EP2225408A2 - Couches de protection déposées sans courant - Google Patents
Couches de protection déposées sans courantInfo
- Publication number
- EP2225408A2 EP2225408A2 EP08853518A EP08853518A EP2225408A2 EP 2225408 A2 EP2225408 A2 EP 2225408A2 EP 08853518 A EP08853518 A EP 08853518A EP 08853518 A EP08853518 A EP 08853518A EP 2225408 A2 EP2225408 A2 EP 2225408A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- substrate
- coating
- substrate according
- layer
- chromium
- 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.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
- C23C18/44—Coating with noble metals using reducing agents
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/48—Coating with alloys
- C23C18/50—Coating with alloys with alloys based on iron, cobalt or nickel
Definitions
- the fuel and an oxygen-containing oxidant for example oxygen, also in the form of air, are spatially separated and preheated via gas supply lines to the fuel cell, i. the fuel to the anode and acting as an oxidant, oxygen-containing gas to the cathode.
- oxygen ions produced at the cathode can be passed through the solid electrolyte to the fuel gas side, i. Anode, arrive. There they react with the fuel gas.
- the hot exhaust gases from the fuel cells may be passed through heat exchangers to preheat, for example, the fuels and the oxidizer.
- Chromium-base alloys and chromium-rich, ferritic steels have a good oxidation resistance, a highly conductive oxidation layer and have a coefficient of thermal expansion adapted to the solid electrolyte material.
- the chromium trioxide of the surface layer itself has only a slight electrical conductivity.
- the chromium oxide hydrates are gaseous species which can be transported through the gas space to the interface between the electrolyte and the cathode. There, the Cr (VI) compounds are deposited. This hinders the oxygen reduction at this point. A significant reduction in the performance and lifetime of the fuel cell is the result.
- PVD Physical Vapor Deposition
- DE 10 2005 015 755 A1 names the PVD methods, CVD methods and the application from the ionized state by electrochemical or chemical deposition in the form of electroplating, anodizing or electrophoretic lacquering for the application of the metallic protective layer.
- the materials used in this periphery of the fuel cells are chromium-containing steels, so that the problem of chromium vaporization also arises here.
- Volatile chromium compounds which are released in the gas supply lines and the heat exchanger can reach the fuel cells where they are just as undesirable as the chromium compounds originating from the interconnector plate.
- the object of the present invention is to propose a substrate which can be produced cost-effectively, in which sufficient chromium retention is ensured under the operating conditions of SOFC fuel cells, and to a process for producing such substrates.
- the coating Due to the electroless deposition of the coating is achieved in comparison to the chemical deposition improved quality of the coating. In addition, the coating can be applied at higher coating rates.
- a substrate is obtained in which the chromium retaining layer can be produced inexpensively.
- the metallic elements used to form the substantially chromium-free coating are preferably selected from copper, cobalt, manganese, iron, nickel and zinc. Mixtures of these metallic elements can also be used.
- the aforementioned metals are also particularly recommended from the point of view of matched thermal shear coefficients of expansion of their oxides. Likewise, their electrical conductivity is advantageous.
- the electroless plating of the present invention also exhibits good adhesion to the substrate, particularly a steel substrate.
- the substrate according to the invention is formed as a sheet material.
- the invention is also applicable with very great advantages in complex component geometries, as e.g. may occur in pipelines and even greater extent in the components of the heat exchangers, in particular their contact surfaces, are required.
- the electrolessly deposited coatings do not know any preferred directions, i. Even with complex geometry of the substrate surface uniform layer thicknesses can be achieved.
- the coating of the substrate according to the invention preferably has a layer thickness of 2 ⁇ m or more, in particular 7 ⁇ m or more.
- the electroless deposition makes it particularly easy to generate homogeneous layer thicknesses of the coating.
- the substrate according to the invention can be produced such that the surface of the coating on the side facing away from the substrate has a lower surface roughness than that of the uncoated substrate surface.
- the uncoated surface of the substrate is first seeded with a catalyst.
- a catalyst Precious metals in particular are suitable for this, in particular Pd and / or Pt are suitable.
- a metallic chromium-containing substrate generally recommend temperature and corrosion resistant ferritic steel substrates, in particular of materials such as Crofer22APU (manufacturer ThyssenKrupp, Germany), F17TNb or F18MT (manufacturer Imphy Ugine Precision, France) and so-called super alloys or ODS alloys, eg ITM -Il (manufacturer Plansee SE, Austria), in particular if the substrates are to be used as interconnector plates.
- materials such as Crofer22APU (manufacturer ThyssenKrupp, Germany), F17TNb or F18MT (manufacturer Imphy Ugine Precision, France) and so-called super alloys or ODS alloys, eg ITM -Il (manufacturer Plansee SE, Austria), in particular if the substrates are to be used as interconnector plates.
