CN117026320A - (Cu,Fe,Mn) 3 O 4 Spinel protective layer, preparation method and application thereof, and SOFC (solid oxide Fuel cell) connector - Google Patents
(Cu,Fe,Mn) 3 O 4 Spinel protective layer, preparation method and application thereof, and SOFC (solid oxide Fuel cell) connector Download PDFInfo
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- CN117026320A CN117026320A CN202310879240.2A CN202310879240A CN117026320A CN 117026320 A CN117026320 A CN 117026320A CN 202310879240 A CN202310879240 A CN 202310879240A CN 117026320 A CN117026320 A CN 117026320A
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- protective layer
- spinel
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- stainless steel
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- 239000011241 protective layer Substances 0.000 title claims abstract description 107
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 53
- 239000011029 spinel Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229910052748 manganese Inorganic materials 0.000 title description 10
- 229910052742 iron Inorganic materials 0.000 title description 5
- 239000000446 fuel Substances 0.000 title description 4
- 239000007787 solid Substances 0.000 title description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 51
- 238000007747 plating Methods 0.000 claims abstract description 43
- 239000000758 substrate Substances 0.000 claims abstract description 43
- 238000009713 electroplating Methods 0.000 claims abstract description 40
- 239000010935 stainless steel Substances 0.000 claims abstract description 37
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 32
- 238000005245 sintering Methods 0.000 claims abstract description 11
- 239000011248 coating agent Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 239000002738 chelating agent Substances 0.000 claims description 2
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 239000001433 sodium tartrate Substances 0.000 claims description 2
- 229960002167 sodium tartrate Drugs 0.000 claims description 2
- 235000011004 sodium tartrates Nutrition 0.000 claims description 2
- 239000001119 stannous chloride Substances 0.000 claims description 2
- 235000011150 stannous chloride Nutrition 0.000 claims description 2
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 abstract description 18
- 230000003647 oxidation Effects 0.000 abstract description 16
- 229910045601 alloy Inorganic materials 0.000 abstract description 4
- 239000000956 alloy Substances 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000010949 copper Substances 0.000 description 47
- 230000000052 comparative effect Effects 0.000 description 24
- 239000000243 solution Substances 0.000 description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 239000011572 manganese Substances 0.000 description 14
- 239000010410 layer Substances 0.000 description 13
- 238000001878 scanning electron micrograph Methods 0.000 description 11
- 239000010965 430 stainless steel Substances 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 8
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 229910000616 Ferromanganese Inorganic materials 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- 239000011651 chromium Substances 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 230000004584 weight gain Effects 0.000 description 5
- 235000019786 weight gain Nutrition 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 229910000914 Mn alloy Inorganic materials 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000011240 wet gel Substances 0.000 description 2
- 241000270728 Alligator Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910002551 Fe-Mn Inorganic materials 0.000 description 1
- 229910015136 FeMn Inorganic materials 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- BQCFCWXSRCETDO-UHFFFAOYSA-N [Fe].[Mn].[Cu] Chemical compound [Fe].[Mn].[Cu] BQCFCWXSRCETDO-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010288 cold spraying Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- HPDFFVBPXCTEDN-UHFFFAOYSA-N copper manganese Chemical compound [Mn].[Cu] HPDFFVBPXCTEDN-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical group [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000003405 preventing effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B1/00—Single-crystal growth directly from the solid state
- C30B1/10—Single-crystal growth directly from the solid state by solid state reactions or multi-phase diffusion
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/22—Complex oxides
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
- C30B29/66—Crystals of complex geometrical shape, e.g. tubes, cylinders
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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
-
- 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 Kinetics & Catalysis (AREA)
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- Crystallography & Structural Chemistry (AREA)
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Abstract
The invention discloses a kind of alloy (Cu, fe, mn) 3 O 4 Spinel protective layer and preparation thereofMethods, applications and SOFC connectors, relating to the field of electrochemical technology, said preparation (Cu, fe, mn) 3 O 4 A method of spinel protection comprising: s1, in Cu-containing 2+ Performing a first electroplating on the substrate in the first electroplating solution; s2 is in the presence of Fe 2+ And Mn of 2+ In the second electroplating solution, performing second electroplating on the substrate obtained in the step S1; s3, sintering the substrate obtained in the step S2 to obtain (Cu, fe, mn) on the surface of the substrate 3 O 4 A spinel protective layer; in step S2, the conditions of the second plating include: the current density is 1-5A/dm 2 The electroplating time is 5-15 min. Compared with the prior binary spinel protective layer, the invention provides (Cu, fe, mn) 3 O 4 The spinel protective layer is more attached to the thermal expansion coefficient of the stainless steel substrate, and the adhesion to the stainless steel connector at high temperature is obviously better than that of (Cu, mn) 3 O 4 A protective layer coated with (Cu, fe, mn) 3 O 4 The weight of the spinel protective layer stainless steel connector is not increased basically after being oxidized for 350 hours at 800 ℃; the protective layer is complete after oxidation for 2000 hours at 800 ℃.
