• Corrosion Science and Technology
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• v.22 no.6
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• pp.408-418
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• 2023

In this study, we synthesized and characterized garnet-type Li_7-xAl_xLa₃Zr_2-(5/4)yNbyO₁₂ (LALZN) solid electrolytes for all-solid-state battery applications. Our novel approach focused on enhancing ionic conductivity, which is crucial for battery efficiency. A systematic examination found that co-doping with Al and Nb significantly improved this conductivity. Al³⁺ and Nb⁵⁺ ions were incorporated at Li⁺ and Zr⁴⁺ sites, respectively. This doping resulted in LALZN electrolytes with optimized properties, most notably enhanced ionic conductivity. An optimized mixture with 0.25 mol each of Al and Nb dopants achieved a peak conductivity of 1.32 × 10^-4 S cm^-1. We fabricated symmetric cells using these electrolytes and observed excellent charge-discharge profiles and remarkable cycling longevity, demonstrating the potential for long-term application in battery systems. The garnet-type LALZN solid electrolytes, with their high ionic conductivity and stability, show great potential for enhancing the performance of all-solid-state batteries. This study not only advances the understanding of effective doping strategies but also underscores the practical applicability of the LALZN system in modern energy storage solutions.

• Journal of Ceramic Processing Research
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• v.19 no.6
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• pp.461-466
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• 2018

The effects of Ca/Sr ratio and the sintering temperature on the properties of $(Ca_xSr_{(1-x)})ZrO_3$ (CSZ) ceramics were investigated in this study. CSZ ceramics were prepared using solid-state reaction process, which were sintered in air at temperatures ranging from $1350^{\circ}C$ to $1450^{\circ}C$. Their structures were characterized by X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), and Transmission Electron Microscopy (TEM). The change in Ca/Sr ratio significantly affected the crystalline phase and the dielectric properties of the $(Ca_xSr_{(1-x)})ZrO_3$ ceramics. The secondary phase, $Ca_{0.15}Zr_{0.85}O_{1.85}$, was observed and increased correspondingly with the rising of sintering temperatures. In order to understand the effects of secondary phase on the dielectric properties of CSZ ceramics, the $Ca_{0.15}Zr_{0.85}O_{1.85}$ phase was prepared individually using solidstate method. The $Ca_{0.15}Zr_{0.85}O_{1.85}$ ceramics sintered at $1500^{\circ}C$ for 2 hours possessed a dielectric constant (${\varepsilon}_r$) of 21.7, a dielectric loss ($tan{\delta}$) of $49.510^{-4}$ and an Insulation Resistance (IR) of $2.1{\times}10^{10}{\Omega}$. The ($Ca_{0.7}Sr_{0.3})ZrO_3$ ceramics exhibited the best dielectric properties, with a permittivity of 29, a dielectric loss ($tan{\delta}$) of $2.7{\times}10^{-4}$, and an Insulation Resistance (IR) of $2.6{\times}10^{12}{\Omega}$.

• Archives of Metallurgy and Materials
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• v.64 no.2
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• pp.579-583
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• 2019

Al and Nb-doped Li₇La₃Zr₂O₁₂ (LLZO) and W-doped LLZO lithium ion conducting electrolyte samples were prepared and their H₂O stability was investigated. The LLZO samples were exposed to 50% humidified air for 48 h. After H₂O exposure, a cubic to tetragonal transformation occurred and acquired SEM images exhibited the presence of reaction phases at the grain boundaries of Al and Nb-LLZO. As a result, the lithium ion conductivity significantly decreased after H₂O exposure. On the contrary, W-LLZO showed good stability against H₂O. Although the cubic to tetragonal transformation was also observed in H₂O-exposed W-LLZO, the decrease in lithium ion conductivity was found to be modest. No morphological changes of the W-LLZO samples were confirmed in the H₂O-exposed W-LLZO samples.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2010.06a
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• pp.307-307
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• 2010

