WO2013157683A1 - Interconnexion céramique et son procédé de synthèse - Google Patents
Interconnexion céramique et son procédé de synthèse Download PDFInfo
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- WO2013157683A1 WO2013157683A1 PCT/KR2012/003164 KR2012003164W WO2013157683A1 WO 2013157683 A1 WO2013157683 A1 WO 2013157683A1 KR 2012003164 W KR2012003164 W KR 2012003164W WO 2013157683 A1 WO2013157683 A1 WO 2013157683A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0236—Glass; Ceramics; Cermets
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/12—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on chromium oxide
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
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- 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
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
- C04B2235/3227—Lanthanum oxide or oxide-forming salts thereof
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3275—Cobalt oxides, cobaltates or cobaltites or oxide forming salts thereof, e.g. bismuth cobaltate, zinc cobaltite
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
- C04B2235/444—Halide containing anions, e.g. bromide, iodate, chlorite
- C04B2235/445—Fluoride containing anions, e.g. fluosilicate
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6562—Heating rate
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6567—Treatment time
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/76—Crystal structural characteristics, e.g. symmetry
- C04B2235/768—Perovskite structure ABO3
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient
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- 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
Definitions
- the present invention relates to a ceramic connecting material of a solid oxide fuel cell and a method of synthesizing it.
- Fuel cells are devices that generate electricity by chemical reactions.
- Various fuel cells have been developed according to the type of electrolyte.
- the solid oxide fuel cell (SOFC) is the first generation phosphate type fuel cell and the second generation molten carbonate.
- SOFC solid oxide fuel cell
- the fuel cell is more efficient and has less pollution, does not require a fuel reformer, and can combine power generation with a fuel cell-gas turbine-steam turbine.
- SOFCs utilize hard ceramic compounds of metal (eg calcium or zirconium) oxides as electrolytes.
- oxygen gas such as 0 2
- oxygen ions O 2-
- fuel gas such as H 2 gas
- a fuel cell is designed as a stack, in which subassemblies each comprising a cathode, an anode, and a solid electrolyte between the cathode and the anode are continuously assembled, whereby an electrical interconnect is connected between the cathode of one subassembly and the anode of the other subassembly. ) Is placed.
- connection material which provides a conductive path for current to flow between the electrodes and into the external circuit.
- the linker also acts as a separating plate to physically separate the fuel in the anode cavity from the air or oxygen in the cathode cavity. Therefore, the connecting material must have good electrical conductivity to minimize resistive losses and must be stable under both oxidation and reduction conditions. Since SOFCs operate at high temperatures, the thermal expansion coefficient (CTE) of the interconnect must be close to that of the rest of the battery components to minimize thermal stress. Other requirements of the connecting material include adequate mechanical strength, relatively low permeability to oxygen and hydrogen, and moderate thermal conductivity.
- metallic connectors have good electrical conductivity, but are generally not stable when exposed to oxidizing conditions at the cathode of the SOFC, so it is generally necessary to coat the surface with a conductive oxide (eg, spinel). Since ceramic interconnects are oxides, they are stable under an oxidizing atmosphere, but usually have lower conductivity compared to metals. High raw material costs and high manufacturing costs in the case of high density ceramic connecting materials impede the application of ceramic connecting materials in SOFCs.
- the present invention has been made to solve the problems of the prior art as described above, the general purpose of the present invention is a ceramic connecting material and its that can substantially compensate for the various problems caused by the limitations and disadvantages in the prior art It is to provide a synthesis method.
- Another specific object of the present invention is to provide a ceramic connecting material having a high electrical conductivity in both the oxidizing atmosphere and the reducing atmosphere, and a method for synthesizing the same.
- Another specific object of the present invention is to provide a ceramic connecting material suitable for mass synthesis, and a method for synthesizing the same, in which properties such as compactness, sinterability, and electrical conductivity do not change significantly even after mass synthesis.
- the ceramic connecting material includes a plurality of cells each consisting of an anode layer, an electrolyte layer, and a cathode layer, each of which is sequentially stacked, wherein the plurality of cells are electrically connected.
- a material of the connecting material to be connected it is represented by the composition formula La 1-x Ca x Cr 1-y Co y O 3 (where each of x and y represents a molar ratio and satisfies 0.1 ⁇ x ⁇ 0.3 and 0.1 ⁇ y ⁇ 0.2). It comprises a ceramic composition as a main component.
