• Title/Summary/Keyword: Ceria-Zirconia

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A Study on the Ceria Stabilized Tetragonal Zirconia Polycrystals (Ce-TZP) (IV) ; Effect of MgO Addition on 12 Ce-TZP Ceramics (CeO2 안정화 정방정 Zirconia 다결정체(Ce-TZP)에 관한 연구(IV) : 12 Ce-TZP 세라믹스에 미치는 MgO 첨가 영향)

  • 김문일;박정현;강대석;이현권;문성환
    • Journal of the Korean Ceramic Society
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    • v.27 no.2
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    • pp.233-243
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    • 1990
  • For theinvestigation of MgO addition effect on 12Ce-TZP ceramics, MgO-CeO2-ZrO2 ceramics was fabricated using commercial powders under sintering condition of 130$0^{\circ}C$-1$600^{\circ}C$ for 2hr. Fully tetragonal phase could be obtained by proper heat treatment and MgO addition amount. Minor cubic phase was appeared in relatively high MgO content composition at each sintering temperature. As alloying amount of MgO increased, tetragonal stability increased and grain size decreased. Grain size dependence on MgO content was verified by SEM observation of fractured surface. Surface bloating was observed from the 2 m/o to 6m/o in the temperature range of 150$0^{\circ}C$ to 1$600^{\circ}C$. In spite of very porous microstructure owing to surface bloating, 100% TZP could be maintained in 2.0m/o MgO composition by heat treatment of 150$0^{\circ}C$. This result indicated that MgO was more powerful stabilizer than CeO2. Mechanical proprties of MgO-CeO2-ZrO2 ceramics were consistent with the stability observation of tetragonal phase very well.

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Dependence of Phase Stability of Tetragonal Zirconia Polycrystal on Dopants

  • Chon, Uong
    • The Korean Journal of Ceramics
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    • v.4 no.4
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    • pp.297-303
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    • 1998
  • The effect of aliovalent dopants, $ Nb_2O_5$ and MnO, on the phase stability of 12 mol% ceria partially-stabilized zirconia (Ce-TZP) polycrystals was studied. Both dopants (MnO and $ Nb_2O_5$) significantly increased the stability of the tetragonal zirconia phase (Mb temperature lower than liquid nitrogen temperature). The enhancement of the stability of the tetragonal phase in Ce-TZP doped with 1 mol% of Mno(Ce-TZP/MnO) andCe-TZP doped with 1 mol% of $ Nb_2O_5$(Ce-TZP/$ Nb_2O_5$) were explained by the significant reduction of the driving force, -${\Delta}$Gchem, for the tetragonal-to-mono-clinic phase transformation caused by the addition of MnO and $ Nb_2O_5$. The enhanced stability of the tetragonal phase in the Ce-TZP and Al2O3 composite (Ce-TZP/$Al_2O_3$) is believed to be caused by smaller grain size, moderate reduction in the chemical driving force and increase in the strain energy barrier to the transformation. Mechanical properties of the Ce-TZP and the Ce-TZP/$Al_2O_3$ with (i) the same grain size and (ii) the same Mb temperature were examined by measuring stress-strain behavior in 3 point bending. The Ce-TZP/$Al_2O_3$ composite doped with 1.3w% MnO (Ce-TZP/$Al_2O_3$/MnO), which had the same grain size as the Ce-TZP and De-TZP/$Al_2O_3$ showed more transformation plasticity than either the Ce-TZP or the Ce-TZP/$Al_2O_3$ composite. The Ce-TZP wihch had the same Mb temperature as that of the Ce-TZP/$Al_2O_3$/MnO did not show any transformation plasticity.

