• 한국세라믹학회지
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• 제41권1호
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• pp.92-95
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• 2004

Micro-Pulling Down (${\mu}$-PD) 법을 이용하여 $MnO_2$와 $Tb_4O_7$를 첨가하여 crack. 열 strain 등의 결함이 없는 화학양론조성의 $LiNbO_3$ 단결정을 c-축으로 직경 1.0mm, 길이 25-30mm의 크기로 성장시켰다. Electron Probe Micro Analysis (EPMA)를 이용하여 결정 내에 $MnO_2$와 $Tb_4O_7$이 균일하게 분포되어 있음을 확인하였다. 또한 Fourier Transform-Infrared Spectrophotometer (FT-IR)을 사용하여 OH 흡수밴드를 관찰하였고, 성장된 결정의 $MnO_2$와 $Tb_4O_7$ 첨가에 따른 형광특성의 변화를 측정하였다.

• Journal of Electrochemical Science and Technology
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• 제14권3호
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• pp.293-300
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• 2023

The global energy storage markets have gravitated to high-energy-density and low cost of lithium-ion batteries (LIBs) as the predominant system for energy storage such as electric vehicles (EVs). High-Ni layered oxides are considered promising next-generation cathode materials for LIBs owing to their significant advantages in terms of high energy density. However, the practical application of high-Ni cathodes remains challenging, because of their structural and surface instability. Although extensive studies have been conducted to mitigate these inherent instabilities, a two-step process involving the synthesis of the cathode and a dry/wet coating is essential. This study evaluates a one-step β-Li₂SnO₃ layer coating on the surface of LiNi_0.8Co_0.2O₂ (NC82) via the thermal segregation of Sn owing to the solubility limit with respect to the synthesis temperature. The doping, segregation, and phase transition of Sn were systematically revealed by structural analyses. Moreover, surface-engineered 5 mol% Sn-coated LiNi_0.8Co_0.2O₂ (NC82_Sn5%) exhibited superior capacity retention compared to bare NC82 owing to the stable surface coating layer. Thus, the developed one-step coating method is suitable for improving the properties of high-Ni layered oxide cathode materials for application in LIBs.

• 전기화학회지
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• 제24권3호
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• pp.52-64
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• 2021

Li_1+xFe_xTi_2-x(PO₄)_3-y(BO₃)_y (x = 0.2, 0.5)계 유리에서 Fe doping과 BO₃ 치환이 유리 또는 결정화유리(glass-ceramics) 전해질의 구조적, 열적 및 전기적 특성에 미치는 영향을 조사하였다. 또한, Li_1.5Fe_0.5Ti_1.5(BO₃)₃ 유리분말을 소결하고, 소결 온도에 따른 결정상과 이온전도도 영향도 검토하였다. Li_1+xFe_xTi_2-x(PO₄)_3-y(BO₃)_y 유리에서 Fe²⁺ 및 Fe³⁺ 이온은 network modifier로서 FeO₆ 팔면체를 형성하거나 network former로서 유리망목구조에 들어가 FeO₄ 유사 사면체를 형성하면서 유리의 구조를 변화시키는 것으로 확인되었다. 한편, BO₃는 BO₃ 또는 BO₄ 그룹을 형성하였는데, BO₃ 치환량이 작은 경우 boron은 (PB)O₄ 망목구조를 형성하지만, BO₃ 치환량이 증가하면 붕소이상현상(boric oxide anomaly)이 생겨나면서 BO₄는 BO₃로 변화하고 이로 인하여 비가교산소(non-bridging oxygen)가 증가하였다. BO₃ 치환은 유리전이온도와 결정화 온도를 낮추는 효과가 있으며, Fe 첨가량이 증가하면 Fe³⁺의 일부는 Fe²⁺로 환원되며, 유리전이온도와 연화온도를 낮아지게 하고 결정화온도를 높아지게 하는 것으로 확인되었다. Li_1+xFe_xTi_2-x(PO₄)_3-y(BO₃)_y (x = 0.2, 0.5) 유리에서 BO₃ 함량이 증가함에 따라 이온전도도는 증가하였으며, x = 0.2 및 0.5에서 각각 8.85×10^-4 및 1.38×10^-4S/cm의 이온전도도값을 나타내었다. 본 연구에서 얻어진 높은 이온전도도는 Fe³⁺의 산화상태 변화와 붕소이상현상에 의한 BO₃ 생성 및 이로 인한 비가교산소의 생성에 기인한 것으로 생각된다. Li_1.5Fe_0.5Ti_1.5(BO₃)₃ 유리를 800℃에서 소결한 결과 이온전도도가 급격히 저하되었는데 이는 결정화유리 분말이 고온에서 유리화되었기 때문으로 생각된다. 따라서 유리분말을 800℃에서 소결한 후, 다시 460℃에서 조핵하고, 600℃에서 결정성장을 시킨 결과, 이온전도도가 열처리전과 동등 수준으로 회복되는 것을 확인하였다.

