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Definitions

• the invention relates to a powdery zirconium oxide containing metal oxides from the group of scandium, yttrium, rare earths and / or mixtures thereof, processes for its preparation, and its use in the fuel cells, in particular for the production of electrolyte substrates for ceramic fuel cells.
• ZrO 2 Pure zirconia
• the cubic high-temperature phase changes below 230O 0 C into metastable tetragonal zirconium oxide, and between 1200 0 C and 95O 0 C, the transition from tetragonal to monoclinic ZrO 2 is observed. Transformations between the monoclinic and the high-temperature phases during heating and cooling are associated with abrupt volume changes.
• the sintering of zirconium dioxide takes place in a temperature range which takes place monoclinically and tetragonally significantly above the temperature of the reversible phase transformation.
• the stabilized zirconium oxides are then present from room temperature to melting point in the same stabilized modification, ie the Voiumen Surgion on cooling for the production of ceramic components are avoided, Ullmann's Encyclopedia of Industrial Chemistry, VoL A28, 1996, p 556ff, Rompp Lexikon Chemie , 10th Edition 1999, p 3073.
• stabilized or partially stabilized zirconium oxide powders are used for the production of ceramic components, in which case the stabilizer oxides must be able to form a solid solution with the zirconium oxide.
• the amount of stabilizer required depends on the desired properties and the nature of the oxide, and inadequate homogeneities of the stabilizer in the ZrO 2 gate lead to the presence of undesirable monoclinic, ie unstabilized, phase-to-phase phosphors.
• zirconium oxide materials having improved properties can be produced which are used, for example, in construction and structural elements in modern mechanical engineering, in human medicine, in cutting tools and in thermal barrier coatings .
• the yttria-doped zirconium oxides have been increasingly used in the production of ceramic fuel cells.
• An important property of the substrates for ceramic fuel cells produced from zirconium oxides is their electrical conductivity, which decisively affects the performance of the fuel cell.
• stabilized zirconium oxides are usually prepared via two main processes in different variants.
• solids which contain both metals are separated from aqueous or organic solutions or suspensions of zirconium and stabilizer precursors.
• the separation of the solids takes place via co-precipitation and filtration of the hydroxides.
• other separation techniques such as SoI-GeI, evaporation, spray pyrolysis and hydrothermal method are used.
• US 3957500 describes a co-precipitation process for producing a homogeneous mixture of zirconium and yttrium hydroxide. After calcination at 900 to 1500 ° C within 1 to 10 hours, the stabilized zirconia forms.
• DE 10138573 discloses a nanoscale pyrogenically produced tetragonal yttrium stabilized zirconia (YSZ) powder and the process for its preparation.
• aqueous and / or alcoholic solutions of Zr and Y precursors such as nitrates and propionates by means of a nozzle in a reaction tube in which an oxyhydrogen flame of hydrogen and air burns, atomized and then burned at temperatures of 800 to 1000X.
• No. 5,750,459 describes the generation of gels or spherical or microsphere particles by dropping a Y / Zr nitrate solution into an ammonium hydroxide solution.
• the other method for producing the stabilized ZrO 2 powder is the mixed-oxide or solid-state process. In this process, mixtures of zirconia and stabilizers are homogenized and then sintered to stabilized ZrO 2 powder.
• the solid-state process is simple and inexpensive to perform. In contrast to wet-chemical processes, apart from recyclable water or steam, there are no by-products or contaminated wastewater and exhaust gases.
• the disadvantages of the process are the high sintering temperatures of> 1300 ° C. and the low homogeneity of the powders which, after sintering, contain from 25 to 30% by volume of monoclinic phase. To minimize the monoclinic phase contributions, the products are repeatedly ground and annealed in multiple stages, resulting in a significant increase in product cost. Stabilized ZrO 2 powders are therefore hardly produced by the mixed-oxide process.
• US 4542110 discloses a process for producing a sintered body by wet grinding a mixture of zirconia and yttria with addition of SiO 2 and Al 2 O 3 as a sintering aid and subsequent drying and sintering of the mixture for 10 to 120 minutes at temperatures> 1300 ° C, preferably of between 1400 and 1500 0 C 0 C. After repeated mixing and subsequent annealing of the cubic phase content increases to at least 95% by volume.
