• Title/Summary/Keyword: Perovskites

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Cathode materials advance in solid oxide fuel cells (고체산화물연료전지 공기극의 재료개발동향)

  • Son, Young-Mok;Cho, Mann;Nah, Do-Baek;Kil, Sang-Cheol;Kim, Sang-Woo
    • Journal of Energy Engineering
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    • v.19 no.2
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    • pp.73-80
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    • 2010
  • A solid oxide fuel cells(SOFC) is a clean energy technology which directly converts chemical energy to electric energy. When the SOFC is used in cogeneration then the efficiency can reach higher than 80%. Also, it has flexibility in using various fuels like natural gases and bio gases, so it has an advantage over polymer electrolyte membrane fuel cells in terms of fuel selection. A typical cathode material of the SOFC in conjunction with yttria stabilized zirconia(YSZ) electrolyte is still Sr-doped $LaMnO_3$(LSM). Recently, application of mixed electronic and ionic conducting perovskites such as Sr-doped $LaCoO_3$(LSCo), $LaFeO_3$(LSF), and $LaFe_{0.8}Co_{0.2}O_3$(LSCF) has drawn much attention because these materials exhibit lower electrode impedance than LSM. However, chemical reaction occurs at the manufacturing temperature of the cathode when these materials directly contact with YSZ. In addition, thermal expansion coefficient(TEC) mismatch with YSZ is also a significant issue. It is important, therefore, to develop cathode materials with good chemical stability and matched TEC with the SOFC electrolyte, as well as with high electrochemical activity.

Crystal Structure and Physical Property of Tetragonal-like Epitaxial Bismuth Ferrites Film

  • Nam, Joong-Hee;Biegalski, Michael;Christen, Hans M.;Kim, Byung-Ik
    • Proceedings of the Korean Magnestics Society Conference
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    • 2011.06a
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    • pp.7-8
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    • 2011
  • Basically, the lattice mismatch between film and substrate can make those BiFeO3(BFO) films distorted with strain structure. BFO phase can be stabilized on LaAlO3(LAO) represents the example of a multiferroic with giant axial ratio. Its crystal structure is not strictly tetragonal, but tetragonal with a slight monoclinic distortion and related to the rotation of the oxygen octahedra. In this study, we show that phases with a tetragonal-like epitaxial BFO films can indeed be ferroelectric and also can be stabilized via epitaxial growth onto LAO. Recent reports on epitaxial BFO films show that the crystal structure changes from nearly rhombohedral ("R-like") to nearly tetragonal("T-like") at strains exceeding approximately -4.5%, with the "T-like" structure being characterized by a highly enhanced c/a ratio. While both the "R-like" and the "T-like" phases are monoclinic, our detailed x-ray diffraction results reveal asymmetry change from MA and MC type, respectively. By applying additional strain or by modifying the unit cell volume of the film by substituting Ba for Bi, the monoclinic distortion in the "T-like" MC phase is reduced, i.e. the system approaches a true tetragonal symmetry. There are two different M-H loops for $Bi_{1-x}Ba_xFeO_{3-{\delta}}$(BBFO) and BFO films on SrTiO3(STO) & LAO substrates. Along with the ferroelectric characterization, these magnetic data indicate that the BFO phase stabilized on LAO represents the first example of a multiferroic with giant axial ratio. However, there is a significant difference between this phase and other predicted ferroelectrics with a giant axial ratio: its crystal structure is not strictly tetragonal, but tetragonal with a slight monoclinic distortion. Therefore, in going from bulk to highly-strained films, a phase sequence of rhombohedral(R)-to-monoclinic ["R-like" MA-to-monoclinic, "T-like" MC-to-tetragonal (T)] is observed. This sequence is otherwise seen only near morphotropic phase boundaries in lead-based solid-solution perovskites (i.e. near a compositionally induced phase instability), where it can be controlled by electric field, temperature, or composition. Our results show that this evolution can occur in a lead-free, stoichiometric material and can be induced by stress alone. Those major results are summarized as follows ; 1) Ba-doping increases the unit cell volume, 2) BBFO on LAO can be fully strained up to x=0.08 as a strain limit (Fig. 1), 3) P(E) & M(H) properties can be tuned by the variation of composition, strain, and film thickness.

