CN116590648A - Preparation method of solid oxide fuel cell metal connector coating - Google Patents
Preparation method of solid oxide fuel cell metal connector coating Download PDFInfo
- Publication number
- CN116590648A CN116590648A CN202210116138.2A CN202210116138A CN116590648A CN 116590648 A CN116590648 A CN 116590648A CN 202210116138 A CN202210116138 A CN 202210116138A CN 116590648 A CN116590648 A CN 116590648A
- Authority
- CN
- China
- Prior art keywords
- powder
- coating
- connector
- manganese cobalt
- cobalt oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011248 coating agent Substances 0.000 title claims abstract description 123
- 238000000576 coating method Methods 0.000 title claims abstract description 123
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 38
- 239000002184 metal Substances 0.000 title claims abstract description 38
- 239000000446 fuel Substances 0.000 title claims abstract description 25
- 239000007787 solid Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 149
- WSHADMOVDWUXEY-UHFFFAOYSA-N manganese oxocobalt Chemical compound [Co]=O.[Mn] WSHADMOVDWUXEY-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000000463 material Substances 0.000 claims abstract description 35
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 29
- 239000011029 spinel Substances 0.000 claims abstract description 29
- 230000007704 transition Effects 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 26
- 229910000604 Ferrochrome Inorganic materials 0.000 claims abstract description 21
- 239000007921 spray Substances 0.000 claims abstract description 17
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 14
- 239000000956 alloy Substances 0.000 claims abstract description 14
- 238000007750 plasma spraying Methods 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 238000007788 roughening Methods 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims description 37
- 239000011572 manganese Substances 0.000 claims description 21
- 238000005245 sintering Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 9
- 230000003746 surface roughness Effects 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 4
- 239000000758 substrate Substances 0.000 description 32
- 239000010935 stainless steel Substances 0.000 description 30
- 229910001220 stainless steel Inorganic materials 0.000 description 30
- 230000003647 oxidation Effects 0.000 description 18
- 238000007254 oxidation reaction Methods 0.000 description 18
- 238000012360 testing method Methods 0.000 description 18
- 239000010410 layer Substances 0.000 description 13
- 239000012298 atmosphere Substances 0.000 description 10
- 230000007774 longterm Effects 0.000 description 7
- 238000005507 spraying Methods 0.000 description 7
- 229910052748 manganese Inorganic materials 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 238000000280 densification Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000004584 weight gain Effects 0.000 description 4
- 235000019786 weight gain Nutrition 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 244000137852 Petrea volubilis Species 0.000 description 2
- 206010040844 Skin exfoliation Diseases 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000005488 sandblasting Methods 0.000 description 2
- 238000005382 thermal cycling Methods 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/134—Plasma spraying
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—Metallic material
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/18—After-treatment
-
- 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
- H01M8/0297—Arrangements for joining electrodes, reservoir layers, heat exchange units or bipolar separators to each other
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Fuel Cell (AREA)
Abstract
The invention belongs to the field of fuel cells, and particularly relates to a preparation method of a solid oxide fuel cell metal connector coating, which comprises the following steps: a) Roughening the Fe-based alloy solid oxide fuel cell metal connector to obtain a pretreated connector; b) Feeding the transition coating material powder into a plasma spray gun, and performing plasma spraying on the surface of the pretreatment connecting body to form a transition coating; the components of the transition coating material powder comprise manganese cobalt oxide powder and ferrochrome alloy powder; c) The powder of the surface coating material is sent into a plasma spray gun, and plasma spraying is carried out on the transition coating to form a surface coating; the components of the surface coating material powder are manganese cobalt oxide powder; d) And c) carrying out heat treatment on the connector treated in the step c), and forming a coating with a double-layer spinel structure on the surface of the connector. The coating prepared by the method is not easy to peel off from the connector, and the service life is longer.
Description
Technical Field
The invention belongs to the field of fuel cells, and particularly relates to a preparation method of a metal connector coating of a solid oxide fuel cell.
Background
There are currently few materials that meet the long-term oxidation resistance and high electrical conductivity requirements for Solid Oxide Fuel Cell (SOFC) connector materials. The research directions of SOFC connector materials mainly include ceramic and metal materials. Compared with the ceramic connector, the metal connector has low production cost, easy preparation, good conductivity and low gas permeability.