• US 4360598 describes a process for producing a YSZ ceramic by mixing amorphous zirconia with yttria or a yttrium-containing salt followed by sintering. After sintering at temperatures of 1000 to 1550 0 C ceramic bodies are obtained which contain mainly tetragonal and cubic zirconia.
• EP 1076036 describes the preparation of zirconium oxides stabilized with yttrium or other metals by melting the precursors in high-frequency or medium-frequency furnaces at temperatures of 2200 to 3000 ° C.
• DD 96467 discloses a fully stabilized cubic zirconia which is prepared by mixing basic zirconium carbonate and stabilizing additives such as calcium or yttria followed by sintering at 800 ° C / 3h.
• WO 03/051790 describes a process for producing tetragonal or mixtures of tetragonal and cubic zirconium dioxide. Disadvantage of the zirconia powder produced by the prior art via the mixed oxide process is their insufficient homogeneity of the stabilizers in the crystal lattice. Nevertheless, to ensure adequate stabilization, high - A -
• the object of this invention is therefore to provide zirconium oxide powders for use in the ceramic fuel cells, which have high electrical conductivities and high mechanical strengths after sintering to gastight bodies.
• the object is achieved by a powdery zirconium oxide containing up to 10 mol% of at least one of the metal oxides from the group of scandium, yttrium, rare earths and / or mixtures thereof, which has a filling density of at least 1.2 to 2.5 g / cm 3 , measured according to ASTM B 417.
• the pulverulent zirconium oxides according to the invention preferably have a filling density of at least 1.2 to 2.3 g / cm 3 , more preferably of at least 1.6 to 2.0 g / cm 3 , particularly preferably of at least 1.3 to 1, 9 g / cm 3 and more preferably from 1, 5 to 1, 7 g / cm 3 .
• the zirconium oxides according to the invention are preferably characterized by a filling density of at least 1.5 to 2.5 g / cm 3 , more preferably of at least 1.6 to 2.3 g / cm 3 .
• the zirconium oxides according to the invention are particularly suitable as precursors for the production of substrates which are used in the ceramic fuel cells due to their high electrical conductivity.
• the zirconium oxides according to the invention preferably contain 3 to 6 mol%, particularly preferably 3 to 5 mol% and particularly preferably 3 to 4 mol% of yttrium oxide.
• the zirconium oxides according to the invention may also contain as stabilizer also preferably 3 to 10 mol%, preferably 3 to 7 mol%, particularly preferably 4 to 6 mol% ytterbium oxide (Yb 2 O 3 ).
• the zirconium oxides according to the invention preferably have a D90 value of the powder particles of 0.5 to 1.2 ⁇ m, preferably 0.5 to 0.9 ⁇ m, particularly preferably 0.6 to 0.9 ⁇ m, measured according to ASTM C 1070.
• the powders according to the invention are also distinguished by their specific surface area (BET).
• BET specific surface area
• the powders have BET values, measured according to ASTM D 3663, from 5 to 18 m 2 / g, preferably from 5 to 15 m 2 / g, preferably from 10 to 16 m 2 / g, preferably from 7 to 13 m7g, particularly preferably from 9 to 12 m 2 / g.
• the zirconium dioxides according to the invention have very high monoclinic phase proportions. Surprisingly, and in contrast to the prior art, according to which due to the reversible phase transformation from monoclinic to tetragonal associated volume change fully or partially stabilized powder with only very low monoclinic phase fractions, up to 10 VoI% are suitable for the production of ceramic components.
• the zirconium oxide powders according to the invention are suitable, despite monoclinic phase fractions, of up to 80% by volume for the production of ceramic substrates and, in particular, for applications in the electrolyte-supported ceramic fuel cells.
• the zirconium oxide powders according to the invention may have from 5 to 80% by volume of monoclinic phase fractions.
• the powders preferably have 20 to 80% by volume, preferably 20 to 60% by weight. %, particularly preferably 40 to 75% by volume, particularly preferably 45 to 70% by volume, of monoclinic phase fractions.
• the particular powders according to the invention have 40 to 55% by volume, preferably 45 to 55% by weight. % monoclinic phase shares.
• the invention further relates to an efficient and economical process for the preparation of the zirconium oxides according to the invention.
