CA2648740C - Multi-layer coating for metal containing surfaces - Google Patents
Multi-layer coating for metal containing surfaces Download PDFInfo
- Publication number
- CA2648740C CA2648740C CA2648740A CA2648740A CA2648740C CA 2648740 C CA2648740 C CA 2648740C CA 2648740 A CA2648740 A CA 2648740A CA 2648740 A CA2648740 A CA 2648740A CA 2648740 C CA2648740 C CA 2648740C
- Authority
- CA
- Canada
- Prior art keywords
- layer
- metal
- oxide
- coating
- multilayer coating
- 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.)
- Active
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 118
- 239000011248 coating agent Substances 0.000 title claims abstract description 102
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 74
- 239000002184 metal Substances 0.000 title claims abstract description 74
- 238000009792 diffusion process Methods 0.000 claims abstract description 55
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 37
- 239000000956 alloy Substances 0.000 claims abstract description 37
- 239000000700 radioactive tracer Substances 0.000 claims abstract description 34
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 33
- 239000001301 oxygen Substances 0.000 claims abstract description 33
- 150000001768 cations Chemical class 0.000 claims abstract description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000758 substrate Substances 0.000 claims abstract description 21
- 239000012298 atmosphere Substances 0.000 claims abstract description 19
- 230000003647 oxidation Effects 0.000 claims abstract description 19
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 19
- 239000007787 solid Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- -1 oxygen ions Chemical class 0.000 claims abstract description 13
- 239000000446 fuel Substances 0.000 claims abstract description 9
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 4
- 229910052596 spinel Inorganic materials 0.000 claims description 40
- 239000011029 spinel Substances 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 16
- 238000000151 deposition Methods 0.000 claims description 15
- 235000002639 sodium chloride Nutrition 0.000 claims description 11
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical group [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 9
- 150000004706 metal oxides Chemical class 0.000 claims description 9
- 229910052593 corundum Inorganic materials 0.000 claims description 7
- 239000010431 corundum Substances 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 229910052712 strontium Inorganic materials 0.000 claims description 7
- 229910052984 zinc sulfide Inorganic materials 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- 239000007769 metal material Substances 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- 235000012255 calcium oxide Nutrition 0.000 claims description 3
- 238000003618 dip coating Methods 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 229910002084 calcia-stabilized zirconia Inorganic materials 0.000 claims description 2
- 238000001652 electrophoretic deposition Methods 0.000 claims description 2
- 238000010285 flame spraying Methods 0.000 claims description 2
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 2
- 150000002602 lanthanoids Chemical class 0.000 claims description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 2
- 229910002085 magnesia-stabilized zirconia Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 238000007750 plasma spraying Methods 0.000 claims description 2
- 238000007650 screen-printing Methods 0.000 claims description 2
- 238000004528 spin coating Methods 0.000 claims description 2
- 238000005118 spray pyrolysis Methods 0.000 claims description 2
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims description 2
- 238000005240 physical vapour deposition Methods 0.000 claims 2
- 238000004549 pulsed laser deposition Methods 0.000 claims 2
- 238000007787 electrohydrodynamic spraying Methods 0.000 claims 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims 1
- 238000007581 slurry coating method Methods 0.000 claims 1
- 238000007592 spray painting technique Methods 0.000 claims 1
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Inorganic materials [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 28
- 150000002739 metals Chemical class 0.000 abstract description 9
- 101150115032 MAOB gene Proteins 0.000 abstract description 4
- 238000005524 ceramic coating Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 174
- 239000011651 chromium Substances 0.000 description 50
- 229910052804 chromium Inorganic materials 0.000 description 46
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 38
- 235000012721 chromium Nutrition 0.000 description 38
- 229940107218 chromium Drugs 0.000 description 38
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 239000002355 dual-layer Substances 0.000 description 10
- 230000008021 deposition Effects 0.000 description 8
- 229910001092 metal group alloy Inorganic materials 0.000 description 8
- 231100000572 poisoning Toxicity 0.000 description 8
- 230000000607 poisoning effect Effects 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 230000007774 longterm Effects 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910002262 LaCrO3 Inorganic materials 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 4
- 239000010436 fluorite Substances 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 229910017060 Fe Cr Inorganic materials 0.000 description 3
- 229910002544 Fe-Cr Inorganic materials 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 239000002737 fuel gas Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 238000001004 secondary ion mass spectrometry Methods 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229910003168 MnCo2O4 Inorganic materials 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 229910002370 SrTiO3 Inorganic materials 0.000 description 2
- QDLZHJXUBZCCAD-UHFFFAOYSA-N [Cr].[Mn] Chemical compound [Cr].[Mn] QDLZHJXUBZCCAD-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 239000010416 ion conductor Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 229960003903 oxygen Drugs 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- 229910002321 LaFeO3 Inorganic materials 0.000 description 1
- 229910018293 LaTiO3 Inorganic materials 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- 208000036366 Sensation of pressure Diseases 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 230000002730 additional effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 239000000788 chromium alloy Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 208000037516 chromosome inversion disease Diseases 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000007590 electrostatic spraying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000003455 independent Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000000155 isotopic effect Effects 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910001175 oxide dispersion-strengthened alloy Inorganic materials 0.000 description 1
- 238000005289 physical deposition Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000003405 preventing effect Effects 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052566 spinel group Inorganic materials 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical class OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0223—Composites
- H01M8/0228—Composites in the form of layered or coated products
-
- 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
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/60—Constructional parts of cells
- C25B9/65—Means for supplying current; Electrode connections; Electric inter-cell connections
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/70—Assemblies comprising two or more cells
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0206—Metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0215—Glass; Ceramic materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0215—Glass; Ceramic materials
- H01M8/0217—Complex oxides, optionally doped, of the type AMO3, A being an alkaline earth metal or rare earth metal and M being a metal, e.g. perovskites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0232—Metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0236—Glass; Ceramics; Cermets
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0241—Composites
- H01M8/0245—Composites in the form of layered or coated products
-
- 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
- H01M8/1286—Fuel cells applied on a support, e.g. miniature fuel cells deposited on silica supports
-
- 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
- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
- H01M8/241—Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes
- H01M8/2425—High-temperature cells with solid electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M2008/1293—Fuel cells with solid oxide electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
- H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
- H01M4/9033—Complex oxides, optionally doped, of the type M1MeO3, M1 being an alkaline earth metal or a rare earth, Me being a metal, e.g. perovskites
-
- 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
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Ceramic Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Fuel Cell (AREA)
- Physical Vapour Deposition (AREA)
- Laminated Bodies (AREA)
Abstract
A multi-layer coating for protection of metals and alloys against oxidation at high temperatures in general is provided. The invention utilizes a multi-layer ceramic coating on metals or alloys for increased oxidation-resistance, comprising at least two layers, wherein the first layer (3) which faces the metal containing surface and the second layer facing the surrounding atmosphere (4) both comprise an oxide, and wherein the first layer (3) has a tracer diffusion coefficient for cations Mm+, where M is the scale forming element of the alloy, and the second layer (4) has a tracer diffusion coefficient for oxygen ions O2- satisfying the following formula: wherein p(O2)in is the oxygen partial pressure in equilibrium between the metallic sub-strate and MaOb, p(O2)ex is the oxygen partial pressure in the reaction atmosphere, DM is the tracer diffusion coefficient of the metal cations Mm+ in the first layer (3), and DO is O2- tracer diffusion coefficient in the second layer (4). The coating may be used in high temperature devices, particularly for coating intercon- nect materials in solid oxide electrolytic devices, including solid oxide fuel cells (SOFCs) and solid oxide electrolysis cells (SOECs).
Description
MULTI-LAYER COATING FOR METAL CONTAINING SURFACES
Field of the Invention The present invention relates to a multi-layer coating for the protection of metals and metal alloys against oxidation at high temperatures. The coating may be used in high temperature devices, particularly for coating interconnect materials in solid oxide electro-lytic devices, including solid oxide fuel cells (SOFCs) and solid oxide electrolysis cells (SOECs).
Background art Applications of solid oxide electrolytic devices include the power generation by SOFCs and production of fuel gases by SOECs. In both devices, SOFCs and SOECs, individual cells are stacked together, with interconnect plates separating the cells, so as to obtain a higher energy output by electricity or by fuel gases, respectively. The interconnect plates separate the fuel gas from the oxidant, which is typically air, and furthermore function as the electrical connection between individual cells in a stack.
Hence, the requirements for an interconnect plate include long term durability, i.e. high oxidation resistance in an oxidizing and reducing atmosphere at high temperatures, i.e.
above 500 C, good electrical conductivity in an oxidizing and reducing atmosphere at high temperatures, further a thermal expansion coefficient (TEC) matching with the cell.
Commonly, metallic materials are employed as interconnect materials, since they pos-sess a high thermal and electrical conductivity, are available at low costs and easy to machine.
However, during aging under operation conditions, oxides form on both sides of the me-tallic interconnect. The growth of said oxides disadvantageously leads to an increased electrical resistance across the interconnect plate and, thus, increased power loss.
Therefore, high temperature resistant alloys have been suggested, which contain Si, Al and/or Cr, which form a dense SiO2 (silica), A1203 (alumina) or Cr203 (chromic) protective oxide layer. Especially alloys forming a chromia layer during operation have been inves-tigated as interconnects due to a good balance of the oxidation kinetics and electrical conductivity of chromia, as compared to silica and alumina. Based on all requirements of the interconnect, ferritic iron-chromium alloys and chromium-rich alloys have so far been considered as the most promising interconnect materials.
US-A-5608174 discloses an oxide dispersion strengthened chromium-rich alloy, having a chromium content of more than 65% by weight. Said alloy forms a chromia scale during aging under operation. The growth rate of chromia at operation temperatures >
800 C is however too high, which in turn results in the electrical resistance across the interconnect plate reaching unacceptable high values due to the low conductivity of chromia.
A further problem when using chromia-forming alloys as interconnects is the evaporation of chromium containing oxides and oxy-hydroxides on the air side of the interconnect during operation. Said evaporation leads to deposition of chromium-containing oxides at the air-electrode-electrolyte interface, which decreases the electrode performance in the long term. This phenomenon is known as "chromium poisoning".
Attempts to avoid the high electrical resistance and chromium poisoning from the chromia scale have been made by designing alloys which form a duplex Cr203-(Mn,Cr)304 oxide scale, with the manganese chromium spinel positioned above a layer of chromia.
US-A1-2003/0059335 proposes a chromium oxide forming iron-based alloy, comprising 12 to 28 wt% chromium and small amounts of La, Mn, Ti, Si, and Al. The material is ca-pable of forming at its surface a MnCr2O4 spinel phase at temperatures of 700 C to 950 C.
EP-B-1298228 relates to a steel material suitable as an interconnect material for fuel cells, the material comprising 15 to 30 wt% Cr and forming oxide films having good elec-trical conductivity at 700 C to 950 C.
The formed manganese chromium spinel has advantageously a lower vaporization pres-sure for chromium containing species than chromia itself, and a higher electrical conduc-tivity. However, the chromium containing spinel still evaporates chromium containing species, and thus a sufficient protection cannot be realized. Moreover, Cr-diffusion is in fact faster in the spinel than in the chromia and thus the formation of a dublex scale leads to an increased rate of the corrosion, thereby reducing the overall lifetime of the device.
It has been further suggested to modify the oxide scale grown on the alloy by applying coatings on the surface of the alloy instead of using the alloy alone. Said coatings may reduce the growth rate of the oxide scale, increase the electrical conductivity of the grown oxide, and reduce the chromium evaporation from the interconnect. The coating of the alloys may, for example, be performed by applying a dense coating on the intercon-nect, or may be done by applying a porous coating.
US-A-6054231 discloses the application of a metallic coating on the chromium-containing interconnect. The coated interconnect will form a conductive oxide layer con-taining chromium during aging. The metallic coating is considered to be a sink for chro-mium diffusing outwards from the alloy.
