• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.37 no.2
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• pp.215-222
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• 2024

Ni-rich cathode materials have been developed as the most promising candidates for next-generation cathode materials for lithium-ion batteries because of their high capacity and energy density. In particular, the electrochemical performance of lithium-ion batteries could be enhanced by increasing the contents of nickel ion. However, there are still limitations, such as low structural stability, cation mixing, low capacity retention and poor rate capability. Herein, we have successfully developed the nanorod-type Ni-rich cathode materials by using co-precipitation method. Particularly, the nanorod-type primary particles of LiNi_0.7Co_0.15Mn_0.15O₂ could facilitate the electron transfer because of their longitudinal morphology. Moreover, there were holes at the center of secondary particles, resulting in high permeability of the electrolyte. Lithium-ion batteries using the prepared nanorod-type LiNi_0.7Co_0.15Mn_0.15O₂ achieved highly improved electrochemical performance with a superior rate capability during battery cycling.

• Journal of Electrochemical Science and Technology
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• v.12 no.2
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• pp.237-245
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• 2021

Atomic layer deposition (ALD) enhances the stability of cathode materials via surface modification. Previous studies have demonstrated that an Ni-rich cathode, such as LiNi_0.8Co_0.1Mn_0.1O₂, is a promising candidate owing to its high capacity, but is limited by poor cycle stability. In this study, to enhance the stability of the Ni-rich cathode, synthesized LiNi_0.8Co_0.1Mn_0.1O₂ was coated with Al₂O₃ using ALD. Thus, the surface-modified cathode exhibited enhanced stability by protecting the interface from Ni-O formation during the cycling process. The coated LiNi_0.8Co_0.1Mn_0.1O₂ exhibited a capacity of 176 mAh g^-1 at 1 C and retained up to 72% of the initial capacity after 100 cycles within a range of 2.8-4.3 V (vs Li/Li⁺. In contrast, pristine LiNi_0.8Co_0.1Mn_0.1O₂ presented only 58% of capacity retention after 100 cycles with an initial capacity of 173 mAh g^-1. Improved cyclability may be a result of the ALD coating, which physically protects the electrode by modifying the interface, and prevents degradation by resisting side reactions that result in capacity decay. The electrochemical impedance spectra and structural and morphological analysis performed using electron microscopy and X-ray techniques establish the surface enhancement resulting from the aforementioned strategy.

• 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 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.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.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.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.

• 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 the Korean Electrochemical Society
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• v.22 no.4
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• pp.172-176
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• 2019

The first commercialized cathode material, $LiCoO_2$, suffers from disadvantages such as high cost and toxicity and also possesses safety problems. The nickel-rich $LiNi_{0.9}Mn_{0.1}O_2$ cathode material, used as an alternative to $LiCoO_2$, has highly reversible capacity and high energy density. So, the nickel-rich $LiNi_{0.9}Mn_{0.1}O_2$ cathode material is widely used as an alternative to $LiCoO_2$ due to its highly reversible capacity and high energy density. However, $LiNi_{0.9}Mn_{0.1}O_2$ has several disadvantages as well, such as poor cycle performance and poor thermal instability. To address these problems, we synthesized a new material, $LiNi_{0.5}Mn_{0.5}O_2$, as a shell on the surface of a core to suppress the surface degradation. The new material showed high structural and thermal stabilities and could also maintain a high capacity. The capacity retention of the core-shell cathode (87.7%) was better than that of the core cathode (76.9%) after 50 cycles. Analysis using differential scanning calorimetry revealed that the heat generation in the core-shell cathode ($65.9Jg^{-1}$) was lower than that in the core cathode ($559.7Jg^{-1}$).