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Water gas shift reaction over ceria-zirconia-supported Pt catalysts at low temperature (저온 수성가스전화반응에서의 $Pt/CeO_2-ZrO_2$ 촉매 연구)

  • 고정봉;김동현
    • 한국전기화학회:학술대회논문집
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    • 2005.07a
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    • pp.317-322
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    • 2005
  • [ $Pt/CeO_2$ ] 촉매에 Zr을 첨가하여 우수한 저온 수성가스전화반응의 활성을 가진 촉매를 만들었다. $Pt/ZrO_2-CeO_2$ 촉매는 $Pt/ZrO_2$$Pt/CeO_2$ 촉매에 비해 Ce와 Zr의 상호작용에 의한 시너지 효과로 인해 CO chemisorption으로 측정한 Pt area가 증가하고 담체에 Pt가 잘 분산되었다. 또한, Zr이 첨가된 $Pt/CeO_2$는 Ce의 redox 능력을 향상시켜 support의 reducibility를 향상시켰다. 담체에 고르게 잘 분산되고 support의 산소저장능력과 reducibility가 향상된 $3\;wt\%\;Pt/ZrO_2-CeO_2$ 촉매들은 반응물에 수소와 이산화탄소의 첨가 유무와 상관없이 $3\;wt\%\;Pt/ZrO_2$$3\;wt\%\;Pt/CeO_2$ 촉매보다 우수한 활성을 보였다.

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Grain-Boundary Conduction in Solid Oxide Electrolyte (산화물 고체전해질의 입계전도)

  • Lee, Jong-Heun
    • Journal of the Korean Ceramic Society
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    • v.44 no.12
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    • pp.683-689
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    • 2007
  • Grain-boundary conduction in the fluorite-structure solid oxide electrolytes such as acceptor-doped zirconia and ceria were reviewed. The siliceous impurity, even several hundreds ppm, affects the ionic conduction across grain boundary to a great extent. Various approaches to improve grain-boundary conduction in fluorite-structure oxide electrolytes have been investigated, which include (1) the scavenging of siliceous phase by the reaction with second phase, (2) the gathering of intergranular siliceous phase into a discrete configuration and (3) the dewetting of intergranular liquid phase by post-sintering heat treatment.

Electrical Characterization of Ultrathin Film Electrolytes for Micro-SOFCs

  • Shin, Eui-Chol;Ahn, Pyung-An;Jo, Jung-Mo;Noh, Ho-Sung;Hwang, Jaeyeon;Lee, Jong-Ho;Son, Ji-Won;Lee, Jong-Sook
    • Journal of the Korean Ceramic Society
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    • v.49 no.5
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    • pp.404-411
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    • 2012
  • The reliability of solid oxide fuel cells (SOFCs) particularly depends on the high quality of solid oxide electrolytes. The application of thinner electrolytes and multi electrolyte layers requires a more reliable characterization method. Most of the investigations on thin film solid electrolytes have been made for the parallel transport along the interface, which is not however directly related to the fuel cell performance of those electrolytes. In this work an array of ion-blocking metallic Ti/Au microelectrodes with about a $160{\mu}m$ diameter was applied on top of an ultrathin ($1{\mu}m$) yttria-stabilized-zirconia/gadolinium-doped-ceria (YSZ/GDC) heterolayer solid electrolyte in a micro-SOFC prepared by PLD as well as an 8-${\mu}m$ thick YSZ layer by screen printing, to study the transport characteristics in the perpendicular direction relevant for fuel cell operation. While the capacitance variation in the electrode area supported the working principle of the measurement technique, other local variations could be related to the quality of the electrolyte layers and deposited electrode points. While the small electrode size and low temperature measurements increaseed the electrolyte resistances enough for the reliable estimation, the impedance spectra appeared to consist of only a large electrode polarization. Modulus representation distinguished two high frequency responses with resistance magnitude differing by orders of magnitude, which can be ascribed to the gadolinium-doped ceria buffer electrolyte layer with a 200 nm thickness and yttria-stabilized zirconia layer of about $1{\mu}m$. The major impedance response was attributed to the resistance due to electron hole conduction in GDC due to the ion-blocking top electrodes with activation energy of 0.7 eV. The respective conductivity values were obtained by model analysis using empirical Havriliak-Negami elements and by temperature adjustments with respect to the conductivity of the YSZ layers.