최근 유한연료의 고갈로 인해 세계 유가가 불안정 됨으로서 대체 에너지에 대한 연구가 많이 진행 되고 있다. 특히 압전 소자를 이용한 에너지 하베스팅은 압전 역효과를 이용한 것으로서 주변에서 무의미하게 버려지는 진동이나 바람, 열 에너지를 실 생활에 사용할 수 있는 전기 에너지로 변환할 수 있는 유망한 기술 중 하나이다. 이러한 에너지 하베스팅 기술은 일본과 같은 선진국에서 이미 지하철 및 일반 다리와 같이 진동이 극히 많은 곳에서 응용되고 있다. 이러한 에너지 하베스팅 기술을 응용 하려면 전압출력 계수($g_{33}$)가 높아야 한다. 이것은 압전 d 상수와 유전상수에 영향을 많이 받는 것으로 알려져 있다. 현재가지 응용되는 압전 하베스팅 조성은 Pb(Zr,Ti)$O_3$ (PZT)를 기초로한 세라믹이 응용되고 있다. Pb(Zr,Ti)$O_3$ (PZT) 세라믹은 Morpohotropic phase boundary(MPB)에서 전기기계 결합계수 (kp) 와 기계적 품질계수 (Qm) 이 각각 0.5와 500으로 우수한 특성을 나타낸다. 또한 큐리온도 (Tc) 도 $400^{\circ}C$로 온도 안정성 또한 높다. 하지만 $1000^{\circ}C$ 이상에서 소결하는 PbO는 소결 중 급격한 휘발로 환경적 오염 뿐 아니라 특성의 저하를 야기시킨다. 그래서 몇몇 나라에서는 그 사용을 제한하고 점차적으로 사용을 줄여 나가고 있는 동시에 PbO가 첨가되어 있지 않은 Lead-Free 세라믹의 연구가 많이 진행되고 있다. Lead-Free 세라믹 중 alkaline niobate를 기초로 한 페로브스카이트 구조의 ($Na_{0.5}K_{0.5})NbO_3$ (NKN) 은 PbO를 기초로 한 세라믹을 대체할 유망한 후보자 중 하나이다. 하지만 NKN세라믹의 K 성분의 조해성 및 고온에서의 휘발로 인해 일반 적인 소결 방법으로는 고밀도의 세라믹을 얻기 매우 어렵다. 그래서 Hot pressing, Hot forging, RTGG(Reactive Template Grain Growth), SPS(Spark plasma Sintering)와 같은 특별한 소결 법을 이용하거나 $K_8CuNb_4O_{23}$(KCN) 이나 $K_{5.4}Cu_{1.3}Ta_{10}O_{29}$(KCT) 등을 첨가하여 그 소결성을 향상 시키는 방법도 있다. 또한 압전 d상수를 향상 시키기 위해 $Nb_2O_5$나, $La_2CO_3$, $CeO_2$, $Li_2CO_3$ 등을 치환함으로써 압전 d상수를 향상 시켜 전압출력 계수를 높이는 연구 또한 많은 보고가 되어 있다. 특히 $Li_2CO_3$의 첨가는 일반 적인 소결 방법으로도 밀도의 조밀함을 향상 시켜 그에 따른 높은 유전율과 전기기계 결합계수, 압전 d상수를 가져 많은 연구가 되어지고 있다. 그래서 본 연구에서는 일반적인 ($K_{0.5}N_{0.5})_{1-x}Li_x(Nb_{0.96}Sb_{0.04})O_3$ + 0.2mol%$La_2O_3$ + 1.2mol%$K_8CuNb_4O_{23}$ 세라믹에 x(=Li) 치환에 따른 유전 및 압전특성을 조사하였다.

• Nuclear Engineering and Technology
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• v.51 no.7
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• pp.1866-1870
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• 2019

Residual salt separation is an essential step in pyroprocessing because its reaction products, as prepared by electrochemical unit processes, contain frozen residual electrolyte species, which are generally composed of alkali-metal chloride salts (e.g., LiCl, KCl). In this study, a simple technique that utilizes high-temperature gas flux as a driving force to melt and push out the residual salt in the reaction products was developed. This technique is simple as it only requires the use of a heating gun in combination with a gas injection system. Consequently, $LiNO_3-ZrO_2$ and $LiCl-ZrO_2$ mixtures were successfully separated by the high-temperature gas injection (separation efficiency > 93%), thereby demonstrating the viability of this simple technique for residual salt separation.

