• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to a component (6) having a metallic base body (7) and a protective layer (8) arranged thereon, wherein the protective layer (8) is multi-layered, at least comprising a first oxide layer (9) and a second oxide Spinel structure forming layer (10), wherein the first oxide layer (9) is arranged closer to the metallic base body (7), as the second, spinel structure forming oxide layer (10). The first oxide layer (9) contains a metal oxide of a rare earth metal group and / or a metal alloy oxide containing at least one element selected from the group of rare earth elements.
    公开号:AT521011A4
    申请号:T50810/2018
    申请日:2018-09-21
    公开日:2019-10-15
    发明作者:
    申请人:High Tech Coatings Gmbh；
    IPC主号:
    专利说明:

    The invention relates to a component having a metallic base body and a protective layer arranged thereon, wherein the protective layer is designed in multiple layers, at least comprising a first, oxidic layer and a second layer forming spinel-structured oxides, wherein the first oxide layer is arranged closer to the metallic base body is, as the second, spinel structure forming oxides.
    Furthermore, the invention relates to a high-temperature fuel cell comprising at least one interconnector.
    In addition, the invention relates to a method for producing a protective layer on a component having a metallic base body, after which the protective layer is formed in multiple layers at least comprising a first oxide layer and a second layer forming spinel-structure oxides, wherein the first oxide layer is closer to the metallic one Main body is arranged, as the second, spinel structure forming oxides.
    Metallic components of the type described in the introduction are used in high-temperature fuel cells (abbreviated to SOFC Solid Oxygen Fuel Cell), in particular for interconnectors (also called bipolar plates). The operating temperatures usually range from about 600 ° C to about 1,000 ° C and allow the use of numerous fuels, the most important among which are H2, CH4 and CO together with air.
    To generate electricity, several fuel cells are usually connected in series. To connect the individual cells is the interconnector, which übli2 / 28
    N2018 / 17100-AT-00 cherweise plate-shaped. These interconnectors are arranged as a fuel gas and oxidant separated zuleitendes link between two fuel cells and can simultaneously act as a supporting component for the entire construction with appropriate design.
    A preferred design of the interconnects is made of metal sheets containing chromium as an essential alloying ingredient, since high-temperature chromium oxide-forming materials have good oxidation resistance. These chromium-containing metallic materials already form under normal conditions chromium oxide-containing surface layers. In the fuel cell operating conditions, the chromium oxides react with oxygen and water to form chromium trioxide (Cr 2 O 3) and / or its hydrates (CrO 2 (OH) 2 (chromic acid) and CrO (OH) 4). However, the chromium trioxide of the surface layer itself has only a slight electrical conductivity. On the other hand, at the operating temperatures of the high-temperature fuel cells, 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. Mechanisms that lead to a reduction in electrical performance and functionality and thus to limit the life of a fuel cell stack are therefore u.a. the growth of an electrically poorly conductive oxide layer on the metallic substrate and the evaporation of Cr compounds (with subsequent deposition and thus poisoning of the cathode).
    Both mechanisms can be controlled by a protective layer on the interconnector. There are a number of approaches in the patent literature for shaping these protective layers. Roughly one can distinguish between non-metallic, mostly oxidic, protective layers and metallic protective layers. For the first group, plasma spraying, PVD deposition or wet chemical deposition are used as coating techniques. However, these oxide protective layers often have layer thicknesses of more than 50 .mu.m, whereby the electrical conductivity is limited. Next, these / 28
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    Protective layers form continuous cracks, which usually does not heal and thus does not effectively prevent the chromium diffusion to the surface and the subsequent evaporation. Commercially, a ceramic protective layer is often used based on lanthanum strontium manganese perovskites, as described for example in WO 2008/003113 A1 or US 2010/0129693 A1.
    Ceramic protective layers consisting of two- or three-phase alloys such as CoMnCr spinels, which are known from US 2017/0054159 A1, proved to be not very effective in reducing chromium evaporation, especially at temperatures> 750 ° C.
    The application of opaque, thin protective layers (thin layers as a rule deposited with PVD methods) is often technically impossible due to the surface roughness of the metallic substrates.
    Metallic protective layers are produced by means of physical vapor deposition (PVD) processes, chemical vapor deposition (CVD) processes or application from the ionized state by electrolytic or chemical deposition (eg electroplating, anodizing, electrophoretic painting). The metallic coating is oxidized during operation and oxidic spinels form, which have a relatively (to chromium oxides) high electrical conductivity.