The proposed coating, however, does not stop chromium containing species from diffus-ing further outwards from the alloy. Therefore, metallic coatings forming a chromium con-taining oxide do not act as an effective diffusion barrier towards chromium diffusion. In-stead, the metal coating merely impedes the chromium diffusion during the initial stages of the oxidation. Furthermore, the metallic coating does not solve the problem regarding chromium poisoning.
US-A-5942349 proposes to deposit an oxide coating on the interconnect such that a layer of chromium containing spinel is formed in a reaction between a chromia scale formed on the interconnect and the applied oxide coating. The coating initially impedes chromium poisoning of the cathode by catching chromium from the interconnect in the coating forming the spinel.
However, the proposed coating does also not act as a sufficient diffusion barrier for chromium from the interconnect. The oxide layer formed on the interconnect will continue to grow in thickness and thereby result in an increasing electrical resistance across the interconnect plate. Furthermore, Cr-poisoning will occur during long term operation, since the formed spinel becomes itself chromium rich and the respective oxides evaporate therefrom into the air-electrode-electrolyte interface.
Field of the Invention The present invention relates to a multi-layer coating for the protection of metals and metal alloys against oxidation at high temperatures. The coating may be used in high temperature devices, particularly for coating interconnect materials in solid oxide electro-lytic devices, including solid oxide fuel cells (SOFCs) and solid oxide electrolysis cells (SOECs).
Background art Applications of solid oxide electrolytic devices include the power generation by SOFCs and production of fuel gases by SOECs. In both devices, SOFCs and SOECs, individual cells are stacked together, with interconnect plates separating the cells, so as to obtain a higher energy output by electricity or by fuel gases, respectively. The interconnect plates separate the fuel gas from the oxidant, which is typically air, and furthermore function as the electrical connection between individual cells in a stack.
Hence, the requirements for an interconnect plate include long term durability, i.e. high oxidation resistance in an oxidizing and reducing atmosphere at high temperatures, i.e.
above 500 C, good electrical conductivity in an oxidizing and reducing atmosphere at high temperatures, further a thermal expansion coefficient (TEC) matching with the cell.
Commonly, metallic materials are employed as interconnect materials, since they pos-sess a high thermal and electrical conductivity, are available at low costs and easy to machine.
However, during aging under operation conditions, oxides form on both sides of the me-tallic interconnect. The growth of said oxides disadvantageously leads to an increased electrical resistance across the interconnect plate and, thus, increased power loss.
Therefore, high temperature resistant alloys have been suggested, which contain Si, Al and/or Cr, which form a dense SiO2 (silica), A1203 (alumina) or Cr203 (chromic) protective oxide layer. Especially alloys forming a chromia layer during operation have been inves-tigated as interconnects due to a good balance of the oxidation kinetics and electrical conductivity of chromia, as compared to silica and alumina. Based on all requirements of the interconnect, ferritic iron-chromium alloys and chromium-rich alloys have so far been considered as the most promising interconnect materials.
US-A-5608174 discloses an oxide dispersion strengthened chromium-rich alloy, having a chromium content of more than 65% by weight. Said alloy forms a chromia scale during aging under operation. The growth rate of chromia at operation temperatures >
800 C is however too high, which in turn results in the electrical resistance across the interconnect plate reaching unacceptable high values due to the low conductivity of chromia.
A further problem when using chromia-forming alloys as interconnects is the evaporation of chromium containing oxides and oxy-hydroxides on the air side of the interconnect during operation. Said evaporation leads to deposition of chromium-containing oxides at the air-electrode-electrolyte interface, which decreases the electrode performance in the long term. This phenomenon is known as "chromium poisoning".
Attempts to avoid the high electrical resistance and chromium poisoning from the chromia scale have been made by designing alloys which form a duplex Cr203-(Mn,Cr)304 oxide scale, with the manganese chromium spinel positioned above a layer of chromia.
US-A1-2003/0059335 proposes a chromium oxide forming iron-based alloy, comprising 12 to 28 wt% chromium and small amounts of La, Mn, Ti, Si, and Al. The material is ca-pable of forming at its surface a MnCr2O4 spinel phase at temperatures of 700 C to 950 C.
EP-B-1298228 relates to a steel material suitable as an interconnect material for fuel cells, the material comprising 15 to 30 wt% Cr and forming oxide films having good elec-trical conductivity at 700 C to 950 C.
The formed manganese chromium spinel has advantageously a lower vaporization pres-sure for chromium containing species than chromia itself, and a higher electrical conduc-tivity. However, the chromium containing spinel still evaporates chromium containing species, and thus a sufficient protection cannot be realized. Moreover, Cr-diffusion is in fact faster in the spinel than in the chromia and thus the formation of a dublex scale leads to an increased rate of the corrosion, thereby reducing the overall lifetime of the device.
It has been further suggested to modify the oxide scale grown on the alloy by applying coatings on the surface of the alloy instead of using the alloy alone. Said coatings may reduce the growth rate of the oxide scale, increase the electrical conductivity of the grown oxide, and reduce the chromium evaporation from the interconnect. The coating of the alloys may, for example, be performed by applying a dense coating on the intercon-nect, or may be done by applying a porous coating.
US-A-6054231 discloses the application of a metallic coating on the chromium-containing interconnect. The coated interconnect will form a conductive oxide layer con-taining chromium during aging. The metallic coating is considered to be a sink for chro-mium diffusing outwards from the alloy.
The proposed coating, however, does not stop chromium containing species from diffus-ing further outwards from the alloy. Therefore, metallic coatings forming a chromium con-taining oxide do not act as an effective diffusion barrier towards chromium diffusion. In-stead, the metal coating merely impedes the chromium diffusion during the initial stages of the oxidation. Furthermore, the metallic coating does not solve the problem regarding chromium poisoning.
US-A-5942349 proposes to deposit an oxide coating on the interconnect such that a layer of chromium containing spinel is formed in a reaction between a chromia scale formed on the interconnect and the applied oxide coating. The coating initially impedes chromium poisoning of the cathode by catching chromium from the interconnect in the coating forming the spinel.
However, the proposed coating does also not act as a sufficient diffusion barrier for chromium from the interconnect. The oxide layer formed on the interconnect will continue to grow in thickness and thereby result in an increasing electrical resistance across the interconnect plate. Furthermore, Cr-poisoning will occur during long term operation, since the formed spinel becomes itself chromium rich and the respective oxides evaporate therefrom into the air-electrode-electrolyte interface.
Coatings of a similar kind, where a spinel is formed in a reaction between the intercon-nect and an oxide coating have been proposed in DE-A1-10306649. Said spinel is ini-tially chromium free due to a reaction between the alloy and a spinel forming element in the coating.
However, this coating nevertheless suffers from the above described problems, since the chromium transport from the alloy is not entirely stopped and the reaction layer, although being initially free from chromium, will eventually contain chromium. Thus, Cr-poisoning and increasing electrical resistance will be the result during long term operation. Said coating is, thus, not suitable for applications requiring a very long durability of SOFC and SOEC stacks.
Furthermore, porous coatings of conductive oxides with a perovskite structure have been applied on interconnects as coatings to increase the electrical conductivity of the formed oxide scale and to stop the chromium poisoning, as described in e.g. Y.
Larring et al., Journal of the Electrochemical Society 147 (9); 3251-3256 (2000). These coatings have the same drawbacks as mentioned in the above examples.
US-A1-2003/0194592 discloses an interconnect structure for solid oxide electrolytic de-vices with a coating consisting of two layers. The first layer comprises a Cr-containing electronic conductive oxide covered by a second layer, which acts as a diffusion barrier for oxygen. The second layer also stops chromium diffusion from the first layer. The sec-ond layer is a metallic layer, preferably a platinum layer. However, platinum is undesira-bly expensive, making a commercialization of SOFC and SOEC technology cumber-some.
WO-A1-2006/059942 relates to a strip for use as an electrical contact consisting of a me-tallic base material which is coated with a metallic layer based on a metal or metal alloy, and further with at least one reactive layer containing at least one element or compound which forms a spinel and/or perovskite structure with the metal or metal alloy when oxi-dized.
The metal layer coating allows a tailor made perovskite/spinel layer due to a precise con-trol the amount of different elements contained in the metal layer so as to be independ-ent from the composition of the metallic base material. When oxidized, a single perovskite/spinel layer is formed on the metallic base material, which provides a surface with high electrical conductivity and a low contact resistance. Said layer is however insuf-ficient to prevent the further growth of the oxide layer during operation.
Furthermore, if a chromium-containing metallic material is employed either as the metallic base material or as a component of the metallic layer, chromium-poisoning will still occur.
WO-A1-2006/059943 discloses a fuel component consisting of a metallic base material coated with at least one metallic layer based on a metal or metal alloy, and at least one reactive layer comprising at least one element or compound which forms at least one complex mixed oxide with the metal or metal alloy when oxidized.
The precise composition of the coating can be tailor-made to achieve the exact formation of the wanted complex metal oxide structure which may be in form of a spinel, perovskite and/or any other ternary or quaternary metal oxide structure upon oxidation with the de-sired properties, such as good conductivity and good corrosion resistance.
However, the formed oxide layer is insufficient to prevent the further growth of the oxide layer during operation of the fuel component. If furthermore a chromium-containing me-tallic material is employed as the metallic base material or metallic coating layer, chro-mium-poisoning will still occur.
The long term durability of the interconnects described in the prior art up to date is not sufficient for many applications. The use of specifically designed alloys for interconnect materials does not eliminate the problem of oxide growth on the interconnect, considera-bly resulting in an insufficient life time when the interconnects are used in solid oxide cells or the like. Moreover, if chromium-containing metallic materials are employed, which are so far the most preferred materials for interconnects, chromium poisoning of the electrode will still occur; the use of the so far proposed coatings on said alloys cannot eliminate the undesired oxide growth, and does not prevent chromium poisoning.
Fur-ther, the use of expensive metals, such as platinum, although leading to better results, is not feasible for the commercial potential of solid state devices, such as SOFCs and SOECs, due to the high price.
Alloys utilized for high temperature applications often form a protective silica layer, alu-mina layer or chromia layer to protect the alloy against further oxidation.
Coatings to be applied on alloys to increase the oxidation protection have been suggested in prior art.
These include coatings in the ternary phase system Ni-Pt-Al, MCrAIY coatings, TBC
coatings, diffusion coatings etc. as described in e.g. J.R. Nicholls, JOM-Journal of the Minerals Metals & Materials Society 52 (1); 28-35 (2000).
Obiect of the present invention It is the object of the present invention to overcome the problems of the prior art coatings and to provide a multi-layer coating suitable for metal containing surfaces for high tem-perature applications, the coating ensuring a long term durability of, for example, metallic interconnects in SOECs and SOFCs, to provide a SOEC and a SOFC comprising said coating, and further to provide a method for producing said coating.
Brief description of the invention The above object is achieved by a multilayer coating suitable for metal containing surfaces comprising at least two layers, wherein the first layer faces the metal containing surface and the second layer faces the surrounding atmosphere, and both the first layer and the second layer comprise an oxide, and wherein the first layer has a tracer diffusion coefficient for cations Mm+, wherein M is the scale forming element of the alloy, and the second layer has a tracer diffusion coefficient for oxygen ions 02 satisfying the following formula:
In P( 2 )ex (Do + 2 DM )d In p(O2) < 5.10-13 cm2 I s l in P(02)h, wherein p(02);,, is the oxygen partial pressure in equilibrium between the metallic substrate and MaOb, P(02)ex is the oxygen partial pressure in the reaction atmosphere, DM is the tracer diffusion coefficient of the metal cations Mm+ in the first layer, and Do is 02 tracer diffusion coefficient in the second layer, wherein the first layer comprises an oxide having a perovskite structure or a fluorite structure, and wherein the second layer comprises an oxide having a spinel structure, a rock salt structure, a corundum structure, or a wurtzite structure.
However, this coating nevertheless suffers from the above described problems, since the chromium transport from the alloy is not entirely stopped and the reaction layer, although being initially free from chromium, will eventually contain chromium. Thus, Cr-poisoning and increasing electrical resistance will be the result during long term operation. Said coating is, thus, not suitable for applications requiring a very long durability of SOFC and SOEC stacks.
