CN113871646A - Method for preparing metal support plate for solid oxide fuel cell - Google Patents
Method for preparing metal support plate for solid oxide fuel cell Download PDFInfo
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- CN113871646A CN113871646A CN202111114431.7A CN202111114431A CN113871646A CN 113871646 A CN113871646 A CN 113871646A CN 202111114431 A CN202111114431 A CN 202111114431A CN 113871646 A CN113871646 A CN 113871646A
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- powder
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Images
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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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0232—Metals or alloys
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1017—Multiple heating or additional steps
- B22F3/1021—Removal of binder or filler
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
- B22F5/006—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of flat products, e.g. sheets
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
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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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0241—Composites
- H01M8/0243—Composites in the form of mixtures
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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]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
- B22F2003/145—Both compacting and sintering simultaneously by warm compacting, below debindering temperature
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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
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M2008/1293—Fuel cells with solid oxide electrolytes
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- 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
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B90/00—Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02B90/10—Applications of fuel cells in buildings
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (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 solid oxide fuel cell, which sequentially comprises the following steps: 1) the metal supporting plate is made of one of sintered stainless steel, heat-resistant steel, nickel-based alloy, cobalt-based alloy, titanium alloy and chromium-based alloy; 2) and (3) granulation: adding a binder into the alloy mixed powder for mixing, cooling and crushing after mixing to obtain granulated powder, wherein the binder consists of a main filler, a framework polymer and an additive; 3) warm pressing: filling the granulation powder obtained in the step 2) into a powder metallurgy die, heating and extruding to obtain a green body, and demoulding after cooling; 4) dewaxing: dewaxing the green body obtained in the step 3); 5) and (3) sintering: and sintering the dewaxed green body. By adopting a plasticizing extrusion forming mode, mixing and granulating metal powder and a binder and combining a powder metallurgy warm pressing technology, the sintering deformation is effectively eliminated, and the combination between the anode layer and the metal substrate is improved.
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 solid oxide 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) have unique advantages over supported SOFCs that use metals or alloys as fuel cells: (1) the cost is low: the cost of the metal material is far lower than that of the metal ceramic composite material; (2) and (3) quick start: the good heat-conducting property of the metal can reduce the temperature gradient in the battery, and the quick start is realized, so that the battery can be applied to the mobile field; (3) workability: compared with ceramics, the metal material has better processability, which greatly reduces the processing difficulty of the SOFC; (4) sealing is facilitated: by utilizing the welding sealing technology of the metal material, the problem that the SOFC is difficult to seal can be avoided. The metal support serves primarily to transport gas, conduct current, and provide stable structural support for the cell. When the MS-SOFC uses the hydrocarbon fuel, the metal support body can be used as an in-situ reforming layer, the hydrocarbon fuel is firstly subjected to chemical reforming in the metal support body, and the generated synthesis gas is subjected to electrochemical oxidation in the anode 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.
As the SOFC metal support body, the SOFC metal support body has the characteristics of certain porosity, good thermal expansion matching property, high-temperature oxidation resistance and the like, and in addition, when the hydrocarbon fuel is directly used, the metal support body needs to have certain catalytic reforming activity and carbon deposition resistance.
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.