Oxygen Permeability, Electronic and ionic Conductivities and Defect Chemistry of Ceria-Zirconia-Calcia

  • Kawamura, Ken-ichi;Watanabe, Kensuke;Nigara, Yutaka;Kaimai, Atsushi;Kawada, Tatsuya;Mizusaki, Junichiro
    • The Korean Journal of Ceramics
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    • v.4 no.2
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    • pp.146-150
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    • 1998
  • The total conductivity and oxygen permeation in (Ce1-xZrxO2)0.9(CaO)0.1 solid solutions were measure das a function of temperature and oxygen partial pressure. Empirically, σ at given x and T was expressed essentially by σ=σo2+σeo Po2-1/4, where σo2 and σeo are constant. Applying a standard defect model in which major defects are Cace", Cece' and Vo in ideal solution, we can assign σo2 as the oxide ion conductivity decreases while the electronic conductivity increases with the increase in Zr content. Using the oxide ion and electronic conductivities thus determined, the oxygen permeation flux was calculated for respective Po2 and T conditions at which the measurements were made. The calculated values were found to agree with the observed ones.

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Fabrication of YSZ/GDC Bilayer Electrolyte Thin Film for Solid Oxide Fuel Cells

  • Yang, Seon-Ho;Choi, Hyung-Wook
    • Transactions on Electrical and Electronic Materials
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    • v.15 no.4
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    • pp.189-192
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    • 2014
  • Yttria-stablized zirconia (YSZ) is the most commonly used electrolyte material, but the reduction in working temperature leads to insufficient ionic conductivity. Ceria based electrolytes (GDC) are more attractive in terms of conductivity at low temperature, but these materials are well known to be reducible at very low oxygen partial pressure. The reduction of electrolyte resistivity is necessary to overcome cell performance losses. So, thin YSZ/GDC bilayer technology seems suitable for decreasing the electrolyte resistance at lower operating temperatures. Bilayer electrolytes composed of a galdolinium-doped $CeO_2$ ($Ce_{0.9}Gd_{0.1}O_{1.95}$, GDC) layer and yttria-stabilized $ZrO_2$ (YSZ) layer with various thicknesses were deposited by RF sputtering and E-beam evaporation. The bilayer electrolytes were deposited between porous Ni-GDC anode and LSM cathode for anode-supported single cells. Thin film structure and surface morphology were investigated by X-ray diffraction (XRD), using $CuK{\alpha}$-radiation in the range of 2ce morphol$^{\circ}C$. The XRD patterns exhibit a well-formed cubic fluorite structure, and sharp lines of XRD peaks can be observed, which indicate a single solid solution. The morphology and size of the prepared particles were investigated by field-emission scanning electron microscopy (FE-SEM). The performance of the cells was evaluated over $500{\sim}800^{\circ}C$, using humidified hydrogen as fuel, and air as oxidant.

Improvement of Open Circuit Voltage (OCV) depending on Thickness of GDC Electrolyte of LT-SOFCs (저온형 SOFC용 GDC 전해질 두께에 따른 Open Circuit Voltage 향상)

