• 산업기술연구
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• 제42권1호
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• pp.1-5
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• 2022

Although the mileage of electric vehicles can be increased based on the excellent energy density of the LiNi_0.9Co_0.05Mn_0.05O₂, it is known that the reason for limiting its use is the low lifespan and poor surface stability due to the structural deformation of the LiNi_0.9Co_0.05Mn_0.05O₂. To improve the structural stability of LiNi_0.9Co_0.05Mn_0.05O₂, electrochemical performance is improved by La coating on the surface. La-modified LiNi_0.9Co_0.05Mn_0.05O₂ shows an initial capacity of 210.6 mAh/g, a capacity retention rate of 89.9 % after 50 cycles, and a retention rate of 52.5% at 6.0 C. These are superior performances than the pristine sample, because the structural stability of the LiNi_0.9Co_0.05Mn_0.05O₂ cathode is improved by the La coating.

• Journal of Electrochemical Science and Technology
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• 제15권1호
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• pp.161-167
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• 2024

Despite the important role of manganese (Mn) in cobalt-free, Ni-rich cathode materials, existing reports on the effects of Mn as a substitute for cobalt are not consistent. In this work, we analyzed the performance of cathodes comprised of Li(Ni_1-xMn_x)O₂ (LNMO). Both beneficial and detrimental results occurred as a result of the Mn substitution. We found that a complex interplay of effects (Li/Ni mixing driven by magnetic frustration, grain growth suppression, and retarded lithium insertion/extraction kinetics) influenced the performance and was intimately related to calcination temperature. This indicates the importance of establishing an optimal reaction temperature for the development of high-performance LNMO.

• Journal of Electrochemical Science and Technology
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• 제13권2호
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• pp.269-278
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• 2022

Utilization of high-voltage electrolyte additive(s) at a small fraction is a cost-effective strategy for a good solid electrolyte interphase (SEI) formation and performance improvement of a lithium-rich layered oxide-based high-energy lithium-ion cell by avoiding the occurrence of metal-dissolution that is one of the failure modes. To mitigate metal-dissolution, we explored fluorinated dual-additives of fluoroethylene carbonate (FEC) and di(2,2,2-trifluoroethyl)carbonate (DFDEC) for building-up of a good SEI in a 4.7 V full-cell that consists of high-capacity silicon-graphite composite (15 wt% Si/C/CF/C-graphite) anode and Li_1.13Mn_0.463Ni_0.203Co_0.203O₂ (LMNC) cathode. The full-cell including optimum fractions of dual-additives shows increased capacity to 228 mAhg^-1 at 0.2C and improved performance from the one in the base electrolyte. Surface analysis results find that the SEI stabilization of LMNC cathode induced by dual-additives leads to a suppression of soluble Mn²⁺-O formation at cathode surface, mitigating metal-dissolution event and crack formation as well as structural degradation. The SEI and structure of Si/C/CF/C-graphite anode is also stabilized by the effects of dual-additives, contributing to performance improvement. The data give insight into a basic understanding of cathode-electrolyte and anode-electrolyte interfacial processes and cathode-anode interaction that are critical factors affecting full-cell performance.

• Journal of Electrochemical Science and Technology
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• 제8권2호
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• pp.162-168
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• 2017

$LiNi_xCo_yMn_zO_2$ cathode materials have been the focus of much attention because of their high specific capacity. However, because of the poor interfacial stability between cathodes and electrolytes, the cycling performance of these materials fades rapidly, especially at high temperatures. In the present paper, we propose the use of tris(trimethylsilyl) phosphate (TMSPO), which contains phosphate and silyl functional groups, as a functional additive in electrolytes. The addition of TMSPO resulted in the formation of cathode electrolyte interphase (CEI) layers on the surfaces of the cathodes and effectively suppressed electrolyte decomposition reactions, even at high temperatures. As a result, cells cycled with TMSPO exhibited remarkable capacity, which remained after 50 cycles (82.0%), compared to cells cycled without TMSPO (64.6%).