- x may be 0.3 and y may be 0.1.
- 0.7 mol La as starting material satisfying the molar ratio x, y 2 O 3 0.1 moles of CaCo 3 , 0.2 moles of CaF 2 , 0.9 mol of Cr 2 O 3 , 0.1 moles Co 3 O 4 It may include.
- connection material of an embodiment of the present invention 0.7 mol La 2 O 3 , 0.2 mol CaCo 3 , 0.1 mol CaF 2 , 0.9 mol Cr 2 O 3 , 0.1 mol as starting materials satisfying the molar ratios x and y It may include Co 3 O 4 .
- the method of synthesizing the linker powder according to an embodiment of the present invention has a basic composition of La 1-x Ca x Cr 1-y Co y O 3 , 0.1 ⁇ x ⁇ 0.3, 0.1 ⁇ y ⁇ 0.2
- a method of synthesizing a powder comprising: pulverizing and mixing a starting material and a first solvent of the linker powder; Drying the starting material in a liquid state and then heat-processing to powder; Grinding the powder by a milling method after the heat treatment and adding an additive; And granulating the powder to which the grinding and additives are added to a predetermined particle size by spray drying.
- the process of powdering by heat treatment is the process of calcining the starting material in the liquid state at a temperature increase rate of 0.5 °C / min to 10 °C / min at 850 °C to 1200 °C, Pulverizing and mixing the calcined powder and the second solvent, and drying the starting material in a liquid state, and then sintering at a temperature increase rate of 0.5 ° C./min to 10 ° C./min at 1100 ° C. to 1400 ° C. It may include.
- the grinding of the powder by the milling method adds at least one of a jet mill, a bead mill or an attrition mill after the ball mill operation.
- the method may further include a step of miniaturizing the particle size.
- the additive may include at least one of a binder, a release agent, a dispersant, an antifoaming agent.
- the method may further include a heat treatment process for burning the additive contained in the spray-dried raw material, and the heat treatment process may be performed at a temperature increase rate of 0.5 ° C./min at a temperature of 450 ° C. to 800 ° C. It may be made by heat treatment at 5 °C / min for 3 to 10 hours.
- the ceramic connecting material and the synthesis method according to the present invention it is possible to provide a ceramic connecting material having a high electrical conductivity in both the oxidizing atmosphere and the reducing atmosphere and the synthesis method thereof.
- FIG. 1 is a view showing the electrical conductivity with time in the oxidation atmosphere (Oxidizing).
- FIG. 2 is a view showing the electrical conductivity with time in the reducing atmosphere (Reducing).
- FIG. 3 is a diagram showing a coefficient of thermal expansion of Sample 3 after synthesizing a connecting material powder.
- FIG. 4 is a diagram showing an XRD spectrum after synthesizing a linking powder.
- 5 is a SEM (scanning electron microscope) photograph showing a sintered shape after synthesis and a shape after grinding.
- FIG. 6 is a view showing the results of electrical conductivity measurement in the oxidizing atmosphere for the mass synthesis sample.
- FIG. 7 is a view showing a result of measuring the density of the heating temperature during calcination or sintering.
- the present inventors are disposed between a plurality of cells each consisting of an anode layer, a solid electrolyte layer, and a cathode layer stacked in order, and interconnecting the plurality of cells electrically in series.
- a connecting material that can be chemically stable in any of the atmospheres of oxidation and reduction
- high electrical conductivity low conductivity
- low ion conductivity low ion conductivity
- low sintering temperature can be considered.
- the commercial materials for mass production of solid oxide fuel cells and their synthesis methods were discussed.
- the present inventors have investigated the use of the La 1-x Ca x Cr 1-y Co y O 3 ceramic composition among the ceramic compositions represented by LCCCO as a connecting material for a solid oxide fuel cell, and La 1-x Ceramic compositions represented by Ca x Cr 1-y Co y O 3 were produced at various composition ratios and their properties were tested.
- Step 1 Raw Material Weighing
- the powder mixed with the solvent As a process for physically mixing the powder mixed with the solvent, it is mixed for 5 hours to 10 hours at 150rpm to 300rpm. At this time, 5mm, 10mm, 15mm zirconia ball is used.