    Multi-layer protective layers are also known, for example from EP 1 819 507 B1, US 2015/0079498 A1, US 2009/0029187 A1 and US Pat. No. 7,875,360 B2.
    The present invention is based on the object to improve the service life of a high-temperature fuel point.
    This object is achieved with the above-mentioned component, in which the first oxide layer contains a metal oxide of a rare earth metal group and / or a metal alloy oxide containing at least one element from the group of rare earths.
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    Further, the object of the invention with the high-temperature fuel spot is solved, which contains a device according to the invention.
    The object of the invention is also achieved with the aforementioned method, which provides that the first, oxidic layer is formed from a metal or a metal alloy containing at least one element from the group of rare earths.
    The applied first, oxidic layer is able to form largely gas-tight ceramic layers at high temperatures and oxidizing atmosphere. This, in turn, has the advantage that even metallic base bodies with a very rough surface can be used directly for the coating. A residual porosity in the oxidic layer after the coating process thus has no negative influence on the layer properties. Due to the metals or metal alloys used for the production of the oxide layer, the oxides have electrical resistances of less than 5 mO / cm 2 . Another advantage is that occurring microcracks during long-term operation, which can be induced, for example, by temperature fluctuations, are capable of healing.
    According to one embodiment variant of the component, provision can be made for the second layer forming oxides having spinel structure to contain at least one element from the group of rare earths. According to one embodiment variant of the method, in addition to the metals of a group consisting of Mn, Co, Fe, Nb, Cr, V, at least one element from the group of the rare earths can also be deposited for formation of the second layer forming an oxide with spinel structure, in particular that element which was also deposited for the formation of the first metallic layer. The advantage here is that due to the protective effect of the second layer, the first, oxidic layer can be made very thin and therefore very stable. This is important, for example, in the manufacture of fuel cell stacks.
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    According to another embodiment variant of the component it can be provided that the proportion of the at least one element from the group of rare earths in the second layer forming an oxide with spinel structure is selected from a range from 0.01 atom% to 10 atom%. It is thus achieved that cracks, which occur due to temperature changes in the first metallic layer, can be better cured by diffusion processes. If the content of the rare earth element is too high, it may form its own rare earth oxides, which do not have the advantageous properties of spinel structures (high electrical conductivity).
    It may be preferred according to a further embodiment of the invention that the metallic base body is formed of an alloy with chromium as an alloying element, in particular of a ferritic chromium alloy with a minimum chromium content of 15 wt .-%. The use of such basic bodies per se is known from the prior art, as stated above. However, it has been found that the protective layer has advantages, in particular with alloying with chromium as the main constituent, because it can be effectively prevented that chromium is removed from the component or converted into a form that is disadvantageous for a high-temperature fuel cell. Thus, according to a further embodiment variant of the component, it is also possible to use chromium alloys which have a proportion of chromium in the chromium alloy of at least 70% by weight without the cell's performance as a result of chromium loss decreasing relatively rapidly. This in turn is advantageous in terms of the electrical conductivity of the device.
    Due to the thin first layer, the protective layer can be made relatively thin overall. According to a preferred embodiment, the protective layer may have a layer thickness which is selected from a range of 1 pm to 20 pm. The above-mentioned effects regarding the reduction of the conductivity by thick oxide layers can thus be significantly reduced.
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    For reasons of better self-healing effect, according to a further embodiment variant of the component, the first, oxidic layer may have a smaller layer thickness than the second layer forming oxides with spinel structure.
    Preferably, the metallic base body is plate-shaped or sheet-shaped or structured, since it makes it easier to carry out its coating with high quality of a constant layer thickness.
    To further improve the above-mentioned effects, it can be provided according to other embodiments of the component that the proportion of the at least one element from the group of rare earths in the second layer forming spinel structure oxides varies over the layer thickness of this layer. It is thus possible to enhance the annealing effects of cracks.
    Preferably, the first oxide layer according to a variant of the method is produced by a PVD method. The first, oxidic layer can thus be deposited many times faster and more economically than conventional ceramic layers by vacuum coating methods.
    Likewise, for the same reasons, according to a further embodiment variant of the method, provision may be made for the second layer forming oxides having spinel structure to be deposited with one another from a group consisting of Mn, Co, Fe, Nb, Cr, V, in particular by cosputters with the proviso that the sum gives oxidation numbers of the metal cations forming the spinel structure +8.
