WO2013157683A1 - Ceramic interconnect and synthesis method therefor - Google Patents
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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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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
The present invention relates to a ceramic interconnect of a solid oxide fuel cell and a synthesis method therefor. The present invention comprises a ceramic composition as a main component for the material of an interconnect which connects a plurality of cells in a solid oxide fuel cell including the plurality of cells each of which have an anode layer, an electrolyte layer, and a cathode layer stacked in series, wherein the ceramic composition is represented by the formula La1-xCaxCr1-yCoyO3(wherein, x and y respectively represent mole ratios and satisfy 0.1≤x≤0.3 and 0.1≤y≤0.2).
Description
본 발명은 고체산화물 연료전지의 세라믹 연결재 및 그 합성방법에 관한 것이다. The present invention relates to a ceramic connecting material of a solid oxide fuel cell and a method of synthesizing it.
연료전지는 화학 반응에 의해 전기를 생성하는 소자이다. 이러한 연료전지는 전해질의 종류에 따라 여러 가지가 개발되어 있는데, 그 중에서 고체산화물 연료전지(Solid Oxide Fuel Cell : SOFC)는 1세대인 인산형 연료전지(Phosphoric Acid Fuel Cell) 및 2세대인 용융탄산염 연료전지(Molten Carbonate Fuel Cell) 등 다른 연료전지들에 비해 효율이 높고 공해가 적으면서, 연료 개질기가 필요 없고, 연료전지-가스터빈-증기터빈과 연계한 복합 발전 가능하다는 장점이 있다.Fuel cells are devices that generate electricity by chemical reactions. Various fuel cells have been developed according to the type of electrolyte. Among them, the solid oxide fuel cell (SOFC) is the first generation phosphate type fuel cell and the second generation molten carbonate. Compared with other fuel cells, such as molten carbonate fuel cells, 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.
SOFC는 금속(예컨대, 칼슘 또는 지르코늄) 산화물의 경질(hard) 세라믹 화합물을 전해질로서 이용한다. 통상, SOFC에서, 02와 같은 산소 가스는 캐소드(공기극)에서 산소 이온(O2-)으로 환원되며, H2 가스와 같은 연료 가스는 애노드(연료극)에서 산소 이온과 함께 산화되어 물을 형성한다. 일반적으로 연료전지는 각각 캐소드, 애노드 및 캐소드와 애노드 사이의 고체 전해질을 포함하는 서브 어셈블리들이 연속적으로 조립되어 스택으로서 설계되는데, 이때 한 서브 어셈블리의 캐소드와 다른 서브 어셈블리의 애노드 사이에는 전기적 연결재(interconnect)가 배치된다.SOFCs utilize hard ceramic compounds of metal (eg calcium or zirconium) oxides as electrolytes. Typically, in SOFC, oxygen gas, such as 0 2 , is reduced to oxygen ions (O 2- ) at the cathode (air electrode), and fuel gas, such as H 2 gas, is oxidized with oxygen ions at the anode (fuel electrode) to form water. do. In general, 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.
이러한 장점을 지닌 SOFC 개발에 있어서 주요 재료의 해결해야할 점은, 전류가 전극들 사이를 통과하여 외부 회로까지 흐르도록 하는 전도성 통로를 제공하는 연결재에 관한 것이다. 연결재는 또한 분리 플레이트로서 작용하여, 애노드 공동(cavity) 내의 연료를 캐소드 공동 내의 공기 또는 산소로부터 물리적으로 분리시킨다. 따라서, 연결재는 저항손실을 최소화하기 위해 양호한 전기 전도성을 지녀야 하고, 산화 및 환원 조건 모두에서 안정적이어야 한다. SOFC는 고온에서 작동하므로, 열응력을 최소화하기 위해서는 연결재의 열팽창계수(CTE)가 기타 나머지 전지 부품들의 열팽창계수에 가까워야 한다. 연결재의 다른 요구조건들에는 적절한 기계적 강도, 산소 및 수소에 대해 상대적으로 낮은 투과도, 및 적당한 열전도도가 포함된다. In developing SOFCs with this advantage, a major material problem has to be addressed in the 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.
SOFC용 연결재를 개발하는데 있어서 일반적으로 두 가지 방법이 있다: 금속성 연결재 및 세라믹 연결재가 이에 해당되는데, 이들 각각은 서로 다른 이점과 해결점을 제공한다. 금속성 연결재는 전기 전도성이 양호하지만, SOFC의 캐소드에서 산화 조건에 노출되면 안정적이지 않으므로 일반적으로 표면을 전도성 산화물(예컨대, 스피넬)로 코팅하는 것이 필요하다. 세라믹 연결재는 산화물이므로 산화분위기 하에서 안정적이지만, 통상 금속과 비교하였을 때 더 낮은 전도성을 가진다. 세라믹 연결재의 높은 원료비용과, 고밀도를 얻고자 할 경우 제조상의 어려움은 SOFC에서의 세라믹 연결재 적용을 방해하는 요인으로 작용한다. There are two general methods for developing connectors for SOFCs: metallic connectors and ceramic connectors, each of which offers different advantages and solutions. 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.
따라서, 본 발명은 상기와 같은 종래기술의 문제점을 해결하기 위하여 안출된 것으로, 본 발명의 일반적인 목적은 종래 기술에서의 한계와 단점에 의해 발생되는 다양한 문제점을 실질적으로 보완할 수 있는 세라믹 연결재 및 그 합성방법을 제공하는 것이다. Accordingly, 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.
