• Title/Summary/Keyword: Perovskites

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In-situ spectroscopic studies of SOFC cathode materials

  • Ju, Jong-Hun
    • Proceedings of the Materials Research Society of Korea Conference
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    • 2012.05a
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    • pp.70.1-70.1
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    • 2012
  • In-situ X-ray photoelectron spectroscopy (XPS) and infrared (IR) spectroscopy studies of SOFC cathode materials will be discussed in this presentation. The mixed conducting perovskites (ABO3) containing rare and alkaline earth metals on the A-site and a transition metal on the B-site are commonly used as cathodes for solid oxide fuel cells (SOFC). However, the details of the oxygen reduction reaction are still not clearly understood. The information about the type of adsorbed oxygen species and their concentration is important for a mechanistic understanding of the oxygen incorporation into these cathode materials. XPS has been widely used for the analysis of adsorbed species and surface structure. However, the conventional XPS experiments have the severe drawback to operate at room temperature and with the sample under ultrahigh vacuum (UHV) conditions, which is far from the relevant conditions of SOFC operation. The disadvantages of conventional XPS can be overcome to a large extent with a "high pressure" XPS setup installed at the BESSY II synchrotron. It allows sample depth profiling over 2 nm without sputtering by variation of the excitation energy, and most importantly measurements under a residual gas pressure in the mbar range. It is also well known that the catalytic activity for the oxygen reduction is very sensitive to their electrical conductivity and oxygen nonstoichiometry. Although the electrical conductivity of perovskite oxides has been intensively studied as a function of temperature or oxygen partial pressure (Po2), in-situ measurements of the conductivity of these materials in contact with the electrolyte as a SOFC configuration have little been reported. In order to measure the in-plane conductivity of an electrode film on the electrolyte, a substrate with high resistance is required for excluding the leakage current of the substrate. It is also hardly possible to measure the conductivity of cracked thin film by electrical methods. In this study, we report the electrical conductivity of perovskite $La_{0.6}Sr_{0.4}CoO_{3-{\delta}}$ (LSC) thin films on yttria-stabilized zirconia (YSZ) electrolyte quantitatively obtained by in-situ IR spectroscopy. This method enables a reliable measurement of the electronic conductivity of the electrodes as part of the SOFC configuration regardless of leakage current to the substrate and cracks in the film.

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Crystal Structure of High Temperature Phase in ${Bi_2}{O_2}$-layered Perovskites ${ABi_2}{M_2}{O_9}$(A=Pb, Sr, M=Nb, Ta)

  • Kim, Jeong-Seog;Cheon, Chae-il;Lee, Chang-Hee;Choo, Woong-Gil
    • Journal of the Korean Ceramic Society
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    • v.38 no.11
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    • pp.962-966
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    • 2001
  • Crystal structure of PbBi$_2$Nb$_2$$O_{9}$ and $Sr_{1.2}$$Bi_{1.8}$Ta$_2$$O_{9}$ were determined by Rietveld method using neutron diffraction data in the temperature range of 300 K~1273K. Phase transition temperature were measured from the dielectric permittivitytemperature curve. The PbBi$_2$Nb$_2$$O_{9}$ showed a phase transition at about 810 K. In the Sr-excess compound $Sr_{1.2}$$Bi_{1.8}$Ta$_2$$O_{9}$ the phase transition was suppressed down to room temperature. Several structural models were tested by the Rietiveld refinement. Based on the \`R\` values and the structural parameters, the B2cb model is judged to be the most feasible one for the high temperature phase at above 810 K of the PbBi$_2$Nb$_2$$O_{9}$. The $Sr_{1.2}$$Bi_{1.8}$Ta$_2$$O_{9}$ sample was refined to show the most reliable results by the Am2m model.sults by the Am2m model.

