• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2010년도 하계학술대회 논문집
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• pp.212-212
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• 2010

Recently, lithium transition metal phosphates with an ordered olivine-type structure, $LiMPO_4$ (M=Fe, Mn, Ni, and Co), have attracted extensive attention due to a high theoretical specific capacity (170 mAh/g). The $LiMPO_4$ is the most attractive because of its high stability, low cost, high compatibility with environment. However, it is difficult to attain its full capacity because its electronic conductivity is very low, and diffusion of Li-ion in the olivine structure is slow and the supervalue cation doping was used. In this research, we are used the supervalue cation doping methode such as Cu, Ti, and Mg were partially replace the Fe. The cycling performance resulted of the used $LiM_xFe_{1_x}PO_4$ cathode materials for lithium batteries exhibit excellent high capacity than $LiFePO_4$/Li cells.

• 한국재료학회:학술대회논문집
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• 한국재료학회 2003년도 춘계학술발표강연 및 논문개요집
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• pp.216-216
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• 2003

현재 상용화되어 있는 리튬 이차전지용 양극재료로는 비교적 작동전압이 높은 층상 암염구조(LiCoO$_2$, LiNiO$_2$) 및 Spinet계(LiMn$_2$O$_4$) 전이금속 산화물이 대부분 이용되고 있다 하지만 LiCoO$_2$나 LiNiO$_2$ 같은 상용화 물질은 비교적 높은 비용과, 강한 독성 때문에 많은 문제점을 가지고 있다. 또 Spinel(LiMn$_2$O$_4$)는 낮은 비용과 환경친화적인 장점에도 불구하고 Jahn-Teller 변형과 관련된 구조적 변형이 심각하기 때문에 사이클시 비가역적인 용량의 감소가 심각하다. 이러한 관점에서 전이금속보다 그 양이 풍부하고 저렴할 뿐만 아니라 독성이 없는 Olivine 구조 (LiFePO$_4$)를 갖는 phosphate계 화합물에 관심을 가지게 되었다. LiFePO$_4$는 리튬 음극과 3.4V의 방전전압을 나타내며, 170mAh/g의 이론용량을 가지고 있어, Fe-base의 장점은 물론 안정적인 결정구조 및 현재 상용화된 재료들과 비슷한 에너지 밀도를 가진다. 따라서 본 연구에서는 양극물질의 기존 두 제조법인 고상반응법과 sol-gel법으로 대표되는 제조법의 단점을 상호 보완될 수 있다고 판단되는 기계적 합금화법(Mechanical Alloying, MA)공정을 도입하여 초미세립 분말 제조에 초점을 맞추어 Olivine phosphate계 양극물질의 제조 및 전기화학적 특성을 연구하였다.

• Journal of Electrochemical Science and Technology
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• 제13권3호
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• pp.407-415
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• 2022

Surface coating of cathodes is an essential process for all-solid-state batteries (ASSBs) based on sulfide electrolytes as it efficiently suppresses interfacial reactions between oxide cathodes and sulfide electrolytes. Based on computational calculations, Li₃PO₄ has been suggested as a promising coating material because of its higher stability with sulfides and its optimal ionic conductivity. However, it has hardly been applied to the coating of ASSBs due to the absence of a suitable coating process, including the selection of source material that is compatible with ASSBs. In this study, polyphosphoric acid (PPA) and (NH₄)₂HPO₄ were used as source materials for preparing a Li₃PO₄ coating for ASSBs, and the properties of the coating layer and coated cathodes were compared. The Li₃PO₄ layer fabricated using the (NH₄)₂HPO₄ source was rough and inhomogeneous, which is not suitable for the protection of the cathodes. Moreover, the water-based coating solution with the (NH₄)₂HPO₄ source can deteriorate the electrochemical performance of high-Ni cathodes that are vulnerable to water. In contrast, when an alcohol-based solvent was used, the PPA source enabled the formation of a thin and homogeneous coating layer on the cathode surface. As a consequence, the ASSBs containing the Li₃PO₄-coated cathode prepared by the PPA source exhibited significantly enhanced discharge and rate capabilities compared to ASSBs containing a pristine cathode or Li₃PO₄-coated cathode prepared by the (NH₄)₂HPO₄ source.

