• Korean Journal of Materials Research
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• v.32 no.4
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• pp.216-222
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• 2022

The capacity of high nickel Li(Ni_xCo_yMn_1-x-y)O₂ (NCM, x ≥ 0.8) cathodes is known to rapidly decline, a serious problem that needs to be solved in a timely manner. It was reported that cathode materials with the {010} plane exposed toward the outside, i.e., a radial structure, can provide facile Li⁺ diffusion paths and stress buffer during repeated cycles. In addition, cathodes with a core-shell composition gradient are of great interest. For example, a stable surface structure can be achieved using relatively low nickel content on the surface. In this study, precursors of the high-nickel NCM were synthesized by coprecipitation in ambient atmosphere. Then, a transition metal solution for coprecipitation was replaced with a low nickel content and the coprecipitation reaction proceeded for the desired time. The electrochemical analysis of the core-shell cathode showed a capacity retention of 94 % after 100 cycles, compared to the initial discharge capacity of 184.74 mA h/g. The rate capability test also confirmed that the core-shell cathode had enhanced kinetics during charging and discharging at 1 A/g.

• Bulletin of the Korean Chemical Society
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• v.31 no.2
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• pp.355-359
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• 2010

A $Li[Co_{1/3}Ni_{1/3}Mn_{1/3}]O_2$ cathode was modified by applying a $ZrF_x$ coating. The surface-modified cathodes were characterized by XRD, SEM, EDS, TEM techniques. XRD patterns of $ZrF_x$-coated $Li[Co_{1/3}Ni_{1/3}Mn_{1/3}]O_2$ revealed that the coating did not affect the crystal structure of the parent powder. SEM and TEM images showed that $ZrF_x$ nano-particles were formed as a coating layer, and EDS data confirmed that $ZrF_x$ distributed uniformly on the surface the powder. Capacity retention of coated samples at high C rates was superior to that of pristine sample. However, as the coating concentration increases beyond the optimum concentration, the rate capability was deteriorated. Whereas, as the increase of coating concentration to 2.0 wt %, the cyclic performances of the electrodes under the severe conditions (high cut-off voltage, 4.8 V, and high measurement temperature, $55^{\circ}C$) were improved considerably.

• Journal of Electrochemical Science and Technology
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• v.14 no.3
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• pp.293-300
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• 2023

The global energy storage markets have gravitated to high-energy-density and low cost of lithium-ion batteries (LIBs) as the predominant system for energy storage such as electric vehicles (EVs). High-Ni layered oxides are considered promising next-generation cathode materials for LIBs owing to their significant advantages in terms of high energy density. However, the practical application of high-Ni cathodes remains challenging, because of their structural and surface instability. Although extensive studies have been conducted to mitigate these inherent instabilities, a two-step process involving the synthesis of the cathode and a dry/wet coating is essential. This study evaluates a one-step β-Li₂SnO₃ layer coating on the surface of LiNi_0.8Co_0.2O₂ (NC82) via the thermal segregation of Sn owing to the solubility limit with respect to the synthesis temperature. The doping, segregation, and phase transition of Sn were systematically revealed by structural analyses. Moreover, surface-engineered 5 mol% Sn-coated LiNi_0.8Co_0.2O₂ (NC82_Sn5%) exhibited superior capacity retention compared to bare NC82 owing to the stable surface coating layer. Thus, the developed one-step coating method is suitable for improving the properties of high-Ni layered oxide cathode materials for application in LIBs.

• Journal of the Korean Ceramic Society
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• v.52 no.5
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• pp.331-337
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• 2015

$LaBO_3$ (B = Cr, Mn, Fe, Co, and Ni) perovskites, the most common perovskite-type mixed ionic-electronic conductors (MIECs), are promising candidates for intermediate-temperature solid oxide fuel cell (IT-SOFC) cathodes. The catalytic activity on MIEC-based cathodes is closely related to the bulk ionic conductivity. Doping B-site cations with other metals may be one way to enhance the ionic conductivity, which would also be sensitively influenced by the chemical composition of the dopants. Here, using density functional theory (DFT) calculations, we quantitatively assess the activation energies of bulk oxide ion diffusion in $LaBO_3$ perovskites with a wide range of combinations of B-site cations by calculating the oxygen vacancy formation and migration energies. Our results show that bulk oxide ion diffusion dominantly depends on oxygen vacancy formation energy rather than on the migration energy. As a result, we suggest that the late transition metal-based perovskites have relatively low oxygen vacancy formation energies, and thereby exhibit low activation energy barriers. Our results will provide useful insight into the design of new cathode materials with better performance.

