• 전기화학회지
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• 제16권2호
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• pp.59-64
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• 2013

$Na_2CO_3$와 [M($SO_4$)(M = Ni, Co, Mn)]을 사용함으로써, Carbonate 공침 합성법에 의해 $[Ni_{0.6}Co_{0.2}Mn_{0.2}]CO_3$ 전구체를 합성하였다. 합성된 전구체는 공기분위기에서 $Li_2CO_3$와 혼합하여 각각, 750, 850 그리고 $950^{\circ}C$에서 소성되었고, 이로 인한 $Li[Ni_{0.6}Co_{0.2}Mn_{0.2}]O_2$ 양극활 물질의 소성온도가 미치는 영향을 조사하였다. $Li[Ni_{0.6}Co_{0.2}Mn_{0.2}]O_2$의 구조와 특성은 X-선 회절 분석(XRD), 시차주사현미경(SEM) 그리고 전기화학적 측정으로 분석되었는데, X-선 회절 결과 $Li[Ni_{0.6}Co_{0.2}Mn_{0.2}]O_2$는 소성온도가 증가함에 따라서 $I_{(003)}/I_{(104)}$는 증가하고 R-factor 는 감소하였으며, 시차주사현미경 결과에서는 1차 입자의 크기가 증가하는 경향을 보였다. 특히, $950^{\circ}C$에서 24시간 동안 소성된 $Li[Ni_{0.6}Co_{0.2}Mn_{0.2}]O_2$는 가역 용량이 $165.3mAhg^{-1}$[cut-off voltage 2.5~4.3 V, 0.1 C($17mAhg^{-1}$)] 그리고 50번째 충 방전 사이클 [cut-off voltage 2.5~4.3 V, 1 C($170mAhg^{-1}$)]까지 95.4%의 우수한 용량 보존율을 가지면서 가장 우수한 전기화학적 특성을 보여주었다.

• 한국분말재료학회지
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• 제23권4호
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• pp.287-296
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• 2016

$Ni_{1/3}Co_{1/3}Mn_{1/3}(OH)_2$ powders have been synthesized in a continuously stirred tank reactor via a co-precipitation reaction between aqueous metal sulfates and NaOH using $NH_4OH$ as a chelating agent. The co-precipitation temperature is varied in the range of $30-80^{\circ}C$. Calcination of the prepared precursors with $Li_2CO_3$ for 8 h at $1000^{\circ}C$ in air results in Li $Ni_{1/3}Co_{1/3}Mn_{1/3}O_2$ powders. Two kinds of obtained powders have been characterized by X-ray diffraction (XRD), scanning electron microscopy, particle size analyzer, and tap density measurements. The co-precipitation temperature does not differentiate the XRD patterns of precursors as well as their final powders. Precursor powders are spherical and dense, consisting of numerous acicular or flaky primary particles. The precursors obtained at 70 and $80^{\circ}C$ possess bigger primary particles having more irregular shapes than those at lower temperatures. This is related to the lower tap density measured for the former. The final powders show a similar tendency in terms of primary particle shape and tap density. Electrochemical characterization shows that the initial charge/discharge capacities and cycle life of final powders from the precursors obtained at 70 and $80^{\circ}C$ are inferior to those at $50^{\circ}C$. It is concluded that the optimum co-precipitation temperature is around $50^{\circ}C$.

• 공업화학
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• 제31권1호
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• pp.97-102
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• 2020