본 발명의 보다 구체적인 다른 목적은, 산화분위기 및 환원분위기 모두에서 높은 전기전도도를 갖는 세라믹 연결재 및 그 합성방법을 제공하는 것이다. 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.
본 발명의 보다 구체적인 다른 목적은, 대량합성 후에도 치밀성, 소결성, 전기 전도성 등의 특성이 크게 변하지 않는 대량합성에 적합한 세라믹 연결재 및 그 합성방법을 제공하는 것이다. 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.
이를 위해 본 발명의 일 실시예에 따른 세라믹 연결재는 각각이 순서대로 적층된 애노드층, 전해질층 및 캐소드층으로 구성되는 복수의 셀을 포함하는 고체산화물 연료전지에 있어서, 상기 복수의 셀을 전기적으로 접속하는 연결재의 재료로서 조성식 La1-xCaxCr1-yCoyO3(단, x, y 각각은 몰비를 나타내고, 0.1≤x≤0.3, 0.1≤y≤0.2를 만족함)로 표현되는 세라믹 조성물을 주성분으로 포함하는 것을 특징으로 한다. To this end, the ceramic connecting material according to an embodiment of the present invention 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. As 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.
본 발명의 일 실시예의 연결재에서, 상기 x는 0.3이고, y는 0.1이 될 수 있다. In the connecting member of an embodiment of the present invention, x may be 0.3 and y may be 0.1.
본 발명의 일 실시예의 연결재에서, 상기 몰비 x, y를 만족하는 출발물질로서 0.7몰의 La2O3, 0.1몰의 CaCo3, 0.2몰의 CaF2, 0.9몰의 Cr2O3, 0.1몰의 Co3O4를 포함할 수 있다. In the connecting material of an embodiment of the present invention, 0.7 mol La as starting material satisfying the molar ratio x, y2O30.1 moles of CaCo3, 0.2 moles of CaF2, 0.9 mol of Cr2O3, 0.1 moles Co3O4It may include.
본 발명의 일 실시예의 연결재에서, 상기 몰비 x, y를 만족하는 출발물질로서 0.7몰의 La2O3, 0.2몰의 CaCo3, 0.1몰의 CaF2, 0.9몰의 Cr2O3, 0.1몰의 Co3O4를 포함할 수 있다. In the 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 .
또한, 본 발명의 일 실시예에 따른 연결재 분말의 합성방법은 기본 조성이 La1-xCaxCr1-yCoyO3이며, 0.1≤x≤0.3, 0.1≤y≤0.2를 만족하는 연결재 분말의 합성방법에 있어서, 상기 연결재 분말의 출발물질과 제1 용매를 분쇄 및 믹싱하는 과정과; 액체상태가 된 상기 출발물질을 건조시킨 후 열처리하여 분말화하는 과정과; 열처리 후 상기 분말을 밀링법에 의해 분쇄하고 첨가제를 첨가하는 과정; 및 분쇄 및 첨가제가 첨가된 상기 분말을 분무건조법에 의해 기설정된 입자사이즈로 과립화하는 과정을 포함하는 것을 특징으로 한다. In addition, 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, the method 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.
본 발명의 일 실시예의 방법에서, 상기 열처리하여 분말화하는 과정은 액체상태가 된 상기 출발물질은 850℃ 내지 1200℃에서 승온 속도를 0.5℃/min 내지 10℃/min으로 하여 하소하는 과정과, 하소한 분말과 제2 용매를 분쇄 및 혼합하는 과정과, 액체상태가 된 상기 출발물질을 건조시킨 후, 1100℃ 내지 1400℃에서 승온 속도를 0.5℃/min 내지 10℃/min으로 하여 소결하는 과정을 포함할 수 있다. In the method of an embodiment of the present invention, 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 ℃ / min to 10 ℃ / min at 850 ℃ to 1200 ℃, 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.
본 발명의 일 실시예의 방법에서, 상기 분말을 밀링법에 의해 분쇄하는 과정은 볼밀 작업 후에 제트밀(Jet mill), 비드밀(Bead mill) 또는 어트리션밀(attrition mill) 공정 중 적어도 하나를 추가로 실시하여 입자 사이즈를 미세화하는 과정을 더 포함할 수 있다. In the method of an embodiment of the present invention, 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.
본 발명의 일 실시예의 방법에서, 상기 첨가제는 결합제, 이형제, 분산제, 소포제 중 적어도 하나를 포함할 수 있다. In the method of an embodiment of the present invention, the additive may include at least one of a binder, a release agent, a dispersant, an antifoaming agent.
본 발명의 일 실시예의 방법에서, 분무건조가 완료된 원료에 함유되어 있는 첨가제를 태우기 위한 열처리 과정을 더 포함할 수 있고, 상기 열처리 과정은 450℃ 내지 800℃의 온도에서 승온 속도 0.5℃/min 내지 5℃/min으로 하여 3시간 내지 10시간 동안 열처리하여 이루어질 수 있다. In an embodiment of the present invention, 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 ℃ / min for 3 to 10 hours.
본 발명에 따른 세라믹 연결재 및 그 합성방법에 의하면, 산화분위기 및 환원분위기 모두에서 높은 전기전도도를 갖는 세라믹 연결재 및 그 합성방법을 제공할 수 있다. According to 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.