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Phase Formation and Protoniz Conduction of La(Ba)$ScO_3$ Perovskites (La(Ba)$ScO_3$계 Perovskite의 생성상 및 Proton 전도)

  • Lee, Kyu-Hyoung;Kim, Hyu-Lim;Kim, Shin;Lee, Hyung-Jik;Lee, Hong-Lim
    • Journal of the Korean Ceramic Society
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    • v.38 no.11
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    • pp.993-999
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    • 2001
  • Phase formation and proton conduction in BaO doped LaSc $O_3$with perovskite structure were studied. L $a_{0.6}$B $a_{0.4}$Sc $O_{2.8}$, viz. 40at% $Ba^{2+}$ ion doped composition, showed a single cubic phase, while the other compositions doped less than 30 at% $Ba^{2+}$ ion showed the cubic phase and the orthorhombic one. Above $650^{\circ}C$ oxygen ion conduction was dominant in $N_2$atmosphere and below this temperature proton conduction was observed in wet atmosphere. All compositions were found to be the pure proton conductors below 30$0^{\circ}C$. The proton conductivity (bulk) of L $a_{0.6}$B $a_{0.4}$Sc $O_{2.8}$ was higher than those of any other composition.osition.ion.

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A Facile Combustion Synthesis Route for Performance Enhancement of La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF6428) as a Robust Cathode Material for IT-SOFC

  • Yoo, Young-Sung;Namgung, Yeon;Bhardwaj, Aman;Song, Sun-Ju
    • Journal of the Korean Ceramic Society
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    • v.56 no.5
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    • pp.497-505
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    • 2019
  • Lanthanum-based transition metal cations containing perovskites have emerged as potential catalysts for the intermediate-temperature (600-800℃) oxygen reduction reaction (ORR). Here, we report a facile acetylacetone-assisted combustion route for the synthesis of nanostructured La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF6428) cathodes for intermediate-temperature solid-oxide fuel cells (IT-SOFCs). The as-prepared powder was analyzed by thermogravimetry analysis-differential scanning calorimetry. The powder calcined at 800℃ was characterized by X-ray diffraction, scanning electrode microscopy, energy dispersive X-ray spectroscopy, and Brunauer-Emmett-Teller surface area measurements. It was found that the porosity of the air electrode significantly increased by utilizing the nanostructured LSCF6428 instead of commercial powder. The performance of a single cell fabricated with the nanostructured LSCF6428 cathode increased by 112%, from 0.4 to 0.85 W cm-2, at 700℃. Electrochemical impedance spectroscopy showed a considerable reduction in the area-specific resistance and activation energy from 133.5 to 61.5 kJ/mol, resulting in enhanced electrocatalytic activity toward ORR and overall cell performance.

Application of Bond Valence Method to Estimate the Valence Charge Distributi on in the Metal-to-Oxygen Bonding Spheres in Perovskites

  • Nhat, Hoang Nam;Chau, Dinh Van;Thuong, Dinh Van;Hang, Nguyen Thi
    • International Journal of Internet, Broadcasting and Communication
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    • v.7 no.1
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    • pp.75-92
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    • 2015
  • This paper presents the application of the bond valence method to estimate the valence charge distribution in several perovskite systems: $La_{{\tilde{1}}x}Pb_xMnO_3$ (x=0.1-0.5), $La_{0.6}Sr_{0.{\tilde{4}}x}Ti_xMnO_3$ (x=0.0-0.25) and $La_{{\tilde{1}}x}Sr_xCoO_3$ (x=0.1-0.5); the reviewing of their crystal structures is also incorporated. The results showed the failure of the elastic bonding mechanism in all studied systems and revealed the general deficit of the valence charge in their unit cells. This valence deficit was not associated with the structural defects and was not equally localized in all coordination spheres. As the content of substitution increased, the charge deficit declined systematically from balanced level, signifying the transfer of valence charge from the ${\tilde{B}}O_6$ to ${\tilde{A}}O_{12}$ spheres. This transfer depended on the valence deviation of spheres and the average reached near 2 electron per unit cell. The possible impact of the limitted accuracy of the available structural data on the bond valence results has also been considered.