The research status and development of the metal support of the direct CH4 solid oxide fuel cell, the material report (A), 2020, 34(9):17149-17154, reports several metal support materials and preparation methods. The MS-SOFC metal support comprises an Fe-based alloy and a Ni-based alloy. Nickel-based alloys include primarily pure metallic nickel, Haynes 230, 242, HastelloyX nickel-based alloys, and the like. Reolon uses Ni-based alloy as a support, prepares an anode, a double-layer electrolyte and a cathode by a pulse laser deposition technology, and the maximum power density of the battery at 650 ℃ is 0.40W-cm－2. However, 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 the internal thermal stress is too large in the operation process of the battery, 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. Most MS-SOFCs use iron-based alloys as support, especially ferritic stainless steels. Ferritic stainless steels are body-centered cubic structures with a high temperature coefficient of thermal expansion CTE (11 x 10)－6～13*10- 6K－1) With YSZ (yttria stabilized zirconia) and GDC (Gd2O3 doped CeO2) (13 x 10)-6～14*10-6K-1) The electrolytes are in close proximity. Fe-based alloys as support body will face two problems: the long-term work under the medium-high temperature and humid atmosphere can easily cause the oxidation of metal materials and the mutual diffusion of Fe and Cr elements in the stainless steel support and Ni-based anode. In the preparation or operation process of the MS-SOFC, Fe and Cr elements in the stainless steel support body diffuse into an 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, resulting in a change in the thermal expansion coefficient of the supportThe internal stress of the battery is increased and the structural stability is reduced.
The present state of research and development of metal supports for direct CH4 solid oxide fuel cells, material report (A), 2020, 34(9):17149-17154, further reports that Fe-Cr alloy supports prepared by casting, anodes and electrolyte blank bodies are laminated and then placed in a reducing atmosphere for high-temperature sintering, anode catalysts are injected into the metal support side of a half cell, cathode functional layers are screen-printed on the electrolyte surface, and the anodes and cathodes are sintered in situ during cell testing. 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 performance of the battery is attenuated quickly. The MS-SOFC is prepared by taking metal oxide as a raw material, and then the porous metal support is obtained by anode in-situ reduction, so that co-sintering of a cathode and the support in air can be realized, and high-temperature oxidation of the metal support can be avoided. NiO and Fe are selected2O3The Ni-Fe porous alloy support body is prepared as a support body raw material, and a new way for preparing MS-SOFC by using metal oxide as a precursor is opened up. But the process is complex and the manufacturing difficulty is large. The preparation and performance research of metal-supported solid oxide fuel cells (master's paper of the university of Harbin, Sunshou, 2017, 6) proposes that a porous metal body with an anode and an electrolyte is prepared by a co-casting method, and the sintering temperature of the metal and the electrolyte is different, so that the sintering deformation, the peeling of the anode or the electrolyte layer and the like are easily caused. The dry press forming method for preparing the metal support and the micro-tube type metal support are also provided. For the dry pressing method, the metal supporting layer is thin, so that the metal supporting plate is easy to have uneven thickness after dry pressing, 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.
Therefore, further improvements in the existing methods of making metal support plates for fuel cells are needed.
Disclosure of Invention
The present invention is directed to provide a method for manufacturing a metal support plate for a solid oxide fuel cell, which improves structural stability and eliminates sintering deformation to improve bonding between an anode and a substrate, in view of the current state of the prior art.
The technical scheme adopted by the invention for solving the technical problems is as follows: a method of making a metal support plate for a solid oxide fuel cell, comprising: the method sequentially comprises the following steps:
1) the metal supporting plate is made of one of sintered stainless steel, heat-resistant steel, nickel-based alloy, cobalt-based alloy, titanium alloy and chromium-based alloy, and the mixed powder of the metal supporting plate 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: the balance;
2) granulating
Adding a binder into the alloy mixed powder for mixing, cooling and crushing after mixing to obtain granulated powder, wherein the binder consists of a main filler, a framework polymer and an additive;
3) warm and pressure
Filling the granulation powder obtained in the step 2) into a powder metallurgy die, heating and extruding to obtain a green body, and demoulding after cooling;
4) dewaxing: dewaxing the green body obtained in the step 3);
5) and (3) sintering: and sintering the dewaxed green body.
