• Korean Journal of Materials Research
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• v.17 no.8
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• pp.447-451
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• 2007

We investigated the dependence of the various annealing conditions and thickness ($6\sim45nm$) of the Ti-doped $Al_2O_3$ coating on the electrochemical properties and the capacity fading of Ti-doped $Al_2O_3$ coated $LiCoO_2$ films. The Ti-doped-$Al_2O_3$-coating layer and the cathode films were deposited on $Al_2O_3$ plate substrates by RF-magnetron sputter. Microstructural and electrochemical properties of Ti-doped-$Al_2O_3$-coated $LiCoO_2$ films were investigated by transmission electron microscopy (TEM) and a dc four-point probe method, respectively. The cycling performance of Ti-doped $Al_2O_3$ coated $LiCoO_2$ film was improved at higher cut-off voltage. But it has different electrochemical properties with various annealing conditions. They were related on the microstructure, surface morphology and the interface condition. Suppression of Li-ion migration is dominant at the coating thickness >24.nm during charge/discharge processes. It is due to the electrochemically passive nature of the Ti-doped $Al_2O_3$ films. The sample be made up of Ti-doped $Al_2O_3$ coated on annealed $LiCoO_2$ film with additional annealing at $400^{\circ}C$ had good adhesion between coating layer and cathode films. This sample showed the best capacity retention of $\sim92%$ with a charge cut off of 4.5 V after 50 cycles. The Ti-doped $Al_2O_3$ film was an amorphous phase and it has a higher electrical conductivity than that of the $Al_2O_3$ film. Therefore, the Ti-doped $Al_2O_3$ coated improved the cycle performance and the capacity retention at high voltage (4.5 V) of $LiCoO_2$ films.

• 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.

• Journal of Electrochemical Science and Technology
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• v.11 no.4
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• pp.411-420
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• 2020

Undesirable interfacial reactions between the cathode and sulfide electrolyte deteriorate the electrochemical performance of all-solid-state cells based on sulfides, presenting a major challenge. Surface modification of cathodes using stable materials has been used as a method for reducing interfacial reactions. In this work, a precursor-based surface modification method using Zr and Mo was applied to a LiNi_0.6Co_0.2Mn_0.2O₂ cathode to enhance the interfacial stability between the cathode and sulfide electrolyte. The source ions (Zr and Mo) coated on the precursor-surface diffused into the structure during the heating process, and influenced the structural parameters. This indicated that the coating ions acted as dopants. They also formed a homogenous coating layer, which are expected to be layers of Li-Zr-O or Li-Mo-O, on the surface of the cathode. The composite electrodes containing the surface-modified LiNi_0.6Co_0.2Mn_0.2O₂ powders exhibited enhanced electrochemical properties. The impedance value of the cells and the formation of undesirable reaction products on the electrodes were also decreased due to surface modification. These results indicate that the precursor-based surface modification using Zr and Mo is an effective method for suppressing side reactions at the cathode/sulfide electrolyte interface.

• Korean Chemical Engineering Research
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• v.58 no.1
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• pp.52-58
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• 2020

Electrochemical characterization and thermal stability were investigated for MgF₂ coated LiNi_0.8Co_0.15Al_0.05O₂ cathode. The ratio of MgF₂ was controlled by 0.5, 1, 3 wt%. Cyclic voltammetry, charge-discharge profiles, rate capability, cycle life were measured for electrochemical properties. DSC analysis was measured for thermal stability. The first discharge capacities of MgF₂ coated LiNi_0.8Co_0.15Al_0.05O₂ were decreased at 0.1C-rate compared to pristine LiNi_0.8Co_0.15Al_0.05O₂. But the rate capability and cycle life of MgF₂ coated LiNi_0.8Co_0.15Al_0.05O₂ were improved at 2C-rate. In DSC analysis result, the exothermic temperature of MgF₂ coated LiNi_0.8Co_0.15Al_0.05O₂ was increased and peak height was decreased.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.20 no.5
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• pp.421-424
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• 2007

Thermal behavior of $Li_{1-x}CoO_2$ has been investigated employing DSC (Differential Scanning calorimetry) and TGA (Thermogravimetry Analyzer), and the crystal parameters were calculated from XRD (X-ray diffraction).for the commercial rectangular pouch cell(1000 mAh).The cathode materials coated over aluminium foil current collector is made up of a blend consisting of active material $LiCoO_2$(size $20\;{\mu}m$, 94 wt%), conducting material super p black (SPB, 3 wt%) and binder polyvinylidene fluoride (PVDF, 3 wt%). The anode is a mix consisting of carbon (92 wt%) and PVDF(8 wt%) coated over copper foil. The cells for the experiments were first preconditioned by cycling three times and stabilized at OCV=3.0, 3.5, 4.2, 4.35 and 4.5 V. The stabilized cathode material was used for thermal and crystal parameter investigations.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2006.06a
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• pp.348-349
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• 2006

$LiNi_{1/3}Mn_{1/3}Co_{1/3}O_2$ cathode material was synthesized by a mixed hydroxide methode. The surface of the $LiNi_{1/3}Mn_{1/3}Co_{1/3}O_2$ was coated with a carbon by using a sol-gel method to improve further its electrochemical properties. Electrochemical studies were performed by assembling 2032 coin cells with lithium metal as an anode. OSC (differential scanning calorimetry) data showed that exothermic reactions of charged to 4.3V vs. Li was suppressed in the carbon-coated materials. The carbon-coated $LiNi_{1/3}Mn_{1/3}Co_{1/3}O_2$ showed the improved rate capability and thermal stability.