• Bulletin of the Korean Chemical Society
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• 제35권12호
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• pp.3553-3558
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• 2014

The reduced graphene oxide(rGO)/aluminum phosphate($AlPO_4$)-coated $LiMn_{1.5}Ni_{0.5}O_4$ (LMNO) cathode material has been developed by hydroxide precursor method for LMNO and by a facile solution based process for the coating with GO/$AlPO_4$ on the surface of LMNO, followed by annealing process. The amount of $AlPO_4$ has been varied from 0.5 wt % to 1.0 wt %, while the amount of rGO is maintained at 1.0 wt %. The samples have been characterized by X-ray diffraction, scanning electron microscopy, and high-resolution transmission electron microscopy. The rGO/$AlPO_4$-coated LMNO electrodes exhibit better cyclic performance compared to that of pristine LMNO electrode. Specifically, rGO(1%)/$AlPO_4$(0.5%)- and rGO(1%)/$AlPO_4$(1%)-coated electrodes deliver a discharge capacity of, respectively, $123mAhg^{-1}$ and $122mAhg^{-1}$ at C/6 rate, with a capacity retention of, respectively, 96% and 98% at 100 cycles. Furthermore, the surface-modified LMNO electrodes demonstrate higher-rate capability. The rGO(1%)/$AlPO_4$(0.5%)-coated LMNO electrode shows the highest rate performance demonstrating a capacity retention of 91% at 10 C rate. The enhanced electrochemical performance can be attributed to (1) the suppression of the direct contact of electrode surface with the electrolyte, resulting in side reactions with the electrolyte due to the high cut-off voltage, and (2) smaller surface resistance and charge transfer resistance, which is confirmed by total polarization resistance and electrochemical impedance spectroscopy.

• Journal of Electrochemical Science and Technology
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• 제2권1호
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• pp.14-19
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• 2011

Quasi-equilibrium profiles are analyzed through galvanostatic intermittent titration technique (GITT) and potentiostatic intermittent titration technique (PITT) to study the charge/discharge mechanism in multicomponent olivine structure ($LiMn_{1/3}Fe_{1/3}Co_{1/3}PO_4$). From GITT data, the degree of polarization is evaluated for the three regions corresponding to the redox couples of $Mn^{2+}/Mn^{3+}$, $Fe^{2+}/Fe^{3+}$ and $Co^{2+}/Co^{3+}$. From PITT data, the current vs. time responses are examined in each titration step to find out the mode of lithium de-intercalation/intercalation process. Furthermore, lithium diffusivities at specific compositions (x in $Li_xMn_{1/3}Fe_{1/3}Co_{1/3}PO_4$) are also calculated. Finally, total capacity ($Q^{total}$) and diffusional capacity ($Q^{diff}$) are obtained for some selected voltage steps. The entire study consistently confirms that the charge/discharge mechanism of multicomponent olivine cathode is associated with a one-phase reaction rather than a biphasic reaction.

• 한국자기학회:학술대회 개요집
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• 한국자기학회 2015년도 자성 및 자성재료 국제학술대회
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• pp.99-99
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• 2015

• Bulletin of the Korean Chemical Society
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• 제32권12호
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• pp.4205-4209
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• 2011