Preferably, the weight ratio of the mixed powder to the binder is A1: a2, wherein A1 is 75-95, A2 is 5-25, and the weight ratio of the main filler, the skeleton polymer and the additive is B1: b2: b3, wherein B1 is 60-95, B2 is 4.9-34, and B3 is 0.1-10. The specific gravity of the mixed powder is high, and uneven mixing can be caused after the binder is added, so that the forming quality of the granulated powder is influenced; the mixed powder has too low specific gravity, which can cause the problems of product collapse, sintering deformation and the like during dewaxing and sintering. The addition proportion of the main filler is set, so that the flowability of the feed can be ensured; the addition proportion of the skeleton polymer is set to ensure that the product has good shape retention after warm pressing, degreasing and sintering, collapse, deformation, cracking and the like are avoided, and the secondary thermal degreasing time is prolonged if the skeleton polymer is excessively added, so that the cost is increased; the additive plays a role in improving wetting, promoting dispersion and preventing the decomposition of the adhesive, and the performance of the additive is not beneficial to the performance of the additive when the additive is added excessively.
Preferably, the main filler is one or a mixture of at least two of polyoxymethylene, paraffin, carnauba wax, microcrystalline wax and polyethylene glycol, and the skeleton polymer is one or a mixture of at least two of high-density polyethylene, polypropylene, polyethylene wax, polystyrene, ethylene-vinyl acetate copolymer, polymethyl methacrylate and polyvinyl butyral; the additive is one or a mixture of at least two of stearic acid and its salts, ethylene bisstearamide, sorbitan fatty acid esters and polyoxyethylene sorbitan fatty acid esters.
Preferably, in the step 2), the mixing temperature of the mixed powder and the binder is 100-180 ℃, and the granulated powder is particles sieved by a screen, and the particle size range is 74-250 μm. The mixing temperature is too low (e.g., < 100 ℃), the binder is not completely melted, resulting in uneven mixing; too high a mixing temperature (e.g., > 180 ℃) causes binder decomposition and mixed powder oxidation, affecting its performance. The granularity of the granulated powder is too fine (such as less than 74um), the flowability is poor, and the powder feeding is influenced; too large particle size (e.g., > 250um) results in uneven heating during warm pressing and poor pressing performance.
Preferably, in the step 3), the forming pressure is 100-600 Mpa, and the mold temperature is 60-80 ℃. The temperature and the forming pressure of the die are too low (for example, the temperature of the die is less than 60 ℃, and the forming pressure is less than 100Mpa), the plasticity of the granulated powder is poor, and the granulation powder is not easy to form; the temperature and the forming pressure of the die are too high (for example, the temperature of the die is more than 80 ℃, and the forming pressure is more than 600Mpa), the binder is easy to lose, and the forming quality is influenced.
Preferably, in the step 4), dewaxing is carried out in a vacuum drying oven, the dewaxing temperature is 200-350 ℃, and the dewaxing time is 60-180 min. The thermal dewaxing process is simple and easy to control. The temperature is too low, the time is short (such as the dewaxing temperature is less than 200 ℃, the dewaxing time is less than 60min), the binder removal speed is too slow, and the production efficiency is low; the defects of bubbling, cracking, collapse, deformation and the like easily occur due to overhigh temperature and long time (such as dewaxing temperature is more than 350 ℃ and dewaxing time is more than 180 min).
In the step 5), the sintering temperature is 1000-1350 ℃, and the sintering time is 5-240 min.
In order to prevent chromium element and the like from evaporating, the sintering is carried out in a protective atmosphere of pure hydrogen, nitrogen, argon, or a ratio of hydrogen to argon of 1-90 vol%.
Compared with the prior art, the invention has the advantages that: the metal substrate of the metal support plate of the fuel cell is sequentially provided with the anode layer, the electrolyte coating and the cathode layer. The metal support has better ductility and thermal conductivity, can reduce the thermal stress and mechanical stress in the SOFC multilayer structure, improves the stability of the structure and performance, effectively eliminates the sintering deformation, and improves the combination between the anode layer and the metal substrate. In addition, the particle size of the metal powder, the proportion of the metal powder to the binder, the forming pressure and the like are adjusted, so that the pores of the metal substrate are controllable, and the gas can conveniently pass through the metal substrate. In addition, the invention uses cheap metal materials to replace most rare earth oxide materials in the traditional SOFC, thereby reducing the cost of raw materials; the preparation process is simple and the production efficiency is high by combining the binder granulation and the traditional powder metallurgy warm pressing technology; in addition, the metal is easier to process than the ceramic, and the subsequent processing cost of the battery is reduced.