- a process for completely drying the powder which becomes a liquid state with a solvent to make it solid state it is dried for 2 to 3 days. At this time, the temperature of the dry oven (Dry oven) to 60 °C to 80 °C ethanol is evaporated, the temperature of the oven is raised to 90 °C to 110 °C completely dried. This is because the powder may overflow due to the low boiling point of ethyl alcohol upon drying at 90 ° C. to 110 ° C. from the beginning.
- the mixed powder is formed into an ABO 3 perovskite structure and is a heat treatment process for burning organic materials. Keep and calcinate.
- the mixture is sufficiently mixed with ethyl alcohol and Z-ball for about 12 to 36 hours.
- the ball-like liquid powder is placed in a drier and completely dried, then placed in a crucible and sintered at 1100 ° C. to 1400 ° C. for 2 to 10 hours at a temperature of 0.5 ° C./min to 10 ° C./min.
- Step 7 Grinding & Binder Mixing
- the particles are agglomerated like ceramic ceramics and mixed with various additives by pretreatment of pulverization and spray drying.
- the additive may be a DI water binder, a mold release agent, a dispersant, an antifoaming agent, or the like. .
- the heat treated powder is ground using a ball mill and the additives are mixed.
- deionized water is used as a solvent and the ratio is 1: 1 to the raw material volume.
- 0.01% to 0.1% of a binder and 0.001% to 0.009% of a dispersant are added.
- the release agent and the antifoaming agent are added at 0.001% to 0.009% and 0.005% to 0.01% before spray drying 2 hours to 8 hours, respectively.
- the zirconia ball is put about 2 times by volume relative to the raw material and mixed thoroughly pulverized 12 hours to 36 hours at 100rpm to 400rpm.
- a jet mill, bead mill, or attrition mill process may be further performed to make the particle size finer.
- a jet mill is a method of pulverizing powder by rotating a disk under the pressure of compressed air.
- the particle size is 0.8-1.0 ⁇ m, which is not significantly different from the particle size during ball milling. It was confirmed that it appeared.
- the bead mill is a method in which a bead (bead) in the chamber and pulverized by the rotational force and centrifugal force, it is possible to obtain particles much smaller than the ball mill or jet mill with a particle size of 0.4 ⁇ 0.6 ⁇ m. At this time, by adjusting the speed of the bead mill chamber or the pump injection speed it is possible to obtain particles of a smaller size.
- Process to make the heat-treated powder particles into the size of plasma coating which is spherical according to the conditions of spray drying, for example, additive, inlet and outlet temperature, dosage, temperature, spray rate (rpm), etc. It is very important to set the process conditions because it is determined whether granules are formed and it has a great influence on the feeding of powder during plasma coating.
- the inlet temperature of the spray dryer is set at 100 ° C to 250 ° C and the outlet temperature is 50 ° C to 200 ° C, and the spraying speed is set to 1000rpm to 5000rpm and then 5000rpm To 12000 rpm.
- the temperature increase rate is 0.5 °C / min to 5 °C / min to allow the additive to gradually escape and to combine with a high density as a spherical shape.
- a process for separating the finished powder to the desired particle size (sieving the powder using a sieve of the desired particle size).
- the synthesized powder is made of pellets for conductivity measurement, and the oxidizing atmosphere is maintained at 800 ° C and the oxidizing gas (80% nitrogen, 20% oxygen) is injected into the furnace (Pot type furnace) at the beginning. Check the resistance value for each gap and the temperature of gas injection.
- Reducing atmosphere is also maintained at 800 °C and after the temperature rises to a certain amount of reducing gas (hydrogen 100%) is injected.
- Conductivity measurement uses a 4-probe measurable digital multimeter to measure the resistance and then calculate the conductivity taking into account the pellet size and the distance between the electrodes.
- FIG. 3 shows the coefficient of thermal expansion of Sample 3 after synthesizing the linking powder, and it can be seen that the coefficient of thermal expansion is appropriate as about 108.4 ⁇ 10 ⁇ 7 / ° C.
- FIG. In general, the thermal expansion coefficient of the connecting member is known to have a range of 100 ⁇ 120x10 -7 / °C.
- Figure 4 shows the XRD spectrum after the synthesis of the linker powder, XRD was measured to determine whether the synthesized powder has a perovskite structure. As a result of the measurement, it can be inferred that it has a single-phase perovskite structure and thus the process is stabilized during calcination and sintering operations.