    Due to the above-mentioned (automatic) formation of a gas-tight first layer can be provided according to a further embodiment, that are mechanically removed before the arrangement of the first oxide layer on the metallic body adhering oxides. These oxides are typical for sintered components, for example. As expected, by removing the oxides, the properties of the component can be improved. However, it is advantageous that this can be achieved with effective, simple procedures
    N2018 / 17100-AT-00, e.g. Sand blasting, can be done, since - as already stated above - it is possible within the scope of the invention to form the first, oxidic layer largely gas-tight.
    For a better understanding of the invention, this will be explained in more detail with reference to the following figures.
    Each shows in a simplified, schematic representation:
    1 shows a detail of a high-temperature fuel cell.
    2 shows a detail of a component;
    Fig. 3 shows the reduction of Cr evaporation compared with an uncoated substrate at a temperature of 850 ° C and 3 vol .-% water vapor in the laboratory atmosphere.
    By way of introduction, it should be noted that in the differently described embodiments, the same parts are provided with the same reference numerals or the same component names, wherein the disclosures contained in the entire description can be mutatis mutandis to the same parts with the same reference numerals or component names. Also, the location information chosen in the description, such as top, bottom, side, etc. related to the immediately described and illustrated figure and these position information in a change in position mutatis mutandis to transfer to the new location.
    FIG. 1 shows a section of a high-temperature fuel cell 1. The high-temperature fuel cell 1 has a plurality of identical modules 2 (only one is shown in FIG. 1), each module 2 having a cathode 3, an electrolyte 4 and an anode 5. Next, the modules 2 and 6 components for the separation of the individual modules, the so-called interconnectors.
    This basic structure of a high-temperature fuel cell 1 is known from the prior art, so reference is made to further details of the high-temperature fuel cell 1 thereto.
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    The present invention is primarily concerned with the device 6.
    As already mentioned, the component 6 is preferably an interconnector. In the context of the invention, however, the component can also be provided for a different application, in particular also for a high-temperature fuel cell 1, such as a Gaszuführelement (gas supply) or a gas discharge (gas discharge). However, the component 6 can also be used in other devices, for example a heat exchanger, in which it is subjected in particular to similar operating conditions, such as in a high-temperature fuel cell 1.
    The component 6 has a metallic main body 7. Preferably, this metallic base body 7 is plate-shaped or sheet-shaped. However, it can also have a different shape, for example a cylindrical, etc. In addition, the surface of the base body 7 may be structured. The structuring may be in the form of a wave pattern or a waffle pattern or in the form of grooves, etc., for example.
    In principle, the metallic main body 7 may consist of a metal or a metal alloy which is selected from a group comprising or consisting of stainless steels having a chromium content of at least 15% by weight, in particular between 15% by weight and 97% by weight.
    For example, the material Crofer® 22 APU from Thyssen Krupp VDK GmbH can be used as stainless steel.
    In the preferred embodiment of the component 6, however, the metallic main body 7 consists of an alloy with chromium as a substantial alloying element (in addition to optionally present further alloying elements), in particular as the main constituent. The chromium content according to one embodiment of the invention is particularly preferably at least 70% by weight, in particular at least 90% by weight, for example 95% by weight. The chromium alloy may have a chromium content of between 70% and 95% by weight.
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    Particularly preferred is a ferritic chromium alloy. The iron content of these alloys can be between 2% by weight and 10% by weight. For example, a ferritic chromium alloy with an iron content of 5 wt .-% and a chromium content of 95 wt .-% can be used.
    For example, the CFY material from Plansee SE can be used as stainless steel.
    A part of the chromium may also be replaced by at least one other alloying element, for example yttrium, manganese, copper or other rare earth metals. The one or more alloying elements of the chromium alloy besides iron may be present in a proportion selected from a range of 0.01 wt% in total and 3 wt%.
    The component 6 has a protective layer 8 on at least one surface. Preferably, a plurality of surfaces of the component 6 are provided with a protective layer 8, in particular those surfaces which come into contact with oxidizing substances, in particular (hot) gases.
    As can be seen better from Fig. 2, which shows a section of the component 6, the protective layer 8 is made of several layers. It comprises a first layer 9 and a second layer 10 or consists thereof. The first layer 9 is oxidic. The first layer has a proportion of perovskite crystal structures.
