• Journal of the Korean Ceramic Society
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• v.53 no.6
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• pp.712-718
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• 2016

In this study, we investigate the effect of the$Li_3BO_3$ additive on the densification and ionic conductivity of garnet-type $Li_7La_3Zr_2O_{12}$ solid electrolytes for all-solid-state lithium batteries. We analyze their densification behavior with the addition of $Li_3BO_3$ in the range of 2-10 wt.% by dilatometer measurements and isothermal sintering. Dilatometry analysis reveals that the sintering of $Li_7La_3Zr_2O_{12}-Li_3BO_3$ composites is characterized by two stages, resulting in two peaks, which show a significant dependence on the $Li_3BO_3$ additive content, in the shrinkage rate curves. Sintered density and total ion conductivity of the system increases with increasing $Li_3BO_3$ content. After sintering at $1100^{\circ}C$ for 8 h, the $Li_7La_3Zr_2O_{12}-8$ wt.% $Li_3BO_3$ composite shows a total ionic conductivity of $1.61{\times}10^{-5}Scm^{-1}$, while that of the pure $Li_7La_3Zr_2O_{12}$ is only $5.98{\times}10^{-6}Scm^{-1}$.

• Journal of Powder Materials
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• v.25 no.2
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• pp.151-157
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• 2018

In this study, the compound $Li_3BO_3$ (LBO) is intended to be prepared by a polymeric complex method as a sintering aid for the densification of $Li_7La_3Zr_2O_{12}$ (LLZ) solid electrolyte. A polymeric precursor containing Li and B is heat-treated in an air atmosphere at a temperature range between $600^{\circ}C$ and $800^{\circ}C$. Instead of LBO, the compound $Li_{2+x}C_{1-x}B_xO_3$ (LCBO) is unexpectedly synthesized after a heat-treatment of $700^{\circ}C$. The effect of LCBO addition on sintering behavior and ion conductivity of LLZ is studied. It is found that the LCBO compound could lead to significant improvements in the densification and ionic conductivity of LLZ compared to pure LLZ. After sintering at $1100^{\circ}C$, the density of the LLZ-12wt%LBO composite is $3.72g/cm^3$, with a high Li-ion conductivity of $1.18{\times}10^{-4}Scm^{-1}$ at $28^{\circ}C$, while the pure LLZ specimen had a densify of $2.98g/cm^3$ and Li-ion conductivity of $5.98{\times}10^{-6}Scm^{-1}$.

• Journal of the Korean Physical Society
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• v.73 no.10
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• pp.1535-1540
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• 2018

In this study, we prepared and characterized Nb-doped $Li_7La_3Zr_{2-x}O_{12}$ (LLZNO) powder and pellets with a cubic garnet structure by using a modified sol-gel synthesis and hot pressing. LLZNO powder with a very small grain size and cubic structure without secondary phases could be obtained by using a synthesis method in which Li and La sources in a propanol solvent were mixed together with Zr and Nb sources in 2-methoxy ethanol. A pure cubic phase LLZNO pellet could be fabricated from the prepared LLZNO and an additional 6-wt% of $Li_2CO_3$ powder by hot pressing at $1050^{\circ}C$ and 15.8 MPa. The hot-pressed LLZNO pellet with a relative density of 99% exhibited a very dense surface morphology. The total Li ionic conductivity of the hot-pressed LLZNO was $7.4{\times}10^{-4}S/cm$ at room temperature, which is very high level compared to other reported values. The activation energy for ionic conduction was estimated to be 0.40 eV.

• Korean Journal of Materials Research
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• v.31 no.11
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• pp.614-618
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• 2021

As the size of market for electric vehicles and energy storage systems grows, the demand for lithium-ion batteries (LIBs) is increasing. Currently, commercial LIBs are fabricated with liquid electrolytes, which have some safety issues such as low chemical stability, which can cause ignition of fire. As a substitute for liquid electrolytes, solid electrolytes are now being extensively studied. However, solid electrolytes have disadvantages of low ionic conductivity and high resistance at interface between electrode and electrolyte. In this study, Li₇La₃Zr₂O₁₂ (LLZO), one of the best ion conducting materials among oxide based solid electrolytes, is fabricated through RF-sputtering and various electrochemical properties are analyzed. Moreover, the electrochemical properties of LLZO are found to significantly improve with co-sputtered Li₂O. An all-solid thin film battery is fabricated by introducing a thin film solid electrolyte and an Li₄Ti₅O₁₂ (LTO) cathode; resulting electrochemical properties are also analyzed. The LLZO/Li₂O (60W) sample shows a very good performance in ionic conductivity of 7.3×10^-8 S/cm, with improvement in c-rate and stable cycle performance.

• Journal of the Korean Chemical Society
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• v.27 no.4
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• pp.273-278
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• 1983

With the synthetic standards, valuable metals $(Ta_2O_5, Nb_2O_5, TiO_2, SnO_2$, and $ZrO_2$) in the tin slags have been determined by the x-ray fluorescence spectrometry. The powder sample and the standards are homogeneously mixed with anhydrous $Li_2B_4O_7$ and La_2O_3$ in weight ratio of 15 : 42 : 3 respectively. The mixed material is fused at $1,150^{\circ}C$ for 30 minutes to be changed into the glass bead. The bead is ground to (-) 325 mesh size and pelletized. The analytical results obtained in this work are consistent with the data obtained by other common methods within allowable error range. The standard deviation for $Ta_2O_5$ in PTS-H sample is 0.12 % at level of 3.40 % content.

• 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.

• 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 Powder Materials
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• v.23 no.5
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• pp.379-383
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• 2016

A thick film of $Li_7La_3Zr_2O_{12}$ (LLZO) solid-state electrolyte is fabricated using the tape casting process and is compared to a bulk specimen in terms of the density, microstructure, and ion conductivity. The final thickness of LLZO film after sintering is $240{\mu}m$ which is stacked up with four sheets of LLZO green films including polymeric binders. The relative density of the LLZO film is 83%, which is almost the same as that of the bulk specimen. The ion conductivity of a LLZO thick film is $2.81{\times}10^{-4}S/cm$, which is also similar to that of the bulk specimen, $2.54{\times}10^{-4}S/cm$. However, the microstructure shows a large difference in the grain size between the thick film and the bulk specimen. Although the grain boundary area is different between the thick film and the bulk specimen, the fact that both the ion conductivities are very similar means that no secondary phase exists at the grain boundary, which is thought to originate from nonstoichiometry or contamination.

• 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.

• Analytical Science and Technology
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• v.10 no.6
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• pp.439-444
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• 1997

Twelve kinds (1set) standard materials of chemical ingredients of lead zirconate titanate[$Pb(ZrTi)O_3$] have been developed in order to determine fast and accurate measurement of X-ray fluorescence spectrometry. Especially, we used diluted(ahout sixteen times) filling compound($Li_2B_4O_7/LiBO_2=4/1$) to consider removal effect of matrix, storage convenience, and homogenous characteristics. As a result from the four different laboratories, we obtained extremly good agreement about the standard curve on twelve standard materials which containing eleven elements, PbO, $ZrO_2$, $TiO_2$, SrO, $WO_3$, $La_2O_3$, $Cr_2O_3$, MgO, $Nb_2O_5$, and $MnO_2$. The correlation factor of standard curve was over 0.998. However, ZnO has relatively low correlation factor, 0.977, because the concentration was 10ppm lower than other original materials. This analysis reveals that ZnO has shown the poor linearity as well as low fluorescence intensity. In present work, XRF standard materials are useful for determining a rapid and accurate results for major and minor elements concentration among PZT.