At present, the metal connector material applied to the SOFC is mainly Fe-based alloy, and compared with other alloys, the Fe-based alloy has the advantages of low price, easiness in processing, close thermal expansion coefficient to that of a cell and the like, but the Fe-based alloy has problems, such as high oxidation rate under high temperature conditions, and an oxide coating on the surface is easy to crack and peel.
Disclosure of Invention
In view of the above, the invention aims to provide a preparation method of a metal connector coating of a solid oxide fuel cell, wherein the coating prepared by the method is not easy to peel off from the connector, and the service life is longer.
The invention provides a preparation method of a solid oxide fuel cell metal connector coating, which comprises the following steps:
a) Roughening the metal connector of the solid oxide fuel cell to obtain a pretreated connector;
the surface material of the solid oxide fuel cell metal connector is Fe-based alloy;
b) Feeding the transition coating material powder into a plasma spray gun, and performing plasma spraying on the surface of the pretreatment connecting body to form a transition coating;
the components of the transition coating material powder comprise manganese cobalt oxide powder and ferrochrome alloy powder;
c) The powder of the surface coating material is sent into a plasma spray gun, and plasma spraying is carried out on the transition coating to form a surface coating;
the components of the surface coating material powder are manganese cobalt oxide powder;
d) And c) carrying out heat treatment on the connector treated in the step c), and forming a coating with a double-layer spinel structure on the surface of the connector.
Preferably, in step a), the surface roughness of the pretreated link is 5 to 10 μm.
Preferably, in step b), the manganese cobalt oxide powder has a composition of Mn 1.5 Co 1.5 O 4 Powder and/or MnCo 2 O 4 A powder; the particle size of the manganese cobalt oxide powder is 200 nm-30 mu m.
Preferably, in the step b), the ferrochrome powder comprises Fe-Cr17 metal powder and/or Fe-Cr20 metal powder; the particle size of the ferrochrome powder is 600 nm-35 mu m.
Preferably, in the step b), the mass ratio of the manganese cobalt oxide powder to the ferrochrome powder is (4-9): (6-1).
Preferably, in step b), the thickness of the transitional coating is 30-60 μm.
Preferably, in step c), the manganese cobalt oxide powder is Mn 1.5 Co 1.5 O 4 Powder and/or MnCo 2 O 4 A powder; the particle size of the manganese cobalt oxide powder is 200 nm-30 mu m.
Preferably, in step c), the topcoat has a thickness of 50 to 80 μm.
Preferably, in step d), the heat treatment process specifically includes: and c) sintering and preserving heat of the connector treated in the step c) in sequence.
Preferably, in the step d), the sintering temperature is 950-1050 ℃; the sintering time is 0.5-1 h; the temperature of the heat preservation is 800-900 ℃; the heat preservation time is 1-2 h.
Compared with the prior art, the invention provides a preparation method of a solid oxide fuel cell metal connector coating. The preparation method comprises the following steps: a) Roughening the metal connector of the solid oxide fuel cell to obtain a pretreated connector; the surface material of the solid oxide fuel cell metal connector is Fe-based alloy; b) Feeding the transition coating material powder into a plasma spray gun, and performing plasma spraying on the surface of the pretreatment connecting body to form a transition coating; the components of the transition coating material powder comprise manganese cobalt oxide powder and ferrochrome alloy powder; c) The powder of the surface coating material is sent into a plasma spray gun, and plasma spraying is carried out on the transition coating to form a surface coating; the components of the surface coating material powder are manganese cobalt oxide powder; d) And c) carrying out heat treatment on the connector treated in the step c), and forming a coating with a double-layer spinel structure on the surface of the connector. According to the method provided by the invention, the plasma spraying technology is utilized to spray the coating material on the surface of the metal connector, so that the bonding degree of the coating and the substrate is improved; furthermore, the adhesive force of the coating on the connector is further improved by roughening the connector before spraying; meanwhile, a transition coating is prepared between the metal connector and the spinel surface coating, so that the thermal expansion coefficients of the coating and the connector are more matched, the bonding strength of the connector and the coating is further increased, the risk of peeling between the coating and the connector under long-term high-temperature oxidation is reduced, and the service cycle of the material is prolonged.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph showing the specific surface resistance of a stainless steel substrate oxidized for a long period of time at 750℃as provided in example 1 of the present invention;
FIG. 2 is a plot of the specific surface resistance of a stainless steel substrate with a spinel coating prepared according to example 1 of the present invention for long-term oxidation at 750 ℃;
FIG. 3 is a graph of the specific resistance of a stainless steel substrate with a spinel coating prepared according to example 1 of the present invention after 100 thermal cycles;
FIG. 4 is a graph showing the weight gain of a stainless steel substrate with/without spinel coating provided in example 2 of the present invention oxidized for 120 hours at 750 ℃;
FIG. 5 is a graph of the surface specific resistance of a stainless steel substrate with/without spinel coating provided in example 3 of the present invention during long-term oxidation and thermal cycling.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a preparation method of a solid oxide fuel cell metal connector coating, which comprises the following steps:
a) Roughening the metal connector of the solid oxide fuel cell to obtain a pretreated connector;
b) Feeding the transition coating material powder into a plasma spray gun, and performing plasma spraying on the surface of the pretreatment connecting body to form a transition coating;
c) The powder of the surface coating material is sent into a plasma spray gun, and plasma spraying is carried out on the transition coating to form a surface coating;
d) And c) carrying out heat treatment on the connector treated in the step c), and forming a coating with a double-layer spinel structure on the surface of the connector.