Drawings
FIG. 1 is a schematic structural view of a porous metal support plate of example 1;
FIG. 2 is the pore morphology after sintering of example 1;
FIG. 3 is the pore morphology after sintering of example 2.
Detailed Description
The invention is described in further detail below with reference to the accompanying examples.
Example 1:
as shown in fig. 1 and 2, the invention is the 1 st preferred embodiment.
The preparation method of the metal support plate for the solid oxide fuel cell sequentially comprises the following steps of:
1) preparing raw materials, wherein 434L stainless steel powder is selected as the raw materials, 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 percent;
2) and (3) granulation: mixing the mixed powder and a binder according to a weight ratio of 90: 10, wherein the binder comprises the following components in percentage by weight: 65% of polyethylene wax: 30 percent of stearic acid and 5 percent of stearic acid, the mixing temperature is 130 ℃, the mixture is cooled and crushed after being uniformly mixed to obtain granulation powder, and the average particle size of the granulation powder for sieving and backup is 200 mu m;
3) warm pressing: filling the granulated powder obtained in the step 2) into a powder metallurgy die, heating and extruding to obtain a green body of the fuel cell support plate, wherein the forming pressure is 150MPa, the temperature of the die is kept at 60 ℃, and demoulding is carried out after cooling;
4) dewaxing: dewaxing in a vacuum drying oven at 200 ℃ for 180 minutes;
5) and (3) sintering: sintering in a vacuum furnace at 1200 ℃ for 120 minutes. The degree of vacuum in the vacuum sintering furnace was 10-3Pa, recharging 4X 10 for preventing chromium element from evaporating4Pa of argon gas.
The metal support plate of the present embodiment comprises a metal substrate 4, an anode layer 2 disposed on the metal substrate 4, an electrolyte coating 3 overlying the anode layer 2, and a cathode layer 1 overlying the electrolyte coating 3.
FIG. 2 is a pore morphology of a metal support portion. As can be seen from fig. 2, the metal support plate has many pores and some portions are in a connected state, and can ensure good gas permeability as a gas passage of the fuel cell. The metal support plate is prepared by using a plasticizing extrusion technology, the pores are controllable, the green strength is high, the sintering deformation degree is reduced compared with an injection molding sintering technology, the thermal expansion matching with an electrolyte material is good, the structural stability is high, the manufacturing process is simple, and the cost is low.
Example 2:
fig. 3 shows a2 nd preferred embodiment of the present invention.
The preparation method of the metal support plate for the solid oxide fuel cell sequentially comprises the following steps of:
1) preparing raw materials, wherein 434L stainless steel powder is selected as the raw materials, 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 percent;
2) and (3) granulation: mixing the mixed powder and a binder according to a weight ratio of 85: 15, wherein the binder comprises paraffin: 55 percent; microcrystalline wax: 15 percent; polyethylene wax: 27%; 3% of stearic acid, the mixing temperature is 130 ℃, the alloy granulation powder is obtained by cooling and crushing after uniform mixing, and the average particle size of the powder for standby after sieving is 200 mu m;
3) warm pressing: filling the granulated powder obtained in the step 2) into a powder metallurgy die, heating and extruding to obtain a fuel cell support plate green body, wherein the forming pressure is 100MPa, the die temperature is kept at 70 ℃, and demoulding is carried out after cooling;
4) dewaxing: dewaxing in a vacuum drying oven at 250 ℃ for 120 minutes;
5) and (3) sintering: sintering in a vacuum furnace at 1250 ℃ for 80 minutes. The degree of vacuum in the vacuum sintering furnace was 10-3Pa, back charging 3X 104Pa of argon gas.
