• 한국세라믹학회지
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• 제47권1호
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• pp.26-38
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• 2010

Degradation in Solid Oxide Fuel Cell performance can be ascribed to the following fundamental processes from the materials chemical point of view; that is, diffusion in solids and reaction with gaseous impurities. For SOFC materials, diffusion in solids is usually slow in operation temperatures $800\sim1000^{\circ}C$. Even at $800^{\circ}C$, however, a few processes are rapid enough to lead to some degradations; namely, Sr diffusion in doped ceria, cation diffusion in cathode materials, diffusion related with metal corrosion, and sintering of nickel anodes. For gaseous impurities, chromium containing vapors are important to know how the chemical stability of cathode materials is related with degradation of performance. For LSM as the most stable cathode among the perovskite-type cathodes, electrochemical reduction reaction of $CrO_3$(g) at the electrochemically active sites is crucial, whereas the rest of the cathodes have the $SrCrO_4$ formation at the point where cathodes meet with the gases, leading to rather complicated processes to the degradations, depending on the amount and distribution of reacted Cr component. These features can be easily generalized to other impurities in air or to the reaction of nickel anodes with gaseous impurities in anode atmosphere.

• 한국세라믹학회지
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• 제42권12호
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• pp.808-815
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• 2005

[ $Bi_xCe_{l-x}O_{2-x/2}$ ](BD C : Bismuth Doped Ceria) powders with x = 0.1, 0.2, and 0.3 were synthesized using the Glycine Nitrate Process (GNP). They were then calcined at $500^{\circ}C$ for 2 hand sintered in a pellet or rod form at 900, 1000 or $1100^{\circ}C$ for 4 h for characterization as the alternative electrolyte material for intermediate temperature solid oxide fuel cells. The BDC powder consisted of a single phase of $CeO_2-Bi_2O_3$ solid solution in the as-synthesized state as well as in the as-calcined state with a mean powder size of 4.5nm in the former state and 6.5 - 10.1nm in the latter. On the contrary, the second phase of $\alpha-Bi_2O_3$ was observed to have been formed in the sinter with its amount increasing roughly with increasing temperature or $Bi_2O_3$ content. The BOC powder was superior in sinterability to other alternative electrolyte materials such as GDC, ScSZ, and LSGM with the minimum sintering temperature for a relative density of $95\%$ or larger as low as $1100^{\circ}C$. The ionic conductivity of BOC increased with $Bi_2O_3$ content and the maximum value of 0.119 S/cm was obtained at $800^{\circ}C$ for $Bi_{0.3}Ce_{0.7}O_{1.85}$.

• 한국세라믹학회지
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• 제49권2호
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• pp.197-203
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• 2012

In this study, in order to improve densification of $La_{0.8}Ca_{0.2}Cr_{0.9}Co_{0.1}O_{3-\delta}$ (LCCC), which is known for one of the most proper candidate interconnector materials in the solid oxide fuel cells, $CaCrO_4$ was prepared via solid oxide synthesis route and added to the LCCC with different amount and particle sizes. As the amount of the $CaCrO_4$ increased, porosity of the sintered samples increased, and the pore size was proportional to the particle size of the $CaCrO_4$. This supports the fact that the $CaCrO_4$ phase forms liquid during sintering and permeate into the matrix leaving behind large pores. Then the liquid reacts with the matrix through the solid solution. However, when the samples were sintered with a slow ramp up rates, the porosity decreased. This is thought to be caused by the progressive solid solution of $CaCrO_4$ before the temperature reach to the melting temperature and forms a fluent amount of liquids. The sintering behavior of the LCCC with the addition of $CaCrO_4$ was analyzed through the transient liquid phase sintering on the basis of the microstructure observation and phase identification by x-ray diffraction.

• 한국세라믹학회지
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• 제39권4호
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• pp.352-358
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• 2002

고체산화물 연료전지의 전해질로서 $LaGaO_3$계를 선정하여 La 대신 Sr을, Ga 대신에 Mg를 치환하여 첨가할 때 첨가량 및 소결 조건에 따라 전해질을 제조하고, 그 특성을 조사하였다. Sr과 Mg가 0.15와 0.20 mole 첨가되었을 때 Sr과 Mg가 La와Ga 자리에 동시 고용되어 (La$_{1-x}Sr_x)(Ga_{1-y}Mg_y)O_{3-\delta}$ 단일상이 나타났고, 일부 조성에서는 $LaSrGa_3O_7$ 상과 $LaSrGaO_4$ 상이 2차상으로 나타났다. $LaSrGa_3O_7$ 상은 Sr과 Mg 첨가에 의한 상이며, $LaSrGaO_4$ 상은 액상형성에 의한 것으로 나타났으며, 또한 $LaSrGaO_4$ 상은 소결온도와 Mg 첨가량이 감소함에 따라 얻어졌다. $(La_{0.8}Sr_{0.2})(Ga_{0.8}Mg_{0.2})O_{3-\delta}$ 상의 경우 소결온도를 증가함에 따라 열팽창계수는 감소하였으며, $1500^{circ}C$에서 1시간 소결한 소결체의 전기전도도는 $800^{circ}C$, 1mA에서 0.14S/cm를 나타내었다.