또한, 본 발명에 따르면 대량합성 후에도 특성 변화가 거의 없는 재현성이 높은 연결재 조성을 도출하고 그 합성방법을 확립함으로써 안정적으로 양산제품을 공급할 수 있다. In addition, according to the present invention, it is possible to stably supply mass-produced products by deriving a highly reproducible composition of linking materials having little change in properties even after mass synthesis and establishing the synthesis method.
도 1은 산화분위기(Oxidizing)에서의 시간에 따른 전기전도도를 나타낸 도면이다. 1 is a view showing the electrical conductivity with time in the oxidation atmosphere (Oxidizing).
도 2는 환원분위기(Reducing)에서의 시간에 따른 전기전도도를 나타낸 도면이다. 2 is a view showing the electrical conductivity with time in the reducing atmosphere (Reducing).
도 3은 연결재 분말 합성 후의 시료 3의 열팽창계수를 나타낸 도면이다. 3 is a diagram showing a coefficient of thermal expansion of Sample 3 after synthesizing a connecting material powder.
도 4는 연결재 분말 합성 후의 XRD 스펙트럼을 나타낸 도면이다. 4 is a diagram showing an XRD spectrum after synthesizing a linking powder.
도 5는 합성 후 소결형상 및 분쇄 후 형상을 나타낸 SEM(주사전자현미경) 사진이다. 5 is a SEM (scanning electron microscope) photograph showing a sintered shape after synthesis and a shape after grinding.
도 6은 대량합성 시료에 대한 산화분위기에서의 전기전도도 측정 결과를 나타낸 도면이다. 6 is a view showing the results of electrical conductivity measurement in the oxidizing atmosphere for the mass synthesis sample.
도 7은 하소 또는 소결시의 승온 온도에 따른 치밀도 측정결과를 나타낸 도면이다. 7 is a view showing a result of measuring the density of the heating temperature during calcination or sintering.
이하, 첨부 도면을 참조하여 본 발명의 실시예를 상세히 설명하면 다음과 같다. Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.
본 발명을 설명함에 있어서, 관련된 공지기능 혹은 구성에 대한 구체적인 설명이 본 발명의 요지를 불필요하게 흐릴 수 있다고 판단되는 경우 그 상세한 설명은 생략한다. 또한, 후술되는 용어들은 본 발명에서의 기능을 고려하여 정의된 용어들로서 이는 사용자, 운용자의 의도 또는 판례 등에 따라 달라질 수 있다. 그러므로 그 정의는 본 명세서 전반에 걸친 내용을 토대로 내려져야 할 것이다. In describing the present invention, if it is determined that the detailed description of the related known function or configuration may unnecessarily obscure the subject matter of the present invention, the detailed description thereof will be omitted. In addition, terms to be described below are terms defined in consideration of functions in the present invention, which may vary according to intention or precedent of a user or an operator. Therefore, the definition should be made based on the contents throughout the specification.
본원 발명자는 고체산화물 연료전지에 있어서 각각이 순서대로 적층된 애노드층, 고체 전해질층 및 캐소드층으로 구성되는 복수의 셀 사이에 배치되고, 복수의 셀을 서로 전기적으로 직렬로 접속하는 연결재(interconnect)의 재료로서, 산화분위기 및 환원분위기 중 어느 분위기에서나 화학적으로 안정되고, 전기전도성(도전성)이 높고, 이온 전도성이 낮으며, 소결 온도를 낮출 수 있는 연결재 재료를 얻기 위하여 여러 관점에서 고찰하였다. 또한, 고체산화물 연료전지의 상용화를 위해 상업적으로 대량생산 할 수 있는 연결재 소재 및 그 합성방법에 대해 고찰하였다. In the solid oxide fuel cell, 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. In order to obtain 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, and low sintering temperature can be considered. In addition, the commercial materials for mass production of solid oxide fuel cells and their synthesis methods were discussed.
이러한 고찰에 의거하여 본원 발명자는 LCCCO로 표현되는 세라믹 조성물 중 특히 La1-xCaxCr1-yCoyO3 세라믹 조성물을 고체산화물 연료전지용 연결재 재료로서 사용하는 것을 검토하였으며, La1-xCaxCr1-yCoyO3로 표현되는 세라믹 조성물을 각종 조성 비율로 제작하여 그 특성을 시험하였다. Based on these considerations, 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.
그 결과, 0.1≤x≤0.3를 만족하고 또한, 0.1≤y≤0.2를 만족할 때 800℃ 정도의 산화분위기 및 환원분위기 모두에서 화학적으로 안정함과 동시에 전기 전도성(도전성)이 높은 것을 확인할 수 있었다. As a result, when 0.1 ≦ x ≦ 0.3 is satisfied and 0.1 ≦ y ≦ 0.2, it was confirmed that both the oxidation atmosphere and the reducing atmosphere at about 800 ° C. were chemically stable and the electrical conductivity (conductivity) was high.
또한, 1회에 수 내지 수십 Kg 정도의 비교적 대량합성 후에도 그 특성이 크게 변하지 않고 성능이 재현되는 것을 확인할 수 있었다. In addition, even after a relatively large amount of synthesis of several to several tens of kilograms at a time, the characteristics were not significantly changed, it was confirmed that the performance is reproduced.
본 발명의 실시예를 단계별로 상세히 설명하면 다음과 같다. When explaining the embodiment of the present invention in detail as follows.