• 한국전기전자재료학회논문지
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• 제27권9호
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• pp.555-560
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• 2014

In this paper, in order to develop outstanding Pb-free composition ceramics, the $Fe_2O_3$-doped ($Na_{0.525}K_{0.443}Li_{0.037}$)($Nb_{0.883}Sb_{0.08}Ta_{0.037}$)$O_3$ + 0.3 wt% $Bi_2O_3$ + x wt% $Fe_2O_3$ (x= 0~1.0 wt%)(abbreviated as NKL-NST) lead-free piezoelectric ceramics have been synthesized using the ordinary solid state reaction method. The effect of $Fe_2O_3$-doping on their microstructure and electrical properties were investigated. XRD diffraction pattern studies confirm that $Fe_2O_3$ completely diffused into the NKL-NST lattice to form a new stable soild solution with $Fe^{3+}$ entering the $Nb^{5+}$, $Sb^{5+}$ and $Ta^{5+}$ of B-site. And, phase structure of all the ceramics exhibited pure perovskite phase and no secondary phase was found in the ceramics. The ceramics doped with 0.6 wt% $Fe_2O_3$ have the optimum values of piezoelectric constant($d_{33}$), planar piezoelectric coupling coefficient($k_p$) and mechanical quality factor($Q_m$) : $d_{33}$ = 233 [pC/N], $k_p$= 0.44, $Q_m$= 95. These results indicate that the ($Na_{0.525}K_{0.443}Li_{0.037}$)($Nb_{0.883}Sb_{0.08}Ta_{0.037}$)$O_3$ +0.3 wt% $Bi_2O_3$ + 0.6 wt% $Fe_2O_3$ ceramic is a promising candidate for lead-free piezoelectric ceramics.

• 한국결정성장학회지
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• 제10권3호
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• pp.239-244
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• 2000

$LiMn_2$$O_4$Spine에 Li 과량 및 Mn 대신 Co를 일부 치환시킨 $_{1+x}$ Co$_{y}$ Mn$_{2-y}$ $O_4$(0$\leq$x$\leq$0.2,y=0,1/9,1/6) spinel에 대한 합성온도 결정, 상의 생성 등 고온 상평형에 대해 연구하였다. 고온 합성에 따른 제 2상의 생성을 방지하기 위해 저온합성이 가능한 습식화학적 합성법중 하나인 oxalate 침전법을 사용하여 $600^{\circ}C$ 이하에서 단일상의 spinel로 합성하였다. 이렇게 합성된 분말에 대해 TG-DTA분석 및 고온에서 급냉한 분말에 대한 XRD분석을 통해 질량(산소)의 증감에 연관된 가역적인 상전이 온도인 $T_1$, $T_2$및 $T_{2'}$ 들을 확인하였으며, 첨가된 Li의 양과 치환된 Co의 양에 따른 격자상수, 상전이 온도의 변화, 고온상의 안정성 등에 대해 연구하였다. 본 연구를 통해 Li$_{1+x}$ Co$_{y}$ Mn$_{2-y}$ $O_4$spinel의 합성온도 및 냉각속도 둥 합성과정 결정에 필요한 결과들을 얻을 수 있었다.

• Bulletin of the Korean Chemical Society
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• 제34권1호
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• pp.89-94
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• 2013

Layered $Li_{1+x}(Mn_{0.4}Ni_{0.4}Fe_{0.2})_{1-x}O_2$ (0 < x < 0.3) solid solutions were synthesized using solgel method with adipic acid as chelating agent. Structural and electrochemical properties of the prepared powders were examined by means of X-ray diffraction, Scanning electron microscopy and galvanostatic charge/discharge cycling. All powders had a phase-pure layered structure with $R\bar{3}m$ space group. The morphological studies confirmed that the size of the particles increased at higher x content. The charge-discharge profiles of the solid solution against lithium using 1 M $LiPF_6$ in EC/DMC as electrolyte revealed that the discharge capacity increases with increasing lithium content at the 3a sites. Among the cells, $Li_{1.2}(Mn_{0.32}Ni_{0.32}Fe_{0.16})O_2$ (x = 0.2)/$Li^+$ exhibits a good electrochemical property with maximum initial capacity of 160 $mAhg^{-1}$ between 2-4.5 V at 0.1 $mAcm^{-2}$ current density and the capacity retention after 25 cycles was 92%. Whereas, the cell fabricated with x = 0.3 sample showed continuous capacity fading due to the formation of spinel like structure during the subsequent cycling. The preparation of solid solutions based on $LiNiO_2-LiFeO_2-Li_2MnO_3$ has improved the properties of its end members.