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Piezoelectric Properties of 0.94(Na0.5K0.5)NbO3-0.06(Sr0.5Ca0.5)TiO3 with 0.1 MnO2 Addition at Varying Sintering Temperatures (소결 온도에 따른 0.94(Na0.5K0.5)NbO3-0.06(Sr0.5Ca0.5)TiO3-0.1 MnO2의 압전 특성)

  • Jung, Hye-Rin;Lee, Sung-Gap;Lee, Tae-Ho;Kim, Min-Ho;Jo, Ye-Won
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.27 no.1
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    • pp.14-17
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    • 2014
  • In this study, lead-free Piezoelectric $(Na_{0.47}K_{0.47}Sr_{0.03}Ca_{0.03})(Nb_{0.94}Ti_{0.06})O_3$-0.1 $MnO_2$ ceramics were fabricated using mixed oxide method and the effects of various sintering temperature on the structural and electrical properties were investigated. For the $(Na_{0.47}K_{0.47}Sr_{0.03}Ca_{0.03})(Nb_{0.94}Ti_{0.06})O_3$-0.1 $MnO_2$ (NKN-SCT-$MnO_2$) ceramics sintered at temperatures of $1,025{\sim}1,100^{\circ}C$. The results indicated that all specimens were perovskite single phase formation without any second phase. It has been shown that relative density is increased to increasing sintering temperature. When the sintered temperature at $1,075^{\circ}C$, highest sintered density and maximum value of $4.45g/cm^3$. Average grain size is increased to increasing sintering temperature. The electromechanical coupling factor, dielectric constant, dielectric loss, d33 and curie temperature at the sintering temperature $1,075^{\circ}C$ of NKN-SCT-$MnO_2$ specimens were 0.22, 511, 0.033, 103 and $380^{\circ}C$, respectively.

Study of Catalytic Performance of $La_{0.7}Sr_{0.3}Cr_{1-x}Ni_{x}O_{3}$ Perovskite for Steam Reforming of Propane ($La_{0.7}Sr_{0.3}Cr_{1-x}Ni_{x}O_{3-{\delta}$ Perovskite 촉매의 프로판 수증기 개질 반응에서의 특성 연구)

  • Kim, Jae-Ro;Kim, Nak-Hyeon;Sohn, Jung-Min
    • Korean Chemical Engineering Research
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    • v.49 no.6
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    • pp.715-719
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    • 2011
  • The $La_{0.7}Sr_{0.3}Cr_{1-x}Ni_{x}O_{3}$(LSCN-x) perovskites were prepared by citric acid and EDTA using a sol-gel method. The LSCN-x was characterized by BET, XRD, SEM, $H_2$-TPR, EA and TEM. The catalytic performance of LSCN-x catalysts in steam reforming of propane in the temperature range 600~$800^{\circ}C$ was investigated. Propane conversion and hydrogen yield increased with an increase in the amount of added Ni up to x=0.5 in the B-site, denoted as LSCN-0.5, under S/C=1 and S/C=1.7 reaction conditions. The LSCN-0.5 catalyst exhibited the best performance under Ni-substitution of which propane conversion and hydrogen yield was 100%, 95.9% at $800^{\circ}C$ in the S/C=1.7 condition, respectively. The morphology of carbon deposited on the catalysts after reaction exhibited filamentous carbon and amount of carbon deposited on the catalysts after reaction increased with an increase in the amount of added Ni.

Promoter Effect on Ni/YSZ Anode Catalyst of Solid Oxide Fuel Cell for Suppressing Coke Formation in the Methane Internal Reforming (고체산화물 연료전지용 Ni/YSZ 음극 촉매에서의 메탄 내부개질 반응 시 탄소 침적 억제를 위한 첨가제 영향)

  • Kim, Hye-Roung;Choi, Ji-Eun;Youn, Hyun-Ki;Chung, Jong-Shik
    • Korean Chemical Engineering Research
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    • v.46 no.4
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    • pp.813-818
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    • 2008
  • Various additives were added in small amounts on Ni/YSZ anode of SOFC (solid oxide fuel cell) in order to improve reactivity and to inhibit deactivation due to coke deposition during methane reforming using a low mole ratio steam ($H_2O/CH_4=1.5$) at $800^{\circ}C$. Ni/YSZ catalysts added with various perovskites did not show any improvement but exhibited a gradual decrease in the methane conversion. K-doped Ni/YSZ showed a steady increase and maintenance of the conversion up to 42 hours, after which there was an abrupt deactivation of catalyst owing to potassium loss by volatilization. Addition of 5% of $K_2Ti_2O_5$ on Ni/YSZ showed a stable maintenance of the conversion without K loss, and was able to prevent coke formation during a long time operation. Deactivation of catalyst during the reaction was mainly caused by the accumulation of graphidic carbon on the catalyst surface.