• Journal of Electrochemical Science and Technology
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• 제10권2호
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• pp.196-205
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• 2019

Ni-rich layered oxides $Li(Ni_xCo_yMn_z)O_2$ (x + y + z = 1) have been extensively studied in recent times owing to their high capacity and low cost and can possibly replace $LiCoO_2$ in the near future. However, these layered oxides suffer from problems related to the capacity fading, thermal stability, and safety at high voltages. In this study, we use surface coating as a strategy to improve the thermal stability at higher voltages. The uniform and conformal $Al_2O_3$ coating on prefabricated electrodes using atomic layer deposition significantly prevented surface degradation over prolonged cycling. Initial capacity of 190, 199, 188 and $166mAh\;g^{-1}$ is obtained for pristine, 2, 5 and 10 cycles of ALD coated samples at 0.2C and maintains 145, 158, 151 and $130mAh\;g^{-1}$ for high current rate of 2C in room temperature. The two-cycle $Al_2O_3$ modified cathode retained 75% of its capacity after 500 cycles at 5C with 0.05% capacity decay per cycle, compared with 46.5% retention for a pristine electrode, at an elevated temperature. Despite the insulating nature of the $Al_2O_3$ coating, a thin layer is sufficient to improve the capacity retention at a high temperature. The $Al_2O_3$ coating can prevent the detrimental surface reactions at a high temperature. Thus, the morphology of the active material is well-maintained even after extensive cycling, whereas the bare electrode undergoes severe degradation.

• Journal of Electrochemical Science and Technology
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• 제14권3호
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• pp.262-271
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• 2023

For electrode stability and the electrochemical performance of the Li-ion cell, it is essential that the active ingredients and unique additives in the polymer binder be well dispersed with the solvent-based slurry. The efficient procedure used to create the slurry affects the rheological characteristics of the electrode slurry. When successively adding different steps of Nmethyl-2-pyrrolidone (NMP) solvent to the cathode composition, it is evenly disseminated. The electrochemical performance of the Li-ion cells and the electrodes made with slurry formed by single step and multiple steps of addition of NMP solvent are examined. To preform rheological properties of cathode electrode slurry on Ni-rich Lithium Nickel-Cobalt-Aluminum Oxide (LiNi_0.80Co_0.15Al_0.05) (NCA). Also, we investigate different step addition of electrode formation and mechanical strength characterization like peel strength. According to the EIS study, a multi-step electrode slurry has lower internal resistance than a single-step electrode slurry, which results in better electrical characteristics and efficiency. Further, microstructure of electrodes is obtained electrochemical performance in the 18650 cylindrical cells with targeted capacity of 1.5 Ah. The slurry of electrodes prepared by single step and multiple steps of addition of NMP solvent and its effect on the fabrication of 1.5 Ah cells. A three-step solvent addition on slurry has been found to be a lower internal resistance than a single-step electrode slurry as confirmed by the EIS analysis, yielding improved electrical properties and efficiency.

• Korean Chemical Engineering Research
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• 제57권6호
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• pp.832-840
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• 2019

양극 활물질의 전기화학적 성능을 개선하기 위하여, 농도 구배형 전구체를 사용한 boron-doped $LiNi_{0.90}Co_{0.05}Ti_{0.05}O_2$를 합성하였다. 제조된 양극 활물질의 특성은 XRD, SEM, EDS, PSA, ICP-OES 및 전기전도도 측정을 통하여 분석하였다. 초기 충 방전 용량, 사이클, 순환전압전류, 율속 특성 및 임피던스 테스트를 통해 전기화학적 성능을 조사하였다. 붕소가 0.5 mol% 도핑된 $LiNi_{0.90}Co_{0.05}Ti_{0.05}O_2$ 양극 활물질은 2.7~4.3 V (vs. $Li/Li^+$)의 전압 범위에서 0.5 C의 전류를 인가했을 때, 187 mAh/g의 용량을 보이며 50 사이클 이후 94.7%의 용량 유지율을 보였다. 상대적으로 고전압인 2.7~4.5 V (vs. $Li/Li^+$)의 전압 범위에서는 200 mAh/g의 높은 용량을 보이며 50 사이클 이후 80.5%의 용량 유지율을 나타냈다.