• Journal of the Korean Ceramic Society
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• v.54 no.4
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• pp.278-284
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• 2017

In this work, Ta-substituted $Li_7La_3Zr_{2-x}O_{12}$ (LLZTO) powder and pellets with garnet cubic structure were fabricated and characterized by modified and optimized sol-gel synthesis. Ta-substituted LLZO powder with the smallest grain size and pure cubic structure with little pyrochlore phase was obtained by synthesis method in which Li and La sources in propanol solvent were mixed together with Zr and Ta sources in 2-methoxy ethanol. The LLZTO pellets made with the prepared powder showed cubic garnet structure for all conditions when the amount of Li addition was varied from 6.2 to 7.4 mol. All the X-ray peaks of the pyrochlore phase disappeared when the Li addition was increased above 7.0 mol. When the final sintering temperature was varied, the LLZTO pellet had a pyrochlore-mixed cubic phase above $1000^{\circ}C$. However, the surface morphology became much denser when the final sintering temperature was increased. The sol-gel-driven LLZTO pellet with a sintering temperature of $1100^{\circ}C$ showed a lithium ionic conductivity of 0.21 mS/cm when Au was adopted as electrode material for the blocking capacitor. The results of this study suggest that modified sol-gel synthesis is the optimum method to obtain cubic phase of LLZTO powder for highly dense and conductive solid electrolyte ceramics.

• Advances in materials Research
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• v.5 no.2
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• pp.93-105
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• 2016

KNN-based ceramics modified with small amounts of $Bi_4Zr_3O_{12}$ (BiZ) has been synthesized using high-throughput experimentation (HTE). The results from X-ray diffraction show that for samples with base composition $(K_{0.5}Na_{0.5})NbO_3$ (KNN), the phase present changes from orthorhombic to pseudo-cubic with more than 0.2 mol% BiZ addition; for samples with base composition $(K_{0.48}Na_{0.48}Li_{0.04})(Nb_{0.9}Ta_{0.1})O_3$ (KNNLT), the phase present changes from a mixture of orthorhombic and tetragonal symmetry to pseudo-cubic with more than 0.4 mol % while for samples with base composition $(K_{0.48}Na_{0.48}Li_{0.04})(Nb_{0.86}Ta_{0.1}Sb_{0.04})O_3$ (KNNLST), the phase present is tetragonal with <0.3 mol% BiZ addition and transforms to pseudo-cubic with more dopant addition. The microstructures of the samples show that addition of BiZ decreases the average grain size and increases the volume of pores at the grain boundaries. The values of dielectric constant for KNN and KNNLT compositions increase slightly with BiZ addition while that for KNNLST decreases gradually with BiZ addition. The dielectric loss values are between 0.02 and 0.04 for KNNLT and KNNLST compositions while they are ~ 0.05 for KNN samples. The resistivity values increases with BiZ addition and values in the range of $10^{10}{\Omega}cm$ and $10^{12}{\Omega}cm$ are obtained. The piezoelectric charge coefficient ($d{^*}_{33}$) is highest for KNNLST samples and decreases gradually from ~400 pm/V to ~100 pm/V with BiZ addition.

• Journal of the Korean Ceramic Society
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• v.51 no.4
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• pp.283-288
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• 2014

PdO-doped $BaZr_{0.85}Y_{0.15}O_{3-\delta}$ (BZPY) proton conductors have been proposed as applicable for intermediate temperature electrolytes for protonic ceramic fuel cells (PCFCs) because the PdO doping is effective for improving the proton conductivity of $BaZr_{0.85}Y_{0.15}O_{3-\delta}$ (BZY) with high affinity for hydrogen. In order to further improve the conductivity of BZPY, two-phase composite electrolytes consisting of a BZPY and molten carbonate were designed. Dense BZPY-based composite electrolytes were fabricated after sintering at $670^{\circ}C$ for 4 h, since molten carbonates fill the grain boundary of the porous BZPY matrix. Furthermore, BZPY/$(Li-0.5Na)_2CO_3$ composites show a significantly enhanced protonic conductivity at intermediate temperatures. This may be because easy proton transport is possible through the interface of the carbonate and oxide phase.