• 한국재료학회지
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• 제19권2호
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• pp.95-101
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• 2009

Glass ceramics were made from coal bottom ash by adding CaO and $Li_2O$ as glass modifiers and $TiO_2$ as a nucleating agent in a process of melting and quenching followed by a thermal treatment. The surface of the glass ceramics has 1.6 times more $Li_2O$ compared to the inner matrix. When $TiO_2$ was not added or when only 2 wt% was added, the surface parts of the glass ceramics were crystalline with a thickness close to $130{\mu}m$. In addition, the matrixes showed only the glass phase and not the crystalline phase. However, doping of $TiO_2$ from 4 wt% to 10 wt% began to create small crystalline phases in the matrix with an increase in the quantity of the crystalline. The matrix microstructure of glass ceramics containing $TiO_2$ in excess of 8 wt% was a mixture of dark-gray crystalline and white crystalline parts. These two parts had no considerable difference in terms of composition. It was thought that the crystallization mechanism affects the crystal growth, direction and shape and rather than the existence of two types of crystals.

• 한국전기화학회:학술대회논문집
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• 한국전기화학회 2003년도 전지기술심포지움
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• pp.141-151
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• 2003

The electrochemical activity of the olivine type $LiMPO_4$ (M=transition metals) cathodes strongly depends on various factors, e.g., the transition metal element M, perturbative doping of the supervalent cations into Li site, composite formation with conductive additives, state of charge/discharge, and particle size and its geometries, etc. This is, therefore, an important issue of interdisciplinary between electrochemistry and solid state science towards practical applications. In order to shed light on this interesting but complicated issue with the transport properties and crystallographic aspects, systematic discussion will be made with the review of our recent publications; (1) first principle derivation of the electronic structures, (2) crystallographic mapping of the selected solid solutions, (3) quantitative elucidation of the electron-lattice interaction, (4) spectroscopic detection of the local environment with Mossbauer and EXAFS, (5) synthetic optimization of the electrode composite, and (6) electrochemical evaluation of the reaction kinetics, particularly on M = Fe, Mn.

• 전기화학회지
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• 제15권2호
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• pp.67-73
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• 2012

본 연구에서는 습식분쇄, 구형화 분무건조 및 열처리 공정을 통해 구형의 $LiMn_{2-x}M_xO_4$(M = Al, Mg, B) 스피넬계 양극소재를 합성하고, 이의 전기화학적 성능을 평가하였다. $MnO_2$ (Tosoh, 91.94%), $Li_2CO_3$ (SQM, 97%), $MgCO_3$ (Aldrich, 99%), $Al(OH)_3$ (Aldrich, 99%) 및 $B_2O_3$ (Aldrich, 99%)를 원료로 사용하였으며, 분무건조공정에서 전구체의 구형화도 증가를 위해 PAAH 바인더를 첨가하였다. 200~500 nm 크기로 분쇄된 혼합 슬러리 용액으로부터 분무건조법을 통해 구형의 전구체를 제조하고, 이를 다양한 조건에서 열처리하여 최종 스피넬계 $LiMn_{2-x}M_xO_4$ (M = Al, Mg, B) 양극소재를 제조하였다. 제조된 구형의 $LiMn_{2-x}M_xO_4$ (M = Al, Mg, B) 양극재료는 이종원소 치환량, 특히 Boron 치환량에 따라 입자 표면 및 내부의 치밀도가 변화하는 것을 확인할 수 있었으며, 치밀도가 증가함에 따라 소재의 출력특성이 향상되었으며, 최적 조성의 양극소재는 상온 5 C 용량이 0.2 C 용량 대비 90% 이상이 됨을 확인하였다. 또한 표면의 치밀도도 증가함에 따라 $60^{\circ}C$ 고온 충방전 조건에서 수명특성이 향상되어 500회 사이클 이후에도 초기용량의 80% 이상을 유지하였다.

• Journal of Electrochemical Science and Technology
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• 제11권4호
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• pp.352-360
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• 2020

Lithium cobalt oxide (LiCoO₂, LCO) has been widely used as a cathode material for Li-ion batteries (LIBs) owing to its excellent electrochemical performance and highly reproducible synthesis even with mass production. To improve the energy density of the LIBs for their deployment in electro-mobility, the full capacity and voltage of the cathode materials need to exploited, especially by operating them at a higher voltage. Herein, we doped LCO with divalent calcium-ion (Ca²⁺) to stabilize its layered structure during the batteries' operation. The Ca-doped LCO was synthesized by two different routes, namely solid-state and co-precipitation methods, which led to different average particle sizes and levels of dopant's homogeneity. Of these two, the solid-state synthesis resulted in smaller particles with a better homogeneity of the dopant, which led to better electrochemical performance, specifically when operated at a high voltage of 4.5 V. Electrochemical simulations based on a single particle model provided theoretical corroboration for the positive effects of the reduced particle size on the higher rate capability.