FIG. 3 is a pore morphology of a metal support portion. As can be seen from fig. 3, the metal support plate has many pores and some portions are in a connected state, and can ensure good gas permeability as a gas passage of the fuel cell. The metal support plate is prepared by using a plasticizing extrusion technology, the pores are controllable, the green strength is high, the sintering deformation degree is reduced compared with an injection molding sintering technology, the thermal expansion matching with an electrolyte material is good, the structural stability is high, the manufacturing process is simple, and the cost is low.
Example 3:
the preparation method of the metal support plate for the solid oxide fuel cell sequentially comprises the following steps of:
1) preparing raw materials, wherein 434L stainless steel powder is selected as the raw materials, 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 percent;
2) and (3) granulation: mixing the mixed powder and a binder according to a weight ratio of 90: 10, wherein the binder comprises paraffin: 55 percent; microcrystalline wax: 13 percent; EVA wax: 10 percent; polyethylene wax: 20 percent; 2 percent of stearic acid, the mixing temperature is 160 ℃, the alloy granulation powder is obtained by cooling and crushing after even mixing, and the average particle size of the powder for standby after sieving is 200 mu m. (ii) a
3) Warm pressing: filling the granulated powder obtained in the step 2) into a powder metallurgy die, heating and extruding to obtain a green body of the fuel cell support plate, wherein the forming pressure is 200MPa, the die temperature is kept at 65 ℃, and demoulding is carried out after cooling;
4) dewaxing: dewaxing in a vacuum drying oven at the dewaxing temperature of 300 ℃ for 90 minutes;
5) and (3) sintering: sintering in a push rod furnace at 1250 ℃ for 60 minutes. The sintering atmosphere was 80 vol% nitrogen and 20 vol% hydrogen.
The metal support plate is prepared by using a plasticizing extrusion technology, the pores are controllable, the green strength is high, the sintering deformation degree is reduced compared with an injection molding sintering technology, the thermal expansion matching with an electrolyte material is good, the structural stability is high, the manufacturing process is simple, and the cost is low.
Example 4:
the preparation method of the metal support plate for the solid oxide fuel cell sequentially comprises the following steps of:
1) preparing raw materials, wherein the raw materials are 430L stainless steel powder, and the 430L stainless steel powder comprises the following components in percentage by mass: c: 0.025%, Cr: 16.8%, Mn: 0.6%, Si: 0.5 percent;
2) and (3) granulation: mixing the mixed powder and a binder according to a weight ratio of 90: 10, wherein the binder comprises paraffin: 55 percent; microcrystalline wax: 13 percent; EVA wax: 10 percent; polyethylene wax: 20 percent; 2% of stearic acid, the mixing temperature is 160 ℃, the alloy granulation powder is obtained by cooling and crushing after uniform mixing, and the average particle size of the powder for standby after sieving is 200 mu m;
3) warm pressing: filling the granulated powder obtained in the step 2) into a powder metallurgy die, heating and extruding to obtain a green body of the fuel cell support plate, wherein the forming pressure is 200MPa, the die temperature is kept at 65 ℃, and demoulding is carried out after cooling;
4) dewaxing: dewaxing in a vacuum drying oven at the dewaxing temperature of 300 ℃ for 90 minutes;
5) and (3) sintering: sintering in a push rod furnace at 1250 ℃ for 60 minutes. The sintering atmosphere was 80 vol% nitrogen and 20 vol% hydrogen.
The metal support plate is prepared by using a plasticizing extrusion technology, the pores are controllable, the green strength is high, the sintering deformation degree is reduced compared with an injection molding sintering technology, the thermal expansion matching with an electrolyte material is good, the structural stability is high, the manufacturing process is simple, and the cost is low.