The $Li_2Mn_{0.5}Fe_{0.5}SiO_4$ silicate was prepared by blending of $Li_2MnSiO_4$ and $Li_2FeSiO_4$ precursors with same molar ratio. The one of the silicates of $Li_2FeSiO_4$ is known as high capacitive up to ~330 mAh/g due to 2 mole electron exchange, and the other of $Li_2FeSiO_4$ has identical structure with $Li_2MnSiO_4$ and shows stable cycle with less capacity of ~170 mAh/g. The major drawback of silicate family is low electronic conductivity (3 orders of magnitude lower than $LiFePO_4$). To overcome this disadvantage, carbon composite of the silicate compound was prepared by sucrose mixing with silicate precursors and heat-treated in reducing atmosphere. The crystal structure and physical morphology of $Li_2Mn_{0.5}Fe_{0.5}SiO_4$ was investigated by X-ray diffraction, scanning electron microscopy, and high resolution transmission electron microscopy. The $Li_2Mn_{0.5}Fe_{0.5}SiO_4$/C nanocomposite has a maximum discharge capacity of 200 mAh/g, and 63% of its discharge capacity is retained after the tenth cycles. We have realized that more than 1 mole of electrons are exchanged in $Li_2Mn_{0.5}Fe_{0.5}SiO_4$. We have observed that $Li_2Mn_{0.5}Fe_{0.5}SiO_4$ is unstable structure upon first delithiation with structural collapse. High temperature cell performance result shows high capacity of discharge capacity (244 mAh/g) but it had poor capacity retention (50%) due to the accelerated structural degradation and related reaction.

• 자원리싸이클링
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• 제21권5호
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• pp.79-87
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• 2012

리튬이온전지의 대형화와 범용화에 따라 경제성과 안정성 관점에서 정극재료의 개발은 중요한 과제로 대두되고 있다. 18650 원통형 전지의 에너지 밀도는 발매 초기인 1991년 230Wh/l에서 2005년 2배 이상의 500Wh/l로 증가하였으며, 제품 대부분의 에너지용량은 450~500 Wh/l, 150~190Wh/kg이고 안전성, 제조비 절감 및 장 수명을 중점적으로 개발하고 있다. $LiCoO_2$ 정극활물질 중의 Co가 고가이므로 Co 사용량을 줄이면서 에너지 용량을 향상시키기 위하여 $LiMn_2O_4$, $LiCo_{1/3}N_{i1/3}Mn_{1/3}O_2$, $LiNi_{0.8}Co_{0.15}Al_{0.05}O_2$, $LiFePO_4$-C복합체 (167 mA/g)등이 개발되고 있다. 전동자전거용 전지는 출력밀도 500 Wh/kg, 전동공구용 1,500Wh/kg, EV나 PHEV용으로는 4,000~5,000Wh/kg의 대용량 출력밀도를 요구하고 있으므로 배터리 소재의 성능을 향상시키려고 많은 연구가 진행되고 있다. 최근 Graphene-sulfur 복합체정극활물질 600 Ah/kg, 2차전지용 분자클러스터(molecular cluster) 320 Ah/kg 등의 새로운 정극활물질이 연구 개발되고 있으므로 실용화가 기대된다.

• 자원환경지질
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• 제50권3호
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• pp.181-193
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• 2017

철원 갈말-김화 지역의 쥐라기 복운모 화강암체 내 페그마타이트에서는 다양한 망간-철 인산염광물의 집합체가 산출되고 있으며, 후기 마그마 단계로부터 열수단계 및 지표 풍화 단계에서 다양한 광물상의 변화가 유도되었다. 철원 복운모 화강암은 낮은 대자율 값을 갖는 전형적인 S-형 화강암으로 중알루미나질~고알루미나질, 후-충돌대 환경을 나타내고 있다. 페그마타이트는 K-Ar 연대가 약 153 Ma로서 복운모 화강암의 K-Ar 연대($151{\pm}4Ma$)와 전반적으로 일치하고 있어 동일 기원의 마그마로 추정된다. 한편 갈말-김화 페그마타이트는 광물조성에 의한 분류기준에 의하면 백운모-희유원소 종, 리튬 세부종, 녹주석 유형에 속하는 녹주석-콜롬바이트-인산염광물으로 구분되며, LCT(Li-Cs-Ta) 계열에 해당한다. 망간 인산염광물 중 트리플라이트는 주로 후기 마그마 단계에 정출되었으며, 열수 단계에서는 망간 인산염광물의 변질광물인 루코포스파이트와 잔사이트로 정출되었다. 풍화 단계에서 트리플라이트는 포스퍼시더라이트와 망간 산화물로 교대되어 산출된다.

• 한국자기학회:학술대회 개요집
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• 한국자기학회 2012년도 자성 및 자성재료 국제학술대회
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• pp.22-23
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• 2012