- 5 is a SEM (scanning electron microscope) photograph showing the sintered shape and the shape after crushing after synthesis, and it can be seen that the fine particles are formed after pulverization and have a particle size of about 0.4 to 0.6 ⁇ m.
- a mass production product can be stably supplied by deriving a highly reproducible composition of linking material having little change in properties even after mass synthesis and establishing the synthesis method.
- the electrical conductivity and the density density change according to the temperature and holding time during calcination or sintering were also considered.
- FIG. 6 shows the results of the electrical conductivity measurement in the oxidation atmosphere for the mass synthesis sample.
- FIG. 6 (a) shows the electrical conductivity of the sample sintered at a temperature of 1.5 ° C./min
- FIG. 6 (b) shows the electrical conductivity of the sample sintered at a temperature of 5 ° C./min.
- the linker powder was synthesized with the composition of (LCCC-3), and the remaining process conditions were the same.
- the electrical conductivity of the sample sintered at an elevated temperature of 1.5 °C / min is an average of 31 S / cm
- the electrical conductivity of the sample sintered at an elevated temperature of 5 °C / min is an average of 2.3 S / cm
- Figure 7 shows the results of the measurement of the density according to the elevated temperature at the time of calcination or sintering, it is enlarged to 1000 times, 5000 times, 10000 times.
- the samples 1 and 2 are calcined at 800 ° C., and then set to 5 ° C./min and 1.5 ° C./min, respectively, to step (having a holding time for complete sintering at elevated temperature and lower temperature).
- step having a holding time for complete sintering at elevated temperature and lower temperature.
- both samples were sintered but it can be seen that a large number of pores were seen.
- Samples 3 and 4 were calcined at 1000 ° C., and then set to 5 ° C./min and 1.5 ° C./min, respectively, followed by sintering.
- Sample 3 was roughly finished, but samples 1, 2 and Similarly, pores appear a lot.
- sample 4 compared to other samples, the structure is almost densified, the sintering is completed, and the pores are almost invisible.
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Abstract
La présente invention concerne une interconnexion céramique d'une pile à combustible à oxyde solide et son procédé de synthèse. Plus particulièrement, l'invention concerne une composition céramique qui est le constituant principal du matériau d'une interconnexion qui relie une pluralité de cellules dans une pile à combustible à oxyde solide. Ladite pile à combustible comprend la pluralité de cellules dont chacune comprend une couche d'anode, une couche d'électrolyte et une couche de cathode empilées en série. La composition céramique est représentée par la formule La1-xCaxCr1-yCoyO3 (où x et y représentent respectivement des rapports molaires et satisfont à 0,1 ≤ x ≤ 0,3 et 0,1 ≤ y ≤ 0,2).
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KR10-2012-0041003 | 2012-04-19 | ||
KR1020120041003A KR20130118093A (ko) | 2012-04-19 | 2012-04-19 | 세라믹 연결재 및 그 합성방법 |
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PCT/KR2012/003164 WO2013157683A1 (fr) | 2012-04-19 | 2012-04-25 | Interconnexion céramique et son procédé de synthèse |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05121060A (ja) * | 1991-07-02 | 1993-05-18 | Tonen Corp | 高温型燃料電池用セパレータ材料 |
US5411767A (en) * | 1992-07-27 | 1995-05-02 | Ngk Insulators, Ltd. | Method for producing interconnector for solid electrolyte type fuel cell |
KR100283207B1 (ko) * | 1998-08-03 | 2001-05-02 | 손재익 | 고체산화물 연료전지용 금속 연결재 및 그 제조방법 |
KR20110075242A (ko) * | 2009-12-28 | 2011-07-06 | 주식회사 포스코 | 고체 산화물 연료 전지용 복합 세라믹 접촉재 및 그 제조방법 |
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2012
- 2012-04-19 KR KR1020120041003A patent/KR20130118093A/ko not_active Application Discontinuation
- 2012-04-25 WO PCT/KR2012/003164 patent/WO2013157683A1/fr active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05121060A (ja) * | 1991-07-02 | 1993-05-18 | Tonen Corp | 高温型燃料電池用セパレータ材料 |
US5411767A (en) * | 1992-07-27 | 1995-05-02 | Ngk Insulators, Ltd. | Method for producing interconnector for solid electrolyte type fuel cell |
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