Description
Technical field:
the invention relates to the technical field of electrochemistry, in particular to a method for preparing (Cu, fe, mn) 3 O 4 Spinel protective layer, preparation method and application thereof, and SOFC connector.
The background technology is as follows:
with the development of industrialization, energy crisis is increasingly advanced, and greenhouse effect caused by fossil fuel is also increasingly serious. To overcome this dilemma, clean energy and renewable energy are important concerns for human research. The solid oxide fuel cell (Solid Oxide Fuel Cell, abbreviated as SOFC) is an energy conversion device for directly converting chemical energy into electric energy, has the advantages of cleanness, high efficiency, compressibility and the like, and is one of the most effective technologies for solving the environmental pollution caused by fossil fuels. The connector is used as a connecting unit of the SOFC, and has the functions of providing a gas flow channel for fuel gas and oxidizing gas and isolating the fuel gas from the oxidizing gas. At present, ceramic materials are generally used as the material of the connector of the high-temperature SOFC cell, but the use of metal connectors is possible with the development of low-temperature SOFC cells. Compared with the ceramic connector, the metal connector has the advantages of low cost, easy processing, good thermoelectric performance and the like.
Stainless steel is one of the most commonly used metal connectors, which has the advantages of good corrosion resistance, high electrical conductivity, high thermal conductivity, etc., but stainless steel is easily oxidized at a high temperature of 600-800 ℃, resulting in an increase in interface resistance and diffusion of Cr element to poison the cathode. In order to improve oxidation resistance of the stainless steel and prevent Cr volatilization, a protective layer of spinel type may be coated on the surface of the stainless steel.
At present, the spinel protection layer commonly used for stainless steel connectors is mainly composed of (Cu, mn) 3 O 4 Spinel protective layer, but (Cu, mn) 3 O 4 The spinel protective layer has large difference in thermal expansion coefficient and poor oxidation resistance with the stainless steel connector, and obvious cracking and falling-off phenomena of the protective layer are caused after the spinel protective layer is operated for a long time at 600-800 ℃.
Compared with the method for preparing the coating by directly spraying spinel powder on the stainless steel connector, the density of the protective layer prepared by the electroplating oxidation process is higher. However, when manganese is contained in the plating solution, since manganese is the metal having the most negative potential that can be electrolytically reduced from the aqueous solution, the reduction potential is-1.42V. It is difficult to co-plate a manganese-containing coating directly on a substrate, such as when co-plating ferro-manganese, only iron and no manganese are present in the coating. In the prior art, a large current density (10A/dm 2 Above) plating to prepare a manganese alloy coating, but a high current density causes hydrogen to be precipitated at the cathode, so that the obtained manganese alloy layer is not dense and gaps appear.
Therefore, it is highly desirable to find a protective layer comprising manganese spinel that has a coefficient of thermal expansion comparable to that of stainless steel connectors and is dense.
The invention comprises the following steps:
the invention aims to overcome the defects of the prior art (Cu, mn) 3 O 4 The spinel protective layer and the stainless steel connector have large thermal expansion coefficient, and are easy to fall off from the stainless steel connector after long-term high-temperature oxidation, thereby providing (Cu, fe, mn) 3 O 4 Spinel protective layer, preparation method and application thereof, and SOFC connector.