- austenitic steels such as e.g. Use grade 1.4301 as the coefficient of thermal expansion is less critical here. Furthermore, the conductivity of the coating plays no role, so that steel grades with aluminum and / or silicon contents of more than 1 wt.% Are used without problems.
- layer thicknesses in the range of a few ⁇ m are often sufficient. Larger layer thicknesses can, however, be chosen without disadvantages with regard to the thermal expansion coefficients and the electrical conductivity. Such larger layer thicknesses (eg, about 100 .mu.m) can be used to compensate for manufacturing tolerances of the substrate and to achieve increased planarity of the surface of the substrate that comes into contact with one of the electrodes during assembly of the fuel cell stack. This results in an improved electrical contact between the interconnector plate and the respective electrode.
- a mixed oxide is formed when the coating is converted into an oxide layer, including the metal oxide / metal oxides present in the MO x -containing layer.
- MnO x , CuO x , NiO x and FeO x -containing layers are used in combination with a co-based coating.
- this mixed oxide layer can be optimized with regard to its electrical conductivity and its thermal expansion coefficient by varying the metal oxides involved.
- the formation of the mixed oxide layer also forces the formation of a Cr-containing spinel layer in the region of the contact surface of the substrate and the coating or even substantially completely avoids it.
- the invention further relates to a substrate obtained by the process according to the invention.
- Another aspect of the present invention resides in the use of a substrate according to the invention as interconnector material in an SOFC fuel cell stack.
- FIG. 1a is an enlarged detail of a sectional view of the interconnector plate obtained in the method according to FIG. 1;
- FIG. 3b shows the SOFC fuel cell of FIG. 3a combined with an interconnector plate according to the invention
- the rate of deposition in the electroless deposition can be selected higher than in the electrodeposition. If the current density and hence the deposition rate is increased in the case of the electrodeposition described in Comparative Example 1, there is a risk that the uniformity of the deposition and thus the uniformity of the layer thickness suffers.
- Substrates 10 prepared according to Examples 1 and 2 with a Co coating 12 were treated at a temperature in the range from about 800 to about 1000 ° C. in an oxidative atmosphere with holding times of about 10 hours.
- the metallic coating 12 deposited without external current transforms into a compact oxide layer 14 (see FIG.
- FIG. 1a shows the layer structure obtained in the oxidation treatment in detail. Between the cobalt oxide layer 14 and the surface of the crofter 22APU substrate 10, a thin Cr 2 O 3 layer 16 forms on the side of the substrate 10, while a Cr-Mn spinel layer 18 is formed on the side of the oxide layer 14 becomes.
- a reactive intermediate layer (Co-Cr spinel) may still come between the layers 14 and 18 (not shown).
- the layer thickness of the Co oxide layer 14 essentially corresponds to the layer thickness of the previously applied Co layer 12.
- Examples 1 and 2 prepared substrates 10 with a co-coating-12 were wet-chemically with an MnO x -containing layer 20 is coated (see FIG. 2).
- a dispersing agent e.g., Dolapix ET 85
- binder e.g., polyvinyl acetate, PVAC
- Example 3 After evaporation of the EtOH portions of the suspension, the substrates thus obtained were subjected to an oxidative temperature treatment as described in Example 3. In this case, mixed oxide layers 22 were formed which, compared to the oxide layers obtained in Example 3, had better electrical conductivity and thermal expansion coefficients better adapted to the properties of the anode material. The formation of Co-Cr-spinel layers can in this case largely be pushed back completely.
- FIG. 3 a schematically shows the structure of an SOFC fuel cell 30 with an anode 32, a solid electrolyte 34 and a cathode 36.
- the anode 32, the solid electrolyte 34 and the cathode 36 are constructed as directly adjacent layers.
- the anode layer of the anode 32 is composed of a porous anode substrate and an anode functional layer of lower porosity, but the anode functional layer is still gas permeable.
- the layer of the cathode 36 is formed of porous oxide ceramic and has a layer thickness which is often in the range of about 10 to about 60 microns.
- the material of the oxide ceramic of the cathode layer is selected, for example, from (La, Sr) MnO 3 or (La, Sr) CoFeO 3 .
- FIG. 3 b schematically shows the fuel cell 30 provided with an interconnector plate 38 on the side of its cathode 36.
- the interconnector plate 38 has a corrugated structure with fins 40, between which gas channels 42 extend.
- the guided in the channels 42 gas supplies the cathode with an oxygen-containing oxidant, such as air.
- Preferred interconnector plates 50 are shown in FIG. They are made from a sheet substrate and have a corrugated structure 52 in the region in which they are in contact with electrodes of the fuel cells.
- the channels 54 provided on one side of the sheet substrates can be used to supply the oxidizing agent to a cathode, while the channels 56 provided on the opposite side of the sheet substrate serve to supply the fuel to an anode.