• Journal of the Korean Electrochemical Society
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• v.10 no.3
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• pp.184-189
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• 2007

The importance of secondary battery industry is getting excited according to the development of battery industry as a high efficiency energy supplier of electronic machine of mobile information such as mobile phone, lap-top computer, PDA. It is rasing the interest about security of safety and high efficiency of cathode material for main part of secondary lithium battery. The cathode material which has been used like $LiCoO_2,\;LiMn_2O_4,\;LiNi_xCo_yMn_zO_2,\;LiNi_xCo_yM_zO_2$ (M=Al, Zr, Mg etc.,) the most typical material is $LiCoO_2$. But it is studying the development of substitute such as efficiency amelioration of $LiCoO_2$, thetiary element, olivine element because of the capacity of $LiCoO_2$, the matter of security; especially the betterment of efficiency, security research of safety has been actively processed in domestic and overseas about surface coating treatment of active cathode which is using oxide ($M_xO_3$). This study analyses side effect of battery according to increase of surface treatment, formation of precipitation for reagent condensation, non-reagent residue of oxide ($M_xO_3$) which is remains during the surface treatment of $LiCoO_2$; conducts study of new process, the consideration of the electrochemical property to improve oxide solution of mixing rate, mixture of surface treatment, dryness, calcinations conditionetc.

• Journal of the Korean Electrochemical Society
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• v.14 no.2
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• pp.77-82
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• 2011

The surface of $Li[Ni_{0.35}Co_{0.3}Mn_{0.35}]O_2$ cathode was modified by $[Li,La]TiO_3$ coating using pH controlled coating solution. At low pH values (acidic solution), cathode powders, which is oxides, have a positive surface charge, whereas, they have a negative surface charge at high pH values. As a result, their charge could affect the formation of the coating layer on the surface of cathode powder. To determine the optimal pH value, the surface coating of the pristine powder was carried out at various pH values of the coating solution. The surface morphology of coated samples was characterization by SEM and TEM analyses. Impedance analysis and cyclic voltammogram presented that internal resistance of the cell was dependent upon the pH of coating solution.

• Proceedings of the Materials Research Society of Korea Conference
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• 2003.11a
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• pp.226-226
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• 2003

The Commercial LiCoO$_2$ particles, which were 7.7${\mu}{\textrm}{m}$ in average diameter, were coated with $Al_2$O$_3$ by a gas suspension spray coating method. The coating amount of $Al_2$O$_3$ on the surface of LiCoO$_2$ was varied from 0.1 to 2 wt.% and compared their electrochemical characteristics with those of bare LiCoO$_2$. $Al_2$O$_3$ coating on the surface of LiCoO$_2$ increased surface area and electrical conductivity, and showed the better cycle and thermal stability even at the higher voltage. The observed optimum A1$_2$O$_3$ coating amount that exhibited the highest capacity retention was 0.2 wt.%.

• Journal of Electrochemical Science and Technology
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• v.7 no.2
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• pp.179-184
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• 2016

The interface between the surface of a cathode material and the electrolyte gives rise to surface reactions such as solid electrolyte interface (SEI) and chemical side reactions. These reactions lead to increased surface resistance and charge transfer resistance. It is consequently necessary to improve the electrochemical characteristics by suppressing these reactions. In order to suppress unnecessary surface reactions, we coated cathode material using polypropylene (PP). The PP coating layer effectively reduced the SEI film that is generated after a 4.3 V initial charging process. By mitigating the formation of the SEI film, the PP-coated Li[(Ni_0.6Co_0.1Mn_0.3)_0.36(Ni_0.80Co_0.15Al0.05)_0.64)]O₂(NCS) electrode provided enhanced transport of Li⁺ ions due to reduced SEI resistance (R_SEI) and charge transfer resistance (R_ct). The initial charge and discharge efficiency of the PP-coated NCS electrode was 96.2 % at a current density of 17 mA/g in a voltage range of 3.0 ~ 4.3 V, whereas the efficiency of the NCS electrode was only 94.7 %. The presence of the protective PP layer on the cathode improved the thermal stability by reducing the generated heat, and this was confirmed via DSC analysis by an increased exothermic peak.