The inventors of the present invention found that ternary copper-iron-manganese (Cu, fe, mn) is formed by doping iron element into a binary copper-manganese spinel protective layer 3 O 4 A spinel protective layer having a coefficient of thermal expansion comparable to that of the stainless steel connector,and the adhesive force with the stainless steel connector is strong, and the oxidation resistance of the stainless steel connector can be improved.
In order to achieve the above object, one of the objects of the present invention is to provide a process for producing (Cu, fe, mn) 3 O 4 A method of spinel protection, the method comprising:
s1, in Cu-containing 2+ Performing a first electroplating on the substrate in the first electroplating solution;
s2 is in the presence of Fe 2+ And Mn of 2+ In the second electroplating solution, performing second electroplating on the substrate obtained in the step S1;
s3, sintering the substrate obtained in the step S2 to obtain (Cu, fe, mn) on the surface of the substrate 3 O 4 And a spinel protective layer.
In step S2, the conditions of the second plating include: the current density is 1-5A/dm 2 The electroplating time is 5-15 min.
It is a second object of the present invention to provide a composition (Cu, fe, mn) obtained according to the method 3 O 4 And a spinel protective layer.
It is a further object of the present invention to provide a method for producing the above-mentioned alloy 3 O 4 Use of a spinel protective layer in a SOFC connector.
The fourth object of the present invention is to provide an SOFC connector comprising a stainless steel substrate and a protective layer coated on the surface of the stainless steel substrate, wherein the protective layer is the above (Cu, fe, mn) 3 O 4 And a spinel protective layer.
Through the technical scheme, the invention has the following technical effects:
1. the invention prepares (Cu, fe, mn) on a stainless steel substrate by an electroplating-oxidation method for the first time 3 O 4 A ternary spinel oxide protective layer.
2. The invention is 1-5A/dm 2 Under the condition of realizing the co-plating of the ferro-manganese to form a ferro-manganese composite plating layer, not only reducing the hydrogen evolution reaction in the plating solution, accelerating the deposition of manganese, improving the current efficiency of a system, but also improving the density of a protective layer; in addition, the low current electroplating is greatly reducedThe high energy consumption of manganese plating is reduced, and the manufacturing cost of the protective layer can be reduced.
3. Relatively conventional (Cu, mn) 3 O 4 Binary spinel, provided by the invention (Cu, fe, mn) 3 O 4 The spinel protective layer is more attached to the thermal expansion coefficient of the stainless steel substrate, and the adhesion to the stainless steel connector at high temperature is obviously better than that of (Cu, mn) 3 O 4 A protective layer coated with (Cu, fe, mn) 3 O 4 The weight of the spinel protective layer stainless steel connector is not increased basically after the spinel protective layer is oxidized for 350 hours at 800 ℃, and the protective layer is complete after the spinel protective layer is oxidized for 2000 hours at 800 ℃.
Description of the drawings:
FIG. 1 is a sectional SEM image of the protective layer prepared in example 1;
FIG. 2 is a sectional SEM image of the protective layer prepared in example 2;
FIG. 3 is a sectional SEM image of the protective layer prepared in comparative example 1;
FIG. 4 is a sectional SEM image of the protective layer prepared in comparative example 2;
FIG. 5 is an SEM image and an EDS image of the protective layer obtained in comparative example 3, which was treated at 800℃for 200 hours;
FIG. 6 is an SEM image and an EDS image of the protective layer obtained in comparative example 4, which was treated at 800℃for 200 hours;
FIG. 7 is an SEM image and an EDS image of the protective layer obtained in example 3 at 800℃for 200 hours;
FIG. 8 is an SEM image and an EDS image of the protective layer obtained in example 1 at 800℃for 200 hours;
FIG. 9 is an SEM image and an EDS image of the protective layer obtained in example 4 at 800℃for 200 hours;
FIG. 10 is an optical photograph showing the protective layer obtained in comparative example 5 at 800℃for 200 hours;
FIG. 11 is an XRD pattern of the protective layer obtained in example 4;
FIG. 12 is an XRD pattern of the protective layer obtained in example 4 and the protective layer obtained in comparative example 6;
FIG. 13 is an XRD pattern (unoxidized) of the electroplated protective layer of comparative example 7;
FIG. 14 is an oxidative weight gain curve for the connectors of comparative example 8 and example 4;
FIG. 15 is an optical photograph of the connectors of comparative example 8 and example 4 after heat treatment;
FIG. 16 is a sectional SEM image of a connector obtained in comparative example 9.