시료분말 합성Sample powder synthesis
단계 1: 원료계량Step 1: Raw Material Weighing
계산된 몰(mole) 비율에 맞게 각각의 분말을 정확하게 혼합하기 위한 공정으로서 ABO3 페로브스카이트(Perovskite) 구조를 형성할 수 있도록 설계된 조성을 이용해 몰 비를 적용하여 각각의 출발원료를 순도까지 고려하여 계산한다. A process for accurately mixing each powder to the calculated mole ratio, taking into account the purity of each starting material by applying the molar ratio using a composition designed to form the ABO 3 Perovskite structure. Calculate
조성식 La1-xCaxCr1-yCoyO3의 x가 0.3이고, y가 0.1인 경우 즉, La0.7Ca0.3Cr0.9Co0.1O3인 경우, 시료 1, 2, 3, 4의 출발재료의 몰 비를 아래 표 1과 같이 계량한다. When x in the composition formula La 1-x Ca x Cr 1-y Co y O 3 is 0.3 and y is 0.1, that is, La 0.7 Ca 0.3 Cr 0.9 Co 0.1 O 3 , the samples 1, 2, 3, 4 Weigh the molar ratio of starting material as shown in Table 1 below.
표 1
Table 1
조성/출발원료 | La2O3 | CaCo3 | CaF2 | Cr2O3 | Co3O4 |
시료 1 | 0.7 | 0.3 | _ | 0.9 | 0.1 |
시료 2 | 0.7 | 0.2 | 0.1 | 0.9 | 0.1 |
시료 3 | 0.7 | 0.1 | 0.2 | 0.9 | 0.1 |
시료 4 | 0.7 | 0.15 | 0.15 | 0.9 | 0.1 |
Subsidies / Departures | La 2 O 3 | CaCo 3 | CaF 2 | Cr 2 O 3 | Co 3 O 4 |
| 0.7 | 0.3 | _ | 0.9 | 0.1 |
| 0.7 | 0.2 | 0.1 | 0.9 | 0.1 |
| 0.7 | 0.1 | 0.2 | 0.9 | 0.1 |
| 0.7 | 0.15 | 0.15 | 0.9 | 0.1 |
CaCo3 47.92g, CaF2 74.76g, Cr2O3 327.50g, Co3O4 38.51g(소수점 둘째 자리까지 계량)을 용기(bottle)에 투입하고, 에틸알코올(Ethyl alcohol)을 용매로 사용하며 1kg 기준으로 1L를 투입한다.47.92 g of CaCo 3, 74.76 g of CaF 2, 327.50 g of Cr 2 O 3, 38.51 g of Co 3 O 4 (measured to two decimal places) are placed in a bottle, and ethyl alcohol is used as a solvent. Inject 1L per 1kg basis.
단계 2: 볼밀(Ball milling(Mix))Step 2: Ball milling (Mix)
용매와 함께 혼합한 분말을 물리적으로 섞어주기 위한 공정으로, 150rpm 내지 300rpm으로 5시간 내지 10시간 정도 혼합한다. 이때, 5mm, 10mm, 15mm 지르코니아 볼을 사용한다.
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.
단계 3: 건조(Drying)Step 3: Drying
용매와 함께 액체상태가 된 분말을 완전히 건조시켜 고체상태로 만들어주기 위한 공정으로, 2일 내지 3일 정도 건조한다. 이때, 드라이 오븐(Dry oven)의 온도를 60℃ 내지 80℃로 하여 에탄올을 증발시킨 후, 오븐의 온도를 90℃ 내지 110℃로 높여 완전 건조시킨다. 처음부터 90℃ 내지 110℃에서 건조시, 에틸알코올의 낮은 끓는점으로 인해 분말이 넘칠 수 있기 때문이다. 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 ℃ to 80 ℃ ethanol is evaporated, the temperature of the oven is raised to 90 ℃ to 110 ℃ 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.
단계 4: 하소(Calcination)Step 4: Calcination
혼합된 분말을 ABO3 페로브스카이트 구조로 형성시키고 유기물질을 태우기 위한 열처리 공정으로, 승하온 속도를 0.5℃/min 내지 10℃/min으로 하여 850℃ 내지 1200℃에서 2시간 내지 10시간 동안 유지하며 하소 한다. The mixed powder is formed into an ABO 3 perovskite structure and is a heat treatment process for burning organic materials. Keep and calcinate.
단계 5: 볼밀(Ball milling)Step 5: Ball milling
하소한 분말을 완전히 식힌 다음, 에틸알코올, Z-ball을 이용하여 12시간 내지 36 시간 정도 충분히 혼합한다. After the calcined powder is completely cooled, the mixture is sufficiently mixed with ethyl alcohol and Z-ball for about 12 to 36 hours.
단계 6: 소결(Sintering)Step 6: Sintering
볼밀한 액체상태의 분말을 건조기에 넣고 완전히 건조시킨 후, 도가니에 넣고 하온 속도를 0.5℃/min 내지 10℃/min으로 하여 1100℃ 내지 1400℃에서 2시간 내지 10시간 동안 소결한다. 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.
단계 7: 분쇄 및 첨가제 혼합(Grinding & Binder Mixing)Step 7: Grinding & Binder Mixing
열처리 후 입자가 세라믹 도자기처럼 뭉쳐져 있는 상태로 되어 분쇄 및 분무건조의 전처리로 각종 첨가제를 섞어주기 위한 공정으로, 첨가제로는 탈이온수(D.I water)결합제, 이형제, 분산제, 소포제 등이 첨가될 수 있다.After heat treatment, 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. .