• Korean Chemical Engineering Research
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• 제55권6호
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• pp.861-867
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• 2017

니켈 함량이 높은 리튬이차전지용 NCA 양극소재의 용량 및 수명특성을 향상시키기 위하여 붕소와 코발트를 상업용 $Li_{1.06}Ni_{0.91}Co_{0.08}Al_{0.01}O_2$ (NCA)에 도핑하여 리튬이차전지의 양극소재로 사용하였다. 상업용 NCA 양극소재는 약 $5{\mu}m$와 $12{\mu}m$ 크기의 2차 입자들이 혼합되어 있고 붕소와 코발트 도핑후 입자크기는 조금 감소되었다. 붕소와 코발트를 도핑한 NCA-B와 NCA-Co의 초기 방전용량은 각각 214 mAh/g과 200 mAh/g으로 도핑하지 않은 NCA에 비해 높게 나타났으며, 특히 NCA-Co는 20번째의 방전용량이 157 mAh/g으로 가장 우수한 방전용량특성을 나타내었다. 이는 코발트를 도핑함으로써 c축 방향으로의 결정이 성장되어 리튬이온의 확산이 용이하기 때문이다.

• 전기화학회지
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• 제17권4호
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• pp.222-228
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• 2014

리튬 이차전지 양극소재인 Ni-rich계의 $Li[Ni_{1-x-y}Co_xMn_y]O_2$는 높은 방전용량을 갖고 있지만 Ni의 함량이 많아짐으로써, 구조적 안정성과 전기화학적 특성이 떨어지는 문제점이 있다. 이러한 문제점을 해결하기 위해 양이온 도핑에 대한 연구가 시행되고 있다. 본 연구는, 공침법을 이용하여 제조한 $Ni_{0.6}Co_{0.1}Mn_{0.3}(OH)_2$ 전구체를 사용하여 바륨(Ba)이 도핑된 $Li[Ni_{0.6-x}Ba_xCo_{0.1}Mn_{0.3}]O_2$ (x=0.01)를 합성하였고, 바륨(Ba)의 도핑에 따른 구조적 안정성 및 전기화학적 특성을 연구하였다. 구조적 특성분석을 위한 X선-회절분석 결과, 바륨(Ba) 도핑시 $I_{(006)}+I_{(102)}/I_{(101)}$(R-factor)비가 감소하는 것을 통해 층상구조의 안정성이 증가한 것을 확인하였고, 전기 화학적 특성이 개선될 것으로 예측하였다. 전기화학적 분석 결과, 바륨(Ba)을 도핑한 전극의 경우 과전압의 감소로 $Li[Ni_{0.6}Co_{0.1}Mn_{0.3}]O_2$ 전극보다 $Li[Ni_{0.6-x}Ba_xCo_{0.1}Mn_{0.3}]O_2$ (x=0.01)전극의 방전용량이 $23mAhg^{-1}$ 증가하였고, 구조적 안정성의 증가로 싸이클 특성의 개선과, 전극과 전해액 간의 전하이동 저항의 감소로 인하여 고율특성 특성이 개선된 것을 확인 하였다.

• 전기화학회지
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• 제24권4호
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• pp.120-132
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• 2021

기존 LiCoO₂의 고전압 사용의 제약에 따른 용량적 한계와 코발트 원료의 높은 가격을 해결하기 위하여 high-Nickel에 대한 개발이 활발히 진행되고 있지만 Ni 함량의 증가에 따른 구조적 안정성의 저하에 의한 전지 특성의 저하는 상용화를 지연시키는 중요한 원인이 되고 있다. 이에 Ni-rich 삼성분계 양극소재 LiNi_0.6Co_0.2Mn_0.2O₂의 고안정성을 높이고자 전구체에 균일한 이종원소 Ti를 치환을 위해서 나노크기의 TiO₂ 서스펜젼 형태 소스를 사용하여 전구체 Ni_0.6Co_0.2Mn_0.2-x(OH)₂/xTiO₂를 제조하였다. Li₂CO₃와 혼합하고, 열처리 후 양극활물질 LiNi_0.6Co_0.2Mn_0.2-xTi_xO₂ 합성하여 Ti 함량에 따른 물리적 특성을 비교하였다. Field Emission Scanning electron Microscope(FE-SEM) 및 Energy Dispersive Spectroscopy (EDS) mapping 분석을 통해 Ti 치환된 구형의 전구체와 입자 크기 측정을 통해 균일한 입자크기를 가지는 양극 활물질 제조를 확인하였고, 내부치밀도와 강도가 증가함을 확인 하고, X-ray Diffractometry (XRD) 구조 분석과 Inductively Coupled Plasma Mass Spectrometry (ICP-MS) 정량분석을 통해 Ti 치환된 양극활물질 제조 및 고온, 고전압에서 충·방전을 지속하더라도 효과적으로 용량이 유지됨을 확인하였다.