In the present invention, in step a), the surface material of the solid oxide fuel cell metal connector is an Fe-based alloy, including but not limited to SUS430, SUS441, and Crofer22 APU; the roughening treatment includes, but is not limited to, one or more of sand blasting, chemical etching, and sanding; the surface roughness (Ry) of the pretreated link is preferably 5 to 10. Mu.m, and may be specifically 5. Mu.m, 5.5. Mu.m, 6. Mu.m, 6.5. Mu.m, 7. Mu.m, 7.5. Mu.m, 8. Mu.m, 8.5. Mu.m, 9. Mu.m, 9.5. Mu.m, or 10. Mu.m.
In the present invention, in step a), the surface roughness of the connection body can be increased by roughening the connection body, and the adhesion force at the time of coating the subsequent coating layer can be increased.
In the present invention, in the step b), the composition of the transition coating material powder includes manganese cobalt oxide powder and ferrochrome alloy powder. Wherein the manganese cobalt oxide powder preferably contains Mn as a component 1.5 Co 1.5 O 4 Powder and/or MnCo 2 O 4 A powder; the particle size of the manganese cobalt oxide powder is preferably 200nm to 30. Mu.m, and specifically 200nm, 250nm, 300nm, 350nm, 400nm, 450nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1. Mu.m, 5. Mu.m, 10. Mu.m, 15. Mu.m, 20. Mu.m, 25. Mu.m, or 30. Mu.m. In one embodiment provided by the invention, the manganese cobalt oxide powder is preferably manganese cobalt oxide powder with the particle size of 250-300 nm or manganese cobalt oxide powder with the particle size of 10-20 mu m, and the manganese cobalt oxide powder is preferably Mn 1.5 Co 1.5 O 4 Powder or MnCo 2 O 4 And (3) powder. In another embodiment of the present invention, the manganese cobalt oxide powder is preferably a mixture (denoted as powder A) of manganese cobalt oxide powder (denoted as powder (1)) having a particle size of 250 to 300nm and manganese cobalt oxide powder (denoted as powder (2)) having a particle size of 10 to 20 μm, the powder (1) is preferably Mn 1.5 Co 1.5 O 4 Powder, powder (2) is preferably MnCo 2 O 4 The mass ratio of the powder (1) in the powder A is preferably not less than 60% by weight.
In the present invention, in step b), the composition of the ferrochrome powder is preferably Fe-Cr17 metal powder and/or Fe-Cr20 metal powder; the particle size of the ferrochrome powder is preferably 600nm to 35. Mu.m, and specifically 600nm, 650nm, 700nm, 750nm, 800nm, 850nm, 900nm, 950nm, 1. Mu.m, 3. Mu.m, 5. Mu.m, 10. Mu.m, 15. Mu.m, 20. Mu.m, 25. Mu.m, 30. Mu.m, or 35. Mu.m. In one embodiment provided by the invention, the ferrochrome powder is preferably ferrochrome powder with the grain size of 700-900 nm or ferrochrome powder with the grain size of 20-30 mu m; the ferrochrome powder is preferably Fe-Cr17 metal powder or Fe-Cr20 metal powder. In another embodiment provided by the present invention, the ferrochrome powder is preferably a mixture (denoted as powder B) of a ferrochrome powder (denoted as powder (3)) having a particle size of 700 to 900nm and a ferrochrome powder (denoted as powder (4)) having a particle size of 20 to 30 μm, the particle size of the powder (3) is more preferably 800nm, the component is preferably a fe—cr20 metal powder, the particle size of the powder (4) is more preferably 25 μm, the component is preferably a fe—cr20 metal powder, and the mass ratio of the powder (4) in the powder B is preferably 50 to 80wt%.