더 구체적으로 설명하면, 열처리 된 분말을 볼밀을 이용하여 분쇄하고 첨가제를 혼합한다. 이때, 용매로는 탈이온수를 사용하고 원료부피대비 1:1로 투입한다. 첨가제로는 결합제 0.01% 내지 0.1%, 분산제 0.001% 내지 0.009%를 투입한다. 이어서, 분무 건조 2시간 내지 8시간 전에 이형제, 소포제를 각각 0.001% 내지 0.009%, 0.005% 내지 0.01% 투입한다. 또한, 지르코니아 볼은 원료대비 부피기준으로 2배 정도 넣어주며 100rpm 내지 400rpm으로 12시간 내지 36시간 정도 충분히 분쇄 혼합한다. More specifically, the heat treated powder is ground using a ball mill and the additives are mixed. At this time, deionized water is used as a solvent and the ratio is 1: 1 to the raw material volume. As an additive, 0.01% to 0.1% of a binder and 0.001% to 0.009% of a dispersant are added. Next, 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. In addition, 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.
한편, 볼밀 작업 후에 제트밀(Jet mill), 비드밀(Bead mill) 또는 어트리션밀(attrition mill) 공정을 추가로 실시하여 입자 사이즈를 더 미세하게 할 수 있다. 예를 들면, 제트밀은 압축공기의 압력으로 디스크를 회전시켜 분말을 분쇄하는 방법으로, 작업 결과 입자 사이즈가 0.8~1.0㎛로 나타나 볼밀 작업시의 입자 사이즈와 크게 차이는 없으나 일부 작은 입자 사이즈가 나타나는 것을 확인할 수 있었다. 또한, 비드밀은 챔버 내에 비드(bead)를 넣고 회전력 및 원심력에 의해 분쇄하는 방법으로, 작업 결과 입자 사이즈가 0.4~0.6㎛로 볼밀 또는 제트밀에 비해 훨씬 작은 입자를 얻을 수 있다. 이때, 비드밀 챔버의 속도나 펌프 주입 속도를 조절하면 더 작은 사이즈의 입자를 얻을 수 있다. On the other hand, after the ball mill operation, a jet mill, bead mill, or attrition mill process may be further performed to make the particle size finer. For example, a jet mill is a method of pulverizing powder by rotating a disk under the pressure of compressed air. As a result, the particle size is 0.8-1.0 μm, which is not significantly different from the particle size during ball milling. It was confirmed that it appeared. In addition, 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㎛. 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.
단계 8: 분무 건조(Spray Drying)Step 8: Spray Drying
열처리된 분말 입자를 플라즈마 코팅 가능한 입자크기로 만들어주기 위한 공정으로, 분무 건조 시의 공정조건 예를 들면, 첨가제, 유입구 및 유출구 온도, 투입량, 온도, 분무 속도(rpm) 등의 조건에 따라 구형의 입자(granul) 생성 여부가 결정되며 이후 플라즈마 코팅 작업시 분말의 피딩(feeding)에 많은 영향을 미치므로 공정조건 설정이 매우 중요하다.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.
본 실시예에서는 분무 건조기의 유입구(Inlet) 온도는 100℃ 내지 250℃, 유출구(Outlet) 온도는 50℃ 내지 200℃로 세팅하며, 분무 속도를 1000rpm 내지 5000rpm으로 시운전(warming-up) 한 다음 5000rpm 내지 12000rpm으로 세팅한다. In the present embodiment, 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.
단계 9: 번 아웃(Burn Out)Step 9: Burn Out
분무 건조가 완료된 원료에 함유되어 있는 첨가제를 태우기 위한 열처리 공정으로, 450℃ 내지 800℃의 온도에서 3시간 내지 10시간 정도 유지시킨다. 이때, 승온 속도는 0.5℃/min 내지 5℃/min으로 천천히 하여 첨가제가 서서히 빠져나갈 수 있도록 하며 구형의 모양 그대로 높은 밀도로 결합할 수 있도록 한다. In the heat treatment process for burning the additive contained in the spray-dried raw material, it is maintained for 3 to 10 hours at a temperature of 450 ℃ to 800 ℃. At this time, the temperature increase rate is 0.5 ℃ / min to 5 ℃ / min to allow the additive to gradually escape and to combine with a high density as a spherical shape.
단계 10: 사분(Sieving)Step 10: Sieving
작업 완료된 분말을 원하는 입자 크기(size)로 분리하기 위한 공정으로, 원하는 입자 크기의 체(sieve)를 이용하여 분말을 쳐준다(sieving 해준다).A process for separating the finished powder to the desired particle size (sieving the powder using a sieve of the desired particle size).
시료분말의 특성 분석Characterization of Sample Powder
(1) 전기전도도(1) electrical conductivity
합성 완료된 분말은 전도도 측정을 위하여 펠리트(pellet)로 제작하며, 산화분위기는 800℃를 유지시켜주고 시작과 함께 산화가스(질소80%, 산소20%)를 퍼니스(Pot type furnace)에 주입하며, 틈틈이 가스 주입상태와 온도별로 저항값을 확인한다. 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.
환원분위기 또한 800℃를 유지시키고 일정 온도로 올라간 후에 환원가스(수소100%)를 주입한다. Reducing atmosphere is also maintained at 800 ℃ and after the temperature rises to a certain amount of reducing gas (hydrogen 100%) is injected.
전도도 측정은 4-프로브(probe) 측정 가능한 디지털 멀티미터를 이용하여 저항값을 측정한 후 펠리트 크기와 전극간의 거리를 고려하여 전도도를 계산한다. 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.