Furthermore, porous coatings of conductive oxides with a perovskite structure have been applied on interconnects as coatings to increase the electrical conductivity of the formed oxide scale and to stop the chromium poisoning, as described in e.g. Y.
Larring et al., Journal of the Electrochemical Society 147 (9); 3251-3256 (2000). These coatings have the same drawbacks as mentioned in the above examples.
US-A1-2003/0194592 discloses an interconnect structure for solid oxide electrolytic de-vices with a coating consisting of two layers. The first layer comprises a Cr-containing electronic conductive oxide covered by a second layer, which acts as a diffusion barrier for oxygen. The second layer also stops chromium diffusion from the first layer. The sec-ond layer is a metallic layer, preferably a platinum layer. However, platinum is undesira-bly expensive, making a commercialization of SOFC and SOEC technology cumber-some.
WO-A1-2006/059942 relates to a strip for use as an electrical contact consisting of a me-tallic base material which is coated with a metallic layer based on a metal or metal alloy, and further with at least one reactive layer containing at least one element or compound which forms a spinel and/or perovskite structure with the metal or metal alloy when oxi-dized.
The metal layer coating allows a tailor made perovskite/spinel layer due to a precise con-trol the amount of different elements contained in the metal layer so as to be independ-ent from the composition of the metallic base material. When oxidized, a single perovskite/spinel layer is formed on the metallic base material, which provides a surface with high electrical conductivity and a low contact resistance. Said layer is however insuf-ficient to prevent the further growth of the oxide layer during operation.
Furthermore, if a chromium-containing metallic material is employed either as the metallic base material or as a component of the metallic layer, chromium-poisoning will still occur.
WO-A1-2006/059943 discloses a fuel component consisting of a metallic base material coated with at least one metallic layer based on a metal or metal alloy, and at least one reactive layer comprising at least one element or compound which forms at least one complex mixed oxide with the metal or metal alloy when oxidized.
The precise composition of the coating can be tailor-made to achieve the exact formation of the wanted complex metal oxide structure which may be in form of a spinel, perovskite and/or any other ternary or quaternary metal oxide structure upon oxidation with the de-sired properties, such as good conductivity and good corrosion resistance.
However, the formed oxide layer is insufficient to prevent the further growth of the oxide layer during operation of the fuel component. If furthermore a chromium-containing me-tallic material is employed as the metallic base material or metallic coating layer, chro-mium-poisoning will still occur.
The long term durability of the interconnects described in the prior art up to date is not sufficient for many applications. The use of specifically designed alloys for interconnect materials does not eliminate the problem of oxide growth on the interconnect, considera-bly resulting in an insufficient life time when the interconnects are used in solid oxide cells or the like. Moreover, if chromium-containing metallic materials are employed, which are so far the most preferred materials for interconnects, chromium poisoning of the electrode will still occur; the use of the so far proposed coatings on said alloys cannot eliminate the undesired oxide growth, and does not prevent chromium poisoning.
Fur-ther, the use of expensive metals, such as platinum, although leading to better results, is not feasible for the commercial potential of solid state devices, such as SOFCs and SOECs, due to the high price.
Alloys utilized for high temperature applications often form a protective silica layer, alu-mina layer or chromia layer to protect the alloy against further oxidation.
Coatings to be applied on alloys to increase the oxidation protection have been suggested in prior art.
These include coatings in the ternary phase system Ni-Pt-Al, MCrAIY coatings, TBC
coatings, diffusion coatings etc. as described in e.g. J.R. Nicholls, JOM-Journal of the Minerals Metals & Materials Society 52 (1); 28-35 (2000).
Obiect of the present invention It is the object of the present invention to overcome the problems of the prior art coatings and to provide a multi-layer coating suitable for metal containing surfaces for high tem-perature applications, the coating ensuring a long term durability of, for example, metallic interconnects in SOECs and SOFCs, to provide a SOEC and a SOFC comprising said coating, and further to provide a method for producing said coating.
Brief description of the invention The above object is achieved by a multilayer coating suitable for metal containing surfaces comprising at least two layers, wherein the first layer faces the metal containing surface and the second layer faces the surrounding atmosphere, and both the first layer and the second layer comprise an oxide, and wherein the first layer has a tracer diffusion coefficient for cations Mm+, wherein M is the scale forming element of the alloy, and the second layer has a tracer diffusion coefficient for oxygen ions 02 satisfying the following formula:
In P( 2 )ex (Do + 2 DM )d In p(O2) < 5.10-13 cm2 I s l in P(02)h, wherein p(02);,, is the oxygen partial pressure in equilibrium between the metallic substrate and MaOb, P(02)ex is the oxygen partial pressure in the reaction atmosphere, DM is the tracer diffusion coefficient of the metal cations Mm+ in the first layer, and Do is 02 tracer diffusion coefficient in the second layer, wherein the first layer comprises an oxide having a perovskite structure or a fluorite structure, and wherein the second layer comprises an oxide having a spinel structure, a rock salt structure, a corundum structure, or a wurtzite structure.
Said object is further achieved by a method of forming the above multilayer coating comprising the steps of:
- forming the first layer (3) on the metal surface; and - depositing the second layer (4) on the first layer (3).
Said object is finally achieved by a solid oxide fuel cell stack and a solid oxide electrolysis cell stack comprising the above multilayer coating.
Figures The invention will in the following be explained with reference to Figure 1 which illus-trates a multi-layer coating in accordance with the present invention.
Detailed description of the invention In the following, the invention will be described in more detail.
The multilayer coating suitable for metal containing surfaces in accordance with the pre-sent invention comprises at least two layers, wherein the first layer (3) which faces the metal containing surface and the second layer facing the atmosphere (4) both comprise an oxide, and wherein the first layer (3) has a tracer diffusion coefficient for cations M"", (where M is the scale forming element of the alloy), and the second layer (4) has a tracer diffusion coefficient for oxygen ions 02' satisfying the following formula:
In P(0i)..
j (Do + 2 DM)d In p(O2) <5.10-"cm2 /s Inp(02)y, 2 wherein p(02);f is the oxygen partial pressure in equilibrium between the metallic sub-strate and Ma0b, p(O2),x is the oxygen partial pressure in the reaction atmosphere, DM is the tracer diffusion coefficient of the metal cations M"" in the first layer (3), and Do is 02-tracer diffusion coefficient in the second layer (4).
The first layer (3) is capable of minimizing the outward diffusion of cations, while the sec-ond layer (4) minimizes the inward diffusion of oxygen ions. Due to said structure, oxide scale growth on the metal containing surfaces can be effectively suppressed.
- forming the first layer (3) on the metal surface; and - depositing the second layer (4) on the first layer (3).
Said object is finally achieved by a solid oxide fuel cell stack and a solid oxide electrolysis cell stack comprising the above multilayer coating.
Figures The invention will in the following be explained with reference to Figure 1 which illus-trates a multi-layer coating in accordance with the present invention.
Detailed description of the invention In the following, the invention will be described in more detail.
The multilayer coating suitable for metal containing surfaces in accordance with the pre-sent invention comprises at least two layers, wherein the first layer (3) which faces the metal containing surface and the second layer facing the atmosphere (4) both comprise an oxide, and wherein the first layer (3) has a tracer diffusion coefficient for cations M"", (where M is the scale forming element of the alloy), and the second layer (4) has a tracer diffusion coefficient for oxygen ions 02' satisfying the following formula:
In P(0i)..
j (Do + 2 DM)d In p(O2) <5.10-"cm2 /s Inp(02)y, 2 wherein p(02);f is the oxygen partial pressure in equilibrium between the metallic sub-strate and Ma0b, p(O2),x is the oxygen partial pressure in the reaction atmosphere, DM is the tracer diffusion coefficient of the metal cations M"" in the first layer (3), and Do is 02-tracer diffusion coefficient in the second layer (4).
The first layer (3) is capable of minimizing the outward diffusion of cations, while the sec-ond layer (4) minimizes the inward diffusion of oxygen ions. Due to said structure, oxide scale growth on the metal containing surfaces can be effectively suppressed.
In the above formula, the tracer diffusion coefficient for cations and the tracer diffusion coefficient for oxygen ions satisfy said formula in a temperature range of from about 500 to about 1000 C. While the coefficients may satisfy said below and/or above said tem-perature range, depending on the respective values, it is however not critical for the pre-sent invention.
The oxygen tracer diffusion coefficient as referred to throughout the present invention can be measured in independent tests, as described in detail in R.A. De Souza et al., Solid State Ionics, 106 (3-4): 175 (1998). The coefficient is determined by means of the Isotopic Exchange Depth Profile method (IEDP). 180/160 exchange anneals are per-formed at different temperatures at P02 of about 1 atm, and the subsequent 180 diffusion profiles are determined by Secondary Ion Mass Spectroscopy (SIMS).
The cation tracer diffusion coefficient as referred to throughout the present invention can be measured by SIMS, as described in 0. Schulz et al., Physical Chemistry Chemical Physics, 5 (11): 2008 (2003).
How to measure said tracer diffusion coefficients is furthermore well known to a person skilled in the art.
Referring to Figure 1, a system in accordance with the present invention is illustrated, having a multi-layer coating (2) on top of the metallic substrate,(1) for example a metallic interconnect. The multi-layer coating comprises a layer (3) closest to the interconnect and a layer (4) closest to the atmosphere of exposure (5). The layer closest to the inter-connect has the property to inhibit cation diffusion, while the layer closest to the atmos-phere has the property to inhibit transport of oxygen (molecules and ions).
The coated interconnect may be preferably used in applications working in the temperature range of 500-1000 C.
The invention is based on the principle that oxygen ions diffuse from the atmosphere, while cations Mm+ diffuse from the metallic surface such that an oxide MaOb will be formed. Due to the respective diffusion coefficients of the first and second layer satisfying the above formula, the growth of the oxide can be effectively reduced.
The oxygen tracer diffusion coefficient as referred to throughout the present invention can be measured in independent tests, as described in detail in R.A. De Souza et al., Solid State Ionics, 106 (3-4): 175 (1998). The coefficient is determined by means of the Isotopic Exchange Depth Profile method (IEDP). 180/160 exchange anneals are per-formed at different temperatures at P02 of about 1 atm, and the subsequent 180 diffusion profiles are determined by Secondary Ion Mass Spectroscopy (SIMS).
The cation tracer diffusion coefficient as referred to throughout the present invention can be measured by SIMS, as described in 0. Schulz et al., Physical Chemistry Chemical Physics, 5 (11): 2008 (2003).
How to measure said tracer diffusion coefficients is furthermore well known to a person skilled in the art.
Referring to Figure 1, a system in accordance with the present invention is illustrated, having a multi-layer coating (2) on top of the metallic substrate,(1) for example a metallic interconnect. The multi-layer coating comprises a layer (3) closest to the interconnect and a layer (4) closest to the atmosphere of exposure (5). The layer closest to the inter-connect has the property to inhibit cation diffusion, while the layer closest to the atmos-phere has the property to inhibit transport of oxygen (molecules and ions).
The coated interconnect may be preferably used in applications working in the temperature range of 500-1000 C.
The invention is based on the principle that oxygen ions diffuse from the atmosphere, while cations Mm+ diffuse from the metallic surface such that an oxide MaOb will be formed. Due to the respective diffusion coefficients of the first and second layer satisfying the above formula, the growth of the oxide can be effectively reduced.
The first layer (3) which faces the metal surface comprises an oxide and preferably has a low cation tracer diffusion coefficient, i.e. less than 10-15 cm2/s, and more preferably less than 10-17 cmZ/s.
The second layer (4) comprises an oxide and preferably has an oxygen ion tracer diffu-sion coefficient of less than 10"15 cmZ/s, more preferably of less than 10"17 cmZ/s.
In a preferred embodiment, the cation tracer diffusion coefficient is the chromium tracer diffusion coefficient of the respective layer.
According to a preferred embodiment, oxides with a perovskite structure or fluorite struc-ture may be used as layer (3) closest to the metallic substrate, since oxides with a perovskite structure or fluorite structure are generally poor cation conductors.