In the present invention, in the step b), the mass ratio of the manganese cobalt oxide powder to the ferrochrome powder is preferably (4 to 9): (6-1), which may be specifically 4:6, 5:5, 6:4, 7:3, 8:2 or 9:1.
In the present invention, in the step b), the powder of the transition coating material is preferably a mixed powder with different particle sizes, which is more suitable for a plasma spraying technology, so that the coating compactness can be increased while the conductivity of the coating can be ensured.
In the present invention, in step b), the thickness of the transition coating is preferably 30 to 60. Mu.m, and may specifically be 30 μm, 31 μm, 32 μm, 33 μm, 34 μm, 35 μm, 36 μm, 37 μm, 38 μm, 39 μm, 40 μm, 41 μm, 42 μm, 43 μm, 44 μm, 45 μm, 46 μm, 47 μm, 48 μm, 49 μm, 50 μm, 51 μm, 52 μm, 53 μm, 54 μm, 55 μm, 56 μm, 57 μm, 58 μm, 59 μm or 60 μm.
In the invention, in the step b), the expansion coefficient between the coating and the connector under the high-temperature condition can be more matched by arranging the transition coating, so that the bonding strength of the connector and the coating is increased.
In the present invention, in the step c), the composition of the powder of the topcoat material is manganese cobalt oxide powder; the manganese cobalt oxide powder preferably has a composition of Mn 1.5 Co 1.5 O 4 Powder and/or MnCo 2 O 4 A powder; the saidThe particle size of the manganese cobalt oxide powder is preferably 200nm to 30. Mu.m, and specifically 200nm, 250nm, 300nm, 350nm, 400nm, 450nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1. Mu.m, 5. Mu.m, 10. Mu.m, 15. Mu.m, 20. Mu.m, 25. Mu.m, or 30. Mu.m. In one embodiment provided by the invention, the manganese cobalt oxide powder is preferably manganese cobalt oxide powder with the particle size of 250-300 nm or manganese cobalt oxide powder with the particle size of 10-20 mu m, and the manganese cobalt oxide powder is preferably Mn 1.5 Co 1.5 O 4 Powder and/or MnCo 2 O 4 Powder of Mn 1.5 Co 1.5 O 4 Powder and MnCo 2 O 4 The mass ratio of the powder is preferably (6-9): (4-1), specifically may be 6:4, 6.5:3.5, 7:3, 7.5:2.5, 8:2, 8.5:1.5 or 9:1. In another embodiment of the present invention, the manganese cobalt oxide powder is preferably a mixture (denoted as powder A) of manganese cobalt oxide powder (denoted as powder (1)) having a particle size of 250 to 300nm and manganese cobalt oxide powder (denoted as powder (2)) having a particle size of 10 to 20 μm, the powder (1) is preferably Mn 1.5 Co 1.5 O 4 Powder or MnCo 2 O 4 Powder, powder (2) is preferably Mn 1.5 Co 1.5 O 4 Powder or MnCo 2 O 4 The mass ratio of the powder (1) in the powder A is preferably not less than 10wt%, and specifically may be 10wt%, 20wt%, 30wt%, 40wt%, 50wt%, 60wt%, 70wt%, 80wt% or 90wt%.
In the invention, in the step c), the powder of the surface coating material is preferably mixed powder with different particle sizes, which is more suitable for a plasma spraying technology, so that the coating compactness can be improved while the conductivity of the coating can be ensured.
In the present invention, in step c), the thickness of the coating is preferably 50 to 80. Mu.m, and may be in particular 50 μm, 51 μm, 52 μm, 53 μm, 54 μm, 55 μm, 56 μm, 57 μm, 58 μm, 59 μm, 60 μm, 61 μm, 62 μm, 63 μm, 64 μm, 65 μm, 66 μm, 67 μm, 68 μm, 69 μm, 70 μm, 71 μm, 72 μm, 73 μm, 74 μm, 75 μm, 76 μm, 77 μm, 78 μm, 79 μm or 80 μm.