• 한국결정성장학회지
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• 제21권2호
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• pp.70-74
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• 2011

다공성 $(Ca,Mg)_{0.15}Zr_{0.7}O_{1.7}$ 세라믹스를 제조하고 기공률 및 기계적 강도를 측정하여 SOFC 세라믹 지지체로서 응용 가능성을 조사하였다. 출발물질로 $ZrO(NO_3)_2{\cdot}2H_2O$를 선정하고 이를 이온 교환수에 용해하여 glycine을 첨가하여 glycine 연소법으로 $ZrO_2$ 분말을 합성하고 $800^{\circ}C$에서 하소하여 $ZrO_2$ 원으로 사용하였다. 합성한 $ZrO_2$ 분말, dolomite, 그리고 pore former로 carbon black을 혼합하고 $1200{\sim}1400^{\circ}C$로 소성하여 다공성 $(Ca,Mg)_{0.15}Zr_{0.7}O_{1.7}$ 세라믹스 소결체를 제조하였다. $(Ca,Mg)_{0.15}Zr_{0.7}O_{1.7}$ 세라믹스의 결정상은 단일상의 cubic상이었다. $1300^{\circ}C$ 에서 소성한 $(Ca,Mg)_{0.15}Zr_{0.7}O_{1.7}$ 세라믹 소결체는 carbon black의 양이 증가할수록 기공률이 32 %에서 55 %까지 증가하였으며 기계적 강도는 90 MPa로부터 30 MPa까지 감소하였다.

• 한국세라믹학회지
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• 제44권1호
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• pp.52-57
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• 2007

We synthesized $(La_{1-x}Sr_x)MnO_3$ as a cathode for SOFC by glycine nitrate process (GNP) and knew the different properties of $(La_{1-x}Sr_x)MnO_3$ by using nitrate solution and oxide solution as a starting material. In case of using nitrate solution as a starting material, main crystal phase peak of $LaMnO_3$ increased as Sr content added up and a peak of $Sr_2MnO_4\;and\;La_2O_3$ was showed as a secondary phase. We added Mn excess to control a crystal phase. In this case, the electrical conductivity had a high value 210.3 S/cm at $700^{\circ}C$. On the other side, when we used oxide solution as a starting material, we found main crystal phase of $LaMnO_3$ to increase as Sr content added up and a peak of $La_2O_3$ as a secondary phase. Similary, we added Mn excess to control a crystal phase in this case. We knew $(La,Sr)MnO_3$ powder to sinter well and the electrical conductivity of the sintered body at $1200^{\circ}C$ for 4 h was 152.7 S/cm at $700^{\circ}C$. The sintered $(La,Sr)MnO_3$ powder at $1000^{\circ}C$ for 4 h got the deoxidization peak, depending on the temperature and in case of using nitrate solution as a starting material, the deoxidization peak was showed at $450^{\circ}C$ which is lower than used a oxide solution as a starting material. As a result, when $(La,Sr)MnO_3$ powder was synthesized to add Mn excess and to use nitrate solution as a starting material, we found it to have the higher deoxidization property and considered it as a cathode for SOFC properly. And we found it to have different electrical conductivity the synthesized $(La,Sr)MnO_3$ powder by using different starting materials like nitrate solution and oxide solution which influence a sintering density and crystal phase.

• 한국세라믹학회지
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• 제39권4호
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• pp.359-366
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• 2002