According to the invention, the perovskite can be any perovskite of the formula ABO3, where A, and B are cations. A is a member of the "scandium family" (Y, La and the lan-thanides (Ce to Yb)) or an alkaline earth element (Mg, Sr, Ca, Ba), or mixtures thereof, and B is a transition metal belonging to either the first or second series, or Ce, Al, Ga, Sn, In, or a mixture thereof. Preferably B is selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo and Ce. Of particular interest are the perovskites with B = Ti, V, Cr and Fe.
Preferred perovskites are selected from the group consisting of LaCrO3, YCrO3, SrTiO3, LaTiO3, YTiO3, LaFeO3, YFeO3, LaVO3 and YVO3, optionally doped with Sr, Ca, Ba and/or Mg. It is also preferred that the perovskite is composed of SrVO3, (La,Sr)V03 or (La,Sr)(Cr,V)03. In a preferred embodiment the perovskite is composed of SrTiO3 which is optionally doped with Nb or La.
According to the invention, the fluorite can be any fluorite of the formula AOZ where A is a cation. Preferred fluorites are selected from the group consisting of stabilized zirconia (yttria, calcia, or magnesia stabilized zirconia).
In a further preferred embodiment, layer (4), being closest to the exposing atmosphere, comprises an oxide having a spinel structure, a rock salt structure, a corundum structure, or a wurtzite structure since oxides having a said structures are generally poor oxygen ion conductors.
According to the invention, the spinel can be any spine) of the formula AB204, where A
and B are transition metals belonging to either the first or second series, or Ce, Al, Ga, Sn or In, or a mixture hereof. Preferably, A and B are selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Ce, and mixtures thereof. Of particular interest are the spinels (Mn, Ni, Co, Cr, Fe, Cu)3O4, with (Mn,Cr,Co)304 being most pre-ferred.
According to the invention, the rock salt can be any rock salt of the formula AB, where A
is a cation and B is oxygen. Particularly preferred are rock salts selected from the group consisting of CaO, SrO, BaO, FeO, CoO, CdO, MgO, and NiO.
According to the invention, the corundum can be any corundum of the formula A2B3, where A is a cation and B is oxygen. Particularly preferred are corundums selected from the group consisting of a-A12O3, Ti203, V203, a-Mn203, a-Ga2O3, and a-Fe2O3.
According to the invention, the wurtzite can be any wurtzite of the formula AB, where A is a cation and B is oxygen. Particularly preferred are wurtzites selected from the group consisting of BeO, ZnO.
In a more preferred embodiment of the invention, layer (4) of the coating comprises a spinel in combination with layer (3) comprising a perovskite. Said combination is espe-cially suitable as a multi-layer coating for interconnects in SOFCs and SOECs due to a reasonable high electronic conductivity of oxides with the spinel and the perovskite struc-ture, for a large range of different element combinations. The spinel structure inhibits oxygen diffusion whereas the perovskite structure inhibits cation diffusion from the inter-connect though the layer. Also preferred for metallic interconnects in SOFCs and SOECs is layer (4) of the coating comprising a rock salt in combination with layer (3) comprising a perovskite. The rock salt structure also efficiently inhibits oxygen diffusion, as de-scribed for the spinel structure above.
For high temperature applications, it is further preferred that layer (3) of the coating com-prises a perovskite in combination with layer (4) comprising a corundum structure, or layer (4) comprising a wurtzite structure.
Alternatively, preferred for high temperature applications is layer (3) of the coating com-prises a fluorite in combination with layer (4) comprising a rock salt structure, a corun-dum structure, a wurtzite structure, or a spinel structure.
Therewith, oxide growth is efficiently inhibited on the metal containing surface, contribut-ing to a longer life time of the high temperature application comprising the coated metal containing layer.
The exact combination of specific materials depends on the respective tracer diffusion coefficients. If the diffusion of cations through layer (3) is very low, the requirements for the transport properties of layer (4) become relatively easy to fulfill (c.f.
the equation above). This allows for more freedom regarding the materials for each layer for a given metal containing surface in the light of the desired application.
The above compositions of the spinel and perovskites are listed as stoichiometric oxides.
The stoichiometry of the materials utilized in the multi-layer coat can, however, be non-stoichiometric without departing from the scope of the present invention. For example, the perovskite may be sub-stoichiometric, i.e. a perovskite ABy03, where y <
1, e.g.
LaCro.9903. In this case, possible oxide scales formed on the interconnect during aging react with the LaCro.9903 so that the cations from the oxide scale are incorporated in the perovskite structure on the B-site. As a result the thickness of the thermally grown oxide scale can be reduced. The materials may also be doped with various elements.
The individual oxide layers of the coating may have a graded composition such that the composition varies through the oxide layer. Furthermore, the two oxide layers may be graded such that the composition of the one layer gradually changes into the composi-tion of the other layer. In another preferred embodiment, either oxide layer contains sec-ondary phases, which exist in the grain boundaries of the oxide. The two individual layers can also be a mixture of oxides with low ionic (cation or oxide) transport and oxides ex-hibiting high electronic conduction.
It is preferred that the coating has two layers. However, additional layers may also be part of the coating besides layers (3) and (4). These layers may be positioned between the interconnect and layer (3), between layer (3) and layer (4), or between layer (4) and the atmosphere. These layers may provide additional properties to the coating, i.e. func-tion as additional diffusion barrier layers, adherence layers, doping layers, strain com-pensating layers or the like.
In case the multi-layer coating is applied on metallic interconnects for SOFCs and SOECs, both layers in the multi-layer coating are electronically conductive.
In a preferred embodiment, the area specific resistance of the coating is less than 0.05 f2cm2 at 600 C.
The multi-layer coating may of course be applied on both sides of the interconnect, i.e.
on the air and the fuel side of the interconnect, if desired.
The thickness of the multi-layer coating is preferably less than 50 pm, and more prefera-bly less than 20 pm.
The thickness of the first layer (3) is preferably less than 25 pm, and more preferably less than 10 pm.
The thickness of the second layer (4) is preferably less than 25 pm, and more preferably less than 10 pm.
The present invention further provides a method of forming a coating suitable for metal containing surfaces comprising at least two layers, wherein the first layer (3) which faces the metal containing surface and the second layer facing the atmosphere of exposure (4) both comprise an oxide, and wherein the first layer (3) has a tracer diffusion coefficient for cations Mm+, (M is the scale forming element of the alloy), and the second layer (4) has a tracer diffusion corefficient for oxygen ions O2- satisfying the following formula:
In p(OZ)u f (D0 + 2 DM )d In p(O2) < 5 10-13 cm2 I S
In p(Oz)N
wherein p(02);n is the oxygen partial pressure in equilibrium between the metallic sub-strate and MaOb, p(02)ex is the oxygen partial pressure in the reaction atmosphere, DM is the tracer diffusion coefficient of the metal cations Mm+ in the first layer (3), and Do is 02"
tracer diffusion coefficient in the second layer (4);
the method comprising the steps of:
- forming the first layer (3) on the metallic substrate; and - depositing the second layer (4) on the first layer (3).
According to a preferred embodiment, oxides with a perovskite structure may be used as layer (3). The perovskite layer may be formed in a reaction between the interconnect and a deposited metal, such as La, Sr, Y, or in a reaction between the interconnect and a deposited metal salt or metal-oxide, such as Y203, SrO, La203, La,_XSrCoO3.
Alterna-tively, any other structure for layer (3) as described above for the dual layer of the pre-sent invention may be used.
The oxide may also be deposited on the interconnect by any other method known in the art, including dip coating, slurry spraying, screen printing, spin coating, electroplating, flame spraying, EPD, electrolytic deposition, physical or chemical deposition from an ox-ide target, sputtering, electrostatic spraying, plasma spraying, laser techniques, or spray pyrolysis.
In another preferred embodiment, layer (4), being closest to the atmosphere of exposure, comprises an oxide having a spinel structure, since oxides having a spinel structure are generally poor oxygen ion conductors. The spinel layer may be formed on top of the perovskite layer in a reaction between the perovskite and precursor materials.
Said pre-cursors include metals, metal-salts and oxides. The spinel and the perovskite may also be formed in a reaction during a heat treatment. The spinel layer may be deposited on the perovskite after a heat treatment of the interconnect-perovskite.
Alternatively, the spinel layer may be deposited on the perovskite layer without any prior heat treatment of the perovskite layer. The spinel layer may furthermore be deposited on the perovskite layer by similar techniques as described above for the perovskite layer.
Of course, the same applies if oxides other than a perovskite and/or a spinel are em-ployed for layers (3) and (4).
The coating may be formed in air, or alternatively in atmospheres containing less oxy-gen. The conditions during the formation of the multi-layer coating may also include a sequential treatment in different atmospheres and at different temperatures, depending on the materials used.
The coating may be sintered in air, or alternatively in atmospheres containing less oxy-gen. The sintering conditions may also include a sequential treatment in different atmos-pheres and at different temperatures, depending on the materials used.
The surface of the metal containing surface may be treated in various ways prior to deposition of the coating. The treatments include grinding, polishing, pickling, sand blast-ing, etc. Furthermore, the metal containing surface may be pre-oxidized to form a small amount of oxide prior to coating. The pre-treatment of the metal containing surface may also include pre-oxidation after deposition of oxides, e.g. reactive elements to improve adhesion, or dopants to improve the electrical conductivity and the like.
The metal containing surface may be the surface of any metal or metal alloy.
Preferably, the coating of the present invention is applied to surfaces of metal containing intercon-nects. In another preferred embodiment the metal containing material is a porous metal or metal alloy support.
According to a preferred embodiment, the multi-layer coating is applied on metallic sub-strates as an oxidation-barrier for metals or alloys such that the coated metal or alloy substrate possesses a high oxidation-resistance. Multi-layer coatings used for intercon-nects may be utilized for this embodiment as well. In addition, other materials may be utilized in the multi-layer coating for this embodiment, since the multi-layer coating is not necessarily electronically conductive in this case. This opens the possibility of using other ceramic materials.
According to the invention, the diffusion preventing effect is achieved by the combination of at least two separate layers. Thereby, each layer can be optimized with regard to its desired characteristics, cation diffusion prevention and oxygen diffusion prevention, which reduces the minimum requirements for each layer, as compared to a single layer oxide which has to fulfill both properties at the same time. It is thus possible to use a great variety of known electron conducting materials for each layer, which may be tai-lored depending on the intended purpose.
The coating of the present invention comprises the oxidation resistant properties so far required for metallic substrates during operation, so that the coated metallic substrates do not necessarily need to possess said oxidation resistance properties, i.e.
the metallic substrate does not need to grow an oxidation resistant chromia, silica or alumina scale during operation. Instead, the metallic substrate possesses as the minimum requirement only the necessary mechanical properties for the application in question.
Therefore, a large freedom with regard to the selection of metals or alloys is given.
Further advantages of the multi-layer coating of the present invention, when applied in SOFCs and SOECs, include the prevention of the problems encountered in the prior art, such as Cr-poisoning, or a large increase of the interface resistance.
According to the invention, Cr-poisoning is effectively inhibited and the rate of increase of electrical resis-tance is strongly reduced.
The coating of the present invention may therefore be advantageously used as coatings for interconnects in SOFCs and SOECs, where the coating can decrease the electrical degradation observed for interconnects and at the same time inhibit chromium poisoning.
If the coating is used in SOFC and SOEC applications, the coating must be electronically conductive. However, the coating is not limited to these applications, but may be em-ployed in high temperature oxidation applications in general.
The SOFCs and SOECs, comprising the coating of the present invention, possess an increased lifetime due to less oxidation of the interconnects and less Cr-poisoning of the electrodes. Furthermore, since more flexibility in the choice of the materials for the inter-connect and design thereof can be realized, the SOFCs and SOECs are more cost effec-tive.
Furthermore, prior to the deposition or after the deposition of the multi-layer coating, the metallic substrate (interconnect or general metallic substrate) may be shaped, e.g. by pressing methods, or a part of the substrate may be removed, e.g. by etching methods, depending on the desired application.
In the following, the invention will be illustrated by examples. Alternative embodiments and examples exist without departing from the scope of the present invention.