In the present invention, in step d), the specific process of the heat treatment preferably includes: and c) sintering and preserving heat of the connector treated in the step c) in sequence. Wherein the sintering and the heat preservation can be performed in an air, hydrogen, argon or nitrogen atmosphere, preferably in an air atmosphere; the sintering temperature is preferably 950-1050 ℃, and can be 950 ℃, 960 ℃, 970 ℃, 980 ℃, 990 ℃, 1000 ℃, 1010 ℃, 1020 ℃, 1030 ℃, 1040 ℃ or 1050 ℃; the sintering time is preferably 0.5 to 1h, and can be specifically 0.5h, 0.6h, 0.7h, 0.8h, 0.9h or 1h; the temperature of the heat preservation is preferably 800-900 ℃, and can be specifically 800 ℃, 810 ℃, 820 ℃, 830 ℃, 840 ℃, 850 ℃, 860 ℃, 870 ℃, 880 ℃, 890 ℃ or 900 ℃; the heat preservation time is preferably 1-2 h, and can be specifically 1h, 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, 1.6h, 1.7h, 1.8h, 1.9h or 2h.
In the invention, in the step d), the densification of the coating is further realized by performing high-temperature treatment, the density of the coating is improved, and the oxidation resistance of the coating is improved.
In order to test the performance of the coating prepared by the method, the method is preferable to preserve heat for different time in the working atmosphere of the cathode of the solid oxide fuel cell after the preparation of the coating is finished, and the initial and long-term high-temperature oxidation behaviors of the material before and after the coating is set are compared and inspected; meanwhile, oxidation is preferably carried out in the cathode working atmosphere of the solid oxide fuel cell after the coating preparation is completed, and the surface specific resistance (ASR) of the formed surface oxide film is measured by adopting a four-electrode method to analyze the electrical property of the surface oxide film.
In the invention, the specific operation process of testing the specific resistance of the surface by using the four-electrode method comprises the following steps: coating a layer of uniform silver paste on the surface of the connector, placing the sample into a baking oven, preserving heat at 140 ℃ for 20min, and operating the other side in the same way; four platinum wires are respectively threaded on two sides of two silver nets and are covered on the surface of the connector, and the silver nets and the platinum wires are used as current collection and test wires; applying a force of 1 N.m on two sides perpendicular to the device by using a torque wrench, so that the interface bonding is better; and then placing the sample into a muffle furnace, and testing the specific surface resistance value of the sample.
According to the method provided by the invention, the plasma spraying technology is utilized to spray the coating material on the surface of the metal connector, so that the bonding degree of the coating and the substrate is improved; furthermore, the adhesive force of the coating on the connector is further improved by roughening the connector before spraying; meanwhile, a transition coating is prepared between the metal connector and the spinel surface coating, so that the thermal expansion coefficients of the coating and the connector are more matched, the bonding strength of the connector and the coating is further increased, the risk of peeling between the coating and the connector under long-term high-temperature oxidation is reduced, and the service cycle of the material is prolonged.
For clarity, the following examples are provided in detail.
Example 1
Grinding the surface of a stainless steel substrate (SUS 441) with 800-1000 mesh sand paper to make the surface roughness Ry reach 10 mu m; mn is adopted 1.5 Co 1.5 O 4 Powder (particle size 10-20 μm), fe-Cr20 metal powder (particle size 25 μm), fe-Cr20 metal powder (particle size 800 nm) are uniformly mixed according to the mass ratio of 5:4:1, and are sent into a plasma spray gun to be sprayed for 60min, so as to obtain a transition coating with the thickness of 40 μm; mn is then added 1.5 Co 1.5 O 4 Powder (particle size 10-20 μm) and Mn 1.5 Co 1.5 O 4 Mixing the powder (with the particle size of 300 nm) according to the mass ratio of 7:3, and then sending the mixture into a plasma spray gun for spraying for 120min to obtain a surface coating with the thickness of 60 mu m; finally, carrying out coating aftertreatment, carrying out densification sintering for 0.5h at the temperature of 1000 ℃ and in the air atmosphere, and then carrying out heat preservation for 2h at the temperature of 800 ℃ in the air atmosphere to obtain a coating with a double-layer spinel structure; wherein the inner layer is (Mn, co) 3 O 4 And Cr (V) 2 O 3 The outer layer of the mixed coating is (Mn, co) 3 O 4 Spinel coating.