The specific embodiment is as follows:
the invention is further described below with reference to specific embodiments and illustrations in order to make the technical means, the creation features, the achievement of the purpose and the effect of the implementation of the invention easy to understand.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Preparation (Cu, fe, mn) 3 O 4 A method of spinel protection, the method comprising:
s1, in Cu-containing 2+ Performing a first electroplating on the substrate in the first electroplating solution;
s2 is in the presence of Fe 2+ And Mn of 2+ In the second electroplating solution, performing second electroplating on the substrate obtained in the step S1;
s3, sintering the substrate obtained in the step S2 to obtain (Cu, fe, mn) on the surface of the substrate 3 O 4 Spinel coating.
In step S2, the conditions of the second plating include: the current density is 1-5A/dm 2 The electroplating time is 5-15 min.
In the invention, too high current density of the second plating can lead to poor density of the protective layer, and the current density of the second plating is preferably 1-5A/dm 2 For example, 1A/dm 2 、2A/dm 2 、3A/dm 2 、4A/dm 2 、5A/dm 2 Or any value in the range formed by any two values described above. The second electroplatedToo short time can lead to the thickness of the protective layer to be small, cr in the connector cannot be effectively prevented from escaping in the high-temperature oxidation process, too long electroplating time can lead to the thickness of the protective layer to be too high, the adhesive force between the protective layer and the connector is reduced, the protective layer is easy to peel off from the connector after high-temperature oxidation, and under the preferred condition, the time of the second electroplating is 5-15 min, for example, can be 5min, 8min, 10min, 12min, 15min or any value in a range formed by any two values.
According to the present invention, preferably, in step S2, the second plating solution contains the following components in the following concentrations:
preferably, the chelating agent is selected from at least one of sodium citrate, disodium edetate and sodium tartrate.
Preferably, the buffer is selected from at least one of boric acid, phthalic acid and sodium acetate.
Preferably, the plating assistant is at least one selected from the group consisting of ammonium chloride, hydroxylamine hydrochloride and stannous chloride.
According to the present invention, preferably, in step S1, the first plating solution contains the following components in the following concentrations:
Cu 2+ 0.25～1.0mol/L
H + 0.1～0.5mol/L。
in the invention, the first electroplating time is too short, which can lead to small thickness of the protective layer, and in the high-temperature oxidation process, cr in the connector cannot be effectively prevented from escaping, while the first electroplating time is too long, which can lead to too high thickness of the protective layer, reduce the bonding strength of the protective layer and the connector, and lead to easy stripping of the protective layer from the connector after high-temperature oxidation. Preferred conditionsNext, in step S1, the conditions of the first plating include: the current density is 1-5A/dm 2 The electroplating time is 5-15 min.
In the present invention, the protective layer obtained in the steps S1 and S2 can be oxidized by sintering to obtain (Cu, fe, mn) 3 O 4 Preferably, in step S3, the conditions for sintering include: the temperature is 700-900 ℃ and the time is 2-10 h.
The invention also provides (Cu, fe, mn) prepared according to the method 3 O 4 And a spinel protective layer.
The invention also provides the (Cu, fe, mn) 3 O 4 Use of a spinel protective layer in a SOFC connector.
The invention also provides an SOFC connector, which comprises a stainless steel matrix and a protective layer coated on the surface of the stainless steel matrix, wherein the protective layer is the (Cu, fe, mn) 3 O 4 And a spinel protective layer. The type of stainless steel may be known to those skilled in the art, and may be 340 stainless steel, for example.
The present invention will be described in detail by way of specific examples.
