• Journal of Electrochemical Science and Technology
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• v.12 no.1
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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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• v.11 no.4
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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.

• Journal of the Korean Electrochemical Society
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• v.20 no.4
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• pp.67-74
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• 2017

Layered Ni-rich NCM cathode materials $Li[Ni_xCo_{(1-x)/2}Mn_{(1-x)/2}]O_2$ ($x{\geq}0.6$) have advantages of high energy density and cost competitive over $LiCoO_2$. The discharge capacity of NCM increases proportionally to the Ni contents. However, there is a problem that it is difficult to realize the stable electrochemical performance due to cation mixing. In this study, synthesis conditions for the layered Ni-rich NCMs are investigated to achieve deliver the ones having good electrochemical performances. Synthesis parameters are atmosphere, lithium source, synthesis time, synthesis temperature and Li/M (M=transition metal) ratio. The degree of cation mixing gets worse as the Ni content is increased from $Li[Ni_{0.6}Co_{0.2}Mn_{0.2}]O_2$ (NCM6) to $Li[Ni_{0.8}Co_{0.1}Mn_{0.1}]O_2$ (NCM8). It is confirmed that higher level of cation mixing affects negatively on the electrochemical performance of NCMs. Optimum synthesis conditions are explored for NCMx (x=6, 7, 8) in order to reduce the cation mixing. Under optimized conditions for three representative NCMx, a high initial discharge capacity and a good cycle life are obtained for $180mAh{\cdot}g^{-1}$, 96.2% (50 cycle) in NCM6, $187mAh{\cdot}g^{-1}$, 94.7% (50 cycle) in NCM7, and $201mAh{\cdot}g^{-1}$, 92.7% (50 cycle) in NCM8, respectively.

• Journal of Electrochemical Science and Technology
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• v.14 no.3
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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.

• Korean Journal of Materials Research
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• v.32 no.4
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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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• v.15 no.1
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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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• v.14 no.4
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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.

• Resources Recycling
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• v.24 no.6
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• pp.9-16
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• 2015

In a recycling scheme of spent lithium ion batteries, a co-precipitation process for the re-synthesis of precursor is essential after the leaching of lithium ion battery scraps. In this study, the effect of ammonia as impurity during the co-precipitation process was investigated in order to re-synthesize a precursor of Ni-rich cathode active material $LiNi_{0.6}Co_{0.2}Mn_{0.2}O_2$ (NCM 622). As ammonia concentration increases from 1 M (the optimum condition for synthesis of the precursors based on 2 M of metal salt solution) to 4 M, the composition of obtained precursors deviates from the designed composition, most notably for Ni. The Ni co-precipitation efficiency gradually decreases from 100% to 87% when the concentration of ammonia solution increases from 1 M to 4 M. Meanwhile, the morphological properties of the obtained precursors such as sphericity, homogeneity and size distribution of particles were also investigated.

• Journal of Electrochemical Science and Technology
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• v.10 no.2
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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 the Korean Electrochemical Society
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• v.24 no.4
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• pp.120-132
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• 2021

Although the development of high-Nickel is being actively carried out to solve the capacity limitation and the high price of raw cobalt due to the limitation of high voltage use of the existing LiCoO₂, the deterioration of the battery characteristics due to the decrease in structural stability and increase of the Ni content. It is an important cause of delaying commercialization. Therefore, in order to increase the high stability of the Ni-rich ternary cathod material LiNi_0.6Co_0.2Mn_0.2O₂, precursor Ni_0.6Co_0.2Mn_0.2-x(OH)₂/xTiO₂ was prepared using a nanosized TiO₂ suspension type source for uniform Ti substitution in the precursor. It was mixed with Li₂CO₃, and after heating, the cathode active material LiNi_0.6Co_0.2Mn_0.2-xTi_xO₂ was synthesized, and the physical properties according to the Ti content were compared. Through FE-SEM and EDS mapping analysis, it was confirmed that a positive electrode active material having a uniform particle size was prepared through Ti-substituted spherical precursor and Particle Size Analyzer and internal density and strength were increased, XRD structure analysis and ICP-MS quantitative analysis confirmed that the capacity was effectively maintained even when the Ti-substituted positive electrode active material was manufactured and charging and discharging were continued at high temperature and high voltage.