Example 5:
the preparation method of the metal support plate for the solid oxide fuel cell sequentially comprises the following steps of:
1) preparing raw materials, wherein the materials are 316L stainless steel powder, and the 316L stainless steel powder 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 percent;
2) and (3) granulation: mixing the mixed powder and a binder according to a weight ratio of 80: 20, wherein the binder comprises paraffin: 69%; EVA wax: 10 percent; polyethylene wax: 20 percent; 2% of stearic acid, the mixing temperature is 160 ℃, the alloy granulation powder is obtained by cooling and crushing after uniform mixing, and the average particle size of the powder for standby after sieving is 200 mu m;
3) warm pressing: filling the granulated powder obtained in the step 2) into a powder metallurgy die, heating and extruding to obtain a green body of the fuel cell support plate, keeping the forming pressure at 300MPa and the die temperature at 65 ℃, and demoulding after cooling;
4) dewaxing: dewaxing in a vacuum drying oven at the dewaxing temperature of 300 ℃ for 120 minutes;
5) and (3) sintering: sintering in a vacuum furnace at 1180 ℃ for 180 minutes. The degree of vacuum in the vacuum sintering furnace was 10-3Pa, back charging 3X 104Pa of argon gas.
The metal support plate is prepared by using a plasticizing extrusion technology, the pores are controllable, the green strength is high, the sintering deformation degree is reduced compared with an injection molding sintering technology, the thermal expansion matching with an electrolyte material is good, the structural stability is high, the manufacturing process is simple, and the cost is low.
Example 6:
the preparation method of the metal support plate for the solid oxide fuel cell sequentially comprises the following 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 percent;
2) and (3) granulation: mixing the mixed powder and a binder according to a weight ratio of 88: 12, wherein the binder comprises paraffin: 79 percent; EVA wax: 10 percent; polyethylene wax: 10 percent; 1% of stearic acid, the mixing temperature is 150 ℃, the alloy granulation powder is obtained by cooling and crushing after uniform mixing, and the average particle size of the powder for standby after sieving is 200 mu m;
3) warm pressing: filling the granulated powder obtained in the step 2) into a powder metallurgy die, heating and extruding to obtain a green body of the fuel cell support plate, keeping the forming pressure at 300MPa and the die temperature at 65 ℃, and demoulding after cooling;
4) dewaxing: dewaxing in a vacuum drying oven at the dewaxing temperature of 200 ℃ for 180 minutes;
5) and (3) sintering: sintering in a vacuum furnace at 1200 ℃ for 120 minutes. The degree of vacuum in the vacuum sintering furnace was 10-3Pa, back charging 4X 104Pa of argon gas.
The metal support plate is prepared by using a plasticizing extrusion technology, the pores are controllable, the green strength is high, the sintering deformation degree is reduced compared with an injection molding sintering technology, the thermal expansion matching with an electrolyte material is good, the structural stability is high, the manufacturing process is simple, and the cost is low.
Example 7:
this embodiment differs from embodiment 1 described above only in that:
the material in the step 1) comprises the following components in percentage by mass: c: 0.03%, Ni: 12%, Cr: 10%, Mo: 4%, Ti: 3%, Nb: 1.5%, Mn: 2%, Al: 10 percent;
in the step 2), the weight ratio of the mixed powder to the binder is 75: 25, the average particle size of the powder after mixing and sieving is 74um, and the mixing temperature is 100 ℃.
Wherein the binder comprises polyethylene glycol: 60%, ethylene-vinyl acetate copolymer: 34% and 6% of polyoxyethylene sorbitan fatty acid ester:
the forming pressure in the step 3) is 600MPa, and the temperature of the die is kept at 80 ℃;
the dewaxing temperature in step 4) was 350 ℃ and the time was 60 minutes.
Example 8:
this embodiment differs from embodiment 1 described above only in that:
the material in the step 1) comprises the following components in percentage by mass: c: 0.03%, Ni: 25%, Nb: 3%, Mo: 4%, Ti: 1.5%, Cr: 30%, Mn: 2%, Si: 1 percent;
in the step 2), the weight ratio of the mixed powder to the binder is 95: 5, the average particle size of the sieved powder is 250um, and the mixing temperature is 180 ℃.