최근 리튬이차전지 양극 소재의 다양한 열화 메커니즘들이 밝혀지면서 이것을 제어하여 새로운 전기화학적 특성을 구현하고 기존 소재의 한계점을 극복하고자 하는 연구결과들이 많이 보고되고 있다. 특히, 리튬과잉산화물은 250 mA h g^-1 이상의 고 용량 차세대 리튬이차전지 양극 물질로 주목받고 있으나, 충방전 과정 중에 소재 특유의 원자 구조 열화로 인해 활용이 제한되고 있다. 본 연구는 0.4Li₂MnO₃_0.6LiNi_1/3Co_1/3Mn_1/3O₂ 리튬과잉소재의 충방전 과정 중에서 겪는 원자 구조 변화 과정을 분석하여 소재의 열화 과정을 밝히고 이를 개선하기 위한 연구 방향을 제시하고자 한다. 이를 위해, 원자 단위의 분해능을 갖는 전자투과현미경을 활용하여 충방전 중 원자 구조의 변화 과정을 분석하고 이러한 구조 변화가 소재의 전기화학적 특성에 어떠한 영향을 미치는지 밝히고자 하였다. 충전 과정 중에 발생한 다량의 리튬 빈자리로 인해 구조 불안정성이 일어났고, 이로 인해 전이 금속이 리튬 빈 자리로 이동하면서 구조 열화가 확인되었다. 결과적으로 이러한 구조 변이는 리튬과잉소재의 가장 큰 문제점인 방전 전압 강하 특성을 야기한다는 것을 알아내었다.

• 한국분말재료학회지
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• 제26권1호
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• pp.49-57
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• 2019

Layered $LiNi_{0.83}Co_{0.11}Mn_{0.06}O_2$ cathode materials single- and dual-doped by the rare-earth elements Ce and Nd are successfully fabricated by using a coprecipitation-assisted solid-phase method. For comparison purposes, non-doping pristine $LiNi_{0.83}Co_{0.11}Mn_{0.06}O_2$ cathode material is also prepared using the same method. The crystal structure, morphology, and electrochemical performances are characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectrometer (EDS) mapping, and electrochemical techniques. The XRD data demonstrates that all prepared samples maintain a typical ${\alpha}-NaFeO_2$-layered structure with the R-3m space group, and that the doped samples with Ce and/or Nd have lower cation mixing than that of pristine samples without doping. The results of SEM and EDS show that doped elements are uniformly distributed in all samples. The electrochemical performances of all doped samples are better than those of pristine samples without doping. In addition, the Ce/Nd dual-doped cathode material shows the best cycling performance and the least capacity loss. At a 10 C-rate, the electrodes of Ce/Nd dual-doped cathode material exhibit good capacity retention of 72.7, 58.5, and 45.2% after 100, 200, and 300 cycles, respectively, compared to those of pristine samples without doping (24.4, 11.1, and 8.0%).

• 한국전기전자재료학회논문지
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• 제35권2호
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• pp.194-198
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• 2022

All-solid-state thin-film battery can realize the integration of electronic circuits into small devices. However, a high voltage cathode material is required to compensate for the low energy density. Therefore, it is necessary to study all-solid-state thin-film battery based on the high voltage cathode material LNMO. Nevertheless, the electrochemical properties deteriorate due to the problem of the interface between LiNi_0.5Mn_1.5O₄ (LNMO) and the solid electrolyte LiPON. In this study, to solve this problem, amorphous V₂O₅ was deposited as an interlayer between LNMO and LiPON. We confirmed the possibility of improving cycle performance of LNMO based thin-film battery. We expect that the results of this study can extend the battery lifespan of small devices using LNMO based all-solid-state thin-film battery.

• 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.

• Journal of Electrochemical Science and Technology
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• 제3권2호
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• pp.72-79
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• 2012

$Li_2MnSiO_4$ was synthesized using the solid-state method under an Ar atmosphere at three different calcination temperatures (900, 950, and $1000^{\circ}C$). The optimization of the carbon coating was also carried out using various molar concentrations of adipic acid as the carbon source. The XRD pattern confirmed that the resulting $Li_2MnSiO_4$ particles exhibited an orthorhombic structure with a $Pmn2_1$ space group. Cyclic voltammetry was utilized to investigate the capacitive behavior of $Li_2MnSiO_4$ along with activated carbon (AC) in a hybrid supercapacitor with a two-electrode cell configuration. The $Li_2MnSiO_4$/AC cell exhibited a high discharge capacitance and energy density of $43.2Fg^{-1}$ and $54Whkg^{-1}$, respectively, at $1.0mAcm^{-2}$. The $Li_2MnSiO_4$/AC hybrid supercapacitor exhibited an excellent cycling stability over 1000 measured cycles with coulombic efficiency over > 99 %. Electrochemical impedance spectroscopy was conducted to corroborate the results that were obtained and described.