    The second layer 10 has oxides with spinel structure or consists thereof (= second oxide layer 10).
    As can be seen from FIG. 2, the first, oxidic layer 9 is arranged closer to the metallic main body 7 than the second, spinel-structured oxide layer 10. In particular, the first, oxidic layer 9 is arranged directly on the metallic main body 7, and in particular associated with it.
    The first oxide layer consists of or comprises a metal of the rare earth group or of a metal alloy which contains at least one element from the group of the rare earths. These are the elements Scandium, Yttrium, / 28
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    Lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium. If the first oxide layer 9 is formed from a metal alloy, it may contain at least one further element from the group of rare earths.
    Furthermore, the first, oxidic layer 9 has a chromium fraction and (corresponding to the chemical stoichiometry) oxygen. The first, oxidic layer 9 may therefore consist, for example, of at least one rare earth metal, chromium and oxygen. Optionally, at least one further element which originates from the metallic basic body 7 can also be contained.
    The proportion of the at least one rare earth metal to the metal alloy of the first oxide layer 9 may be selected from a range of 10 wt% to 50 wt%. If a plurality of rare earth metals are present, their sum content of the metal alloy may be selected from a range of 10 wt% to 50 wt%. The remainder to 100 wt .-% chromium, and optionally another alloying element or several other alloying elements of the metallic base body 7, and oxygen.
    According to a preferred embodiment of the component 6, the second, spinel-structured oxide layer 10 also has at least one element from the group of rare earths. The proportion of the at least one element from the group of rare earths in the second layer 10 forming the spinel structure can, according to a further embodiment, be selected from a range from 0.01 atom% to 10 atom%, in particular from one Range from 0.1 at% to 5 at%.
    For example, the second spinel structure-forming layer 10 may have one of the following compositions:
    - CoMnLa, wherein the proportion of La is 5 atomic% and the remainder is divided into 100 atomic% to 50% each on Co and Mn. The first layer may here preferably be formed by La, Cr and oxygen.
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    - CoMnCe, wherein the proportion of Ce is at least approximately 7 atomic% and the remainder to 100 atomic% is divided into 50% each on Co and Mn. The first layer can here preferably be formed by Ce, Cr and oxygen.
    As already stated, the first, oxidic layer 9 can be made very thin. A layer thickness 11 of the entire protective layer 8 can be selected from a range of 1 μm to 20 μm, in particular from a range of 1 μm to 11 μm. In this case, the first, oxidic layer 9 is preferably made thinner than the second, oxide with spinel structure forming layer 10. The first oxide layer 9 may preferably have a layer thickness 12, which is selected from a range of 2 nm to 0.5 pm , in particular from a range of 50 nm to 200 nm. The remainder to the entire layer thickness 11 of the protective layer is formed by the second layer 10 forming spinel-structured oxides.
    The concentration of the at least one element from the group of rare earths in the second layer 10 forming spinel-structured oxide layers may be constant over the entire layer thickness of this layer 10 (in the context of production-related fluctuations). However, according to an alternative embodiment of the component 6, there is also the possibility that the proportion of the at least one element from the group of rare earths in the second layer 10 forming oxide with spinel structure varies over the layer thickness of this layer 10, ie has a concentration gradient. For example, this concentration gradient of 50 atomic% at the interface to the first oxide layer 9 to 0.1 atomic% over the layer thickness of the layer 10 drop.
    In the case of more than one rare earth element in the second layer 10 forming the spinel structure, all or several or even only one of these elements may be formed with a concentration gradient over the layer thickness of the layer 10.
    The concentration gradient can be designed to be linear or as a function of x 2 or x 3 or logarithmically, etc., extending.
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    According to a further embodiment variant of the component 6, it can be provided that the first, oxidic layer 9 has at least two elements from the group of the rare earths, and that their proportion varies over the layer thickness 12 of this layer 9. With regard to the possible course of the concentration gradients, reference is made to the above statements. In this case, the proportion of rare earths at the interface with the metallic base body 7 of the component is preferably higher than the fraction of MnCo and decreases in the direction of the second layer 10 forming the spinel structure.
    The production of the metallic component 6 whose metallic base body 7 is provided. This can be made by a casting or sintering process. In both variants of the method, of course, subsequent (machining) processing steps can be carried out. On at least one surface of this metallic Grundköpers 7 then the protective layer 8 described above is arranged.