Synthesis of High-Aspect-Ratio BaTiO3 Platelets by Topochemical Conversion and Fabrication of Textured Pb(Mg1/3Nb2/3)O3-32.5PbTiO3 Ceramics

  • Zhao, Wei;E, Lei;Ya, Jing;Liu, Zhifeng;Zhou, Heping
    • Bulletin of the Korean Chemical Society
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    • v.33 no.7
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    • pp.2305-2308
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    • 2012
  • Perovskite structured barium titanate particles ($BaTiO_3$) platelets were synthesized by molten salt synthesis and topochemical microcrystal conversion. As the precursors of $BaTiO_3$, plate-like $BaBi_4Ti_4O_{15}$ particles were first synthesized by the reaction of $Bi_4Ti_3O_{12}$, $BaCO_3$, and $TiO_2$ at $1080^{\circ}C$ for 3 h in $BaCl_2$-KCl molten salt. After the topochemical reactions, layer-structured $BaBi_4Ti_4O_{15}$ particles transformed to the perovskite $BaTiO_3$ platelets. $BaTiO_3$ particles with thickness of approximately $0.5{\mu}m$ and a length of $10-15{\mu}m$ retained the morphology feature of the $BaBi_4Ti_4O_{15}$ precursor. For <001> $Pb(Mg_{1/3}Nb_{2/3})O_3-32.5PbTiO_3$ (PMNT)-5 wt % PbO piezoelectric ceramics textured with 5 vol % of $BaTiO_3$ templates, the Lotgering factor reached 0.82, and $d_{33}$ was 870 pC/N.

Improvement of the Resistivity in High Field for the New Piezoelectric Compositions in the Bi(NiaX1-a)O3-PbTiO3(X=Ti,Nb) System (Bi(NiaX1-a)O3-PbTiO3 계 압전 신조성(X-Ti,Nb)의 내전압 특성 향상)

  • Choi, Soon-Mok;Seo, Won-Seon
    • Journal of the Korean Ceramic Society
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    • v.45 no.4
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    • pp.220-225
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    • 2008
  • Lead-free ferroelectric ceramics are widely researched today for industrial applications as sensors, actuators and transducers. Since $Pb(Zr_aTi_{1-a})O_3$-(PZT) has high Curie temperature($T_C$), high piezoelectric properties near its morphotropic phase boundary(MPB) composition and small temperature dependence electrical behavior, it has been used to commercial materials for wide temperature range and different application fields. According to the tolerance factor concept, since the $Bi^{3+}$ cation with 12-fold coordinate has a smaller ionic radius than 12-fold coordinate $Pb^{2+}$, most bismuth based perovskites possess a smaller tolerance factor. Therefore, MPBs with a higher $T_C$ may be expected in $Bi(Me^{3+})O_3PbTiO_3$ solid solutions. As in lead based perovskite systems, it is clear that we need to explore more materials in simple or complex bismuth based MPB systems. The objective of this study is to investigate the $Bi(Ni_{1_a}X_a)O_3-PbTiO_3(X=Ti^{4+},\;Nb^{5+})$ perovskite solid-solution. For improving the electronic conduction problem, the magnesium and manganese modified system was also studied.

Halide Perovskite Single Crystals (할라이드 페로브스카이트 단결정)

  • Choi, Jin San;Jo, Jae Hun;Woo, Do Hyun;Hwang, Young-Hun;Kim, Ill Won;Kim, Tae Heon;Ahn, Chang Won
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.34 no.5
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    • pp.283-295
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    • 2021
  • For the last decades, a research hotspot for the halide perovskites (HPs) is now showing great progress in terms of improving efficiency for numerous photovoltaic devices (PVDs). However, it still faces challenges in the case of long-term stability in the air atmosphere. Defect-free high-quality HP single crystals show their promising properties for the remarkable development of highly efficient and stable PVDs. Here, we summarize the growth processing routes for the stable HP single crystals as well as briefly discuss the pros and cons of those well-established synthesis routes. Furthermore, we briefly include the comparison note between the HP single crystals and polycrystalline perovskite films regarding their device applications. Based on the future progress, the review concludes subjective perspectives and current challenges for the development of HPs high-quality PVDs.