  • Ko, Hyun-Jun;Lee, Jong-Jin;Hyun, Sang-Hoon
    • Journal of the Korean Ceramic Society
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    • v.47 no.2
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    • pp.195-198
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    • 2010
  • It has been considered to apply GDC ($Gd_{0.1}Ce_{0.9}O_{1-X}$) for low-temperature SOFC electrolytes because it has higher ionic conductivity than YSZ at low temperature. However, open circuit voltage with using GDC ($Gd_{0.1}Ce_{0.9}O_{1-X}$) electrolyte in SOFCs, becomes lower than using YSZ (8 mol% Yttria stabilized Zirconia) electrolyte because GDC has electronic conductivity. In this work, the effect of changing GDC electrolyte thickness on the open circuit voltage has been investigated. Ni-GDC anode-supported unit cells were fabricated as follows. Mixed NiO-GDC powders were pressed and pre-sintered at $1200^{\circ}C$. And then, GDC electrolyte material was dip-coated on the anode and sintered at $1400^{\circ}C$. Finally the LSCF-GDC cathode material was screen-printed on the electrolyte and sintered at $1000^{\circ}C$. Electrolyte thickness was controlled by the number of dip-coating times. Open circuit voltage was measured depending on electrolyte thickness at $650^{\circ}C$ and found that the thicker GDC electrolyte was, the better OCV was.

Microstructure of Yttria-doped Ceria-Stabilized Zirconia Polycrystals (Yttria를 도핑한 세리아 안정화 지르코니아 세라믹스의 미세구조)

  • Lee, J.K.;Kang, H.H.;Seo, D.S.;Lee, E.G.;Kim, H.
    • Korean Journal of Materials Research
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    • v.9 no.8
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    • pp.768-774
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    • 1999
  • Yttia-doped ceria-stabilized ziconia polycrystals(Ce-TZP) was prepared by dipping method and its microstructure was investigated. By controlling doped-yttria content and annealing condition, yttria-doped Ce-TZP showed the microstructure with irregular grain shape and undulated grain boundary. Irregularity of grain shape increased with the amount of yttria doped, and severe undulated grain boundary was observed mainly at the surface region. In the case of yttria-doped Ce-TZP annealed at 1$650^{\circ}C$ for 2h after two dipping times into yttrium nitrate solution of 0.2M, it showed irregular grain shape both at the surface and at the interior region as well as the most severe irregularity. Hot pressed specimen had mean grain size of 0.3$\mu\textrm{m}$ and undulated grain boundary. All specimens with irregular grain shape were retained the tetragonal phase. The fracture toughness of yttria-doped Ce-TZP with irregular grain shape was over the value of 17.6MPa.m(sup)1/2.

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Maximizing TPBs through Ni-self-exsolution on GDC based composite anode in solid oxide fuel cells

  • Tan, Je-Wan;Lee, Dae-Hui;Kim, Bo-Gyeong;Kim, Ju-Seon;Mun, Ju-Ho
    • Proceedings of the Korean Vacuum Society Conference
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    • 2016.02a
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    • pp.402.1-402.1
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    • 2016
  • The performance of solid oxide fuel cells (SOFCs) is directly related to the electrocatalytic activity of composite electrodes in which triple phase boundaries (TPBs) of metallic catalyst, oxygen ion conducting support, and gas should be three-dimensionally maximized. The distribution morphology of catalytic nanoparticle dispersed on external surfaces is of key importance for maximized TPBs. Herein in situ grown nickel nanoparticle onto the surface of fluorite oxide is demonstrated employing gadolium-nickel co-doped ceria ($Gd0.2-xNixCe0.8O2-{\delta}$, GNDC) by reductive annealing. GNDC powders were synthesized via a Pechini-type sol-gel process while maximum doping ratio of Ni into the cerium oxide was defined by X-ray diffraction. Subsequently, NiO-GNDC composite were screen printed on the both sides of yttrium-stabilized zirconia (YSZ) pellet to fabricate the symmetrical half cells. Electrochemical impedance spectroscopy (EIS) showed that the polarization resistance was decreased when it was compared to conventional Ni-GDC anode and this effect became greater at lower temperature. Ex situ microstructural analysis using scanning electron microscopy after the reductive annealing exhibited the exsolution of Ni nanoparticles on the fluorite phases. The influence of Ni contents in GNDC on polarization characteristics of anodes were examined by EIS under H2/H2O atmosphere. Finally, the addition of optimized GNDC into the anode functional layer (AFL) dramatically enhanced cell performance of anode-supported coin cells.

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