    In the preferred embodiment of the method, to produce the protective layer 8, the first, oxidic layer 9 is deposited on the metallic base body 7 by means of a PVD method.
    The first oxide layer 9 is deposited in particular by means of magnetron sputtering, preferably an unbalanced configuration, of one or more purely metallic targets or metal alloys. The substrates are in continuous rotational motion. Typical coating rates are 0.1 nm / s to 10 nm / s at a gas pressure of 5 * 10 -4 mbar to 1 * 10 -2 mbar. During the deposition process, a negative voltage is applied to the metallic target, with a pulsed or constant DC voltage between -300V and -500V being chosen.
    On this first, oxidic layer 9, the second, spinel-structured oxide layer 10 is then deposited. This is preferably done by the deposition of at least two metals from a group consisting of Mn, Co, Fe, Nb, Cr, V with each other, in particular by cosputters, with the proviso, / 28
    N2018 / 17100-AT-00 that the sum gives oxidation numbers of the metal cations forming the spinel structure +8.
    Preferably, the second spinel structure-forming layer 10 is deposited by means of magnetron sputtering, preferably an unbalanced configuration, of one or more pure metallic targets or metal alloys.
    The substrates are in continuous rotational motion. Typical coating rates are 0.1 nm / s to 10 nm / s at a gas pressure of 5 * 10 -4 mbar to 1 * 10 -2 mbar. During the deposition process, a negative voltage is applied to the metallic target, with a pulsed or constant DC voltage between -300 V and -500 V being selected.
    For example, the following combinations of metals can be made: Co with Mn, Co with Mn and Fe, Co with Mn and Al.
    As stated above, the second spinel structure-forming layer 10 may also comprise at least one rare earth element, in particular that element of the first oxide layer 9. The at least one rare earth element is preferred Embodiment variant of the method is not diffused from the first, oxidic layer 9, but mitabgeschieden with the above-mentioned elements to form the second, spinel-forming oxide layer 10, in particular simultaneously with said elements.
    It is envisaged that the second spinel structure-forming layer 10 will be at least partially oxidized after deposition of the first and second metals. This can be done before the device 6 is used, that is, before it is used in particular in the high-temperature fuel cell 1. However, it is also possible for this oxidative aftertreatment to take place during the joining of the fuel cell 1 (joining takes place at approximately 950 ° C.) or during "retraction" during use of the end product.
    This oxidative after-treatment of the protective layer 8 is preferably carried out at a temperature of 750 ° C to 970 ° C and an oxygen partial pressure between / 28
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    10-12 bar and 0.2 bar. The duration depends on the selected temperature and varies between 0.1 hours and 10 hours. The higher the temperature is chosen, the shorter the duration can be.
    According to another embodiment variant of the method, provision can be made for mechanical removal of the adhering oxides prior to the arrangement of the first, oxidic layer 9 on the metallic base body 7. This can be done for example by grinding, sandblasting, etc. Preferably, the base body 7 is sandblasted before the arrangement of the protective layer 8 and this sandblasted surface, optionally after a cleaning of the abrasive grains, is used without a further (smoothing) aftertreatment. The surface on which the protective layer 8 is disposed can therefore have a surface roughness (average roughness depth) Rz> 20 μm, in particular between Rz = 20 μm to 50 μm. Rz is determined according to DIN EN ISO 25178 in the version valid at the filing date of the application.
    The protective layer 8 contains all elements for the formation of an effective protection of the device 6 at high temperatures in oxidizing atmospheres. Subsequent diffusion of elements into the protective layer is therefore not necessary. The protective layer 8 is also able to heal thermal cracks. Thus, a crack-free protective layer 8 can be provided.
    EXAMPLES
    Example 1:
    In a first exemplary embodiment, an interconnector has been coated with a sintered metallic base body 7 made of a chromium-iron yttrium alloy mentioned above. In a first step, the native oxidation layer (from the pre-processes in the basic body production) by Sand15 / 28
    N2018 / 17100-AT-00 emit radiation. Thereafter, the base body 7 is introduced into a vacuum system and, after reaching the desired starting pressure, via an Ar plasma treatment (argon pressure about 5 10 -3 mbar, pulsed negative voltage at the substrate between - 300 V and - 1200 V, duration 5 Minutes to 30 minutes). A first 0.1 μm thick metallic layer 9 with lanthanum is applied by means of magnetron sputtering (argon pressure about 5 × 10 -3 mbar, constant negative voltage at the target between -300 V and -400 V, duration 0.1 minutes to 10 minutes) , In a second step, an approximately 4 μm thick second layer 10 of CoMn forming oxides with spinel structure is deposited by means of magnetron sputtering (argon pressure about 5 × 10 -3 mbar, constant negative voltage at the target or at the targets between 300 V and -400 V, Duration 0.1 minutes to 10 minutes). This CoMn layer was doped with an average of 5 at% lanthanum deposited together with the Co and the Mn.