Elucidating the Optoelectronic Properties of Metal Halide Perovskites (페로브스카이트 소재의 광전자 특성 분석)

  • Lee, Wonjong;Choi, Hajeong;Lim, Jongchul
    • Prospectives of Industrial Chemistry
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    • v.24 no.5
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    • pp.1-14
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    • 2021
  • 유무기 하이브리드 금속-할라이드계 페로브스카이트(organic-inorganic metal halide perovskite) 페로브스카이트 반도체 소재는 광전자 소자와 소재 연구에 새로운 연구 흐름을 만들고 있다. 태양전지 성능이 불과 과거 몇 년 사이의 짧은 연구 기간에도 불구하고, 광-전 변환 소자 중에서도 단일 소자와 적층 소자(tandem)에서 높은 광-전 변환 효율을 나타내기 때문이다. 이러한 급격한 연구 성과와 성장에도 불구하고, 페로브스카이트 소재의 다양한 광전자 특성의 평가와 결과에 대한 논의가 필요한 상황이다. 특히 내부 이온 이동이 광전자 원거리 이동 특성 평가와 해석에 영향을 주는 경우, 페로브스카이트 소재를 기반으로 한 다양한 광전자 소자의 성능 향상과 해석에 여전히 모호함을 준다. 달리 얘기하면, 이 소재의 기초 특성을 이해하고자 적용하는 다양한 기존 특성 평가 분석법의 활용과 해석에도 복잡한 영향을 미치고 있다고 할 수 있다. 이러한 페로브스카이트 소재 내에서 광전자 원거리 이동을 측정하는 새로운 방법을 소개하고자 한다. 첫 번째 방법으로, Quasi-steady 상태에서 광전도도를 전기적 특성으로 측정하고, 광조사 하에 투과 및 반사를 광학적으로 측정하여, 전도도와 광전자 밀도를 동시에 평가하는 방법으로, photo-induced transmission and reflection (PITR) 분광분석법이다. 이 분광분석법은 실제 소자의 구동조건을 구현한 상태에서 광전자의 원거리 이동에서 발생하는 광전자 밀도 변화를 반영한 광전자 이동도 특성 평가라는 장점을 가지고 있다. 두 번째 방법으로, 기존의 연속 전압 인가 방법 대신 펄스형 전압 인가 방식을 도입하는 방법으로, pulsed voltage space charge limited current (PV-SCLC) 분석법이다. 이는 펄스형 전압 인가 방법으로 이온의 이동을 최소화하여, 전류-전압 측정에서 히스테리시스가 없고 측정결과의 재현성과 신뢰도가 매우 높은 장점이 있다.

Calcination Condition of CsPbBr3-SiO2 Composite Nanoparticles (CsPbBr3-SiO2 복합 나노입자의 소결 조건 연구)

  • Jeon, Min-Gi;Kabir, Rezaul MD;Kirakosyan, Artavazd;Choi, Jihoon
    • Composites Research
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    • v.35 no.4
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    • pp.298-302
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    • 2022
  • Owing to the superior optoelectronic properties, halide perovskites have emerged as next-generation materials for display application. In this study, we reported a novel route for CsPbBr3 calcination into porous SiO2 nanoparticles to overcome the stability issues of halide perovskite via a spatial confinement of crystal growth within SiO2 pores. The resulting CsPbBr3-SiO2 nanoparticles exhibited the photoluminescence (PL) emission peak at 515 nm under optimal calcination condition. In several polar solvents, PL properties of CsPbBr3-SiO2 nanoparticles was maintained owing to the enclosed pores during calcination process, suggesting their promising application for display color conversion film.