Examples Example 1 A dual layer coating was deposited on a Cr203-forming Fe-22Cr alloy. The first oxide layer was deposited by PLO on the alloy surface with the composition LaO.95Sr0.05CrO3 with a thickness of 5 pm, said composition having a perovskite structure.
Afterwards, a 5 pm MnCr2O4 layer having a spinel structure was deposited on the perovskite layer by PLO so as to form a dual layer coating. The Cr tracer diffusion coefficient for La0.95SrO.05CrO3 has been measured to be 1.07 x 10"17 cm2/s at 1000 C (N.
Sakai et al., Solid State Ionics, 135 (2000) p. 469). The oxygen tracer diffusion coefficient of the MnCr2O4 layer has been measured to be 6 x 10"15 cm2/s at 800 C (N. Sakai et al., Solid State Ionics, 176 (2005) p. 681).
Example 2 A dual-layer coating was formed on a ferritic Fe-Cr interconnect. The first oxide layer was directly deposited on the metal by slurry spraying LaCrO3 having a perovskite structure.
Afterwards, a 5 pm thin MnCr2O4 layer having a spinel structure was deposited on the perovskite layer by PLD so as to form the dual-layer coating.
Example 3 A coating as described in Example 2 was formed, followed by deposition of a layer of MnCo2O4 by PLD on top of the spinel layer.
Example 4 A dual-layer coating was formed on a Fe-Cr-based interconnect. The first oxide layer was formed by depositing a metallic La layer by PLD, followed by a reaction between the La layer and the interconnect at 1000 C in air, thereby forming LaCrO3 having a perovskite structure. Afterwards, a thin MnCr2O4 layer having a spine) structure was de-posited on the perovskite layer by PLD.
Example 5 A dual-layer coating was formed on a ferritic alloy. The first oxide layer was formed as described in Example 1, followed by depositing Mn203 on top of the perovskite layer by slurry spraying. Afterwards, a spinel layer was formed by the reaction between the perovskite layer and the deposited oxide at 950 C in air.
Example 6 Same as Example 5, wherein 00304 was used instead of Mn203.
Example 7 Same as Example 5, wherein Fe203 was used instead of Mn203.
Example 8 Same as Example 2, wherein the surface finish of the metallic alloy before deposition of the coating was pre-oxidized at about 900 C in an H2/H20 atmosphere for 30 min.
Example 9 A small amount of Ni(N03)2 was applied onto the interconnect of Example 2 by dip coat-ing the metallic interconnect in a nitrate-solution prior to the formation of the dual-layer coating. The interconnect with the applied Ni(N03)2 was pre-oxidized at about 900 C in air for 24 h.
Example 10 A coating was formed on a Fe-Cr metallic substrate. A layer of stabilized zirconia (e.g.
yttria stabilized zirconia) having a fluorite structure was deposited on the metallic sub-strate by PLD. Afterwards, a thin MnCr2O4 layer having a spinel structure was deposited on the YSZ layer by PLD so as to form a dual-layer coating. The tracer diffusion coeffi-cient of Ti has been measured to be 5 x 10"16 cm2/s at 1200 C (K. Kowalski et al., Journal of the European Ceramic Society, 20 (2000) p. 951). The tracer diffusion coefficients of other transition metals (e.g. Cr, Fe, and Al) will be of similar magnitude.
Example 11 A dual layer coat was formed on the surface in a Fe22Cr porous metal support for SOFC
by a two step impregnation. First a nitrate solution of LaCrO3 is impregnated into the structure by vacuum impregnation. After a subsequent heat treatment to 800 C a nitrate solution of MnCr2O4 is impregnated. The protective dual coat layer is completed by a heat treatment to 800 C.
Example 12 As Example 11 but using MnCo2O4 for the second layer.
The coating system of the present application can also be applied as an oxidation resis-tant coating of metallic substrates for other high temperature (> 500 C) applications than the applications as SOFC and SOEC interconnects outlined above. Alloys utilized for high temperature applications often form a protective silica layer, alumina layer or chromia layer to protect the alloy against further oxidation. By using an oxidation resis-tant coating, the metallic substrate does not need to be oxidation resistant itself. This means that a larger number of metals and alloys may be used for high temperature ap-plications. Importantly, the coating does not in general need to be electronically conduc-tive for this purpose.
The second layer (4) comprises an oxide and preferably has an oxygen ion tracer diffu-sion coefficient of less than 10"15 cmZ/s, more preferably of less than 10"17 cmZ/s.
In a preferred embodiment, the cation tracer diffusion coefficient is the chromium tracer diffusion coefficient of the respective layer.
According to a preferred embodiment, oxides with a perovskite structure or fluorite struc-ture may be used as layer (3) closest to the metallic substrate, since oxides with a perovskite structure or fluorite structure are generally poor cation conductors.
According to the invention, the perovskite can be any perovskite of the formula ABO3, where A, and B are cations. A is a member of the "scandium family" (Y, La and the lan-thanides (Ce to Yb)) or an alkaline earth element (Mg, Sr, Ca, Ba), or mixtures thereof, and B is a transition metal belonging to either the first or second series, or Ce, Al, Ga, Sn, In, or a mixture thereof. Preferably B is selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo and Ce. Of particular interest are the perovskites with B = Ti, V, Cr and Fe.
Preferred perovskites are selected from the group consisting of LaCrO3, YCrO3, SrTiO3, LaTiO3, YTiO3, LaFeO3, YFeO3, LaVO3 and YVO3, optionally doped with Sr, Ca, Ba and/or Mg. It is also preferred that the perovskite is composed of SrVO3, (La,Sr)V03 or (La,Sr)(Cr,V)03. In a preferred embodiment the perovskite is composed of SrTiO3 which is optionally doped with Nb or La.
According to the invention, the fluorite can be any fluorite of the formula AOZ where A is a cation. Preferred fluorites are selected from the group consisting of stabilized zirconia (yttria, calcia, or magnesia stabilized zirconia).
In a further preferred embodiment, layer (4), being closest to the exposing atmosphere, comprises an oxide having a spinel structure, a rock salt structure, a corundum structure, or a wurtzite structure since oxides having a said structures are generally poor oxygen ion conductors.
According to the invention, the spinel can be any spine) of the formula AB204, where A
and B are transition metals belonging to either the first or second series, or Ce, Al, Ga, Sn or In, or a mixture hereof. Preferably, A and B are selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Ce, and mixtures thereof. Of particular interest are the spinels (Mn, Ni, Co, Cr, Fe, Cu)3O4, with (Mn,Cr,Co)304 being most pre-ferred.
According to the invention, the rock salt can be any rock salt of the formula AB, where A
is a cation and B is oxygen. Particularly preferred are rock salts selected from the group consisting of CaO, SrO, BaO, FeO, CoO, CdO, MgO, and NiO.
According to the invention, the corundum can be any corundum of the formula A2B3, where A is a cation and B is oxygen. Particularly preferred are corundums selected from the group consisting of a-A12O3, Ti203, V203, a-Mn203, a-Ga2O3, and a-Fe2O3.
According to the invention, the wurtzite can be any wurtzite of the formula AB, where A is a cation and B is oxygen. Particularly preferred are wurtzites selected from the group consisting of BeO, ZnO.
In a more preferred embodiment of the invention, layer (4) of the coating comprises a spinel in combination with layer (3) comprising a perovskite. Said combination is espe-cially suitable as a multi-layer coating for interconnects in SOFCs and SOECs due to a reasonable high electronic conductivity of oxides with the spinel and the perovskite struc-ture, for a large range of different element combinations. The spinel structure inhibits oxygen diffusion whereas the perovskite structure inhibits cation diffusion from the inter-connect though the layer. Also preferred for metallic interconnects in SOFCs and SOECs is layer (4) of the coating comprising a rock salt in combination with layer (3) comprising a perovskite. The rock salt structure also efficiently inhibits oxygen diffusion, as de-scribed for the spinel structure above.
For high temperature applications, it is further preferred that layer (3) of the coating com-prises a perovskite in combination with layer (4) comprising a corundum structure, or layer (4) comprising a wurtzite structure.
Alternatively, preferred for high temperature applications is layer (3) of the coating com-prises a fluorite in combination with layer (4) comprising a rock salt structure, a corun-dum structure, a wurtzite structure, or a spinel structure.
Therewith, oxide growth is efficiently inhibited on the metal containing surface, contribut-ing to a longer life time of the high temperature application comprising the coated metal containing layer.
The exact combination of specific materials depends on the respective tracer diffusion coefficients. If the diffusion of cations through layer (3) is very low, the requirements for the transport properties of layer (4) become relatively easy to fulfill (c.f.
the equation above). This allows for more freedom regarding the materials for each layer for a given metal containing surface in the light of the desired application.
The above compositions of the spinel and perovskites are listed as stoichiometric oxides.
The stoichiometry of the materials utilized in the multi-layer coat can, however, be non-stoichiometric without departing from the scope of the present invention. For example, the perovskite may be sub-stoichiometric, i.e. a perovskite ABy03, where y <
1, e.g.
LaCro.9903. In this case, possible oxide scales formed on the interconnect during aging react with the LaCro.9903 so that the cations from the oxide scale are incorporated in the perovskite structure on the B-site. As a result the thickness of the thermally grown oxide scale can be reduced. The materials may also be doped with various elements.
The individual oxide layers of the coating may have a graded composition such that the composition varies through the oxide layer. Furthermore, the two oxide layers may be graded such that the composition of the one layer gradually changes into the composi-tion of the other layer. In another preferred embodiment, either oxide layer contains sec-ondary phases, which exist in the grain boundaries of the oxide. The two individual layers can also be a mixture of oxides with low ionic (cation or oxide) transport and oxides ex-hibiting high electronic conduction.
It is preferred that the coating has two layers. However, additional layers may also be part of the coating besides layers (3) and (4). These layers may be positioned between the interconnect and layer (3), between layer (3) and layer (4), or between layer (4) and the atmosphere. These layers may provide additional properties to the coating, i.e. func-tion as additional diffusion barrier layers, adherence layers, doping layers, strain com-pensating layers or the like.
In case the multi-layer coating is applied on metallic interconnects for SOFCs and SOECs, both layers in the multi-layer coating are electronically conductive.
In a preferred embodiment, the area specific resistance of the coating is less than 0.05 f2cm2 at 600 C.
The multi-layer coating may of course be applied on both sides of the interconnect, i.e.
on the air and the fuel side of the interconnect, if desired.
The thickness of the multi-layer coating is preferably less than 50 pm, and more prefera-bly less than 20 pm.
The thickness of the first layer (3) is preferably less than 25 pm, and more preferably less than 10 pm.
The thickness of the second layer (4) is preferably less than 25 pm, and more preferably less than 10 pm.
The present invention further provides a method of forming a coating suitable for metal containing surfaces comprising at least two layers, wherein the first layer (3) which faces the metal containing surface and the second layer facing the atmosphere of exposure (4) both comprise an oxide, and wherein the first layer (3) has a tracer diffusion coefficient for cations Mm+, (M is the scale forming element of the alloy), and the second layer (4) has a tracer diffusion corefficient for oxygen ions O2- satisfying the following formula:
In p(OZ)u f (D0 + 2 DM )d In p(O2) < 5 10-13 cm2 I S
In p(Oz)N
wherein p(02);n is the oxygen partial pressure in equilibrium between the metallic sub-strate and MaOb, p(02)ex is the oxygen partial pressure in the reaction atmosphere, DM is the tracer diffusion coefficient of the metal cations Mm+ in the first layer (3), and Do is 02"
tracer diffusion coefficient in the second layer (4);
the method comprising the steps of:
- forming the first layer (3) on the metallic substrate; and - depositing the second layer (4) on the first layer (3).
According to a preferred embodiment, oxides with a perovskite structure may be used as layer (3). The perovskite layer may be formed in a reaction between the interconnect and a deposited metal, such as La, Sr, Y, or in a reaction between the interconnect and a deposited metal salt or metal-oxide, such as Y203, SrO, La203, La,_XSrCoO3.