    If necessary, the areas not to be coated can be masked.
    The coated body 7 was then subjected to a post-treatment at a temperature> 800 ° C in an oxidizing atmosphere (air or argon-oxygen mixture). In this step, the metallic coating was converted into a multilayer oxide layer having an inner Cr 2 O 3 layer formed from the metallic base body 7, a crystalline oxide intermediate layer and an oxide CoMnCr spinel layer 10.
    The inner Cr 2 O 3 layer, which was formed from the metallic base body 7, can generally also be formed in other embodiments of the invention if the protective layer 8 is subjected to oxidative aftertreatment.
    As could be determined by investigations, the entire rough surface of the metallic base body 7 was covered with a covering gas-tight layer. The interconnector can be installed with it.
    In general, the oxidative aftertreatment can also be carried out after installation in the already functional stack of the high-temperature fuel cell 1.
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    In Fig. 3, the reduction of Cr evaporation from the base body 7 in the device 6 according to the invention (lower curve) in comparison with an uncoated base body (upper curve) at a temperature of 850 ° C and 3 vol .-% water vapor in represented in the laboratory atmosphere. The improvement achieved with the protective layer 8 according to the invention can be clearly seen. The time in hours is plotted on the x-axis and the Cr-evaporation in kg / m 2 on the y-axis
    Example 2.
    In a second embodiment, an interconnector was coated with a base body 7 of a metallic alloy Crofer22APU. In a first step, the native oxidation layer and possibly existing organic contaminants (from the preliminary processes during the production of the base body) were removed by chemical cleaning processes. Thereafter, the main body 7 was introduced into a vacuum system and, after reaching the desired starting pressure, activated via an Ar-plasma treatment (see Example 1). An approximately 100 nm thick first layer 9 with lanthanum was applied by means of magnetron sputtering (see Example 1). In a second step, an approximately 2 μm thick CoMn layer 10 was applied via magnetron sputtering (see Example 1). This CoMn layer 10 is doped with up to 1 at% lanthanum.
    Also in this example, the reduction in chromium evaporation was noted as compared to prior art designs.
    The component 6 preferably has a two-layer oxide layer. The first layer 9 preferably consists of an oxide with a high La content, Cr and oxygen. This first layer 9 may have a crystal structure with a high perovskite part.
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    The second layer 10 preferably consists of Co, Mn, La, slightly (<5%) Cr and oxygen. This oxide has a high spinel content.
    Preferably, both layers 9, 10 flow into each other.
    Although the production of the protective layer 8 preferably takes place by deposition of the two layers of the metals and their subsequent oxidation, it is possible in principle for the first, oxidic layer 9 and / or the second, oxidic layer 10 to be produced by deposition of the corresponding metal oxides. become.
    The embodiments show possible embodiments, it being noted at this point that combinations of the individual embodiments are also possible with each other.
    Independently of the component 6, the invention also relates to a protective layer 8 and its use for a metallic component 6 which is used at high temperatures in oxidizing atmospheres, in particular in high-temperature fuel cells 1 and their periphery. This protective layer 8 is assembled in accordance with the preceding embodiments.
    Furthermore, the invention also relates to a precursor for a component 6 having a metallic base body 7 and a protective layer 8 arranged thereon, wherein the protective layer 8 is multi-layered, at least comprising a first, metallic layer 9 and a second layer 10 forming spinel-structured oxides, wherein the first metallic layer 9 is disposed closer to the metallic base body 7 than the second spinel structure forming oxide layer 10, and wherein the first metallic layer 9 is made of a rare earth metal or a metal alloy containing at least one of them Contains element from the group of rare earths. From this precursor, the component 6 or the protective layer 8 according to the invention is produced via the aforementioned oxidative after-treatment.
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    For the sake of order, it should finally be pointed out that in order to better understand the construction of the high-temperature fuel cell 1 or the component 6, these are not necessarily shown to scale.