• the invention therefore also provides a process for the preparation of zirconium oxides doped with metal oxides from the group of scandium, yttrium and rare earths and / or mixtures thereof, comprising the following steps:
• the inventive method is shown schematically.
• the process according to the invention produces from an zirconium oxide with a purity of at least 95%, preferably> 99% and at least one of the oxides from the group scandium, yttrium, rare earths and / or mixtures thereof in the desired stoichiometric ratio, an aqueous suspension which is at least 50% Wt% mixed oxide solids content.
• the zirconium oxides used as raw materials may contain up to 3% by mass of HfO 2 .
• these dispersants are added on a polyacrylate, polyelectrolyte or polyacryic acid base. Good results were achieved, for example, when using, based on the solids content of the suspensions, 1 to 12 percent by mass, preferably 3 to 8 percent by mass of the dispersants Doiapix CE 64 and / or Doiapix CA Zschimmer & Schwarz achieved.
• An important role in the process according to the invention is played by the morphological properties of the zirconium oxide precursor.
• the zirconium oxide precursors have a specific surface area (BET) of 3 to 30 m.sup.2 / g, preferably 6 to 15 m.sup.2 / g, particularly preferably 6 to 11 m.sup.a / g, measured according to ASTM D 3663 lead to the zirconium oxides according to the invention.
• BET specific surface area
• Decisive for the preparation of the zirconium oxides according to the invention is an intensive homogenization of the suspension by wet grinding.
• Various apparatuses can be used to carry out the grinding operations. Suitable for this are different types of ball mills.
• the comminution is preferably carried out in stirred ball mills.
• the net grinding energy input (E NE ⁇ o) is determined as the difference between the gross grinding energy input (EBRUTT O ) and the energy input when the mill is idling (E EMPTY ).
• EBRUTTO we d recorded with a mounted on the mill power / energy meter (D 122 Gönnheimer).
• E EMPTY is the product of the no-load power (PL EER ) of the mill and the grinding time (t).
• Idle power is the power that is called the mill is required for operation at a given speed without filling with grinding media and suspension. The power consumption of the mill can be directly measured by
• ENETTO EBRUTTO - EUEER (in kWh)
• ELEER P LE ER * t.
• MEE specific effective grinding energy input
• the specific effective grinding energy input is preferably 0.2 to 1.5 kWh / kg, preferably 0.1 to 1.0 kW / h, preferably 0.2 to 1.0 kWh / kg, preferably 0.3 to 1.0 kWh / kg, more preferably 0.2 to 0.7 kWh / kg, more preferably 0.6 to 0.8 kW / kg of solid used, and particularly preferably 0.2 to 0.5 kWh / kg of solid used.
• the oxide mixture is sintered at temperatures of at least 1200 0 C.
• Sintering at temperatures of 1200-1350 0 C is preferred, most preferably carried out at 1250-1300 0 C.
• the sintered powders are then subjected to intensive wet grinding in order to obtain good, dispersible to the primary particle range powder for further processing.
• the solids concentration in the suspension can be up to 80
• Percent by mass preferably up to 70 percent by mass.
• Solids concentration in the suspension 40 to 70 mass% preferably 60 to 70, particularly preferably 50 to 60 mass%.
• the wet grinding at a specific effective grinding energy input from 0.4 to 2.5 kWh / kg, more preferably from 0.7 to 1, 9 kWh / kg, particularly preferably from 0.4 to 1, 0 kWh / kg, in particular preferably from 0.4 to 0.8 kWh / kg and more preferably from 0.4 to 0.6 kWh / kg of solid carried out.
• the suspension is dried at temperatures of ⁇ 8O 0 C.
• the drying in a spray dryer at temperatures of ⁇ 80 0 C is preferred, preferably from ⁇ 100 0 C, particularly preferably of> 11O 0 C.
• novel zirconium oxide powders produced by the process according to the invention are particularly suitable for the production of substrates and in particular for the production of electrolyte substrates for ceramic fuel cells.
• the zirconium oxide powders according to the invention can be pressed into particularly dense compacts.
• the invention also relates to compacts consisting of zirconium oxides according to the invention.
• the compacts according to the invention have a Green density, which is 54 to 65%, preferably 56 to 62%, particularly preferably 56 to 58% of the theoretical density.
