• KEPCO Journal on Electric Power and Energy
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• v.6 no.4
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• pp.461-466
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• 2020

There are many application fields of electrical energy storage such as load shifting, integration with renewables, frequency or voltage supports, and so on. Especially, the frequency regulation is needed to stabilize the electric power system, and there have to be more than 1 GW as power reserve in Korea. Ni-rich layered oxide cathode materials have been investigated as a cathode material for Li-ion batteries because of their higher discharge capacity and lower cost than lithium cobalt oxide. Nonetheless, most of them have been investigated using small coin cells, and therefore, there is a limit to understand the deterioration mode of Ni-rich layered oxides in commercial high energy Li-ion batteries. In this paper, the pouch-type 20 Ah-scale Li-ion full cells are fabricated using Ni-rich layered oxides as a cathode and graphite as an anode. Above all, two test conditions for the application of frequency regulation were established in order to examine the performances of cells. Then, the electrochemical performances of two types of Ni-rich layered oxides are compared, and the long-term performance and degradation mode of the cell using cathode material with high nickel contents among them were investigated in the frequency regulation conditions.

• Journal of Industrial and Engineering Chemistry
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• v.68
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• pp.124-128
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• 2018

Titanium doping is employed to enhance the structural strength of a high-Ni layered cathode material in lithium ion batteries during high temperature cycling. After Ti-doping, the external morphology remains similar, but the lattice parameters of the layered structure are slightly shifted toward larger values. With application of the prepared materials as cathodes in lithium-ion batteries, the initial capacities are similar but the cycling performance at $25^{\circ}C$ is enhanced by Ti-doping. During high temperature cycling at $60^{\circ}C$, furthermore, highly improved capacity retention is achieved with the Ti-doped material (95% of initial capacity at 50th cycles), while cycle fading is accelerated with the bare electrode. This enhancement is attributed to better retention of the compressive strength of the particles and retarded crack formation within the particles. In addition, impedance increase is reduced in the Ti-doped electrode, which is attributed to an improvement in the structural strength of the high-Ni cathode material with Ti-doping.

• Journal of Electrochemical Science and Technology
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• v.12 no.2
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• pp.272-278
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• 2021

In this study, high nickel layered LiNi_0.8Co_0.1Mn_0.1O₂ cathode materials for lithium-ion batteries were modified by yttrium doping and poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) coating. The effects of yttrium doping and PEDOT:PSS coating on the structural and electrochemical properties of the LiNi_0.8Co_0.1Mn_0.1O₂ cathode material were investigated and compared. The substitution of nickel with an electrochemically inert yttrium was confirmed to be successful in stabilizing the layered structure framework. Moreover, coating the surfaces of the LiNi_0.8Co_0.1Mn_0.1O₂ particles with a conductive polymer, PEDOT:PSS, improved the capacity retention, thermal stability, and impedance of the cathode material by increasing its ionic and electric conductivities.

• Korean Journal of Materials Research
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• v.28 no.5
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• pp.273-278
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• 2018

Lithium-ion batteries have been considered the most important devices to power mobile or small-sized devices due to their high energy density. $LixCoO_2$ has been studied as a cathode material for the Li-ion battery. However, the limitation of its capacity impedes the development of high capacity cathode materials with Ni, Mn, etc. in them. The substitution of Mn and Ni for Co leads to the formation of solid solution phase $LiNi_xMn_yCo_{1-x-y}O_2$ (NMC, both x and y < 1), which shows better battery performance than unsubstituted $LiCoO_2$. However, despite a high discharge capacity in the Ni-rich compound (Ni > 0.8 in the metal site), poor cycle retention capability still remains to be overcome. In this study, aiming to improve the stability of the physical and chemical bonding, we investigate the stabilization effect of Ca in the Ni-rich layered compound $Li(Ni_{0.83}Co_{0.12}Mn_{0.05})O_2$, and then Ca is added to the modified secondary particles to lower the degree of cationic mixing of the final particles. For the optimization of the final grains added with Ca, the Ca content (x = 0, 2.5, 5.0, 10.0 at.%) versus Li is analyzed.