The manganese cobalt oxide spinel coated and uncoated stainless steel substrates were heated to 750 ℃ in a tube furnace and maintained at a constant temperature, respectively, and surface specific resistance was measured using a four electrode method. The test results are shown in FIGS. 1-2. FIG. 1 is a graph showing the specific surface resistance of a stainless steel substrate oxidized at 750℃for a long period of time according to example 1 of the present invention, and FIG. 2 is a graph showing a stainless steel substrate oxidized at 750℃for a long period of time according to example 1 of the present invention, which is coated with spinelSurface specific resistance curve graph. As can be seen by comparing FIGS. 1-2, the surface specific resistance of the coating of the manganese cobalt oxide spinel is significantly lower than that of the uncoated stainless steel substrate, and the surface specific resistance of the stainless steel substrate after 720 hours of oxidation is basically stabilized at 26mΩ cm 2 The experiment was stopped, and the specific surface resistance of the manganese cobalt oxide spinel coating at this time was 12mΩ·cm 2 After oxidation is continued for a period of time, thermal cycle is carried out, so that the specific surface resistance is obviously increased, but is still lower than 22mΩ cm within 1000h 2 。
Placing the stainless steel substrate with the manganese cobalt oxide spinel coating into a tube furnace, heating to 750 ℃ from room temperature and maintaining the temperature for 1h, adopting a four-electrode method to perform a surface specific resistance test, completing a thermal cycle test, and simulating the start-stop environment of the solid oxide fuel cell stack; then cooling to room temperature and raising the temperature to 750 ℃ again, carrying out 100 times of thermal cycle tests, wherein the total thermal cycle time is about 12 hours, and the total thermal cycle time lasts 1189 hours, and the test result is shown in figure 3. FIG. 3 is a graph of the surface specific resistance after 100 thermal cycles of a stainless steel substrate provided with a spinel coating according to example 1 of the present invention. As can be seen by comparing FIG. 3, the specific surface resistance after oxidation for 720 hours relative to the stainless steel substrate was 26mΩ cm 2 The specific surface resistance of the coated stainless steel substrate was 3.1mΩ·cm 2 Reduced by about 90%.
Example 2
The stainless steel substrate (SUS 441) was subjected to sand blasting treatment to have a surface roughness Ry of 10 μm; taking a proper amount of Mn 1.5 Co 1.5 O 4 Powder (particle size 250-300 nm) and MnCo 2 O 4 Powder (particle size of 20 μm) is uniformly mixed according to a mass ratio of 6:4; mixing Fe-Cr20 metal powder (particle size of 25 μm) with the mixed powder according to the ratio of 7:3, and spraying for 60min to obtain a transition coating with the thickness of 40 μm; and then MnCo is added 2 O 4 Powder (particle size 10-20 μm) and Mn 1.5 Co 1.5 O 4 Mixing the powder (particle size of 10-20 μm) in a mass ratio of 2:8, and then sending into a plasma spray gun for spraying for 120min to obtain a surface coating with a thickness of 60 μm; finally, coating post-treatment is carried out, densification and sintering are carried out at 1050 ℃ and under air atmosphereForming 1h, and then preserving heat for 3h in an air atmosphere at 800 ℃ to obtain a coating with a double-layer spinel structure; wherein the inner layer is (Mn, co) 3 O 4 And Cr (V) 2 O 3 The outer layer of the mixed coating is (Mn, co) 3 O 4 Spinel coating.
The manganese cobalt oxide spinel coating and the stainless steel substrate without the coating are respectively placed into a tubular furnace in air atmosphere, heated to 750 ℃ and kept at constant temperature, and the oxidation weight increase test is continuously carried out, wherein the specific test operation is as follows: respectively placing 15 test samples into five tube furnaces, placing three samples in each furnace, and heating to 750 ℃ from room temperature; taking out 3 samples from one furnace at intervals of 24 hours, weighing, and calculating an average value to obtain oxidation weight gain data of the samples in the heating time; five experiments were performed together, with a maximum oxidation of 120h. The test results are shown in FIG. 4, which is a graph showing the weight gain of the stainless steel substrate with/without spinel coating provided in example 2 of the present invention oxidized for 120 hours at 750 ℃, in which 441 represents the uncoated stainless steel substrate and 441+MOC represents the stainless steel substrate with manganese cobalt oxide spinel coating. As can be seen from fig. 4, the oxidation weight gain of the coated stainless steel substrate was reduced by about 90% relative to the stainless steel substrate.