Wherein the binder comprises palm wax: 95%, polyvinyl butyral: 4.9 percent and 0.1 percent of ethylene bis stearamide.
The main filler can also be polyformaldehyde, and the skeleton polymer can also be one or a mixture of at least two of high-density polyethylene, polypropylene, polystyrene and polymethyl methacrylate; the additive is sorbitan fatty acid ester.
The material can also be one of heat-resistant steel, nickel-based alloy, cobalt-based alloy, titanium alloy and chromium-based alloy.
Claims (8)
1. A method of making a metal support plate for a solid oxide fuel cell, comprising: the method sequentially comprises the following steps:
1) the metal supporting plate is made of one of sintered stainless steel, heat-resistant steel, nickel-based alloy, cobalt-based alloy, titanium alloy and chromium-based alloy, and the mixed powder of the metal supporting plate 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: the balance;
2) granulating
Adding a binder into the alloy mixed powder for mixing, cooling and crushing after mixing to obtain granulated powder, wherein the binder consists of a main filler, a framework polymer and an additive;
3) warm and pressure
Filling the granulation powder obtained in the step 2) into a powder metallurgy die, heating and extruding to obtain a green body, and demoulding after cooling;
4) dewaxing: dewaxing the green body obtained in the step 3);
5) and (3) sintering: and sintering the dewaxed green body.
2. The method of claim 1, wherein: the weight ratio of the mixed powder to the binder is A1: a2, wherein A1 is 75-95, A2 is 5-25, and the weight ratio of the main filler, the skeleton polymer and the additive is B1: b2: b3, wherein B1 is 60-95, B2 is 4.9-34, and B3 is 0.1-10.
3. The method of claim 1, wherein: the main filler is one or a mixture of at least two of polyformaldehyde, paraffin, carnauba wax, microcrystalline wax and polyethylene glycol, and the skeleton polymer is one or a mixture of at least two of high-density polyethylene, polypropylene, polyethylene wax, polystyrene, an ethylene-vinyl acetate copolymer, polymethyl methacrylate and polyvinyl butyral; the additive is one or a mixture of at least two of stearic acid and its salts, ethylene bisstearamide, sorbitan fatty acid esters and polyoxyethylene sorbitan fatty acid esters.
4. The method of claim 1, wherein: in the step 2), the mixing temperature of the mixed powder and the binder is 100-180 ℃, and the granulated powder is particles sieved by a screen, and the particle size range is 74-250 μm.
5. The method of claim 1, wherein: in the step 3), the forming pressure is 100-600 Mpa, and the mold temperature is 60-80 ℃.
6. The method of claim 1, wherein: and 4) dewaxing in a vacuum drying oven at the dewaxing temperature of 200-350 ℃ for 60-180 min.
7. The method of claim 1, wherein: in the step 5), the sintering temperature is 1000-1350 ℃, and the sintering time is 5-240 min.
8. The method of claim 7, wherein: the sintering is carried out in a protective atmosphere of pure hydrogen, or nitrogen, or argon, or a proportion of hydrogen and argon of 1-90 vol%.
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| CN101745640A (en) * | 2010-02-02 | 2010-06-23 | 哈尔滨工业大学 | Preparation method for metal ceramic composite special-shaped piece |
| CN103236548A (en) * | 2013-04-27 | 2013-08-07 | 华南理工大学 | Preparation method of multihole anode support of solid oxide fuel cell |
| CN104419855A (en) * | 2013-08-20 | 2015-03-18 | 东睦新材料集团股份有限公司 | Chromium-based alloy and manufacturing method thereof |
| CN111644625A (en) * | 2020-06-04 | 2020-09-11 | 东睦新材料集团股份有限公司 | Preparation method of chromium alloy fuel cell connecting piece |
| CN113067005A (en) * | 2021-03-19 | 2021-07-02 | 东睦新材料集团股份有限公司 | Preparation method of metal support plate for fuel cell |
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