• 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.

• 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 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.

• Korean Journal of Materials Research
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• v.30 no.11
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• pp.636-640
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• 2020

Due to the serious air pollution problem, interest in eco-friendly vehicles is increasing. Solving the problem of pollution will necessitate the securing of high energy storage technology for batteries, the driving force of eco-friendly vehicles. The reason for the continuing interest in the transition metal oxide LiMO₂ as a cathode material with a layered structure is that lithium ions reveal high mobility in two-dimensional space. Therefore, it is important to investigate the effective intercalation and deintercalation pathways of Li⁺, which affect battery capacity, to understand the internal structure of the cathode particle and its effect on the electrochemical performance. In this study, for the cathode material, high nickel Ni_0.8Co_0.1Mn_0.1(OH)₂ precursor is synthesized by controlling the ammonia concentration. Thereafter, the shape of the primary particles of the precursor is investigated through SEM analysis; X-ray diffraction analysis is also performed. The electrochemical properties of LiNi_0.8Co_0.1Mn_0.1O₂ are evaluated after heat treatment.

• Proceedings of the Materials Research Society of Korea Conference
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• 2010.05a
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• pp.37.2-37.2
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• 2010

Recently $Li_{1.2}Ni_{0.2}Mn_{0.6}O_2$ has been consistently examined and investigated by scientists because of its high lithium storage capacity, which exceeds beyond the conventional theoretical capacity based on conventional chemical concepts. Consequently, $Li_{1.2}Ni_{0.2}Mn_{0.6}O_2$ is considered as one of the most promising cathode candidates for next generation in Li rechargeable batteries. Yet the mechanism and the origin of the overcapacity have not been clarified. Previously, many authors have demonstrated simultaneous oxygen evolution during the first delithiation. However, it may only explain the high capacity of the first charge process, and not of the subsequent cycles. In this work, we report a clarified interpretation of the structural evolution of $Li_{1.2}Ni_{0.2}Mn_{0.6}O_2$, which is the key element in understanding its anomalously high capacity. We identify how the structural evolution of $Li_{1.2}Ni_{0.2}Mn_{0.6}O_2$ occurs upon the electrochemical cycling through careful study of electrochemical profiles, ex-situ X-ray diffraction (XRD), HR-TEM, Raman spectroscopy, and first principles calculation. Moreover, we successfully separated the structural change at subsequent cycles (mainly cation rearrangement) from the first charge process (mainly oxygen evolution with Li extraction) by intentionally synthesizing sample with large particle size. Consequently, the intermediate states of structural evolution could be well resolved. All observations made through various tools lead to the result that spinel-like cation arrangement and lithium environment are created and embedded in layered framework during repeated electrochemical cycling.

• Journal of the Korean Electrochemical Society
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• v.16 no.3
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• pp.169-176
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• 2013

Solid state lithium oxide compounds of layered structure, which has high stability of structure, are mainly used as the cathode materials in lithium-ion batteries (LIBs). Recently, the investigation of Solid Electrolyte Interphase (SEI) between active materials and electrolyte has been focusing to improve the performance of lithium-ion batteries. For the investigation of the SEI, the study of surface properties of cathode materials and anode materials is also required in advance. $LiNiO_2$ and $LiCoO_2$ are very similar layered structure of cathode active materials and representative solid state lithium oxide compounds in LIBs. Various experimental and theoretical studies have been doing for $LiCoO_2$. The theoretical investigation of $LiNiO_2$ is not sufficient, however, even if experimental studies of $LiNiO_2$ are enough. In this study, the surface energies of nine facets of $LiNiO_2$ crystal facets were calculated by Density Functional Theory. In XRD data of $LiNiO_2$, (003), (104), (101), et al. facets are main surfaces in order. However, the results of calculation are different with XRD data. Thus, both (104) and (101) facets, which are energetically stable and measured in XRD, are mainly exposed in the surface of $LiNiO_2$ and it is expected that intercalation and de-intercalation of Li-ion will be affected by them.