본 실시예에서는 측정 결과, 도 1 및 도 2에 도시된 바와 같은 전기전도도가 측정되었다. 도 1은 800℃의 산화분위기(Oxidizing)에서 시간에 따른 전기전도도를 나타낸 것이고, 도 2는 800℃의 환원분위기(Reducing)에서 시간에 따른 전기전도도를 나타낸 것으로, 전기전도도의 평균값은 아래 표 2와 같다. In this embodiment, as a result of the measurement, the electrical conductivity as shown in Figs. 1 and 2 was measured. Figure 1 shows the electrical conductivity with time in the oxidation atmosphere (Oxidizing) of 800 ℃, Figure 2 shows the electrical conductivity with time in the reducing atmosphere (Reducing) of 800 ℃, the average value of the electrical conductivity is shown in Table 2 below Same as
표 2
TABLE 2
조성/가스분위기 | 산화분위기(S/cm) | 환원분위기(S/cm) |
시료 1(LCCC-1) | 31.2 | 1.52 |
시료 2(LCCC-2) | 26.5 | 1.62 |
시료 3(LCCC-3) | 33.7 | 3.73 |
시료 4(LCCC-4) | 29.2 | 1.34 |
Composition / gas atmosphere | Oxidation atmosphere (S / cm) | Reducing atmosphere (S / cm) |
Sample 1 (LCCC-1) | 31.2 | 1.52 |
Sample 2 (LCCC-2) | 26.5 | 1.62 |
Sample 3 (LCCC-3) | 33.7 | 3.73 |
Sample 4 (LCCC-4) | 29.2 | 1.34 |
표 2를 통해, 시료 3의 전기전도도는 산화분위기에서는 평균 33.7 S/cm, 환원분위기에서는 평균 3.73 S/cm이며, 시료 1(LCCC-1), 2(LCCC-2), 4(LCCC-4)에 비해 전기전도도가 크다는 것을 알 수 있다. 참고로, N.Q.Minh et al, Proc. 25th Intersociety Energy Conversion Engineering Conference, AICE, New York, Vol.13, 256 (1990) 등에 의하면 SOFC 연결재로 사용하기 위해서는 적어도 1 S/cm의 값을 가져야 한다고 알려져 있다. Through Table 2, the electrical conductivity of Sample 3 is 33.7 S / cm in the oxidation atmosphere, 3.73 S / cm in the reducing atmosphere, and Samples 1 (LCCC-1), 2 (LCCC-2), and 4 (LCCC-4). It can be seen that the electrical conductivity is greater than that of. For reference, see N. Q. Minh et al, Proc. According to the 25th Intersociety Energy Conversion Engineering Conference, AICE, New York, Vol. 13, 256 (1990), etc., it must be at least 1 S / cm for use as SOFC interconnects.
(2) 열팽창계수 (2) coefficient of thermal expansion
도 3은 연결재 분말 합성 후의 시료 3의 열팽창계수를 나타낸 것으로, 열팽창계수가 108.4x10-7/℃ 정도로서 적절함을 알 수 있다. 일반적으로 연결재의 열팽창계수는 100~120x10-7/℃의 범위를 가져야 한다고 알려져 있다. 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 / ℃.
(3) XRD 측정 (3) XRD measurement
도 4는 연결재 분말 합성 후의 XRD 스펙트럼을 나타낸 것으로, 합성 완료된 분말이 페로브스카이트 구조를 갖는지 여부를 확인하기 위하여 XRD를 측정하여 나타낸 것이다. 측정 결과, 단일상의 페로브스카이트 구조를 가지며 이에 따라 하소 및 소결 작업시 공정이 안정화됨을 유추할 수 있다. 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.
(4) SEM(Scanning Electron Microscope) 사진(4) Scanning Electron Microscope (SEM) Photo
도 5는 합성 후 소결형상 및 분쇄 후 형상을 나타낸 SEM(주사전자현미경) 사진으로, 분쇄 후 치밀한 구조의 입자가 형성되었으며 입자 크기는 0.4 내지 0.6㎛ 정도로 미세한 크기의 입자로 형성됨을 알 수 있다. 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 μm.
전술한 바와 같이, 본 실시예에 따르면 대량합성 후에도 특성 변화가 거의 없는 재현성이 높은 연결재 조성을 도출하고 그 합성방법을 확립함으로써 안정적으로 양산제품을 공급할 수 있다. As described above, according to the present embodiment, 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.
한편, 연결재 분말 합성 공정 중에서 하소 또는 소결시의 온도나 유지시간에 따른 전기전도도, 치밀도 특성 변화에 대해서도 고찰하였다. On the other hand, in the process of synthesizing the powder of the connecting material, the electrical conductivity and the density density change according to the temperature and holding time during calcination or sintering were also considered.
도 6은 대량합성 시료에 대한 산화분위기에서의 전기전도도 측정 결과를 나타낸 것이다. 도 6의 (a)는 승온 1.5℃/min으로 소결한 시료의 전기전도도를 나타낸 것이고, 도 6의 (b)는 승온 5℃/min으로 소결한 시료의 전기전도도를 나타낸 것으로, 전술한 시료 3(LCCC-3)의 조성으로 연결재 분말을 합성하였고, 나머지 공정조건은 동일하다. Figure 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, and 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.
