• Journal of Electrochemical Science and Technology
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• 제15권1호
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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.

• 한국수소및신에너지학회논문집
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• 제16권4호
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• pp.372-378
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• 2005

Ni/YSZ ($Y_2O_3$-stabilized $ZrO_2$) composite powder for a cathode material in high temperature electrolysis(HTE) was synthesized by a mechanical alloying method with Ni and YSZ powder. Microstructure of the composite and cell thickness for HTE reaction has been analyzed with various techniques of XRD, SEM to investigate effects of fabrication conditions. Employing the composite material, furthermore, the unit cell for HTE has been studied to evolve hydrogen from water. XRD patterns showed that the composites after wet mechanical alloying were composed of respective nano-sized crystalline Ni and YSZ. While ethanol as additive for mechanical alloying increased to $20\;{\mu}m$ of average particle size of the composites, alpha-terpineol effectively decreased to sub-micro size of that. This study has been found out the evolution of hydrogen by HTE reaction employing the fabricated cathode material, showing 1.4 ml/min of $H_2$ generation rate as increasing $20\;{\mu}m$ of cathode thickness.

• 한국분말재료학회지
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• 제21권4호
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• pp.286-293
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• 2014

The electrochemical properties of cells assembled with the $LiNiO_2$ (LNO) recycled from cathode materials of waste lithium secondary batteries ($Li[Ni,Co,Mn]O_2$), were evaluated in this study. The leaching, neutralization and solvent extraction process were applied to produce high-purity $NiSO_4$ solution from waste lithium secondary batteries. High-purity NiO powder was then fabricated by the heat-treatment and mixing of the $NiSO_4$ solution and $H_2C_2O_4$. Finally, $LiNiO_2$ as a cathode material for lithium ion secondary batteries was synthesized by heat treatment and mixing of the NiO and $Li_2CO_3$ powders. We assembled the cells using the $LiNiO_2$ powders and evaluated the electrochemical properties. Subsequently, we evaluated the recycling possibility of the cathode materials for waste lithium secondary battery using the processes applied in this work.

• 한국재료학회지
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• 제28권5호
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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.

• 한국세라믹학회지
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• 제51권4호
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• pp.265-270
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• 2014

Among the Ruddlesden-Popper series, $La_4Ni_3O_{10}$ has received widespread attention as a promising cathode material by reason of its favorable properties for realizing high performance of intermediate temperature solid oxide fuel cells (IT-SOFCs). The $La_4Ni_3O_{10}$ cathode is prepared using the facile sol-gel method by employing tri-blockcopolymer (F127) to obtain a single phase in a short sintering time. There are no reactions between the $La_4Ni_3O_{10}$ cathode and the $Ce_{0.9}Gd_{0.1}O_{2-\delta}$ (GDC) electrolyte upon sintering at $1000^{\circ}C$, indicating that the $La_4Ni_3O_{10}$ cathode has good chemical compatibility with the GDC electrolyte. The maximum electrical conductivity of $La_4Ni_3O_{10}$ reaches approximately 240 S $cm^{-1}$ at $100^{\circ}C$ and gradually decreases with increasing temperaturein air atmosphere. The area specific resistance value of $La_4Ni_3O_{10}$ composite with 40 wt% GDC is $0.435{\Omega}cm^2$ at $700^{\circ}C$. These data allow us to propose that the $La_4Ni_3O_{10}$-GDC composite cathode is a good candidate for IT-SOFC applications.

• Journal of Electrochemical Science and Technology
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• 제4권1호
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• pp.34-40
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• 2013

The structural and electrochemical properties of $Li_{0.99}Ni_{0.46}Mn_{1.56}O_4$ ($Fd{\bar{3}}m$, disordered spinel) cathode material were studied and compared with stoichiometric $LiNi_{0.5}Mn_{1.5}O_4$ ($P4_332$, ordered spinel). First cycle discharge capacity of $Li_{0.99}Ni_{0.46}Mn_{1.56}O_4$ was similar to that of $LiNi_{0.5}Mn_{1.5}O_4$ at C/3 and 1C rate, but cycling performance of $Li_{0.99}Ni_{0.46}Mn_{1.56}O_4$ was better than that of $LiNi_{0.5}Mn_{1.5}O_4$ especially at high rate of 1C. This can be explained by performing synchrotron based in-situ XRD and results of GITT measurements. It is considered that faster lithium ion diffusion in the $Li_{0.99}Ni_{0.46}Mn_{1.56}O_4$ cathode results in the improvement of the rate capability. To study structural changes during cycling, synchrotron in-situ XRD patterns of both the samples were recorded at C/3 and 1C rate. Compared to stoichiometric $LiNi_{0.5}Mn_{1.5}O_4$, disordered $Li_{0.99}Ni_{0.46}Mn_{1.56}O_4$ spinel sample has pseudo one phase behavior and one step phase transition between two cubic phases. So, $LiNi_{0.5}Mn_{1.5}O_4$ would experience a much greater strain and stress, originating from the two phase transitions between three cubic phases and suffer from capacity loss during cycling especially at high rate.

• Journal of Electrochemical Science and Technology
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• 제9권3호
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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 Industrial and Engineering Chemistry
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• 제68권
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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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• 제12권1호
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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.

• KEPCO Journal on Electric Power and Energy
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• 제6권4호
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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.