In the following examples, the oxidation weight gain parameters were measured by the method of calculating the square of the oxidation weight gain per unit area from the difference in sample weights at different times of high temperature oxidation, as follows:
accurately weighing the dried stainless steel connector, and recording the mass m of the stainless steel connector 0 The method comprises the steps of carrying out a first treatment on the surface of the Placing the stainless steel connector into a pre-heated crucible, placing the crucible into a high-temperature muffle furnace, oxidizing in air at 800 ℃ for a certain time, cooling the oxidized sample to normal temperature in a dryer, accurately weighing again, and recording the mass m 1 The square of the oxidation weight gain is calculated according to formula (1):
in the formula (1), S is the area of the stainless steel connector.
In the plating of the following examples, a platinum electrode (20 mm. Times.20 mm. Times.1 mm) was used as the anode and 430 stainless steel was used as the cathode.
Before electroplating, the 430 stainless steel is pretreated by the following steps: polishing 430 stainless steel (with the size of 10mm multiplied by 2 mm) with 400-mesh, 600-mesh, 1000-mesh and 2000-mesh sand paper in sequence, and then sequentially placing the polished stainless steel in alkaline solution for degreasing and pickling to remove oxide films; and then sequentially ultrasonically cleaning with deionized water and absolute ethyl alcohol, and finally drying.
Example 1
S1, plating copper on the surface of 430 stainless steel, wherein the first electroplating solution comprises the following components:
CuSO 4 ·5H 2 O 0.5mol/L
H 2 SO 4 0.2mol/L
HCl 0.1g/L。
s2, co-plating an iron-manganese coating on the substrate obtained in the step S1, wherein the second electroplating solution comprises the following components (the pH value of the second electroplating solution is adjusted to be=5):
s3, placing the substrate obtained in the step S2 in a muffle furnace, sintering for 10h at 800 ℃ and forming (Cu, fe, mn) on the surface of 430 stainless steel 3 O 4 And (5) protecting the layer to obtain the connector.
Example 2 and comparative examples 1 to 2
Electroplating was performed using the electroplating solution of example 1, except that: the current density and plating time are shown in table 1.
TABLE 1
As can be seen from the comparison of FIGS. 1 to 3, the density of the protective layer decreases with the increase of the current density under the condition that the electroplating time is unchangedThe smaller the protective layer obtained by sintering is, the more compact; the invention realizes the control of the current density (2-5A/dm 2 ) Then, the surface of the copper plating layer is co-plated to prepare the ferro-manganese composite plating layer, and the ferro-manganese composite plating layer is prepared by further sintering and oxidizing (Cu, fe, mn) 3 O 4 And a spinel protective layer.
As can be seen from FIG. 4, when the current is increased to 15A/dm 2 When the high current is used, the hydrogen evolution effect is aggravated, so that hydrogen can be evolved in the electroplating process, the adhesion between the plating layer and the substrate is poor, and gaps are generated between the sintered protective layer and the substrate.
Examples 3-4 and comparative examples 3-5
Electroplating was performed using the electroplating solution of example 1, except that: the current density and plating time are shown in table 2.
TABLE 2
As can be seen from comparison of FIGS. 5 to 9, under the condition of constant current density, the volatilization inhibition effect of the protective layer on chromium element in the substrate is obviously enhanced along with the extension of the electroplating time, and the effect is better within 10-20 min (example 1/3/4) of the total electroplating time.
As shown in fig. 10, after the total plating time reached 40min (comparative example 5), the protective layer was peeled off after the connector was air-treated at 800 ℃ for 100 hours; in example 4, however, the total plating time was 20 minutes (FIG. 15A), and the protective layer did not change significantly when the connector was air-treated at 800℃for 2000 hours.
FIG. 11 is an XRD pattern of the protective layer obtained in example 4. As can be seen from FIG. 11, the main crystal phase of the protective layer obtained in example 4 is Cu of spinel structure 0.5 FeMn 1.5 O 4 。
Comparative examples 6 to 7
In comparative examples 6 to 7, the first plating, i.e., copper plating on the 340 stainless steel substrate surface was not performed, and the 340 stainless steel substrate surface was directly plated with a ferro-manganese plating layer, the composition of the plating solution was the same as in example 1, and the plating process was as shown in Table 3.