도 6에 도시된 바와 같이, 승온 1.5℃/min으로 소결한 시료의 전기전도도는 평균 31S/cm이고, 승온 5℃/min으로 소결한 시료의 전기전도도는 평균 2.3S/cm이며, 실험을 통해 승온 온도를 달리함에 따라 전기전도도가 크게 변하는 것을 확인할 수 있었다. As shown in Figure 6, the electrical conductivity of the sample sintered at an elevated temperature of 1.5 ℃ / min is an average of 31 S / cm, the electrical conductivity of the sample sintered at an elevated temperature of 5 ℃ / min is an average of 2.3 S / cm, through an experiment As the temperature rises, the electrical conductivity changes significantly.
도 7은 하소 또는 소결시의 승온 온도에 따른 치밀도 측정결과를 나타낸 것으로, 1000배, 5000배, 10000배로 확대한 사진이다. 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.
도 7을 참조하면, 시료 ①, ②는 800℃에서 하소 한 후 각각 승온 5℃/min, 1.5℃/min으로 설정하여 스텝(step: 승온과 하온 시 완전한 소결을 위해 유지시간을 가지는 것)을 주어 소결한 경우로, 두 시료 모두 소결이 진행되었으나 큰 기공(pore)이 다수 보이는 것을 알 수 있다. 시료 ③, ④는 1000℃에서 하소 한 후 각각 승온 5℃/min, 1.5℃/min으로 설정하고 스텝(step)을 주어 소결한 경우로, 시료 ③은 대략적으로 소성이 완료되었으나 시료 ①, ②와 마찬가지로 기공이 많이 나타난다. 시료 ④의 경우, 다른 시료에 비해 조직이 거의 치밀화가 되어 있고 소결이 완료되었으며 기공이 거의 보이지 않음을 알 수 있다. Referring to FIG. 7, 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). In the case of primary sintering, 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. In the case of sample ④, compared to other samples, the structure is almost densified, the sintering is completed, and the pores are almost invisible.
한편, 본 발명의 상세한 설명 및 첨부도면에서는 구체적인 실시예에 관해 설명하였으나, 본 발명은 개시된 실시예에 한정되지 않고 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에게 있어 본 발명의 기술적 사상을 벗어나지 않는 범위 내에서 여러 가지 치환, 변형 및 변경이 가능하다. 따라서, 본 발명의 범위는 설명된 실시예에 국한되어 정해져서는 안되며 후술하는 특허청구범위뿐만 아니라 이 특허청구범위와 균등한 것들을 포함하는 것으로 해석되어야 할 것이다. On the other hand, the detailed description and the accompanying drawings of the present invention have been described with respect to specific embodiments, the present invention is not limited to the disclosed embodiments and those skilled in the art to which the present invention pertains the technical idea of the present invention Many substitutions, modifications and variations are possible without departing from the scope of the invention. Therefore, the scope of the present invention should not be limited to the described embodiments, but should be construed as including not only the claims below but also equivalents thereof.
Claims (10)
- 각각이 순서대로 적층된 애노드층, 전해질층 및 캐소드층으로 구성되는 복수의 셀을 포함하는 고체산화물 연료전지에 있어서,In a solid oxide fuel cell comprising a plurality of cells each consisting of an anode layer, an electrolyte layer and a cathode layer stacked in order,상기 복수의 셀을 전기적으로 접속하는 연결재의 재료로서 조성식 La1-xCaxCr1-yCoyO3(단, x, y 각각은 몰비를 나타내고, 0.1≤x≤0.3, 0.1≤y≤0.2를 만족함)로 표현되는 세라믹 조성물을 주성분으로 포함하는 것을 특징으로 하는 세라믹 연결재. As a material of the connecting material for electrically connecting the plurality of cells, a composition formula La 1-x Ca x Cr 1-y Co y O 3 (wherein x and y each represents a molar ratio, and 0.1 ≦ x ≦ 0.3 and 0.1 ≦ y ≦). Ceramic connection material comprising a ceramic composition represented by the main component).
- 제 1 항에 있어서, 상기 x는 0.3이고, y는 0.1인 것을 특징으로 하는 세라믹 연결재.The ceramic connecting material of claim 1, wherein x is 0.3 and y is 0.1.
- 제 2 항에 있어서, 상기 몰비 x, y를 만족하는 출발물질로서 The method of claim 2, wherein as a starting material satisfying the molar ratio x, y0.7몰의 La2O3, 0.1몰의 CaCo3, 0.2몰의 CaF2, 0.9몰의 Cr2O3, 0.1몰의 Co3O4를 포함하는 것을 특징으로 하는 세라믹 연결재. 0.7 mo La2O30.1 moles of CaCo3, 0.2 moles of CaF2, 0.9 mol of Cr2O3, 0.1 moles Co3O4Ceramic connecting material comprising a.
- 제 2 항에 있어서, 상기 몰비 x, y를 만족하는 출발물질로서 The method of claim 2, wherein as a starting material satisfying the molar ratio x, y0.7몰의 La2O3, 0.2몰의 CaCo3, 0.1몰의 CaF2, 0.9몰의 Cr2O3, 0.1몰의 Co3O4를 포함하는 것을 특징으로 하는 세라믹 연결재. A ceramic connecting material comprising 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 Co 3 O 4 .