- the substrates of the invention can be used advantageously not only as interconnector plates as described above, but beyond even with considerable advantages as Gaszu- and -ableitonne for the fuel gases (fuel gas, oxygen-containing gas, exhaust gases) of the fuel cell and components of heat exchangers, by means of which the fuel gases and oxygen-containing gases are heated to a temperature similar to the operating temperature of the fuel cell.
- the heat content of the exhaust gases is advantageously used.
- FIG. 1 A schematic representation of such a fuel cell system 100 according to the invention is shown in FIG.
- the fuel cell system 100 includes an SOFC fuel cell stack 102 which is supplied with fuel gas or an oxidant (e.g., air) via fuel gas supply lines 104, 106. These gases supplied to the system via lines 108, 110 are first brought to a temperature close to the operating temperature of the fuel cell stack 102 via heat exchangers 112, 114 before being supplied thereto.
- fuel gas or an oxidant e.g., air
- the gases derived from the system i. on the one hand consumed oxidizing agent (oxygen-depleted air) and fuel gas with a proportion of water and a residual content of fuel gas are discharged via leads 116, 118 from the fuel cell stack, passed through heat exchangers 120, 122 and then, in the case of the fuel offgas, to the fuel supply line 108 returned and thermally conditioned again via the heat exchanger 112 or in the case of the spent oxidant, ie the oxygen-depleted air, removed as exhaust air from the system.
- oxygen-depleted air oxygen-depleted air
- fuel gas with a proportion of water and a residual content of fuel gas are discharged via leads 116, 118 from the fuel cell stack, passed through heat exchangers 120, 122 and then, in the case of the fuel offgas, to the fuel supply line 108 returned and thermally conditioned again via the heat exchanger 112 or in the case of the spent oxidant, ie the oxygen-depleted air, removed as exhaust air from the system
- the heat recovered in the heat exchangers 120, 122 may be used to thermally condition the oxidant (s) in the heat exchangers 112, 114, respectively, and therefore, in some systems, the heat exchanger units 112, 114, and 120, 122 are combined in one block ,
- the electrical lines and the control lines and control systems have been omitted in FIG. 5, since these are of no significance for the explanation of the invention.
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Fuel Cell (AREA)
Abstract
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102007058907A DE102007058907A1 (de) | 2007-11-30 | 2007-11-30 | Chromhaltiges, metallisches Substrat und Verfahren zu dessen Herstellung |
DE102008032498A DE102008032498A1 (de) | 2008-07-05 | 2008-07-05 | Stromlos abgeschiedene Schutzschichten |
PCT/EP2008/066477 WO2009068674A2 (fr) | 2007-11-30 | 2008-11-28 | Couches de protection déposées sans courant |
Publications (1)
Publication Number | Publication Date |
---|---|
EP2225408A2 true EP2225408A2 (fr) | 2010-09-08 |
Family
ID=40679058
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP08853518A Withdrawn EP2225408A2 (fr) | 2007-11-30 | 2008-11-28 | Couches de protection déposées sans courant |
Country Status (2)
Country | Link |
---|---|
EP (1) | EP2225408A2 (fr) |
WO (1) | WO2009068674A2 (fr) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EA201391684A1 (ru) * | 2011-05-26 | 2014-05-30 | Топсёэ Фуль Селл А/С | Электрическое восстановление анода твердого оксидного топливного элемента |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AUPN173595A0 (en) * | 1995-03-15 | 1995-04-06 | Ceramic Fuel Cells Limited | Fuel cell interconnect device |
DE19836352A1 (de) * | 1998-08-11 | 2000-02-17 | Siemens Ag | Hochtemperatur-Brennstoffzelle mit Nickelnetz und Hochtemperatur-Brennstoffzellenstapel mit einer solchen Zelle |
EP1978582A1 (fr) * | 2007-04-05 | 2008-10-08 | Atotech Deutschland Gmbh | Procédé pour la préparation d'électrodes à utiliser dans une pile à combustible |
-
2008
- 2008-11-28 WO PCT/EP2008/066477 patent/WO2009068674A2/fr active Application Filing
- 2008-11-28 EP EP08853518A patent/EP2225408A2/fr not_active Withdrawn
Non-Patent Citations (1)
Title |
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None * |
Also Published As
Publication number | Publication date |
---|---|
WO2009068674A3 (fr) | 2009-10-15 |
WO2009068674A2 (fr) | 2009-06-04 |
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RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: TIETZ, FRANK Inventor name: ZERFASS, HANS-RAINER Inventor name: KIEFER, THOMAS |
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DAX | Request for extension of the european patent (deleted) | ||
17Q | First examination report despatched |
Effective date: 20161209 |
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Effective date: 20190226 |