming agent, wherein the powder accounts for 92-95% and the forming agent accounts for 5-8% by mass percent, and uniformly mixing to obtain powder of the semi-solid metal fluid;
4) putting the powder obtained in the step 3) into a rolling mill for rolling so as to form a metal substrate;
5) 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;
6) 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;
7) 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;
the sintering process is carried out between step 4) and step 5) or, alternatively, after step 7).
2. The method of claim 1, wherein: the sintering treatment is to place the metal substrate or the metal support plate with the required size on a sintering bearing plate for sintering, wherein the sintering temperature is 1000-1350 ℃, the sintering time is 5-240 min, and the vacuum degree is 10-3Pa~102Pa。
3. The method of claim 2, wherein: and when the sintering treatment is between the step 4) and the step 5), flattening the sintered metal substrate, and then performing 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, and taking out the metal substrate after the wax melt permeates into pores in the metal substrate and cooling.
4. 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: 0-4%, 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 method of claim 1, wherein: the forming agent in the step 2) comprises the following components in percentage by mass: paraffin wax: 40-60%; microcrystalline wax: 20-30%; castor oil: 0.5-20%; polyethylene wax: 5-15%; EVA wax: 5-15%; stearic acid: 1 to 2 percent.
6. The article of claim 1The preparation method is characterized by comprising the following steps: sintering is carried out after drying in the steps 5), 6) and 7), sintering temperature adopted in the sintering in the step 5) and the sintering in the step 6) is 1050-1400 ℃, sintering time is 10-300 min, sintering temperature adopted in the sintering in the step 7) is 800-1200 ℃, sintering time is 5-300 min, and vacuum degree is 10-300 min-3Pa~102Pa。
7. The method of claim 1, wherein: in the step 4), the metal fiber felt with the porosity of more than 50% is also added into a rolling mill, and the metal fiber felt and the powder are rolled into a metal substrate.
8. The method of claim 7, wherein: the metal fiber felt comprises the following components in percentage by mass: carbon: < 0.03%, 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.
9. The production method according to any one of claims 1 to 8, 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 is 0, 0.1, 0.3, 0.5.
10. The method of claim 9, wherein: 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.
11. The method of manufacturing according to claim 10, wherein: the cathode slurry is Sr2- xCaxFe1.5Mo0.5O6-δ、LSM(La1-xSrxMn03)、LSCF((La,Sr)(Co,Fe)O3) And a pyrochlore-structured A2Ru2O 7-x (a ═ Pb, Bi) ceramic, an Ag-YDB composite ceramic, and a perovskite-structured L-type ceramic, wherein x is 0, 0.1, 0.3, or 0.5.
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