A Growth and Characterization of CsPbBr3 Thin Film Grown by Thermal Chemical Vapor Deposition (열화학기상증착법을 이용한 CsPbBr3 박막 성장 및 특성 연구)

  • Ga Eun Kim;Min Jin Kim;Hyesu Ryu;Sang Hyun Lee
    • Journal of the Microelectronics and Packaging Society
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    • v.30 no.2
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    • pp.71-75
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    • 2023
  • In this study, inorganic perovskite films with different compositions were grown by thermal chemical vapor deposition depending on the substrate and their optical properties were compared. Inorganic perovskite crystals were grown on SiO2/Si and c-Al2O3 substrates using CsBr and PbBr2, respectively, under the same growth conditions. Cs4PbBr6-CsPbBr3 crystallites were grown on the SiO2 with polycrystalline structure, while a CsPbBr3 (100) dominant thin film was formed on the c-Al2O3 substrate with single crystal structure. From the photoluminescence measurement, CsPbBr3 showed typical green emission centered at 534 nm with a full width at half maximum (FWHM) of about 91 meV. The Cs4PbBr6-CsPbBr3 mixed structure exhibits blue-shifted emission at 523 nm with a narrow FWHM of 63 meV and a fast decay time of 6.88 ns. These results are expected to be useful for application in photoelectric devices such as displays, solar cells, and light sensors based on inorganic metal perovskites.

Crystallization and Magnetic Properties of Iron Doped La-Ba-Mn-O (Fe이 치환된 LaBaMnO계 산화물의 중성자 회절 및 Messbauer분광학연구)

  • Choi, Kang-Ryong;Kim, Sam-Jin;Shim, In-Bo;Kim, Chul-Sung
    • Journal of the Korean Magnetics Society
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    • v.14 no.1
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    • pp.38-44
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    • 2004
  • The iron doped colossal magnetoresistance materials with La-Ba-Mn-O perovskites structure have been synthesized by chemical reaction of sol-gel methods. Their crystallographic and magnetic properties have been studied with x-ray diffraction, VSM, RBS, Mossbauer spectroscopy, and magnetoresistance measurements. The crystal structure of the La$\_$0.67/Ba$\_$0.33/Mn$\_$0.99/Fe$\_$0.01/ $O_3$ at room temperature was determined to be orthorhombic of Pnma. The lattice parameters a$\_$0/ and c$\_$0/ increased gradually, but b$\_$0/ deceased with increase of iron substitution. The magnetization and coercivity deceased, also the Curie temperature decreased from 360 K as x increased from 0.00 to 0.05. Magnetoresistence measurements were carried out, and the maximum MR ($\Delta$$\rho$/$\rho$(0)) was observed at 281 K, about 9.5 % in 10 kOe. The temperature of maximum resistance (R$\_$MAX/) decreased with increasing substitution of Fe ions and a semiconductor-metal transition temperature (T$\_$SC-M/) decreased too. This phenomena show that ferromagnetic transition temperature decreased by substituting Fe for Mn ions, it decreases double exchange interaction. This result accords with magnetic structure of neutron diffraction. Mossbauer spectra of La$\_$0.67/Ba$\_$0.33/Mn$\_$0.99/Fe$\_$0.01/ $O_3$were taken at various temperatures ranging from 15 to 350 K. With lowering temperature of the sample, two magnetic phases were increased and finally it showed the two sharp sextets of spectra at 15 K. The isomer shift at all temperature range is about 0.3 mm/s relative to Fe metal, which means that both Fe ions are Fe$\^$3+/ states.Fe$\^$3+/ states.