TABLE 3 Table 3
FIG. 12 is an XRD pattern of the protective layer obtained in example 4 and the protective layer obtained in comparative example 6, and it can be seen from FIG. 12 that when the iron-manganese plating layer is directly plated on the surface of 340 stainless steel substrate with a large current, the sintered product of the plating layer is Mn 2 O 3 And Fe (Fe) 2 O 3 Does not form a spinel phase.
FIG. 13 is an XRD pattern (unoxidized) of the electroplated coating of comparative example 7, as can be seen from FIG. 13, when the Fe-Mn coating was co-plated directly on the 430 stainless steel substrate with a small current, only the more pronounced Fe element peaks and no Mn and Cr peaks were present in the XRD pattern of the coating, indicating that only the Fe layer could be plated on the 430 stainless steel substrate with a small current, but not the co-Mn coating; furthermore, since no chromium peaks appear in the XRD pattern, it is suggested that iron originates from the plating layer rather than the stainless steel substrate.
Comparative example 8
The procedure of example 4 is followed, except that the second plating solution does not contain FeSO 4 ·7H 2 The composition of the second plating solution was as follows, and the plating process was as shown in Table 4.
TABLE 4 Table 4
The linker obtained in comparative example 8 (coated (Cu, mn) 3 O 4 Protective layer) and the linker ((Cu, fe, mn) obtained in example 4 3 O 4 Spinel protective layer) was treated at 800 ℃ for 350 hours, respectively, and the oxidative weight gain of both linkers at different times was recorded, and the results are shown in fig. 14. As can be seen from FIG. 14, the oxidation weight of the connector in example 4 was significantly lower than that of the connector in comparative example 8 when oxidized for 100 hours or more, indicating (Cu, fe, mn) 3 O 4 Spinel protective layer having a specific (CuMn) 3 O 4 The protective layer has better oxidation resistance.
FIG. 15 shows the connector (coating (Cu, mn)) obtained in comparative example 8 3 O 4 Protective layer) and the linker ((Cu, fe, mn) obtained in example 4 3 O 4 Spinel protective layer) after 2000 hours of treatment at 800 c, it can be seen from fig. 15 that the protective layer starts to develop large-area cracks and peeling off after the connector of comparative example 8 is treated in air at 800 c for 2000 hours. In example 4, the protective layer was only slightly cracked at the locations clamped by the alligator clip, thereby further illustrating (Cu, fe, mn) 3 O 4 Spinel protective layer having a specific (CuMn) 3 O 4 The protective layer has better protective effect.
The cracking and falling off of the protective layer are mainly related to the surface treatment of the substrate, the compactness of the protective layer and the difference of the thermal expansion coefficients of the protective layer and the substrate. In the invention, the material of the substrate and the surface treatment method are consistent, so that the influence of the substrate can be ignored. Therefore, in the invention, the difference of cracks and falling of the protective layer in each embodiment is mainly influenced by the density of the coating and the thermal expansion coefficient of the protective layer and the substrate, and the lower the density of the protective layer is, the easier the substrate is oxidized, so that the protective layer falls off; the larger the difference of the thermal expansion coefficients is, the more serious the cracking and falling-off phenomena of the protective layer are; in addition, cracking caused by the difference in thickness of the protective layer is because the thicker the protective layer is, the more serious the thermal expansion and contraction becomes, and thus the more serious the peeling and cracking become.