• 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.9 no.3
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• pp.195-201
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• 2018

To enhance the performance of cathodes at low temperatures, a Cu-coated cathode is prepared, and its electrochemical performance is examined by testing its use in a single cell. At $620^{\circ}C$ and a current density of $150mAcm^{-2}$, a single cell containing the Cu-coated cathode has a significantly higher voltage (0.87 V) during the initial operation than does that with an uncoated cathode (0.79 V). According to EIS analysis, the high voltage of the cell with the Cu-coated cathode is due to the dramatic decrease in the high-frequency resistance related to electrochemical reactions. From XPS analysis, it is confirmed that the Cu is initially in the form of $Cu_2O$ and is converted into CuO after 150 h of operation, without any change in the state of the Ni or Li. Therefore, the high initial cell voltage is confirmed to be due to $Cu_2O$. Because $Cu_2O$ is catalytically active toward $O_2$ adsorption and dissociation, $Cu_2O$ on a NiO cathode enhances cell performance and reduces cathode polarization. However, the cell with the Cu-coated cathode does not maintain its high voltage because $Cu_2O$ is oxidized to CuO, which demonstrates similar catalytic activity toward $O_2$ as NiO.

• 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.

• Proceedings of the KIEE Conference
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• 2003.10a
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• pp.293-296
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• 2003

We report on the fabrication and field emission of carbon nanotube field emitters for mass spectrometer. Due to its high aspect ratio and mechanical strength, we use vertically aligned multi-wall carbon nanotubes prepared by thermal chemical vapour deposition as cathodes, Electrons emitted from a CNT are to ionize some sample molecules. We have successfully attained patterned carbon nanotubes grown on two-dimensional 0.7 mm by 0.7 mm Ni square blocks on Si. The emission characteristics show that the field emission initiates at 200 V.

• Journal of Electrochemical Science and Technology
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• v.9 no.3
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• pp.176-183
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• 2018

In this study, a $Li_2ZrO_3$ coated $Li[Ni_{0.8}Co_{0.15}Al_{0.05}]O_2$ (NCA) cathode was applied to an all-solid-state cell employing a sulfide-based solid electrolyte. Sulfide-based solid electrolytes are preferable for all-solid-state cells because of their high ionic conductivity and good softness and elasticity. However, sulfides are very reactive with oxide cathodes, and this reduces the stability of the cathode/electrolyte interface of all-solid-state cells. $Li_2ZrO_3$ is expected to be a suitable coating material for the cathode because it can suppress the undesirable reactions at the cathode/sulfide electrolyte interface because of its good stability and high ionic conductivity. Cells employing $Li_2ZrO_3$ coated NCA showed superior capacity to those employing pristine NCA. Analysis by X-ray photoelectron spectroscopy and electron energy loss spectroscopy confirmed that the $Li_2ZrO_3$ coating layer suppresses the propagation of S and P into the cathode and the reaction between the cathode and the sulfide solid electrolyte. These results show that $Li_2ZrO_3$ coating is promising for reducing undesirable side reactions at the cathode/electrolyte interface of all-solid-state-cells.

• Bulletin of the Korean Chemical Society
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• v.28 no.12
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• pp.2226-2230
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• 2007

As a cathode material of lithium rechargeable batteries, charged Li[Co0.1Ni0.15Li0.2Mn0.55]O2 electrodes, which were aged thermally at 25 oC and 90 oC respectively, were characterized by means of charge/discharger, impedance spectroscopy, and X-ray diffraction. The discharge capacity diminution of the electrodes aged at 25 oC and 90 oC for 1 week was 4% and 23%, respectively. The cell aged at 25 oC was recovered on cycling. However, the capacity loss after ageing at 90 oC was not recovered in a subsequent cycling test, which demonstrates that the reaction occurring during ageing at 90 oC is irreversible. A significant impedance increase of aged electrode at 90 oC is associated with irreversible capacity loss. The structural changes including phase transformation were not detected by XRD analysis, because it could be due to out of detection limit. After ageing, impedance was slightly decreased during subsequent cycling test. It could be explained the cyclic performance of aged sample is stable. The thermal stability was not deteriorated by ageing even at the high temperature of 90 oC.