• Bulletin of the Korean Chemical Society
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• 제31권2호
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• pp.309-314
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• 2010

The surface modified $LiMn_2O_4$ materials with Li-Fe composites were prepared by a sol-gel method to improve the electrochemical performance of $LiMn_2O_4$ and were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS), and transmission electron microscopy (TEM)-EDS. XRD results indicate that all the samples (modified and pristine samples) have cubic spinel structures, and XRD, XPS, and TEM-EDS data reveal the formation of $Li(Li_xFe_xMn_{2-2x})O_4$ solid solution on the surface of particles. For the electrochemical properties, the modified material demonstrated dramatically enhanced reversibility and stability even at elevated temperature. These improvements are attributed to the formation of the solid solution, and thus-formed solid solution phase on the surface of $LiMn_2O_4$ particle reduces the dissolution of Mn ion and suppresses the Jahn-Teller effect.

• Korean Chemical Engineering Research
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• 제57권4호
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• pp.547-552
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• 2019

Electrochemical properties of $LiMn_{0.8}Fe_{0.2}PO_4$ cathode were investigated with gel polymer electrolyte (GPE). To access fast and efficient transport of ions and electrons during the charge/discharge process, a pure and well-crystallized $LiMn_{0.8}Fe_{0.2}PO_4$ cathode material was directly synthesized via spray-pyrolysis method. For high operation voltage, polyacrylonitrile (PAN)-based gel polymer electrolyte was then prepared by electrospinning process. The gel polymer electrolyte showed high ionic conductivity of $2.9{\times}10^{-3}S\;cm^{-1}$ at $25^{\circ}C$ and good electrochemical stability. $Li/GEP/LiMn_{0.8}Fe_{0.2}PO_4$ cell delivered a discharge capacity of $159mAh\;g^{-1}$ at 0.1 C rate that was close to the theoretical value ($170mAh\;g^{-1}$). The cell allows stable cycle performance (99.3% capacity retention) with discharge capacity of $133.5mAh\;g^{-1}$ for over 300 cycles at 1 C rate and exhibits high rate-capability. PAN-based gel polymer is a suitable electrolyte for application in $LiMn_{0.8}Fe_{0.2}PO_4/Li$ batteries with perspective in high energy density and safety.

• 전기화학회지
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• 제10권1호
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• pp.48-51
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• 2007

리튬이온전지의 스피넬형 양극활물질 $LiMn_2O_4$의 입자 크기 및 비표면적의 전기화학 특성상의 영향을 고찰하기 위하여 스피넬 물질을 공침법과 고상법에 의해 합성되었다. X-선 회절분석을 통하여 합성된 두 물질 모두 Fd3m space group을 갖는 스피넬 구조가 형성된 것을 확인하였다. 공침법을 사용하여 얻은 물질은 상대적으로 높은 충진 밀도와 균일한 입도 분포를 갖는 구형의 분말이었다. 그러나 고상법을 사용하여 얻은 활물질은 비교적 입자 크기가 작고 넓은 입도분포를 나타내었다. 측정된 두 물질의 비표면적(BET)은 각각 $0.8m^2g^{-1}$(공침법)과 $3.6m^2g^{-1}$(고상법)로 큰 차이를 보였다. 두 물질의 전기화학적 특성을 평가하기 위하여 코인타입(CR2032)전지를 제작하여 고온($55^{\circ}C$)에서 충 방전테스트를 하였다. 공침법으로 합성된 물질의 고온에서 방전용량 유지율은 50사이클 이후 고상법으로 합성된 물질의 68.3% 보다 14% 향상된 82.3%로 향상된 방전용량 유지율을 보였다.