• the green density of the compacts can be determined by the geometric method. In this case, specimens of 1 cm 2 surface and a height of 5-10 mm are pressed uniaxially with a pressure of 100 MPa. Thereafter, the specimens are post-densified isostatically with 2000 MPa and then their volume (V) according to the formula
• V a x b x c calculated, where a, b, c - mean edge lengths of the specimens.
• the green density is determined by dividing the mass of the specimens by the volume of the sample.
• the pul verförmigen zirconium oxides according to the invention are also distinguished by their high sintering activity.
• the compacts produced from the zirconium oxide powders of the invention are characterized in that they form gas-tight sintered bodies of high strength after sintering.
• the density of a sintered compact can be determined by the buoyancy method. For this purpose, the mass of the specimen in air and in water at 21 0 C is measured and the density according to the formula
• Density of the sample mass of the sample in air x density (water at 21 ° C)
• the invention also sintered substrates for electrolyte-supported ceramic fuel cells consisting of zirconium oxides according to the invention.
• the sintered substrates according to the invention are distinguished by their high specific electrical conductivity, later also called SEL.
• the level of specific electrical conductivity depends on the type and concentration of the added metal oxide component and the temperature.
• substrates of the zirconium oxides according to the invention with 3.5 mol% Y 2 O 3 show a SEL of at least 2.5 S / m, preferably of at least 2.7 S / m, particularly preferably of at least 2.9 S / m, measured at 850 ° C.
• the substrates of zirconium oxides according to the invention with 4 mol% Yb 2 O 3 have an SEL of at least 3.8 S / m, preferably at least 4.2 S / m.
• the substrates with 6 mol% Yb 2 O 3 are distinguished by a SEL of at least 6.6 S / m, preferably 6.8 S / m.
• the specific electrical conductivity can be determined by means of a 4-point direct current measurement.
• ceramic test pieces of about 50 mm in length, 10 mm in width and a thickness of about 100 ⁇ m are produced by film casting.
• the film casting slip is prepared by adding 250g of powder to 202g of a commercial target! available binder (eg Ferro, Binder B73208) with the addition of grinding aids 418 g 3YSZ-Mahtzyltndem (12mm diameter) and 418 g 3YSZ grinding cylinder (10mm diameter) from Tosoh be mixed in a 1 liter plastic bottle.
• the Folieng woolschlicker is homogenized for 48 hours on a roller bench.
• the grinding cylinders are separated and the slurry degassed for 24 hours by slowly rotating in a 0.5 liter PE bottle.
• the slurry is poured through a filter on a flat surface and brought by means of a doctor blade to a height of about 250 microns. After 7-24h drying strips are cut from the film, which after 1 hour sintering at 1500 ° C, the above-mentioned test specimens.
• the polarity and magnitude of the current are varied.
• the independence of the conductivity of polarization or contact effects on the inner electrodes is ensured by the fact that the change in the polarity and magnitude of the current lead to no change in the conductivity.
• the specific electrical conductivity (SEL) of the sample is calculated according to the formula
• the substrates according to the invention are also distinguished by their high mechanical properties
• the substrates with 8.9 mol% Y 2 O 3 show a strength of 900 to 1000 MPa.
• the 4 mol% Yb 2 O 3 substrates have a strength of 2000 to 2100 MPa, with 6 mol% Yb 2 O 3 of 1050 to 1150 MPa.
• the mechanical strength can be determined by the ball-ring method, based on DIN 52292.
• the zirconium oxides according to the invention are preferably used for the production of electrolyte substrates and / or functional layers in fuel cells.
• the invention therefore relates to a fuel cell containing a substrate of zirconium oxide according to the invention.
• the invention also provides a fuel cell which has at least one functional layer which contains at least one of the zirconium oxide powders according to the invention.
• the fuel cell according to the invention is an anode-supported or an electrolyte-supported cell.
• the mill space was filled with 10 kg of mahic balls, 0.6 mm diameter yttria-stabilized zirconia (YSZ).
• the speed of the stirrer shaft was 1950 min '1 .
• the net grinding energy input (ENETT O ) was determined as the difference between the gross grinding energy input (E BR u ⁇ o) and the energy input at idling of the mill (ELEER).