고체산화물 연료전지의 운전온도를 낮추기 위해 구성재 중 LSGM 전해질과 LSM 양극을 합성하고, 그 특성을 조사한 후 최적 조성과 공정으로 단위전지를 제작하고 출력을 측정하였다. 전해질 조성인 $(La_{0.85}Sr_{0.15})(Ga_{0.8}Mg_{0.2})O_{3-\delta}와 (La_{0.8}Sr_{0.2})(Ga_{0.8}Mg_{0.2})O_{3-\delta}$를 $1500^{\circ}$에서 6시간 소결한 경우 두 조성 모두 $LaGaO_3$의 단일상을 형성하였고, $10∼3{\mu}m$의 결정 크기를 갖는 치밀한 미세구조를 얻었으며, 저기전도도는 $800^{\circ}$에서 0.13S/cm를 나타내었다. 양극의 경우 GNP법으로 $(La1-xSrx)MnO_3$를 합성한 경우 Sr의 양이 0.2mole일 때까지는 $LaMnO_3$ perovskite 단일상이 생성되었으며, 입자의 크기는 약 40nm였다. 단위전지는 $(La_{0.8}Sr_{0.2})(Ga_{0.8}Mg_{0.2})O_{3-\delta}$ 조성으로 소결한 전해질 양면에 $(La_{0.9}Sr_{0.1})MnO_3$ 양극과 음극의 입자크기는 $1{\mu}m$ 정도였고 다공성을 나타내었다. 이때 단위전지의 출력은 $800^{\circ}$에서 약 $0.3W/cm^2$를 나타내었다

• 한국전기전자재료학회논문지
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• 제25권6호
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• pp.486-490
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• 2012

$La_{7.33}Bi_2(SiO_4)_6O_2$ specimens were fabricated by standard solid-state synthesis route for solid oxide electrolytes. The calcined powders exhibited uniform particles with a mean particle size of about $28{\mu}m$. The room-temperature structure of $La_{7.33}Bi_2(SiO_4)_6O_2$ specimens was analyzed as hexagonal, space group P63 or P63/m, and the unit cell volume increased with increase a sintering temperature. The specimens sintered at $1,175^{\circ}C$ showed X-ray patterns of homogeneous apatite single phase without the second phase such as $La_2Si_2O_7$ and $La_2SiO_5$. The specimen sintered at $1,175^{\circ}C$ showed the maximum sintered density of 5.49 $g/cm^3$. Increasing the sintering temperature, total conductivities increased, activation energy decreased and the values were $1.98{\times}10^{-5}Scm-1$ and 1.23 eV, respectively.

• 한국세라믹학회지
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• 제51권4호
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• pp.265-270
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• 2014

Among the Ruddlesden-Popper series, $La_4Ni_3O_{10}$ has received widespread attention as a promising cathode material by reason of its favorable properties for realizing high performance of intermediate temperature solid oxide fuel cells (IT-SOFCs). The $La_4Ni_3O_{10}$ cathode is prepared using the facile sol-gel method by employing tri-blockcopolymer (F127) to obtain a single phase in a short sintering time. There are no reactions between the $La_4Ni_3O_{10}$ cathode and the $Ce_{0.9}Gd_{0.1}O_{2-\delta}$ (GDC) electrolyte upon sintering at $1000^{\circ}C$, indicating that the $La_4Ni_3O_{10}$ cathode has good chemical compatibility with the GDC electrolyte. The maximum electrical conductivity of $La_4Ni_3O_{10}$ reaches approximately 240 S $cm^{-1}$ at $100^{\circ}C$ and gradually decreases with increasing temperaturein air atmosphere. The area specific resistance value of $La_4Ni_3O_{10}$ composite with 40 wt% GDC is $0.435{\Omega}cm^2$ at $700^{\circ}C$. These data allow us to propose that the $La_4Ni_3O_{10}$-GDC composite cathode is a good candidate for IT-SOFC applications.

• 한국세라믹학회지
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• 제43권10호
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• pp.666-672
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• 2006

GDC20($Ce_{0.8}Gd_{0.2}O_{1.9}$) powder was synthesized by oxalate co-precipitation and milling and its thermal decomposition, phase formation, and sinterability were investigated. As-prepared precipitates were non-crystalline due to the milling process and completely decomposed at 400$^{\circ}C$ The powder calcined at 800$^{\circ}C$ for 2 h contained fine p]sty particles with an average size of 0.69 $\mu$m. Attrition milling of the calcined powder for 2 h had a little milling effect, resulting in a slight decrease in the particle size to 0.45 $\mu$m. The milled powder consisted of small spherical primary particles and some large particles, which had been agglomerated during calcination. Due to the excellent sinterability of the powder, sintering of the powder compacts for 4 h showed relative densities of 78.7% at 1000$^{\circ}C$ and 97.8% at 1300$^{\circ}C$, respectively. Densification was found to almost complete at temperature above 1200$^{\circ}C$ and a dense and homogeneous microstructure was obtained. A rapid grain growth occurred between 1200$^{\circ}C$ and 1300$^{\circ}C$. Grains in 0.1$\sim$0.5 $\mu$m sizes at 1200$^{\circ}C$ grew to 0.2$\sim$2 $\mu$m and their size distribution became broader at 1300$^{\circ}C$.