Alterna-tively, any other structure for layer (3) as described above for the dual layer of the pre-sent invention may be used.
The oxide may also be deposited on the interconnect by any other method known in the art, including dip coating, slurry spraying, screen printing, spin coating, electroplating, flame spraying, EPD, electrolytic deposition, physical or chemical deposition from an ox-ide target, sputtering, electrostatic spraying, plasma spraying, laser techniques, or spray pyrolysis.
In another preferred embodiment, layer (4), being closest to the atmosphere of exposure, comprises an oxide having a spinel structure, since oxides having a spinel structure are generally poor oxygen ion conductors. The spinel layer may be formed on top of the perovskite layer in a reaction between the perovskite and precursor materials.
Said pre-cursors include metals, metal-salts and oxides. The spinel and the perovskite may also be formed in a reaction during a heat treatment. The spinel layer may be deposited on the perovskite after a heat treatment of the interconnect-perovskite.
Alternatively, the spinel layer may be deposited on the perovskite layer without any prior heat treatment of the perovskite layer. The spinel layer may furthermore be deposited on the perovskite layer by similar techniques as described above for the perovskite layer.
Of course, the same applies if oxides other than a perovskite and/or a spinel are em-ployed for layers (3) and (4).
The coating may be formed in air, or alternatively in atmospheres containing less oxy-gen. The conditions during the formation of the multi-layer coating may also include a sequential treatment in different atmospheres and at different temperatures, depending on the materials used.
The coating may be sintered in air, or alternatively in atmospheres containing less oxy-gen. The sintering conditions may also include a sequential treatment in different atmos-pheres and at different temperatures, depending on the materials used.
The surface of the metal containing surface may be treated in various ways prior to deposition of the coating. The treatments include grinding, polishing, pickling, sand blast-ing, etc. Furthermore, the metal containing surface may be pre-oxidized to form a small amount of oxide prior to coating. The pre-treatment of the metal containing surface may also include pre-oxidation after deposition of oxides, e.g. reactive elements to improve adhesion, or dopants to improve the electrical conductivity and the like.
The metal containing surface may be the surface of any metal or metal alloy.
Preferably, the coating of the present invention is applied to surfaces of metal containing intercon-nects. In another preferred embodiment the metal containing material is a porous metal or metal alloy support.
According to a preferred embodiment, the multi-layer coating is applied on metallic sub-strates as an oxidation-barrier for metals or alloys such that the coated metal or alloy substrate possesses a high oxidation-resistance. Multi-layer coatings used for intercon-nects may be utilized for this embodiment as well. In addition, other materials may be utilized in the multi-layer coating for this embodiment, since the multi-layer coating is not necessarily electronically conductive in this case. This opens the possibility of using other ceramic materials.
According to the invention, the diffusion preventing effect is achieved by the combination of at least two separate layers. Thereby, each layer can be optimized with regard to its desired characteristics, cation diffusion prevention and oxygen diffusion prevention, which reduces the minimum requirements for each layer, as compared to a single layer oxide which has to fulfill both properties at the same time. It is thus possible to use a great variety of known electron conducting materials for each layer, which may be tai-lored depending on the intended purpose.
The coating of the present invention comprises the oxidation resistant properties so far required for metallic substrates during operation, so that the coated metallic substrates do not necessarily need to possess said oxidation resistance properties, i.e.
the metallic substrate does not need to grow an oxidation resistant chromia, silica or alumina scale during operation. Instead, the metallic substrate possesses as the minimum requirement only the necessary mechanical properties for the application in question.
Therefore, a large freedom with regard to the selection of metals or alloys is given.
Further advantages of the multi-layer coating of the present invention, when applied in SOFCs and SOECs, include the prevention of the problems encountered in the prior art, such as Cr-poisoning, or a large increase of the interface resistance.
According to the invention, Cr-poisoning is effectively inhibited and the rate of increase of electrical resis-tance is strongly reduced.
The coating of the present invention may therefore be advantageously used as coatings for interconnects in SOFCs and SOECs, where the coating can decrease the electrical degradation observed for interconnects and at the same time inhibit chromium poisoning.
If the coating is used in SOFC and SOEC applications, the coating must be electronically conductive. However, the coating is not limited to these applications, but may be em-ployed in high temperature oxidation applications in general.
The SOFCs and SOECs, comprising the coating of the present invention, possess an increased lifetime due to less oxidation of the interconnects and less Cr-poisoning of the electrodes. Furthermore, since more flexibility in the choice of the materials for the inter-connect and design thereof can be realized, the SOFCs and SOECs are more cost effec-tive.
Furthermore, prior to the deposition or after the deposition of the multi-layer coating, the metallic substrate (interconnect or general metallic substrate) may be shaped, e.g. by pressing methods, or a part of the substrate may be removed, e.g. by etching methods, depending on the desired application.
In the following, the invention will be illustrated by examples. Alternative embodiments and examples exist without departing from the scope of the present invention.
Examples Example 1 A dual layer coating was deposited on a Cr203-forming Fe-22Cr alloy. The first oxide layer was deposited by PLO on the alloy surface with the composition LaO.95Sr0.05CrO3 with a thickness of 5 pm, said composition having a perovskite structure.
Afterwards, a 5 pm MnCr2O4 layer having a spinel structure was deposited on the perovskite layer by PLO so as to form a dual layer coating. The Cr tracer diffusion coefficient for La0.95SrO.05CrO3 has been measured to be 1.07 x 10"17 cm2/s at 1000 C (N.
Sakai et al., Solid State Ionics, 135 (2000) p. 469). The oxygen tracer diffusion coefficient of the MnCr2O4 layer has been measured to be 6 x 10"15 cm2/s at 800 C (N. Sakai et al., Solid State Ionics, 176 (2005) p. 681).
Example 2 A dual-layer coating was formed on a ferritic Fe-Cr interconnect. The first oxide layer was directly deposited on the metal by slurry spraying LaCrO3 having a perovskite structure.
Afterwards, a 5 pm thin MnCr2O4 layer having a spinel structure was deposited on the perovskite layer by PLD so as to form the dual-layer coating.
Example 3 A coating as described in Example 2 was formed, followed by deposition of a layer of MnCo2O4 by PLD on top of the spinel layer.
Example 4 A dual-layer coating was formed on a Fe-Cr-based interconnect. The first oxide layer was formed by depositing a metallic La layer by PLD, followed by a reaction between the La layer and the interconnect at 1000 C in air, thereby forming LaCrO3 having a perovskite structure. Afterwards, a thin MnCr2O4 layer having a spine) structure was de-posited on the perovskite layer by PLD.
Example 5 A dual-layer coating was formed on a ferritic alloy. The first oxide layer was formed as described in Example 1, followed by depositing Mn203 on top of the perovskite layer by slurry spraying. Afterwards, a spinel layer was formed by the reaction between the perovskite layer and the deposited oxide at 950 C in air.
Example 6 Same as Example 5, wherein 00304 was used instead of Mn203.
Example 7 Same as Example 5, wherein Fe203 was used instead of Mn203.
Example 8 Same as Example 2, wherein the surface finish of the metallic alloy before deposition of the coating was pre-oxidized at about 900 C in an H2/H20 atmosphere for 30 min.
Example 9 A small amount of Ni(N03)2 was applied onto the interconnect of Example 2 by dip coat-ing the metallic interconnect in a nitrate-solution prior to the formation of the dual-layer coating. The interconnect with the applied Ni(N03)2 was pre-oxidized at about 900 C in air for 24 h.
Example 10 A coating was formed on a Fe-Cr metallic substrate. A layer of stabilized zirconia (e.g.
yttria stabilized zirconia) having a fluorite structure was deposited on the metallic sub-strate by PLD. Afterwards, a thin MnCr2O4 layer having a spinel structure was deposited on the YSZ layer by PLD so as to form a dual-layer coating. The tracer diffusion coeffi-cient of Ti has been measured to be 5 x 10"16 cm2/s at 1200 C (K. Kowalski et al., Journal of the European Ceramic Society, 20 (2000) p. 951). The tracer diffusion coefficients of other transition metals (e.g. Cr, Fe, and Al) will be of similar magnitude.
Example 11 A dual layer coat was formed on the surface in a Fe22Cr porous metal support for SOFC
by a two step impregnation. First a nitrate solution of LaCrO3 is impregnated into the structure by vacuum impregnation. After a subsequent heat treatment to 800 C a nitrate solution of MnCr2O4 is impregnated. The protective dual coat layer is completed by a heat treatment to 800 C.
Example 12 As Example 11 but using MnCo2O4 for the second layer.
The coating system of the present application can also be applied as an oxidation resis-tant coating of metallic substrates for other high temperature (> 500 C) applications than the applications as SOFC and SOEC interconnects outlined above. Alloys utilized for high temperature applications often form a protective silica layer, alumina layer or chromia layer to protect the alloy against further oxidation. By using an oxidation resis-tant coating, the metallic substrate does not need to be oxidation resistant itself. This means that a larger number of metals and alloys may be used for high temperature ap-plications. Importantly, the coating does not in general need to be electronically conduc-tive for this purpose.
Claims (20)
1. A multilayer coating suitable for metal containing surfaces comprising at least two layers, wherein the first layer faces the metal containing surface and the second layer faces the surrounding atmosphere, and both the first layer and the second layer comprise an oxide, and wherein the first layer has a tracer diffusion coefficient for cations M m+, wherein M is the scale forming element of the alloy, and the second layer has a tracer diffusion coefficient for oxygen ions O2 satisfying the following formula:
wherein p(O2)in is the oxygen partial pressure in equilibrium between the metallic substrate and M a O b, P(O2)ex is the oxygen partial pressure in the reaction atmosphere, D M is the tracer diffusion coefficient of the metal cations M m+ in the first layer, and D O is O2 tracer diffusion coefficient in the second layer, wherein the first layer comprises an oxide having a perovskite structure or a fluorite structure, wherein the perovskite structure is of the formula ABO3, wherein A is selected from the group consisting of Y, La, a Lanthanide element, Mg, Ca, Sr, Ba, or mixtures thereof, and B is selected from the group consisting of Ti, V, Fe, or mixtures thereof, wherein the fluorite structure is selected from the group consisting of yttria, calcia or magnesia stabilized zirconia, and wherein the second layer comprises an oxide having a spinel structure, a rock salt structure, a corundum structure, or a wurtzite structure.
wherein p(O2)in is the oxygen partial pressure in equilibrium between the metallic substrate and M a O b, P(O2)ex is the oxygen partial pressure in the reaction atmosphere, D M is the tracer diffusion coefficient of the metal cations M m+ in the first layer, and D O is O2 tracer diffusion coefficient in the second layer, wherein the first layer comprises an oxide having a perovskite structure or a fluorite structure, wherein the perovskite structure is of the formula ABO3, wherein A is selected from the group consisting of Y, La, a Lanthanide element, Mg, Ca, Sr, Ba, or mixtures thereof, and B is selected from the group consisting of Ti, V, Fe, or mixtures thereof, wherein the fluorite structure is selected from the group consisting of yttria, calcia or magnesia stabilized zirconia, and wherein the second layer comprises an oxide having a spinel structure, a rock salt structure, a corundum structure, or a wurtzite structure.
2. The multilayer coating of claim 1, wherein the first layer comprises an oxide having a perovskite structure.
3. The multilayer coating of claim 2, wherein the second layer comprises an oxide having a spinel structure, or rock salt structure.
4. The multilayer coating of claim 1, wherein the first layer comprises an oxide having a fluorite structure.
5. The multilayer coating of any one of claims 1 to 4, wherein the first and/or second layer is electrically conducting.
6. The multilayer coating of any one of claims 1 to 5, wherein the first and/or the second layer displays a graded composition so that the composition varies through the layer.
7. The multilayer coating of claim 1, 2, or 4, wherein the spinel structure is of the formula AB2O4, wherein A and B are cations selected from the group consisting of transition metals belonging to either the first or second series, Ce, Al, Ga, Sn, In, or mixtures thereof.
8. A method of forming the multilayer coating of any one of claims 1 to 7 comprising the steps of:
- forming the first layer on the metal containing surface; and - depositing the second layer on the first layer.