Example 3
Sequentially polishing the surface of a stainless steel substrate (SUS 430) by using sand paper with 800-1400 meshes to ensure that the surface roughness Ry reaches 8 mu m; mn is adopted 1.5 Co 1.5 O 4 Uniformly mixing powder (particle size of 20 μm) and Fe-Cr17 metal powder (particle size of 30 μm) according to a mass ratio of 8:2, and spraying for 60min in a plasma spray gun to obtain a transition coating with a thickness of 50 μm; mn is then added 1.5 Co 1.5 O 4 Powder (particle size 250-300 nm) and MnCo 2 O 4 Uniformly mixing the powder (with the particle size of 10-20 mu m) in a mass ratio of 9:1, and sending into a plasma spray gun for spraying for 120min to obtain a surface coating with the thickness of 60 mu m; finally, carrying out coating aftertreatment, carrying out densification sintering for 0.8h at the temperature of 1000 ℃ and in the air atmosphere, and then carrying out heat preservation for 3h at the temperature of 850 ℃ in the air atmosphere to obtain a coating with a double-layer spinel structure; wherein the inner layer is (Mn, co) 3 O 4 And Cr (V) 2 O 3 MixingThe coating layer is an outer layer (Mn, co) 3 O 4 Spinel coating.
Respectively placing a stainless steel substrate with a manganese cobalt oxide spinel coating and a stainless steel substrate without the manganese cobalt oxide spinel coating into a tubular furnace with air atmosphere, heating to 750 ℃ and preserving heat for 142 hours, and carrying out surface specific resistance test by adopting a four-electrode method; and (3) placing the sample subjected to high-temperature oxidation into a tube furnace, heating to 750 ℃ from room temperature, maintaining the temperature for 1h, performing surface specific resistance test by adopting a four-electrode method, and then cooling to the room temperature to complete one-time thermal cycle test, and simulating the start-stop environment of the solid oxide fuel cell stack. The thermal cycle test was continued for a total of 320 hours. The test results are shown in FIG. 5. Fig. 5 is a graph showing the surface specific resistance of a stainless steel substrate with/without spinel coating provided in example 3 of the present invention during long-term oxidation and thermal cycling, in which SUS430 refers to a stainless steel substrate without coating and SUS430+ MOC refers to a stainless steel substrate prepared with manganese cobalt oxide spinel coating. As can be seen from fig. 5, the specific surface resistance of the coated stainless steel substrate increases more smoothly during the thermal cycle phase than the stainless steel substrate.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A method for preparing a coating of a metal connector of a solid oxide fuel cell, comprising the steps of:
a) Roughening the metal connector of the solid oxide fuel cell to obtain a pretreated connector;
the surface material of the solid oxide fuel cell metal connector is Fe-based alloy;
b) Feeding the transition coating material powder into a plasma spray gun, and performing plasma spraying on the surface of the pretreatment connecting body to form a transition coating;
the components of the transition coating material powder comprise manganese cobalt oxide powder and ferrochrome alloy powder;
c) The powder of the surface coating material is sent into a plasma spray gun, and plasma spraying is carried out on the transition coating to form a surface coating;
the components of the surface coating material powder are manganese cobalt oxide powder;
d) And c) carrying out heat treatment on the connector treated in the step c), and forming a coating with a double-layer spinel structure on the surface of the connector.
2. The method according to claim 1, wherein in step a), the surface roughness of the pretreated link is 5 to 10 μm.
3. The method according to claim 1, wherein in the step b), the manganese cobalt oxide powder has a composition of Mn 1.5 Co 1.5 O 4 Powder and/or MnCo 2 O 4 A powder; the particle size of the manganese cobalt oxide powder is 200 nm-30 mu m.
4. The method according to claim 1, wherein in step b), the ferrochrome powder is composed of Fe-Cr17 metal powder and/or Fe-Cr20 metal powder; the particle size of the ferrochrome powder is 600 nm-35 mu m.
5. The method according to claim 1, wherein in the step b), the mass ratio of the manganese cobalt oxide powder to the ferrochrome powder is (4 to 9): (6-1).
6. The method according to claim 1, wherein in step b), the thickness of the transitional coating is 30-60 μm.
7. The method according to claim 1, wherein in step c), the manganese cobalt oxide powder is Mn 1.5 Co 1.5 O 4 Powder and/or MnCo 2 O 4 A powder; the particle size of the manganese cobalt oxide powder is 200 nm-30 mu m.