- 기본 조성이 La1-xCaxCr1-yCoyO3이며, 0.1≤x≤0.3, 0.1≤y≤0.2를 만족하는 연결재 분말의 합성방법에 있어서, In the method for synthesizing a linker powder having a basic composition of La 1-x Ca x Cr 1-y Co y O 3 and satisfying 0.1 ≦ x ≦ 0.3 and 0.1 ≦ y ≦ 0.2,상기 연결재 분말의 출발물질과 제1 용매를 분쇄 및 믹싱하는 과정과;Grinding and mixing the starting material and the first solvent of the linker powder;액체상태가 된 상기 출발물질을 건조시킨 후 열처리하여 분말화하는 과정과;Drying the starting material in a liquid state and then heat-processing to powder;열처리 후 상기 분말을 밀링법에 의해 분쇄하고 첨가제를 첨가하는 과정; 및Grinding the powder by a milling method after the heat treatment and adding an additive; And분쇄 및 첨가제가 첨가된 상기 분말을 분무건조법에 의해 기설정된 입자사이즈로 과립화하는 과정을 포함하는 것을 특징으로 하는 세라믹 연결재의 합성방법.A method for synthesizing a ceramic connecting material, comprising granulating the powder to which the grinding and additives are added to a predetermined particle size by spray drying.
- 제 5 항에 있어서, 상기 열처리하여 분말화하는 과정은 The process of claim 5, wherein the process of powdering by heat treatment액체상태가 된 상기 출발물질은 850℃ 내지 1200℃에서 승온 속도를 0.5℃/min 내지 10℃/min으로 하여 하소하는 과정과, The starting material in the liquid state is calcined at a temperature increase rate of 0.5 ℃ / min to 10 ℃ / min at 850 ℃ to 1200 ℃,하소한 분말과 제2 용매를 분쇄 및 혼합하는 과정과, Grinding and mixing the calcined powder and the second solvent,액체상태가 된 상기 출발물질을 건조시킨 후, 1100℃ 내지 1400℃에서 승온 속도를 0.5℃/min 내지 10℃/min으로 하여 소결하는 과정을 포함하는 것을 특징으로 하는 세라믹 연결재의 합성방법. And drying the starting material in a liquid state, followed by sintering at a temperature rising rate of 0.5 ° C / min to 10 ° C / min at 1100 ° C to 1400 ° C.
- 제 5 항에 있어서, 상기 분말을 밀링법에 의해 분쇄하는 과정은The process of claim 5, wherein the grinding of the powder by milling볼밀 작업 후에 제트밀(Jet mill), 비드밀(Bead mill) 또는 어트리션밀(attrition mill) 공정 중 적어도 하나를 추가로 실시하여 입자 사이즈를 미세화하는 과정을 더 포함하는 것을 특징으로 하는 세라믹 연결재의 합성방법.After the ball mill operation further comprising the step of further performing at least one of a jet mill, bead mill or attrition mill process to refine the particle size of the ceramic connecting member Synthesis method.
- 제 5 항에 있어서, 상기 첨가제는 The method of claim 5, wherein the additive결합제, 이형제, 분산제, 소포제 중 적어도 하나를 포함하는 것을 특징으로 하는 세라믹 연결재의 합성방법.A method of synthesizing a ceramic connecting material comprising at least one of a binder, a release agent, a dispersant, and an antifoaming agent.
- 제 5 항 내지 제 8 항 중 어느 하나의 항에 있어서, The method according to any one of claims 5 to 8,분무건조가 완료된 원료에 함유되어 있는 첨가제를 태우기 위한 열처리 과정을 더 포함하는 것을 특징으로 하는 세라믹 연결재의 합성방법. A method of synthesizing a ceramic connecting material, further comprising a heat treatment process for burning the additive contained in the spray-dried raw material.
- 제 9 항에 있어서, 상기 열처리 과정은 The method of claim 9, wherein the heat treatment process450℃ 내지 800℃의 온도에서 승온 속도 0.5℃/min 내지 5℃/min으로 하여 3시간 내지 10시간 동안 열처리하여 이루어지는 것을 특징으로 하는 세라믹 연결재의 합성방법. A method of synthesizing a ceramic connecting material, characterized in that the heat treatment for 3 to 10 hours at a temperature increase rate of 0.5 ℃ / min to 5 ℃ / min at a temperature of 450 ℃ to 800 ℃.
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JPH05121060A (en) * | 1991-07-02 | 1993-05-18 | Tonen Corp | Separator material for high temperature type fuel cell |
US5411767A (en) * | 1992-07-27 | 1995-05-02 | Ngk Insulators, Ltd. | Method for producing interconnector for solid electrolyte type fuel cell |
KR100283207B1 (en) * | 1998-08-03 | 2001-05-02 | 손재익 | Metal Connecting Material for Solid Oxide Fuel Cell and Manufacturing Method Thereof |
KR20110075242A (en) * | 2009-12-28 | 2011-07-06 | 주식회사 포스코 | Composite ceramic contact material for solid oxide fuel cell and method of preparing ceramic contact material |
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JPH05121060A (en) * | 1991-07-02 | 1993-05-18 | Tonen Corp | Separator material for high temperature type fuel cell |
US5411767A (en) * | 1992-07-27 | 1995-05-02 | Ngk Insulators, Ltd. | Method for producing interconnector for solid electrolyte type fuel cell |
KR100283207B1 (en) * | 1998-08-03 | 2001-05-02 | 손재익 | Metal Connecting Material for Solid Oxide Fuel Cell and Manufacturing Method Thereof |
KR20110075242A (en) * | 2009-12-28 | 2011-07-06 | 주식회사 포스코 | Composite ceramic contact material for solid oxide fuel cell and method of preparing ceramic contact material |
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