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    LIST OF REFERENCE NUMBERS
    High temperature fuel cell
    module
    cathode
    electrolyte
    anode
    module
    body
    protective layer
    location
    location
    layer thickness
    layer thickness
    权利要求:
    Claims (15)
    [1]
    claims
    1. component (6) having a metallic base body (7) and a protective layer arranged thereon (8), wherein the protective layer (8) is made of several layers, at least comprising a first, oxide layer (9) and a second, forming oxides with spinel structure Layer (10), wherein the first oxide layer (9) is arranged closer to the metallic base body (7), as the second, spinel-structure forming oxide layer (10), characterized in that the first oxide layer (9) Contains metal oxide of a rare earth metal group and / or contains a metal alloy oxide containing at least one element from the group of rare earths.
    [2]
    2. The component (6) according to claim 1, characterized in that the second, spinel structure forming oxide layer (10) contains at least one element from the group of rare earths.
    [3]
    A device (6) according to claim 2, characterized in that the proportion of the at least one rare earth element in the second spinel structure-forming layer (10) is selected from a range of 0.01 atomic%. to 10 atomic%.
    [4]
    4. The component (6) according to any one of claims 1 to 3, characterized in that the metallic base body (7) is formed of an alloy with chromium as an alloying element, in particular of a ferritic chromium alloy with a minimum chromium content of 15 wt .-% ,
    [5]
    5. The component (6) according to claim 4, characterized in that the proportion of chromium in the chromium alloy is at least 70 wt .-%.
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    [6]
    6. The component (6) according to any one of claims 1 to 5, characterized in that the protective layer (8) has a layer thickness (11) which is selected from a range of 1 pm to 20 pm.
    [7]
    7. The component (6) according to any one of claims 1 to 6, characterized in that the first, oxidic layer (9) has a smaller layer thickness (12) than the second, forming spinel structure with layers (10).
    [8]
    8. The component (6) according to any one of claims 1 to 7, characterized in that the metallic base body (7) is plate-shaped or sheet-shaped and / or formed with a textured surface.
    [9]
    9. The component (6) according to any one of claims 2 to 8, characterized in that the proportion of the at least one element from the group of rare earths in the second, oxides with spinel structure forming layer (10) on the layer thickness of this layer (10) varied.
    [10]
    10. High-temperature fuel cell comprising at least one interconnector, characterized in that the interconnector is designed as a component (6) according to one of claims 1 to 9.
    [11]
    11. A method for producing a protective layer (8) on a component (6) with a metallic base body (7), after which the protective layer (8) is formed in multiple layers at least comprising a first oxide layer (9) and a second, spinel-type oxides forming layer (10), wherein the first oxide layer (9) is arranged closer to the metallic base body (7), than the second, spinel-structure forming oxide layer (10), characterized in that the first oxide layer (9) is formed of a metal or a metal alloy containing at least one element from the group of rare earths.
    22/28
    N2018 / 17100 AT-00
    [12]
    12. The method according to claim 11, characterized in that the first, metallic layer (9) is produced by a PVD process.
    [13]
    13. The method according to claim 11 or 12, characterized in that for the second, forming spinel oxide layer (10) at least two metals from a group consisting of Mn, Co, Fe, Nb, Cr, V are deposited together with the Assuming that the sum gives oxidation numbers of the metal cations forming the spinel structure +8.
    [14]
    14. The method according to claim 13, characterized in that for forming the second, spinel-forming oxide layer (10) in addition to the two metals from the group consisting of Mn, Co, Fe, Nb, Cr, V and at least one element of the Group of rare earths mitabgeschieden, in particular that element, which was also deposited for the formation of the first, metallic layer (9).
    [15]
    15. The method according to any one of claims 11 to 14, characterized in that before the arrangement of the first, metallic layer (9) on the metallic base body (7) adhering oxides are mechanically removed.
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    引用文献:
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    法律状态:
    优先权:
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    ATA50810/2018A|AT521011B1|2018-09-21|2018-09-21|Component with a two-layer, oxidic protective layer|ATA50810/2018A| AT521011B1|2018-09-21|2018-09-21|Component with a two-layer, oxidic protective layer|
    EP19790421.2A| EP3853935A1|2018-09-21|2019-09-18|Component having a two-layered, oxidic protective layer|
    PCT/AT2019/060308| WO2020056440A1|2018-09-21|2019-09-18|Component having a two-layered, oxidic protective layer|
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