8. The method according to claim 1, wherein in step c), the thickness of the topcoat is 50 to 80 μm.
9. The method according to claim 1, wherein in step d), the heat treatment process specifically comprises:
and c) sintering and preserving heat of the connector treated in the step c) in sequence.
10. The method according to claim 9, wherein in step d), the sintering temperature is 950-1050 ℃; the sintering time is 0.5-1 h;
the temperature of the heat preservation is 800-900 ℃; the heat preservation time is 1-2 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210116138.2A CN116590648A (en) | 2022-02-07 | 2022-02-07 | Preparation method of solid oxide fuel cell metal connector coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210116138.2A CN116590648A (en) | 2022-02-07 | 2022-02-07 | Preparation method of solid oxide fuel cell metal connector coating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116590648A true CN116590648A (en) | 2023-08-15 |
Family
ID=87599597
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210116138.2A Pending CN116590648A (en) | 2022-02-07 | 2022-02-07 | Preparation method of solid oxide fuel cell metal connector coating |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116590648A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116023808A (en) * | 2022-12-30 | 2023-04-28 | 山东能源集团有限公司 | Protective coating and preparation method thereof |
| CN117778939A (en) * | 2024-02-28 | 2024-03-29 | 北矿新材科技有限公司 | Preparation method of connector coating, connector and battery or electrolytic cell group |
-
2022
- 2022-02-07 CN CN202210116138.2A patent/CN116590648A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116023808A (en) * | 2022-12-30 | 2023-04-28 | 山东能源集团有限公司 | Protective coating and preparation method thereof |
| CN117778939A (en) * | 2024-02-28 | 2024-03-29 | 北矿新材科技有限公司 | Preparation method of connector coating, connector and battery or electrolytic cell group |
| CN117778939B (en) * | 2024-02-28 | 2024-04-30 | 北矿新材科技有限公司 | Preparation method of connector coating, connector and battery or electrolytic cell group |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN116590648A (en) | Preparation method of solid oxide fuel cell metal connector coating | |
| JP5134949B2 (en) | Conductive steel-ceramic composite and method for producing the same | |
| JP2002289248A (en) | Unit cell for fuel cell and solid electrolytic fuel cell | |
| JP5315476B1 (en) | Current collecting member and fuel cell | |
| JP5572146B2 (en) | Protective film forming method, cell connecting member, and solid oxide fuel cell | |
| JPH01189866A (en) | Electrode for fuel cell and manufacture thereof | |
| JP5731683B2 (en) | Cell connecting member, cell for solid oxide fuel cell, and electrodeposition coating used for production thereof | |
| WO2022193524A1 (en) | Method for preparing metal support plate for fuel cell | |
| CN112609141B (en) | Protective coating for fuel cell connector and method for preparing same | |
| CN107275656A (en) | SOFC spinelle/metal connector composite and preparation method thereof | |
| JP2017063012A (en) | Method for manufacturing fuel cell member | |
| CN108998789B (en) | Alloy connector with surface coated with Mn-Co spinel coating and preparation method thereof | |
| JP6486107B2 (en) | Manufacturing method of fuel cell member | |
| CN112290070A (en) | Composite coating for SOFC connector and preparation method thereof | |
| JP5832405B2 (en) | Method for forming protective film, method for manufacturing cell connecting member, and method for manufacturing cell for solid oxide fuel cell | |
| CN111690926B (en) | Method for preparing compact Mn-Co spinel protective layer of stainless steel connector by hot-pressing sintering method | |
| JP2004142971A (en) | Process for joining ceramic material to stainless steel | |
| JP6742104B2 (en) | Method for producing inter-cell connecting member, and method for producing solid oxide fuel cell cell | |
| JP2011165652A (en) | Method of manufacturing interconnector for fuel cell, and interconnector for fuel cell | |
| Lee et al. | Development of metal supported solid oxide fuel cell based on interconnect coating | |
| JP2008234927A (en) | Manufacturing method of solid oxide fuel cell | |
| JP2015201422A (en) | Method of manufacturing cell for solid oxide fuel cell, method for joining inter-cell connection member, and joining method | |
| CN112261743B (en) | Ni-based thick film heating element for in-situ generation of alumina insulating layer and preparation method thereof | |
| JP2019087370A (en) | Collector | |
| JP6948791B2 (en) | Manufacturing method of cell-to-cell connection member and manufacturing method of cell for solid oxide fuel cell |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |