EP1313892A1 - Verfahren zum erzeugen einer festelektrolytschicht auf einem substrat - Google Patents
Verfahren zum erzeugen einer festelektrolytschicht auf einem substratInfo
- Publication number
- EP1313892A1 EP1313892A1 EP01965211A EP01965211A EP1313892A1 EP 1313892 A1 EP1313892 A1 EP 1313892A1 EP 01965211 A EP01965211 A EP 01965211A EP 01965211 A EP01965211 A EP 01965211A EP 1313892 A1 EP1313892 A1 EP 1313892A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- layer
- sintering
- solid electrolyte
- gas
- electrolyte layer
- 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.)
- Pending
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/403—Cells and electrode assemblies
- G01N27/406—Cells and probes with solid electrolytes
- G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
- G01N27/4073—Composition or fabrication of the solid 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
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
- C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
-
- 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
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
- H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
- H01M8/1253—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing zirconium oxide
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the invention relates to a method for producing a solid electrolyte layer, consisting of a fully stabilized zirconium oxide layer, on a substrate.
- the solid electrolyte layer made of fully stabilized zirconium oxide
- Fully stabilized zirconium oxide is understood to mean the stable cubic phase of zirconium oxide.
- the zirconium oxide is doped with an oxide of one of the rare earth metals, in particular with yttrium oxide.
- An amount of about 8 to 12 mol% of yttrium oxide is added to the zirconium oxide to ensure that the zirconium oxide is present in the stable cubic phase regardless of the temperature.
- the cubic phase has a significantly higher ion conductivity.
- the cubic phase is therefore sought for the solid electrolyte layer, as can be seen, for example, from EP 0 414 575 A1.
- the inclusion of metal oxides in the fully stabilized zirconium oxide is proposed in this document.
- zirconium oxide which is partially stabilized with only 2 to 2.5 mol% of yttrium oxide is used in many technical applications > c ⁇ ) r h- 1 h- 1 cn o C ⁇ O C ⁇ o ⁇ r + ⁇ Q ⁇ tr co ⁇ Cd sQ ⁇ n er rt ⁇ tsi 0 ⁇ ! ⁇ ⁇ QL co ⁇ -3 3 ⁇ ⁇ n X rt • n co H tc QL O
- the Zr0 2 layer as a solid electrolyte layer must therefore have good ion conductivity on the one hand and be largely gas-tight on the other to avoid direct contact between fuel gas and oxygen.
- the invention has for its object to provide an inexpensive method for producing a high quality solid electrolyte layer.
- the object is achieved according to the invention by a method for producing a solid electrolyte layer, consisting of a fully stabilized and in particular gas-tight ZrO 2 layer on a substrate, in which
- the sintering additive forms a liquid phase by subsequent heating, and in that
- the green layer is compacted by a liquid phase sintering at a reduced sintering temperature compared to the necessary sintering temperature without the sintering additive.
- this method enables the most cost-effective production of the fully stabilized ZrO 2 layer, in particular provided with 8-12 mol% of Y 2 O 3 (yttrium oxide), as a solid electrolyte layer. Due to the low sintering temperature, a high quality solid electrolyte layer is formed, the quality of which is comparable to that of a solid electrolyte layer applied by means of an EVD process.
- Y 2 O 3 yttrium oxide
- the invention is based on the knowledge that when producing the solid electrolyte layer by means of conventional sintering processes, there is the problem that, due to the high sintering temperatures of 1400 ° C. for Zr0 2, a foreign phase layer forms between the substrate and the actual gas-tight layer.
- This is a major disadvantage, particularly in the field of high-temperature fuel cells. This is because the foreign phase layer that occurs in the conventional sintering process hinders ion conduction and leads to a low efficiency of the fuel cell.
- the formation of an external phase layer is largely prevented by the lower sintering temperature compared to the “normal” sintering temperature for Zr0 2 of approximately 1400 ° C.
- the formation of the external phase layer as a thermodynamic process is essentially dependent on the temperature.
- the sample prepared for sintering is generally understood as a green sheet or green body.
- a green body has for example not only the doped for example with 8- 12mol% Y 2 0 3 Zr0 2 powder, a binder and a relatively high humidity, so that the molding processability and is enables.
- boron nitride BN
- bismuth oxide Bi0 2
- copper oxide CuO
- a combination of these compounds is added as a sintering additive.
- B 2 0 3 Boron nitride, which is oxidized in air to boron oxide (B 2 0 3 ) during the sintering process, has proven to be particularly suitable.
- B 2 0 3 is already in a liquid phase at temperatures above about 400 ° C. and is responsible for a partial Zr0 2 dissolution and a Zr0 2 transport within the layer, which affects the sintering, so the condensation, favors.
- B 2 0 3 is therefore preferably used directly as the sintering additive.
- the process parameters such as heating rate, sintering temperature and holding time are preferably selected such that the liquid phase is still present when the reduced sintering temperature is reached and that the compacted layer is largely free of the sintering additive at the end of the sintering process.
- This ensures that, on the one hand, liquid phase sintering is ensured at a reduced temperature and the formation of a foreign phase layer is largely prevented.
- the completely sintered gas-tight layer has no residues of the sintering additive which could lead to an impairment of the properties of the layer.
- a maximum sintering temperature of below 1400 ° C. and in particular below 1300 ° C. is preferably set here.
- the sintering temperature is expediently between 1100 ° C and 1300 ° C. At these temperatures, compression already takes place due to the presence of the liquid phase and the formation of a foreign phase layer is prevented.
- a heating rate of 4 to 7 K / min is expediently set in the process.
- a green layer with a sintering additive and a ZrO 2 layer without a sintering additive are preferably applied to the substrate.
- the two layers are therefore layered on the substrate.
- the Zr0 2 layer without a sintering additive can also be formed as a green layer or already be presintered.
- the two layers combine to form a homogeneous gas-tight layer.
- the sintering process is favorably influenced by the layered structure and a good sintering result is achieved.
- a completely sintered ZrO 2 layer with a porosity of less than 5 vol% is formed in the process.
- the porosity is thus at least a factor of 2 below the porosity of a conventionally sintered layer.
- a layer thickness between 5 and 100 ⁇ m is expediently applied. On the one hand, this ensures a mechanically stable coating. On the other hand, good electrochemical properties and high gas impermeability are achieved, which is essential for use in a fuel cell.
- Air permeability (leak rate) of ⁇ 10 ⁇ 3 mbar'1 / s'cm 2 , and in particular of about 2'10 ⁇ 4 mbar'1 / s'cm 2 .
- This means that the air permeability is about 2 orders of magnitude lower than the values achieved with a conventional sintering process.
- airtightness is achieved that is comparable to the airtightness that can be achieved by an EVD process.
- the method with the addition of a suitable sintering additive to reduce the sintering temperature due to the favor of a liquid phase sintering therefore enables the formation of a gas-tight layer which is comparable in quality to an EVD-vapor-deposited layer, but is considerably less expensive than the EVD method.
- FIG. 1 shows a process sequence for applying a gas-tight Zr0 2 layer
- FIG. 2 shows an alternative process sequence
- FIG. 3 shows a sketch of a planar high-temperature fuel cell
- FIG. 4 shows the arrangement of a gas sensor designed as a ⁇ probe in a line
- FIG. 5 shows a structure for determining the air permeability (leak rate) of the gas-tight layer.
- Both the sintering additive 4 and the ZrO 2 starting material are preferably in powder form.
- Zr0 2 starting material here means a powder mixture of Zr0 2 with additions of usually 8-12 mol% yttrium oxide (Y 2 0 3 ) and / or magnesium oxide (MgO) and / or calcium oxide (CaO).
- Aluminum oxide (A1 2 0) and cerium oxide (Ce0 2 ) can be added as further additives. These additives form a so-called fully stabilized gas-tight Zr0 layer.
- the powder mixture of Zr0 2 and boron nitride is dispersed and processed into a processable paste, the so-called green material 6.
- a processable paste the so-called green material 6.
- water and binder in particular are added to the powder mixture.
- the green material 6 is applied as a green layer 8 to a substrate 10. This is done for example by means of screen printing, vacuum slip casting, pressure filtration or so-called slip casting, a special type of slip casting. Depending on the consistency, the green material 6 can also be applied to the substrate 10 by means of wet powder spraying.
- the green layer 8 has, for example, a green thickness Dl of 80 ⁇ m and a porosity of about 50 vol.%.
- the substrate 10 with the applied green layer 8 is heated up to a maximum sintering temperature of 1300 ° C. with a heating rate between 4 and 7 K / min and sintered at the sintering temperature for about 5 hours, so that a gas-tight layer 12 is formed - forms standing from fully stabilized zirconium oxide. Due to the shrinkage process during sintering, the gas-tight layer 12 after sintering only has a layer thickness D2 of approximately 30 to 40 ⁇ m. Their porosity is below 5% by volume. Their air permeability, also known as the leak rate, is around 2'10 ⁇ 4 mbar'l / s * cm 2 . The determination of the leak rate is based on DIN 28402.
- a liquid phase sintering of Zr0 2 is initiated by adding the sintering additive 4, in particular boron nitride.
- the sintering temperature required for sintering is reduced by Zr0 2 (reduced sintering temperature).
- Zr0 2 reduced sintering temperature
- the BN is oxidized to B 2 0 3 in air at temperatures above 800 ° C.
- B 2 0 3 is already in the liquid phase at temperatures above 400 ° C.
- the B 2 0 3 liquid phase causes a partial Zr0 2 dissolution and the Zr0 2 transport within the layer is made possible even at the reduced sintering temperature.
- the layer is therefore already compacted at temperatures between 1100 ° C and 1300 ° C, i.e. significantly below the usual sintering temperature co co IV) N3 h- 1 h- 1
- DJ DJ Hl oo ⁇ - DJ ⁇ hj hj hj DJ hi ⁇ tr rt tr ⁇ ⁇ 3 ⁇ tr ⁇ QL hj CQ m tr DJ 3> ⁇ ⁇ tr ⁇ -> ⁇ - ⁇ - 3 N 0: ⁇ - rt ⁇ - 3 hj H tr ⁇ O ⁇ ⁇ o rt rt hi o QL tr tr hj rt 0 ⁇ DJ rt DJ X 3 00 DJ ⁇ ⁇ Hi ta 3 t ⁇ 00 3 tr ⁇ - ⁇ ⁇ ⁇ - ⁇ rt ⁇ - rt Hi 3 H * rt H ⁇ 00 ⁇ - 00 tr r ⁇ DJ ⁇ 3 ) 3
- Hi DJ co ⁇ 3 ⁇ ⁇ - 0 s: CQ 3 DJ ⁇ - 3 s j rt 0- rt DJ ⁇ Q O hj DJ QL ⁇ CQ DJ ⁇ ⁇ hj ⁇ -
- Such a method for applying a gas-tight Zr0 2 layer 12 is particularly suitable for applying a Zr0 2 electrolyte layer 14 on an electrode, in particular on the cathode 16 of a high-temperature fuel cell 18, as is shown in a very simplified manner in a planar embodiment according to FIG. 3.
- tubular fuel cells 18 are also known.
- the solid electrolyte layer 14 is surrounded between an inner cathode tube and an outer anode tube.
- the green layer 8, which forms the solid electrolyte layer 14 after sintering, is applied to the cathode tube, for example, by means of circular screen printing.
- a porous perovskite material (La ⁇ _ x Ca x Mn0 3 ) is generally used as the material for the cathode 16 and the anode 20.
- the solid electrolyte layer 14 is arranged between the cathode 16 and an anode 20.
- the cathode 16 is swept with air or with oxygen 0 2 and the anode 20 with fuel gas, for example hydrogen H 2 .
- fuel gas for example hydrogen H 2 .
- the electrolyte layer 14 is of the air-gas side a Sauerstoffio- nentransport instead to the combustion gas side, and an electric voltage "is generated.
- the electrolyte layer 14 on the one hand must be as gas-tight as possible in order to prevent direct contact between the oxygen and the fuel gas.
- it must have good oxygen ion conductivity. To do this, it is first necessary that the zirconium oxide is in the cubic phase, i.e. fully stabilized. However, the oxygen ion conduction would be deteriorated by the formation of a foreign phase layer between the cathode 16 and the solid electrolyte layer 14, as is formed in a conventional sintering process.
- the leak rate q L (or the specific leak rate q LF ) is determined using the following formulas,
- a sample 40 for example a tubular porous cathode 16 for a fuel cell 18 with the electrolyte layer 14 applied thereon, is introduced into a special adapter 42. This has a window 44 with a defined area F and, apart from the window 44, completely seals off the sample 40 from the surroundings.
- a pump line 46 air is pumped out of the cavity of the tubular sample 40 via a first valve 48A and a second valve 48B and a negative pressure is generated.
- the valves 48B, 48A are closed and the course of the pressure rise is recorded by means of a pressure gauge 52 on the basis of the leakage area defined by the window 44.
- the pressure curve 52 is evaluated by an evaluation unit 54.
- Another valve 48C is available for venting after the measuring cycle.
- the pressure rise is recorded over a measuring time dt of 30 to 600 s.
- the initially set differential pressure (negative pressure between the cavity of the sample and the outside environment) is 1 bar, the measurement is carried out at room temperature and the test gas is air.
- a specific leak rate q L F of approximately 2'10 -4 mbar "l / s-cm 2 is determined for a gas-tight layer 12 applied according to the method described above.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Electrochemistry (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Metallurgy (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Analytical Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Biochemistry (AREA)
- Organic Chemistry (AREA)
- Molecular Biology (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- General Chemical & Material Sciences (AREA)
- Fuel Cell (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP01965211A EP1313892A1 (de) | 2000-08-24 | 2001-08-23 | Verfahren zum erzeugen einer festelektrolytschicht auf einem substrat |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP00118429 | 2000-08-24 | ||
EP00118429 | 2000-08-24 | ||
PCT/EP2001/009761 WO2002016669A1 (de) | 2000-08-24 | 2001-08-23 | Verfahren zum erzeugen einer festelektrolytschicht auf einem substrat |
EP01965211A EP1313892A1 (de) | 2000-08-24 | 2001-08-23 | Verfahren zum erzeugen einer festelektrolytschicht auf einem substrat |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1313892A1 true EP1313892A1 (de) | 2003-05-28 |
Family
ID=8169640
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01965211A Pending EP1313892A1 (de) | 2000-08-24 | 2001-08-23 | Verfahren zum erzeugen einer festelektrolytschicht auf einem substrat |
Country Status (4)
Country | Link |
---|---|
US (1) | US7087336B2 (de) |
EP (1) | EP1313892A1 (de) |
AU (1) | AU2001285902A1 (de) |
WO (1) | WO2002016669A1 (de) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10212966B4 (de) * | 2002-03-22 | 2006-08-03 | Siemens Ag | Hochtemperatur-Brennstoffzelle und Verfahren zu deren Herstellung |
US7625653B2 (en) * | 2005-03-15 | 2009-12-01 | Panasonic Corporation | Ionic conductor |
CN101919093B (zh) * | 2009-03-26 | 2012-11-14 | 丰田自动车株式会社 | 电解质膜的形成方法、膜电极接合体及膜电极接合体的制造方法 |
JP6240761B2 (ja) * | 2013-07-31 | 2017-11-29 | エルジー・ケム・リミテッド | 固体酸化物燃料電池およびその製造方法 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4303447A (en) * | 1980-04-02 | 1981-12-01 | University Of Illinois Foundation | Low temperature densification of zirconia ceramics |
US4764491A (en) * | 1987-05-11 | 1988-08-16 | General Motors Corporation | Low temperature sintering of yttria stabilized zirconia with lanthana borate additions |
US5130210A (en) * | 1989-08-25 | 1992-07-14 | Tonen Corporation | Stabilized zirconia solid electrolyte and process for preparation thereof |
US5171645A (en) * | 1991-01-08 | 1992-12-15 | Gas Research Institute, Inc. | Zirconia-bismuth oxide graded electrolyte |
-
2001
- 2001-08-23 EP EP01965211A patent/EP1313892A1/de active Pending
- 2001-08-23 WO PCT/EP2001/009761 patent/WO2002016669A1/de not_active Application Discontinuation
- 2001-08-23 AU AU2001285902A patent/AU2001285902A1/en not_active Abandoned
-
2003
- 2003-02-24 US US10/373,322 patent/US7087336B2/en not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
---|
See references of WO0216669A1 * |
Also Published As
Publication number | Publication date |
---|---|
US7087336B2 (en) | 2006-08-08 |
WO2002016669A1 (de) | 2002-02-28 |
US20030148163A1 (en) | 2003-08-07 |
AU2001285902A1 (en) | 2002-03-04 |
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