- forming the first layer on the metal containing surface; and - depositing the second layer on the first layer.
9. The method of claim 8, wherein the first and second layer are formed by slurry coating, spray painting or electrospraying.
10. The method of claim 8, wherein the first layer is formed by depositing the oxide on the metal by dip-coating, slurry spraying, screen printing, spin coating, PLD, PVD, flame spraying, EPD or spray pyrolysis, and/or wherein the second layer is formed by PLD, PVD or by plasma spraying.
11. The method of claim 8, wherein the first layer is formed by:
- depositing a metal, metal salt or metal oxide on the metal containing surface;
and - reacting the metal of the metal containing surface with the metal, metal salt or metal oxide so as to form the first layer.
- depositing a metal, metal salt or metal oxide on the metal containing surface;
and - reacting the metal of the metal containing surface with the metal, metal salt or metal oxide so as to form the first layer.
12. The method of claim 8, wherein the coating is applied to a porous metal, wherein the first layer is formed by:
- impregnation of a metal, metal salt or a metal oxide; and - reacting the metal of the metal containing surface with the metal, metal salt or metal oxide so as to form the first layer.
- impregnation of a metal, metal salt or a metal oxide; and - reacting the metal of the metal containing surface with the metal, metal salt or metal oxide so as to form the first layer.
13. The method of any one of claims 8 to 12, wherein the second layer is formed by:
- impregnation of a metal, metal salt or a metal oxide; and - reacting the metal, metal salt or metal oxide so as to form the second layer on top of the first layer.
- impregnation of a metal, metal salt or a metal oxide; and - reacting the metal, metal salt or metal oxide so as to form the second layer on top of the first layer.
14. The method of claim 11, wherein the deposited metal is La, Sr, or Y.
15. The method of claim 11, wherein the deposited oxide is Y2O3, SrO, La2O3, or La1-x Sr x CoO3.
16. Use of the multilayer coating of any one of claims 1 to 7 as an oxidation resistant multilayer coating on metal based materials for high temperature applications.
17. Use of the multilayer coating of any one of the claims 1 to 7 for metal supported solid oxide fuel cells.
18. Use of the multilayer coating of any one of claims 1 to 7 for metal supported solid oxide electrolyser cells.
19. A solid oxide fuel cell stack, comprising the multilayer coating of any one of claims 1 to 7.
20. A solid oxide electrolysis cell stack, comprising the multilayer coating of any one of claims 1 to 7.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP06008678.2 | 2006-04-26 | ||
| EP06008678A EP1850412A1 (en) | 2006-04-26 | 2006-04-26 | A multi-layer coating |
| PCT/EP2007/003593 WO2007121986A1 (en) | 2006-04-26 | 2007-04-24 | A multi-layer coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2648740A1 CA2648740A1 (en) | 2007-11-01 |
| CA2648740C true CA2648740C (en) | 2012-10-23 |
Family
ID=36803466
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2648740A Active CA2648740C (en) | 2006-04-26 | 2007-04-24 | Multi-layer coating for metal containing surfaces |
Country Status (10)
| Country | Link |
|---|---|
| US (2) | US8859116B2 (en) |
| EP (2) | EP1850412A1 (en) |
| JP (1) | JP5382722B2 (en) |
| KR (2) | KR20080109084A (en) |
| CN (1) | CN101438439B (en) |
| AU (1) | AU2007241321B2 (en) |
| CA (1) | CA2648740C (en) |
| NO (1) | NO20084125L (en) |
| RU (1) | RU2404488C2 (en) |
| WO (1) | WO2007121986A1 (en) |
Families Citing this family (54)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1850412A1 (en) * | 2006-04-26 | 2007-10-31 | Technical University of Denmark | A multi-layer coating |
| US8241817B2 (en) * | 2008-01-24 | 2012-08-14 | Battelle Memorial Institute | Approach for improved stability and performance of SOFC metallic interconnects |
| JP5266930B2 (en) * | 2008-07-25 | 2013-08-21 | 日産自動車株式会社 | Solid oxide fuel cell stack and manufacturing method thereof |
| DE102008049608A1 (en) * | 2008-09-30 | 2010-04-01 | Siemens Aktiengesellschaft | Process for producing an interconnector for high-temperature fuel cells, associated high-temperature fuel cell and fuel cell system constructed therewith |
| FR2948821B1 (en) * | 2009-08-03 | 2011-12-09 | Commissariat Energie Atomique | ELECTROCHEMICAL METAL SUPPORT CELL AND METHOD OF MANUFACTURING THE SAME |
| CN101671829B (en) * | 2009-09-27 | 2011-08-03 | 中国科学院上海硅酸盐研究所 | Preparation of High Temperature Oxidation Resistant Nanostructure Conductive Coating on Alloys by Reduction of Spinel Powder |
| CA2784650A1 (en) | 2009-12-22 | 2011-06-30 | Topsoe Fuel Cell A/S | Manufacture and calibration process for an interconnect for a fuel cell or a fuel cell stack |
| US8802304B2 (en) * | 2010-08-10 | 2014-08-12 | Eos Energy Storage, Llc | Bifunctional (rechargeable) air electrodes comprising a corrosion-resistant outer layer and conductive inner layer |
| KR101272512B1 (en) | 2010-12-03 | 2013-06-10 | 현대자동차주식회사 | Device and method for manufacturing membrane-electrode assembly |
| KR101220744B1 (en) * | 2010-12-28 | 2013-01-09 | 주식회사 포스코 | Separator of solid oxide fuel cell and method for manufacturing the same |
| US9054348B2 (en) | 2011-04-13 | 2015-06-09 | NextTech Materials, Ltd. | Protective coatings for metal alloys and methods incorporating the same |
| WO2012155333A1 (en) * | 2011-05-17 | 2012-11-22 | 中国科学院宁波材料技术与工程研究所 | Heat-resistant metal connecting component, method producing the same and solid oxide fuel cell stack |
| WO2013045230A1 (en) * | 2011-09-27 | 2013-04-04 | Siemens Aktiengesellschaft | Method for the production of a solid electrolyte fuel cell |
| JP5711093B2 (en) * | 2011-10-12 | 2015-04-30 | 一般財団法人ファインセラミックスセンター | Gas separation material for solid oxide fuel cell and solid oxide fuel cell |
| TWI552417B (en) * | 2011-11-17 | 2016-10-01 | 博隆能源股份有限公司 | Multi-layer coating that provides corrosion resistance to zirconia-based electrolytes |
| WO2013090680A2 (en) | 2011-12-14 | 2013-06-20 | Eos Energy Storage, Llc | Electrically rechargeable, metal anode cell and battery systems and methods |
| US10431833B2 (en) | 2012-03-01 | 2019-10-01 | Bloom Energy Corporation | Coatings for metal interconnects to reduce SOFC degradation |
| US9452475B2 (en) | 2012-03-01 | 2016-09-27 | Bloom Energy Corporation | Coatings for SOFC metallic interconnects |
| TWI566461B (en) * | 2012-03-01 | 2017-01-11 | 博隆能源股份有限公司 | Coatings for sofc metallic interconnects |
| KR20130118582A (en) | 2012-04-20 | 2013-10-30 | 삼성에스디아이 주식회사 | Electrode for fuel cell, method of preparing same, membrane-electrode assembly and fuel cell system including same |
| FR2990700A1 (en) | 2012-05-15 | 2013-11-22 | Commissariat Energie Atomique | CHROMO-FORMER METAL ALLOY COMPONENT, USE OF SUCH COMPONENT IN WATER-VAPOR RICH ATMOSPHERE, EHT ELECTROLYSIS INTERCONNECTOR, AND SURFACE TREATMENT METHOD THEREFOR. |
| FR3001977B1 (en) * | 2013-02-13 | 2015-10-30 | Air Liquide | METHOD FOR DEPOSITING COATING AGAINST CORROSION FROM SUSPENSION |
| JP6511431B2 (en) * | 2013-03-15 | 2019-05-15 | エルジー フューエル セル システムズ インクＬｇ Ｆｕｅｌ Ｃｅｌｌ Ｓｙｓｔｅｍｓ Ｉｎｃ． | Fuel cell system configured to capture chromium |
| DE102014204177A1 (en) | 2013-03-28 | 2014-10-02 | Robert Bosch Gmbh | Aerosol coating by means of eddy current actuators |
| ITVR20130200A1 (en) * | 2013-08-13 | 2015-02-14 | Sofcpower S P A | METHOD OF DEPOSITION OF A MATERIAL LAYER ON A METAL SUPPORT FOR FUEL CELLS OR CELLS FOR ELECTROLYSIS |
| US9468736B2 (en) | 2013-11-27 | 2016-10-18 | Bloom Energy Corporation | Fuel cell interconnect with reduced voltage degradation over time |
| US10079393B1 (en) | 2014-01-09 | 2018-09-18 | Bloom Energy Corporation | Method of fabricating an interconnect for a fuel cell stack |
| US9806344B2 (en) * | 2014-01-09 | 2017-10-31 | Chaozhou Three-Circle (Group) Co., Ltd. | Electrochemical energy conversion devices and cells, and negative electrode-side materials for them |
| US9634335B2 (en) | 2014-01-09 | 2017-04-25 | Bloom Energy Corporation | Duplex coating for SOFC interconnect |
| US9993874B2 (en) | 2014-02-25 | 2018-06-12 | Bloom Energy Corporation | Composition and processing of metallic interconnects for SOFC stacks |
| US9559366B2 (en) * | 2014-03-20 | 2017-01-31 | Versa Power Systems Ltd. | Systems and methods for preventing chromium contamination of solid oxide fuel cells |
| US10084192B2 (en) | 2014-03-20 | 2018-09-25 | Versa Power Systems, Ltd | Cathode contact layer design for preventing chromium contamination of solid oxide fuel cells |
| US9923211B2 (en) | 2014-04-24 | 2018-03-20 | Bloom Energy Corporation | Fuel cell interconnect with reduced voltage degradation over time |
| CN104167562B (en) * | 2014-07-14 | 2016-08-17 | 宁波大学 | All-solid-state thin film battery based on electrostatic spray pyrolysis combined with flame spraying and preparation method |
| CA2956069A1 (en) | 2014-07-21 | 2016-01-28 | Lg Fuel Cell Systems, Inc. | Composition for fuel cell electrode |
| CA2978236C (en) * | 2015-03-03 | 2019-05-28 | Nippon Steel & Sumitomo Metal Corporation | Titanium product, separator, and proton exchange membrane fuel cell, and method for producing titanium product |
| CN104912936A (en) * | 2015-05-14 | 2015-09-16 | 广西梧州运龙港船机械制造有限公司 | Anticorrosion processing method for rudder pintle bearing |
| KR101716287B1 (en) * | 2015-06-04 | 2017-03-15 | 한국에너지기술연구원 | Protective Ceramic Bilayer For Metallic Interconnect of Solid Oxide Fuel Cell, And Method of Manufacturing the Same |
| DE112016000044T5 (en) * | 2015-07-01 | 2017-08-17 | Ngk Insulators, Ltd. | fuel cell |
| US10115974B2 (en) | 2015-10-28 | 2018-10-30 | Lg Fuel Cell Systems Inc. | Composition of a nickelate composite cathode for a fuel cell |
| GB2550317B (en) * | 2016-03-09 | 2021-12-15 | Ceres Ip Co Ltd | Fuel cell |
| JP6234628B1 (en) * | 2016-07-27 | 2017-11-22 | 日本碍子株式会社 | Fuel cell |
| JP6947295B2 (en) * | 2017-09-08 | 2021-10-13 | エルジー・ケム・リミテッド | Connecting material for solid oxide fuel cell, its manufacturing method and solid oxide fuel cell |
| AT521011B1 (en) * | 2018-09-21 | 2019-10-15 | High Tech Coatings Gmbh | Component with a two-layer, oxidic protective layer |
| FR3090695B1 (en) * | 2018-12-21 | 2020-12-04 | Safran | hot conforming core coating |
