• Journal of Electrochemical Science and Technology
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• 제12권1호
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• pp.67-73
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• 2021

Nickel-rich lithium nickel-cobalt-manganese oxides (NCM) are viewed as promising cathode materials for lithium-ion batteries (LIBs); however, their poor cycling performance at high temperature is a critical hurdle preventing expansion of their applications. We propose the use of a functional electrolyte additive, triphenyl phosphate (TPPa), which can form an effective cathode-electrolyte interphase (CEI) layer on the surface of Ni-rich NCM cathode material by electrochemical reactions. Linear sweep voltammetry confirms that the TPPa additive is electrochemically oxidized at around 4.83 V (vs. Li/Li+) and it participates in the formation of a CEI layer on the surface of NCM811 cathode material. During high temperature cycling, TPPa greatly improves the cycling performance of NCM811 cathode material, as a cell cycled with TPPa-containing electrolyte exhibits a retention (133.7 mA h g-1) of 63.5%, while a cell cycled with standard electrolyte shows poor cycling retention (51.3%, 108.3 mA h g-1). Further systematic analyses on recovered NCM811 cathodes demonstrate the effectiveness of the TPPa-based CEI layer in the cell, as electrolyte decomposition is suppressed in the cell cycled with TPPa-containing electrolyte. This confirms that TPPa is effective at increasing the surface stability of NCM811 cathode material because the TPPa-initiated POx-based CEI layer prevents electrolyte decomposition in the cell even at high temperatures.

• Journal of Electrochemical Science and Technology
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• 제11권4호
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• pp.361-367
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• 2020

Recently, layered nickel-rich cathode materials (NCM) have attracted considerable attention as advanced alternative cathode materials for use in lithium-ion batteries (LIBs). However, their inferior surface stability that gives rise to rapid fading of cycling performance is a significant drawback. This paper proposes a simple and convenient coating method that improves the surface stability of NCM using sulfate-based solvents that create artificial cathode-electrolyte interphases (CEI) on the NCM surface. SO_x-based artificial CEI layer is successfully coated on the surface of the NCM through a wet-coating process that uses dimethyl sulfone (DMS) and dimethyl sulfoxide (DMSO) as liquid precursors. It is found that the SO_x-based artificial CEI layer is well developed on the surface of NCM with a thickness of a few nanometers, and it does not degrade the layered structure of NCM. In cycling performance tests, cells with DMS- or DMSO-modified NCM811 cathodes exhibited improved specific capacity retention at room temperature as well as at high temperature (DMS-NCM811: 99.4%, DMSO-NCM811: 88.6%, and NCM811: 78.4%), as the SO_x-based artificial CEI layer effectively suppresses undesired surface reactions such as electrolyte decomposition.

• 전기화학회지
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• 제20권4호
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• pp.67-74
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• 2017

층상구조의 Ni-rich NCM계 양극활물질 $Li[Ni_xCo_{(1-x)/2}Mn_{(1-x)/2}]O_2$ ($x{\geq}0.6$)은 $LiCoO_2$ 대비 높은 에너지밀도와 가격 경쟁력의 장점을 가진다. Ni 함량에 비례하여 가역 방전용량이 증가하는 장점이 있는 반면, 합성 중에 발생하는 양이온 혼합으로 인해 안정적인 전기화학성능을 구현하기 어려운 문제가 있다. 본 연구에서는 합성 분위기, 리튬 원료물질, 합성 시간, 합성 온도, Li/M (M=transition metal) 비율 등의 다양한 합성조건을 변수로 하여 Ni 함량 증가에 따라 최적의 층상구조 Ni-rich NCM을 각각 합성하고 이에 대한 전기화학성능을 보고하였다. $Li[Ni_{0.6}Co_{0.2}Mn_{0.2}]O_2$ (NCM6)을 기준으로 Ni 함량이 증가한 $Li[Ni_{0.7}Co_{0.15}Mn_{0.15}]O_2$ (NCM7)와 $Li[Ni_{0.8}Co_{0.1}Mn_{0.1}]O_2$ (NCM8)의 합성시 전이금속 중 Ni의 비율이 증가함에 따라 양이온 혼합이 증가하는 것이 관찰되었고, 이는 전기화학 성능에 부정적인 영향을 끼치는 것으로 확인되었다. Ni 비율별 NCM에 대한 연구결과 비율 내확인한 최적의 조건에서 NCM6은 $180mAh{\cdot}g^{-1}$, 96.2% (50회), NCM7은 $187mAh{\cdot}g^{-1}$, 94.7% (50회), NCM8은 $201mAh{\cdot}g^{-1}$, 92.7% (50회)의 초기 방전용량 및 수명평가 후 용량유지율 값을 각각 구현하였다.

• Journal of Electrochemical Science and Technology
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• 제14권3호
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• pp.272-282
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• 2023

Ni-rich layered oxides cathode has recently gained attention as an advanced cathode material due to their applicable energy density. However, as the Ni component in the layered site is increased, the high reactivity of Ni⁴⁺ results in parasitic reaction associated with decomposing electrolyte, which leads to a rapid decreasing the lifespan of the cell. The electrolyte additive triallyl borate (TAB) improves interfacial stability, leading to a stable cathode-electrolyte interphase (CEI) layer on the LNCM83 cathode. A multi-functionalized TAB additive can produce a uniformly distributed CEI layer via electrochemical oxidation, which implies an increase in long-term cycling performance. After 100 cycles at elevated temperature, the cell tested by 0.75 TAB retained 88.3% of its retention ratio, whereas the cell performed by TAB-free electrolyte retained 64.1% of its retention. Once the TAB additive formed CEI layers on the LNCM83 cathode, it inhibited the decomposition of carbonate-based solvents species in addition to the dissolution of transition metal components from the cathode. The addition of TAB to LNCM83 cathode material is believed to be a promising way to increase the electrochemical performance.