• E BR U T ⁇ O is measured using a letst / energy meter mounted on the mill (D. 122 from Gönnheimer).
• E EMPTY is the product of the no-load power (PLEER) of the mowing and grinding time (t).
• MEE specific effective grinding energy input
• the suspension was spray-dried.
• the inlet temperature of the spray dryer was 300 0 C, the outlet temperature of 105 0 C.
• spray drying, cyclone discharge and material were combined and protection sieved through a 250 micron sieve.
• the spray dried product had a specific surface area of 15.9 rrvVg.
• the homogenized material Vorstoff mixture was sintered in a hood furnace type "NT 440" from Nabertherm with blowing air at 1300 "C with a holding time of 2 hours, the heating and cooling rate was 5 K / min.
• the sintered product was in turn comminuted in the stirred ball mill with a specific net grinding energy input of 0.75 kWh / kg and then spray-dried.
• the milling was carried out in two stages with YSZ grinding balls, using milling beads with a diameter of 2 mm in the first stage and grinding beads of 0.6 mm in the second stage.
• Mahlkugel change took place after a specific net Mahlenergäeeintrag of 0.3 Wh / kg, in contrast to the Vorstoffmahlept proved in the crushing of the sintered products a one-time addition of 1% dispersing aid, based on the solid used, as sufficient.
• the zirconia powder obtained had a specific surface area of 10.63 m 2 / g, a dgo value of 0.71 ⁇ m and a bulk density of 1.81 g / cm 3 .
• the Y 2 O 3 content was 3.5% by volume.
• the monoclinic phase fraction was 41% by volume.
• the powder was pressed uniaxially with a pressure of 100 MPa into compacts. Thereafter, the specimens were post-densified isostatically with 2000 MPa. The compacts showed a green density of 3.44 g / cm 3 . The density of the compacts after sintering at 1500 ° C / 1 h was 6.01 g / cm 3 (98.2% of the theoretical density).
• the powder was very easy to process via foil casting, drying and sintering for one hour at 1500 0 C to electrolyte substrates.
• the sintered at 850 0 C substrates showed a specific electrical conductivity of 2.70 S / m.
• the mechanical strength of 90 ⁇ m thick substrates, determined by the ball-ring method, was 2413 MPa. The zirconia in the sintered substrates was nearly completely stabilized, the monoclinic phase content was ⁇ 1 Vo! %.
• the zirconia powder obtained had a specific surface area of 9.43 m 2 / g, a d 90 value of 0.57 ⁇ m and a filling density of 1.84 g / cm 3 .
• the Y 2 O 3 content was 3.5 mol%.
• the monoclinic phase fraction of the powder was 39% by volume.
• the powder was pressed uniaxially with a pressure of 100 MPa into compacts. Thereafter, the specimens were post-densified isostatically with 2000 MPa.
• the compacts showed a green density of 3.49 g / cm 3 .
• the density of the compacts after sintering at 1500 ° C / 1h was 6.01 g / cm 3 .
• the powder can be processed very well by film casting, drying and sintering at 1500 ° C. for one hour to form electrolyte substrates.
• the sintered substrates showed an electrical conductivity (SEL) of 2.72 S / m at 850 ° C.
• the mechanical strength of 90 ⁇ m thick substrates was 1954 MPa.
• the zirconia in the sintered substrates was completely stabilized, ie monoclinic ZrO 2 phase was no longer detectable by X-ray analysis.
• the precursor grinding was carried out at a specific net Mahienergieeintrag of 0.50 kWh / kg solid.
• the homogenized precursor mixture showed a specific surface area of 14 m.sup.2 / g after spray-drying.
• the further implementation of the example was carried out analogously to Example 1.
• the product obtained had a specific surface area of 10.60 m 2 / g, a d ⁇ 0 value of 0.64 ⁇ m and a filling density of 1.72 g / cm 3 .
• the Y 2 O 3 content was 3.5 mol%.
• the monoclinic phase fraction of the powder was 50% by volume. The powder was pressed uniaxially with a pressure of 100 MPa into compacts.
• the specimens were post-densified isostatically with 2000 MPa.
• the compacts showed a green density of 3.46 g / cm 3.
• the density after sintering at 1500 ° C / 1 h was 6.01 g / cm 3 .
