• Corrosion Science and Technology
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• v.22 no.1
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• pp.36-43
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• 2023

Single-crystal Ni-rich NCM is a material that has drawn attention in the field of lithium-ion batteries due to its high energy density and long cycle life. In this study, we investigated the properties of single-crystal NCM 811 and its potential for use in lithium-ion batteries. High-quality single crystals of NCM 811 were successfully synthesized by crystal growth via a flux method. The single-crystal nature of the samples was confirmed through detailed characterization techniques, such as scanning electron microscopy and x-ray diffraction with Rietveld refinement. The crystal structure and electrochemical performances of the single-crystal NCM 811 were analyzed and compared to its poly-crystal counterpart. The results indicated that single-crystal NCM 811 had electrochemical performance and thermal stability superior to poly-crystalline NCM 811, making it a suitable candidate for high-performance batteries. The findings of this study contribute to a better understanding of the characteristics and potential of single-crystal NCM 811 for lithium-ion batteries.

• 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 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 the Korean Crystal Growth and Crystal Technology
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• v.32 no.2
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• pp.61-67
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• 2022

A metal salt solution was prepared from valuable metals (Ni, Co, Mn) recovered from a scrap of waste lithium secondary batteries, and an NCM811 precursor was synthesized from the solution. The effect on precursor formation according to reaction time was confirmed by SEM, PSA, and ICP analysis. Based on the analysis results, the electrochemical properties of the synthesized NCM811 precursor and the commercial NCM811 precursor were investigated. The Galvano charge-discharge cycle, rate performance, and Cycle performance were compared, and as a result, there was no significant difference from commercial precursors.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.34 no.3
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• pp.103-107
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• 2024

In this study, nickel, a pure metal material, was proposed as a saggar for synthesizing NCM [Li(Ni_xCo_yMn_z)O₂] cathode active material. Nickel is known as a metal that is resistant to oxidation and has a high melting point. Nickel is one of the main components of NCM cathode material and was expected to be free from problems with contamination from saggar during cathode material synthesis. We sought to confirm the possibility of nickel as a saggar for synthesizing NCM cathode active materials. When a Ni metal crucible and Ni_0.8Co_0.1Mn_0.1(OH)₂ (NCM 811) precursor material were reacted at 900℃ for a long time, the change in the reaction layer on the surface of the crucible over time was analyzed. The nickel crucible reaction layer formed during heat treatment at 900℃ was nickel oxide, and is thought to have been created by simultaneous oxygen diffusion from the cathode precursor oxide and reaction with oxygen in the atmosphere. The change in thickness of the oxide layer appears to slow down after 480 hours, which suggests that the rate of oxygen diffusion from the precursor is reduced. It remained combined without falling out of the crucible until 480 hours. However, it was confirmed that the oxide layer falls off after 720 hours, so it is thought that it can be used as saggar for NCM synthesis only for a certain period of time.

• Journal of the Korean Electrochemical Society
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• v.24 no.4
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• pp.100-105
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• 2021

Recently, all-solid-state batteries have attracted much attention to improve safety of rechargeable lithium batteries, but the solid-state batteries of conductive ceramics or solid polymer electrolytes show poor electrochemical properties because of several problems such as high interfacial resistance and undesired reactions. To solve the problems of the reported all-solid-state batteries, a hybrid solid electrolyte is suggested, in this study, NASICON-type nanoparticle Li_1.5Al_0.5Ti_1.5P₃O₁₂ (LATP) conductive ceramic, PVdF-HFP, and a carbonate-based liquid electrolyte were composited to prepare a quasi-solid electrolyte. The hybrid solid electrolyte has a high voltage stability of 5.6 V and shows an suppress effect of lithium dendrite growth in the stripping-plating test. The LiNi_0.83Co_0.11Mn_0.06O₂ (NCM811)-based battery with the hybrid solid electrolyte exhibits a high discharge capacity of 241.5 mAh/g at a high charge-cut-off voltage of 4.8V and stable electrochemical reaction. The NCM811-based battery also shows 139.4 mAh/g discharge capacity without short circuit or explosion at 90℃. Therefore, the LATP-based hybrid solid electrolyte can be an effective solution to improve the safety and electrochemical properties of rechargeable lithium batteries.

• 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.

• 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.