• 한국재료학회지
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• 제32권4호
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• pp.210-215
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• 2022

Extensive research is being carried out on Ni-rich Li(Ni_xCo_yMn_1-x-y)O₂ (NCM) due to the growing demand for electric vehicles and reduced cost. In particular, Ni-rich Li(Ni_xCo_yMn_1-x-y-zAl_z)O₂ (NCMA) is attracting great attention as a promising candidate for the rapid development of Co-free but electrochemically more stable cathodes. Al, an inactive element in the structure, helps to improve structural stability and is also used as a doping element to improve cycle capability in Ni-rich NCM. In this study, NCMA was successfully synthesized with the desired composition by direct coprecipitation. Boron and tin were also used as dopants to improve the battery performance. Macro- and microstructures in the cathodes were examined by microscopy and X-ray diffraction. While Sn was not successfully doped into NCMA, boron could be doped into NCMA, leading to changes in its physicochemical properties. NCMA doped with boron revealed substantially improved electrochemical properties in terms of capacity retention and rate capability compared to the undoped NCMA.

• Journal of Electrochemical Science and Technology
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• 제15권1호
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• pp.168-177
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• 2024

Ni-rich cathode is one of the promising candidates for high-energy lithium-ion battery applications. Due to its specific capacity, easy industrialization, and good circulation ability, Ni-rich cathode materials have been widely used for lithium-ion batteries. However, due to the limitation of the co-precipitation method, including sewage pollution, and the instability of the long production cycles, developing a new efficient and environmentally friendly synthetic approach is critical. In this study, the Ni_0.91Co_0.06Mn_0.03CO₃ precursor powder was successfully synthesized by an efficient spray-drying method using carbonate compounds as a raw material. This Ni_0.91Co_0.06Mn_0.03CO₃ precursor was calcined by mixing with LiOH·H₂O (5 wt% excess) at 480℃ for 5 hours and then sintered at two different temperatures (780℃/800℃) for 15 hours under an oxygen atmosphere to complete the cathode active material preparation, which is a key component of lithium-ion batteries. As a result, LiNi_0.91Co_0.06Mn_0.03O₂ cathode active material powders were obtained successfully via a simple sintering process on the Ni_0.91Co_0.06Mn_0.03CO₃ precursor powder. Furthermore, the obtained LiNi_0.91Co_0.06Mn_0.03O₂ cathode active material powders were characterized. Overall, the material sintered at 780℃ shows superior electrochemical performance by delivering a discharge capacity of 190.76 mAh/g at 1^st cycle (0.1 C) and excellent capacity retention of 66.80% even after 50 cycles.

• Journal of Electrochemical Science and Technology
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• 제14권4호
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• pp.320-325
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• 2023

In Li-ion batteries, a thick electrode is advantageous for lowering the inactive current collector portion and obtaining a high energy density. One of the critical failure mechanisms of thick electrodes is inhomogeneous lithiation and delithiation owing to the axial location of the electrode. In this study, it was confirmed that the top layer of the composite electrode contributes more to the charging step owing to the high ionic transport from the electrolyte. A high-loading multilayered electrode containing LiFePO₄ (LFP) and LiNi_0.8Co_0.1Mn_0.1O₂ (NCM811) was developed to overcome the inhomogeneous electrochemical reactions in the electrode. The electrode laminated with LFP on the top and NCM811 on the bottom showed superior cyclability compared to the electrode having the reverse stacking order or thoroughly mixed. This improvement is attributed to the structural and interfacial stability of LFP on top of the thick electrode in an electrochemically harsh environment.

• 자원리싸이클링
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• 제24권6호
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• pp.9-16
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• 2015

폐리튬이차전지 양극재 재활용기술에 있어 침출과정을 통해 회수된 유가금속을 다시 원하는 조성의 전구체로 재합성하는 공침공정은 필수적이다. 본 연구에서는 고용량 특성의 Ni-rich 조성인 $LiNi_{0.6}Co_{0.2}Mn_{0.2}O_2$ (NCM 622) 양극재의 전구체 재합성 시 암모니아가 불순물로서 미치는 영향을 확인하는 공침실험을 수행하였다. SEM 및 EDS 분석결과 양극재 전구체 최적 합성조건(금속염 용액 농도 2 M 기준 암모니아수 농도 1 M)에서 암모니아 농도가 증가할수록 원하는 조성의 전구체가 제조되지 않음을 확인하였다. Ni의 설계함량인 60 mol%를 기준하여 암모니아수 농도 1 M ~ 4 M 조건에서 각각 100%, 98%, 95%, 87%에 해당하는 공침효율을 보여주었다. 또한 제조된 전구체 입자들의 구형화도, 균일도 및 크기분포특성 등의 형상학적 특징을 확인하였다.

• 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.

• 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.