Electrochemical properties of $Gd_{0.8}Ca_{0.2}Co_{1-x}Fe_xO_3$ cathodes for medium-temperature SOFC (중간온도형 고체산화물 연료전지의 양극재료로서 $Gd_{0.8}Ca_{0.2}Co_{1-x}Fe_xO_3$의 전기화학특성)

  • Ryu Ji-H.;Jang Jong-H.;Lee Hee-Y.;Oh Seung-M.
    • Journal of the Korean Electrochemical Society
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    • v.1 no.1
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    • pp.1-7
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    • 1998
  • For the purpose of finding new cathode materials for medium-temperature $(700\~800^{\circ}C)$ solid oxide fuel cells, $Gd_{0.8}Ca_{0.2}Co_{1-x}Fe_xO_3,\;(x=0.0\~0.5)$ are prepared, and their thermal stability and conductivity characteristics are investigated. Also, the cathodic activities are measured after the cathode layer being attached on CGO (cerium-gadolinium oxide) electrolyte disk. The X-ray analyses indicate that the materials prepared by calcining the citrate-gels at $800^{\circ}C$ have the orthorhombic perovskite structure without discernible impurities. The thermal stability of the undoped Co perovskite is so poor that it is decomposed to the individual binary oxide even at $1300^{\circ}C$. But the partially Fe-doped cobaltates exhibit a better thermal stability to retain their structural integrity up to $1400^{\circ}C$. The observation whereby both the undoped and Fe-doped cobaltates melt at ca. $1300^{\circ}C$ leads us to perform the electrode adhesion at <$1300^{\circ}C$. The cathodic activity of $Gd_{0.8}Ca_{0.2}Co_{1-x}Fe_xO_3,\;(x=0.0\~0.5)$, electrodes is superior to $La_{0.9}Sr_{0.1}MnO_3$, among the samples of $x=0.0\~0.5$, the x=0.2 cathode shows the best activity for the oxygen reduction reaction. It is likely that the Fe-doping provides a better thermal stability to the materials but in turn imparts an inferior cathodic activity, such that the optimum trade-off is made at x=0.2 between the two factors. The total electrical conductivity and ion conductivity of $Gd_{0.8}Ca_{0.2}Co_{1-x}Fe_xO_3$, are measured to be 51 S/cm and $6.0\times10^{-4}S/cm\;at\;800^{\circ}C$, respectively. The conductivity values illustrate that the materials are a mixed conductor and the reaction sites can be expanded to the overall electrode surface, thereby providing a better cathodic activity than $La_{0.9}Sr_{0.1}MnO_3$.

Characteristics of Sr0.92Y0.08Ti1-xVxO3-δ (x = 0.01, 0.04, 0.07, 0.12) Anode for Using H2S Containing Fuel in Solid Oxide Fuel Cells (H2S를 포함하는 연료를 사용하기 위한 고체산화물 연료전지용 Sr0.92Y0.08Ti1-xVxO3-δ 연료극 특성)

  • Jang, Geun Young;Kim, Jun Ho;Mo, Su In;Park, Gwang Seon;Yun, Jeong Woo
    • Korean Chemical Engineering Research
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    • v.59 no.4
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    • pp.557-564
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    • 2021
  • Sr0.92Y0.08Ti1-xVxO3-δ (SYTV) with perovskite structure was investigated as an alternative anode to utilize H2S containing fuels in solid oxide fuel cells. To improve the electrochemical performance of Sr0.92Y0.08TiO3-δ (SYT), vanadium(V) was substituted to titanium(Ti) at the B-site of the SYT perovskites. The SYTV synthesized by the Pechini method was chemically compatible with the YSZ electrolyte without additional by-products formation under the cell fabricating conditions. As increasing V substitution amounts, the oxygen vacancies increased, resulting to increasing ionic conductivity of the anode. The cell performance in pure H2 at 850 ℃ is 19.30 mW/cm2 and 34.87 mW/cm2 for a 1 mol.% and 7 mol.% of V substituted anodes, respectively. The cell performance using H2 fuel containing 1000 ppm of H2S at 850 ℃ was 23.37 mW/cm2 and 73.11 mW/cm2 for a 1 mol.% and 7 mol.% of V substituted anodes, respectively.