Comparative example 9
Is prepared by cold spraying (Cu, fe, mn) 3 O 4 A spinel protective layer, the method comprising:
1)(Cu,Fe,Mn) 3 O 4 preparation of powder
S1, 0.01mol Fe (NO) 3 ) 3 ·9H 2 O，0.01mol Cu(NO 3 ) 2 ·3H 2 O，0.01mol Mn(NO 3 ) 2 ·4H 2 O is dissolved in 200mL of deionized water to obtain solution 1;
0.02mol of citric acid and 0.01mol of EDTA are dissolved together in 200mL of deionized water, and NH is used 3 ·H 2 O adjusts the pH to 6.5 to obtain solution 2;
s2, dropwise adding the solution 1 into the solution 2 under the stirring condition, keeping the pH of the solution to be 6.5, reacting the mixed solution at 25 ℃ for 6 hours after the dropwise adding, stirring at the constant temperature of 80 ℃ for 12 hours to obtain wet gel, and drying the wet gel in an oven at 260 ℃ for 12 hours to obtain xerogel;
s3, placing the xerogel in a muffle furnace, sintering for 10 hours at 800 ℃, and ball milling to obtain (Cu, fe, mn) 3 O 4 Powder;
2) Spraying (Cu, fe, mn) on the substrate 3 O 4 Powder body
Will (Cu, fe, mn) 3 O 4 The powder is prepared into spray liquid and sprayed onto a 430 stainless steel (10 mm multiplied by 2 mm) sheet, and then the sheet is placed in a muffle furnace and treated for 2 hours at 800 ℃ to obtain cladding (Cu, fe, mn) 3 O 4 The spinel protective layer 430 stainless steel sheet, i.e., the connector.
A cross-sectional SEM image of the connector obtained in comparative example 9 is shown in FIG. 16, in which FIG. B is a partially enlarged view of the protective layer in FIG. A. As can be seen from FIG. 16, the cold spray method is used to prepare the alloy (Cu, fe, mn) 3 O 4 The spinel protective layer is loose and porous and has low density.
In conclusion, the alloy (Cu, fe, mn) was prepared on the surface of 430 stainless steel by electroplating-oxidation 3 O 4 The spinel oxide protective layer has good antioxidation effect on metal connector and good chromium volatilization preventing effect, and is adhered to substrate at high temperatureThe force is far stronger than (Cu, mn) 3 O 4 Spinel oxide, the protective layer meets technical requirements for SOFC connectors.
The foregoing has shown and described the basic principles and main features of the present invention and the advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. Preparation (Cu, fe, mn) 3 O 4 A method of spinel protection, the method comprising:
s1, in Cu-containing 2+ Performing a first electroplating on the substrate in the first electroplating solution;
s2 is in the presence of Fe 2+ And Mn of 2+ In the second electroplating solution, performing second electroplating on the substrate obtained in the step S1;
s3, sintering the substrate obtained in the step S2 to obtain (Cu, fe, mn) on the surface of the substrate 3 O 4 A spinel coating;
in step S2, the conditions of the second plating include: the current density is 1-5A/dm 2 The electroplating time is 5-15 min.
2. The method of claim 1, wherein in step S2, the second plating solution comprises the following concentrations of components:
3. the method of claim 2, wherein the chelating agent is selected from at least one of sodium citrate, disodium edetate, and sodium tartrate;
preferably, the buffer is selected from at least one of boric acid, phthalic acid and sodium acetate;
preferably, the plating assistant is at least one selected from the group consisting of ammonium chloride, hydroxylamine hydrochloride and stannous chloride.
4. The method of claim 1, wherein in step S1, the first plating solution comprises the following concentrations of components:
Cu 2+ 0.25～1.0mol/L
H + 0.1～0.5mol/L。
5. the method according to claim 4, wherein in step S1, the conditions of the first plating include: the current density is 1-5A/dm 2 The electroplating time is 5-15 min.
6. The method according to any one of claims 1 to 5, wherein in step S3, the sintering conditions include: the temperature is 700-900 ℃ and the time is 2-10 h.
7. (Cu, fe, mn) prepared by the process according to any one of claims 1 to 6 3 O 4 And a spinel protective layer.
8. The method of claim 7 (Cu, fe, mn) 3 O 4 Use of a spinel protective layer in a SOFC connector.
9. An SOFC connector comprising a stainless steel substrate and a protective layer coated on the surface of the stainless steel substrate, wherein the protective layer is (Cu, fe, mn) as claimed in claim 7 3 O 4 And a spinel protective layer.
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| CN202310879240.2A CN117026320A (en) | 2023-07-18 | 2023-07-18 | (Cu,Fe,Mn) 3 O 4 Spinel protective layer, preparation method and application thereof, and SOFC (solid oxide Fuel cell) connector |
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