• Journal of the Korean earth science society
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• v.27 no.1
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• pp.49-60
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• 2006

The purpose of this study is to investigate geochemical characteristics for stream sediments in the Naju area. We collected 139 stream sediments samples from primary channels. Samples were dried slowly in the laboratory and chemical analysis was carried out using XRF. ICP-AES and NAA. In order to investigate geochemical characteristics, the geological groups categorized into granitic gneiss area, schist area, granite area, arenaceous rock area, tuff area, andesite area, and rhyolite area. Average contents of major elements for geological groups are $SiO_2\;58.37{\sim}66.06wt.%,\;Al_2O_3\;13.98{\sim}18.41wt.%,\;Fe_2O_3\;4.09{\sim}6.10wt.%,\;CaO\;0.54{\sim}1.33wt.%,\;MgO\;0.86{\sim}1.34wt.%,\;K_2O\;2.38{\sim}4.01wt.%,\;Na_2O\;0.90{\sim}1.32wt.%,\;TiO_2\;0.82{\sim}1.03wt.%,\;MnO\;0.09{\sim}0.15wt.%,\;P_2O_5\;0.11{\sim}0.18wt.%$. According to the comparison of average contents of major elements, $Al_2O_3\;and\;K_2O$ are higher in granitic gneiss area, $Fe_2O_3,\;CaO,\;P_2O_5$ are higher in tuff area, MgO and $TiO_2$ are higher in andesite area, $Na_2O_$ is higher in rhyolite area, $SiO_2$, and MnO are higher in arenaceous rock area. Average contents of minor and rare earth elements for geological groups are $Ba\;1278{\sim}1469ppm,\;Be\;1.1{\sim}1.5ppm,\;Cu\;18{\sim}25ppm,\;Nb\;25{\sim}37ppm,\;Ni\;16{\sim}25ppm,\;Pb\;21{\sim}28ppm,\;Sr\;83{\sim}155ppm,\;V\;64{\sim}98ppm,\;Zr\;83{\sim}146ppm,\;Li\;32{\sim}45ppm,\;Co\;7.2{\sim}12.7ppm,\;Cr\;37{\sim}76ppm,\;Cs\;4.8{\sim}9.1ppm,\;Hf\;7.5{\sim}25ppm,\;Rb\;88{\sim}178ppm,\;Sc\;7.7{\sim}12.6ppm,\;Zn\;83{\sim}143ppm,\;Pa\;11.3{\sim}37ppm,\;Ce\;69{\sim}206ppm,\;Eu\;1.1{\sim}1.5ppm,\;Yb\;1.8{\sim}4.4ppm$. According to the comparison of average contents of minor and rare earth elements for geological groups, Pb, Li, Cs, Hf, Rb, Sb, Pa, Ce, Eu, and Yb are higher in granitic gneiss area; Ba, Co, and Cr in schist area; Nb, Ni, and Zr in arenaceous rock area; Sr in tuff area: and Be, Cu, V, Sc, and Zn are such in andesite area.

• Analytical Science and Technology
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• v.9 no.4
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• pp.382-391
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• 1996

In this study, 12 different chemical species of fine ceramic($BaTiO_3$) were synthesized as the standard materials for the fast and accurate measurements of X-ray fluorescence spectrometry. Samples were diluted to sixteen times with the filling compound ($Li_2B_4O_7+LiBO_2$) in order to remove the matrix effect, and to get the convenient storage and homogeneity of ingredients. The matrix effects among the ingredients were corrected by the empirical coefficient method based on the Lucas-Tooth and Price model. The standard curve on 12 standard materials containing 15 elements were obtained by using X-ray fluorescence spectrometry at three different laboratories. The correlation factors of BaO, PbO, SrO, $Fe_2O_3$, $La_2O_3$, $SnO_2$, ZnO, $ZrO_2$, CaO indicated the relati vely good agreement over 0.995 among the three different laboratories. $SiO_2$ and $Al_2O_3$ showed the poor linearity because of their low fluorescence intensities.