| JP2020119626A (en) * | 2019-01-18 | 2020-08-06 | 大阪瓦斯株式会社 | Inter-cell connecting member, solid oxide fuel cell, sofc mono generation system, sofc cogeneration system, and manufacturing method inter-cell connecting member |
| JP7118910B2 (en) * | 2019-03-04 | 2022-08-16 | 東芝エネルギーシステムズ株式会社 | Electrochemical cell stack and its separator |
| WO2021009100A1 (en) * | 2019-07-17 | 2021-01-21 | Haldor Topsøe A/S | A method for chromium upgrading of ferritic steel interconnects for solid oxide cell stack applications |
| US11205783B2 (en) * | 2019-07-31 | 2021-12-21 | Robert Bosch Gmbh | Fuel cell bipolar plate including corrosion-resistant ferric oxide layer |
| AT523864B1 (en) * | 2020-05-20 | 2022-12-15 | High Tech Coatings Gmbh | Process for producing a protective layer on a component |
| CN112290070A (en) * | 2020-10-30 | 2021-01-29 | 潮州三环（集团）股份有限公司 | Composite coating for SOFC connector and preparation method thereof |
| US20230016315A1 (en) * | 2021-07-14 | 2023-01-19 | Battelle Energy Alliance, Llc | Electrochemical cells comprising a ternary oxide material and related systems and methods |
| CN116970895B (en) * | 2023-09-22 | 2023-12-05 | 北矿新材科技有限公司 | Yttrium chromate suspension, low infrared emissivity coating, method of making same and weapon |
| CN120555942B (en) * | 2025-07-29 | 2025-09-30 | 长沙晶优新材料科技有限公司 | Sr-doped LaFeO3High emissivity coating and preparation method thereof |
Family Cites Families (33)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3613997A1 (en) | 1986-04-25 | 1987-10-29 | Sigri Gmbh | ANODE FOR ELECTROLYTIC PROCESSES |
| JP2604437B2 (en) | 1987-10-15 | 1997-04-30 | 東燃株式会社 | High-temperature fuel cell interelectrode assembly and high-temperature fuel cell cathode current collector |
| JPH01228547A (en) * | 1988-03-04 | 1989-09-12 | Mazda Motor Corp | Catalyst for cleaning exhaust gas |
| JPH03138373A (en) | 1989-10-24 | 1991-06-12 | Nippon Steel Corp | Ceramic coated material having excellent wear resistance and thermal impact resistance |
| JPH07118327B2 (en) * | 1990-07-07 | 1995-12-18 | 日本碍子株式会社 | Solid oxide fuel cell and porous electrode body used therefor |
| MXPA94009540A (en) * | 1993-07-30 | 2005-04-29 | Martin Marietta Energy Systems | Process for growing a film epitaxially upon an oxide surface and structures formed with the process. |
| AUPN173595A0 (en) * | 1995-03-15 | 1995-04-06 | Ceramic Fuel Cells Limited | Fuel cell interconnect device |
| JPH08255626A (en) * | 1995-03-17 | 1996-10-01 | Tonen Corp | Solid oxide fuel cell |
| ATE175525T1 (en) * | 1995-07-21 | 1999-01-15 | Siemens Ag | HIGH TEMPERATURE FUEL CELL AND HIGH TEMPERATURE FUEL CELL STACK WITH COMPOSITE CIRCUIT BOARDS CARRYING A CHROME SPINEL CONTACT LAYER |
| US5939219A (en) * | 1995-10-12 | 1999-08-17 | Siemens Aktiengesellschaft | High-temperature fuel cell having at least one electrically insulating covering and method for producing a high-temperature fuel cell |
| DE19627504C1 (en) * | 1996-07-08 | 1997-10-23 | Siemens Ag | Connection lead plate for high temperature fuel cell stack |
| EP0914498B1 (en) * | 1996-07-25 | 2001-09-19 | Siemens Aktiengesellschaft | Metal substrate with an oxide layer and an improved anchoring layer |
| RU2163942C2 (en) * | 1996-07-25 | 2001-03-10 | Сименс Акциенгезелльшафт | Metal substrate with oxide layer and improved reinforcing layer |
| RU2146360C1 (en) * | 1997-06-10 | 2000-03-10 | Институт высокотемпературной электрохимии Уральского отделения РАН | Material for oxygen electrode in electrochemical devices |
| JP2001521993A (en) | 1997-11-03 | 2001-11-13 | シーメンス アクチエンゲゼルシヤフト | Products, especially structural members of gas turbines with ceramic insulation layers |
| AUPP798898A0 (en) | 1998-12-31 | 1999-01-28 | Ceramic Fuel Cells Limited | Electrically conductive ceramics |
| JP3290976B2 (en) | 2000-03-30 | 2002-06-10 | 川崎重工業株式会社 | Ceramic thermal barrier coating |
| EP1247941A1 (en) | 2001-04-03 | 2002-10-09 | Siemens Aktiengesellschaft | Gas turbine blade |
| JPWO2003026052A1 (en) * | 2001-09-18 | 2005-01-06 | 株式会社フルヤ金属 | Bipolar plate for fuel cell and manufacturing method thereof |
| RU2224336C2 (en) * | 2002-01-28 | 2004-02-20 | Федеральное государственное унитарное предприятие УРАЛЬСКИЙ ЭЛЕКТРОХИМИЧЕСКИЙ КОМБИНАТ | Nickel-oxide plate and its manufacturing process |
| US20030194592A1 (en) * | 2002-04-10 | 2003-10-16 | Hilliard Donald Bennett | Solid oxide electrolytic device |
| RU2224337C1 (en) * | 2002-10-22 | 2004-02-20 | ООО "Салют Текнолоджис Вест" | Method and installation for manufacturing high- temperature fuel cell |
| WO2004068235A1 (en) * | 2003-01-27 | 2004-08-12 | Fujitsu Limited | Optical deflection device, and manufacturing method thereof |
| DE10306649A1 (en) * | 2003-02-18 | 2004-09-02 | Forschungszentrum Jülich GmbH | Protective layer for substrates exposed to high temperatures, and method for producing the same |
| JP2006032183A (en) | 2004-07-20 | 2006-02-02 | Nissan Motor Co Ltd | Electrically conductive material and solid oxide fuel cell using the same. |
| KR20070042961A (en) | 2004-08-10 | 2007-04-24 | 자이단호징 덴료쿠추오켄큐쇼 | Tabernacle |
| US7190568B2 (en) * | 2004-11-16 | 2007-03-13 | Versa Power Systems Ltd. | Electrically conductive fuel cell contact materials |
| US7208044B2 (en) * | 2004-11-24 | 2007-04-24 | Mark A. Zurbuchen | Topotactic anion exchange oxide films and method of producing the same |
| SE528303C2 (en) * | 2004-11-30 | 2006-10-17 | Sandvik Intellectual Property | Band product with a spinel or perovskite coating, electrical contact and method of making the product |
| SE528379C2 (en) * | 2004-11-30 | 2006-10-31 | Sandvik Intellectual Property | Fuel cell component with a complex oxide-forming coating, devices comprising the component and method of preparing the component |
| EP1850412A1 (en) * | 2006-04-26 | 2007-10-31 | Technical University of Denmark | A multi-layer coating |
| EP1950824B8 (en) * | 2007-01-09 | 2011-05-04 | The Technical University of Denmark | A method of producing a multilayer barrier structure for a solid oxide fuel cell |
| AU2008282747A1 (en) * | 2007-08-02 | 2009-02-05 | Trustees Of Boston University | Protective oxide coatings for SOFC interconnections |
-
2006
- 2006-04-26 EP EP06008678A patent/EP1850412A1/en not_active Withdrawn
-
2007
- 2007-04-24 US US12/298,458 patent/US8859116B2/en not_active Expired - Fee Related
- 2007-04-24 WO PCT/EP2007/003593 patent/WO2007121986A1/en not_active Ceased
- 2007-04-24 KR KR1020087027642A patent/KR20080109084A/en not_active Ceased
- 2007-04-24 EP EP07724523A patent/EP2011184A1/en not_active Withdrawn
- 2007-04-24 CA CA2648740A patent/CA2648740C/en active Active
- 2007-04-24 CN CN2007800151283A patent/CN101438439B/en not_active Expired - Fee Related
- 2007-04-24 RU RU2008138068/07A patent/RU2404488C2/en not_active IP Right Cessation
- 2007-04-24 JP JP2009506967A patent/JP5382722B2/en not_active Expired - Fee Related
- 2007-04-24 AU AU2007241321A patent/AU2007241321B2/en not_active Ceased
- 2007-04-24 KR KR1020127021698A patent/KR101278701B1/en not_active Expired - Fee Related
-
2008
- 2008-09-29 NO NO20084125A patent/NO20084125L/en not_active Application Discontinuation
-
2014
- 2014-09-08 US US14/480,339 patent/US20150056535A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| RU2404488C2 (en) | 2010-11-20 |
| KR20120104439A (en) | 2012-09-20 |
| US8859116B2 (en) | 2014-10-14 |
| EP2011184A1 (en) | 2009-01-07 |
| WO2007121986A1 (en) | 2007-11-01 |
| JP2009534538A (en) | 2009-09-24 |
| KR20080109084A (en) | 2008-12-16 |
| US20100015473A1 (en) | 2010-01-21 |
| JP5382722B2 (en) | 2014-01-08 |
| CN101438439A (en) | 2009-05-20 |
| US20150056535A1 (en) | 2015-02-26 |
| AU2007241321B2 (en) | 2010-07-01 |
| NO20084125L (en) | 2008-11-12 |
| CN101438439B (en) | 2011-02-02 |
| RU2008138068A (en) | 2010-06-10 |
| EP1850412A1 (en) | 2007-10-31 |
| CA2648740A1 (en) | 2007-11-01 |
| AU2007241321A1 (en) | 2007-11-01 |
| KR101278701B1 (en) | 2013-06-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2648740C (en) | Multi-layer coating for metal containing surfaces | |
| US5942349A (en) | Fuel cell interconnect device | |
| Yang et al. | Conductive protection layers on oxidation resistant alloys for SOFC interconnect applications | |
| Huang et al. | Characterization of iron-based alloy interconnects for reduced temperature solid oxide fuel cells | |
| US10446854B2 (en) | Coatings for metal interconnects to reduce SOFC degradation | |
| JP5607903B2 (en) | Barrier coating for interconnect, related apparatus and forming method | |
| RU2480865C2 (en) | Reversible solid oxide fuel element (its versions) | |
| JP5133695B2 (en) | Fuel cell components | |
| GB2368450A (en) | Fuel cells | |
| KR20110020781A (en) | Solid Oxide Fuel Cell Cell | |
| EP1284519B1 (en) | Solid electrolyte fuel cell and related manufacturing method | |
| US9054348B2 (en) | Protective coatings for metal alloys and methods incorporating the same | |
| Brouzgou et al. | Interconnects for solid oxide fuel cells | |
| CA2613878C (en) | Electrically conductive steel-ceramic composite and process to manufacture it | |
| Molin et al. | Evaluation of 316 L porous stainless steel for SOFC support | |
| Pattarkine et al. | Oxygen transport resistant and electrically conductive perovskite coatings for solid oxide fuel cell interconnects | |
| KR100639118B1 (en) | Cr-MN-Ｙ coating layer formation method excellent in oxidation resistance and high temperature conductivity | |
| Yu | The Performance of Spinel-Based Interconnect Coating and Cathode-Side Contact Layer for Solid Oxide Fuel Cell | |
| AU704511B2 (en) | Fuel cell interconnect device | |
| Song | Chromium Tolerant, Highly Active and Stable Electrocatalytic Internal Surface Coating for Cathode of Commercial SOFCs | |
| WO2025196425A1 (en) | Electrochemical cell | |
| Mohamed | Oxidation Behavior of Some Cr Ferritic Steels for High Temperature Fuel Cells | |
| Zhen | Investigation on interaction reaction mechanism between metallic interconnect and electrodes in solid oxide fuel cell | |
| Gannon | Study of solid oxide fuel cell interconnects, protective coatings and advanced physical vapor deposition techniques | |
| Liu et al. | Interconnect materials for SOFC stacks |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request |