• the powder was very easy to process via Foiieng discernen, drying and sintering for 1 hour at 1500 0 C to electrolyte substrates.
• the sintered substrates showed a specific electrical conductivity (SEL) of 2.73 S / m at 850 ° C.
• the mechanical strength of 90 ⁇ m thick substrates was 2390 MPa.
• the zirconia in the sintered substrates was completely stabilized, ie monoclinic ZrO 2 ⁇ phase was undetectable by X-ray analysis.
• the compacts showed a green density of 3.35 g / cm 3 .
• the density after sintering at 1500 ° C / 1h was 6.09 g / cm 3 .
• the powder was very easy to process via foil casting, drying and sintering for one hour at 1500 0 C to electrolyte substrates.
• the sintered substrates had a (SEL), measured at 850 ° C., of 2.83 S / m.
• the mechanical strength of 90 ⁇ m thick substrates was 2191 MPa.
• the zirconia in the sintered substrates was completely stabilized, ie monocrystalline ZrO 2 phase was undetectable by X-ray analysis.
• the compacts showed a green density of 3.5 g / cm 3 -
• the density after sintering at 1500 ° C / 1 h was 6.02 g / cm 3 .
• the powder was very easy to process via foil casting, drying and sintering for one hour at 1500 0 C to electrolyte substrates.
• the sintered substrates had a (SEL), measured at 850 ° C., of 2.87 S / m.
• the mechanical strength of 90 ⁇ m thick substrates was 2285 MPa.
• the zirconia in the sintered substrates was completely stabilized, ie monoclinic ZrO 2 phase was undetectable by X-ray analysis,
• Table 1 The properties of the resulting powders, compacts and substrates are shown in Table 1. The table shows that with increasing amounts of yttrium oxide, the specific electrical conductivity increases.
• FIG. 2 shows the mechanical strength and specific electrical conductivity of substrates produced in Examples 1 to 6 from zirconium oxides according to the invention, as a function of the Y 2 O 3 content. Table 1
• Example 5 used ZrO 2 and 2.9 kg of Yb 2 O 3 having a specific surface area of
• the product obtained had a specific surface area of 10.89 m 2 / g, a d go value of 0.79 ⁇ m and a filling density of 1.73 g / cm 3 .
• Powder was 30% by volume. The powder was added uniaxially with a pressure of 100 MPa
• the compacts showed a green density of 3.66 g / cm 3
• the density after sintering at 1500 ° C / 1 h was 6.32 g / cm 3
• the powder was very good at film casting
• the sintered substrates of ytterbium oxide doped ZrO 2 (YbSZ) at 850 0 C exhibited a specific electric conductivity of 4.21 S / m, which was thus significantly higher than comparable substrates having 4 mol% Y 2 O 3 doped ZrO 2 (YSZ), example! 6.
• the mechanical strength of 95 microns thick substrates was 2066 MPa.
• the zirconia in the sintered substrates was completely stabilized, ie monoclinic ZrO 2 phase was undetectable by X-ray analysis.
• Example 7 a ZrO 2 powder doped with ⁇ rnol% Yb 2 O 3 was prepared, starting from 20.8 kg ZrO 2 and 4.2 kg Yb 2 O 3.
• the product obtained had a specific surface area of 9.07 m 2 / g, a d 90 value of 0.77 ⁇ m and a filling density of 1.84 g / cm 3 .
• the monoclinic phase content of the powders was 13% by volume.
• the powder was pressed uniaxially with a pressure of 100 MPa into compacts. Thereafter, the specimens were post-densified isostatically with 2000 MPa.
• the compacts showed a green density of 3.74 g / cm 3 .
• the density after sintering at 1500 ° C / 1h was 6.49 g / cm 3 .
• the powder was very easy to process via foil casting, drying and sintering at 1500 0 C for 1 hour to form electrolyte substrates.
• the sintered substrates (6YbSZ) show at 850 0 C, a conductivity of 6.85 S / m, which is thus significantly higher than comparable substrates containing 6 mol% of Y 2 O 3 doped ZrO 2 from example 6.
• the mechanical strength of 95 ⁇ m thick substrates was 1108 MPa.
• the zirconia in the sintered substrates was completely stabilized, ie monoclinic ZrO 2 phase was undetectable by X-ray analysis.

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