• Journal of Electrochemical Science and Technology
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• v.13 no.3
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• pp.407-415
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• 2022

Surface coating of cathodes is an essential process for all-solid-state batteries (ASSBs) based on sulfide electrolytes as it efficiently suppresses interfacial reactions between oxide cathodes and sulfide electrolytes. Based on computational calculations, Li₃PO₄ has been suggested as a promising coating material because of its higher stability with sulfides and its optimal ionic conductivity. However, it has hardly been applied to the coating of ASSBs due to the absence of a suitable coating process, including the selection of source material that is compatible with ASSBs. In this study, polyphosphoric acid (PPA) and (NH₄)₂HPO₄ were used as source materials for preparing a Li₃PO₄ coating for ASSBs, and the properties of the coating layer and coated cathodes were compared. The Li₃PO₄ layer fabricated using the (NH₄)₂HPO₄ source was rough and inhomogeneous, which is not suitable for the protection of the cathodes. Moreover, the water-based coating solution with the (NH₄)₂HPO₄ source can deteriorate the electrochemical performance of high-Ni cathodes that are vulnerable to water. In contrast, when an alcohol-based solvent was used, the PPA source enabled the formation of a thin and homogeneous coating layer on the cathode surface. As a consequence, the ASSBs containing the Li₃PO₄-coated cathode prepared by the PPA source exhibited significantly enhanced discharge and rate capabilities compared to ASSBs containing a pristine cathode or Li₃PO₄-coated cathode prepared by the (NH₄)₂HPO₄ source.

• Journal of the Korean Electrochemical Society
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• v.10 no.3
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• pp.213-218
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• 2007

In order to find out proper PVdF gel polymer electrolyte for Li/S battery, we investigated PVdF gel polymer electrolytes with various glyme type plasticizer such as polyglyme, tetraglyme, triglyme. The organic solvents as triglyme, tetraglyme, polyglyme (Mn = 250, 500) has different chain length of ethylene oxide(EO) in solvent of glyme system. ionic conductivity decreased as increasing chain length of EO in plasticizers. Ionic conductivity of PVdF gel electrolyte with tetraglyme, triglyme, polyglyme (Mn = 250, 500) at room temperature was $5{\times}10^{-4},\;3{\times}10^{-4},\;6{\times}10^{-5},\;3{\times}10^{-5}\;S/cm$, respectively. Li/S cell with PVdF gel polymer electrolyte using tetraglyme plasticizer had low interfacial resistance and the highest initial discharge capacity of 1232 mAh/g of active sulfur, which was about 70% utilization of theoretical value.

• Korean Journal of Materials Research
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• v.8 no.3
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• pp.268-273
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• 1998

Standard Zircaloy-4 sheets, charged with 230-250ppm hydrogen by the gas-charging method and homogenized at $400^{\circ}C$ for 72hrs in a vacuum, were corroded in pure water and aqueous LiOH solutions using static autoclaves at $350^{\circ}C$. Their corrosion behaviors were characterized by measuring their weight gains with the corrosion time and observing their microstructures using an optical microscope and a scanning electron microscope. The elemental depth profiles for hydrogen and lithium were measured using a secondary ion mass spectrometry(S1MS) to confirm their distributions at the oxidelmetal interface. The normal Zircaloy-4 specimens corroded abruptly and heavily at the concentration of Li ions more than 30ppm in the aqueous solution. This is due to accelerations by the rapid oxidation of many Zr- hydrides formed by the large amount of absorbed hydrogen, resulting from the increased substitution of $Li^{+}$ ions with $Zr^{4+}$-sites in the oxide as the Li ion concentration increased. The specimens that had been charged with amounts of hydrogen greater than its solubility corroded early with a more rapid acceleration than normal specimens, regardless of the corrosion solutions. At longer corrosion times. however, normal specimens showed a rather accelerated corrosion rate compared to the hydrogen-charged specimens. These slower corrosion rates of the hydrogen-charged specimens at the longer corrosion times would be due to the pre-existent Zr-hydride in the matrix, which causes the hydrogen pick- up into the specimen to be depressed, when the oxide with an appropriate thickness formed.

• Journal of the Korean Electrochemical Society
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• v.20 no.1
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• pp.7-12
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• 2017

Using a precursor of $LiNi_{0.6}Co_{0.2}Mn_{0.2}O_2$ as a starting material, a surface-modified cathode material was obtained by coating with KCl, where the added KCl reduces residual Li compounds such as $Li_2CO_3$ and LiOH, on the surface. The resulting electrochemical properties were investigated. The amounts of $Li_2CO_3$ and LiOH decreased from 8,464 ppm to 1,639 ppm and from 8,088 ppm to 6,287 ppm, respectively, with 1 wt% KCl added $LiNi_{0.6}Co_{0.2}Mn_{0.2}O_2$ that had been calcined at $800^{\circ}C$. X-ray diffraction results revealed that 1 wt% of KCl added $LiNi_{0.6}Co_{0.2}Mn_{0.2}O_2$ did not affect the parent structure but enhanced the development of hexagonal crystallites. Additionally, the charge transfer resistance ($R_{ct}$) decreased dramatically from $225{\Omega}$ to $99{\Omega}$, and the discharge capacity increased to 182.73mAh/g. Using atomic force microscopy, we observed that the surface area decreased by half because of the exothermic heat released by the Li residues. The reduced surface area protects the cathode material from reacting with the electrolyte and hinders the development of a solid electrolyte interphase (SEI) film on the surface of the oxide particles. Finally, we found that the introduction of KCl into $LiNi_{0.6}Co_{0.2}Mn_{0.2}O_2$ is a very effective method of enhancing the electrochemical properties of this active material by reducing the residual Li. To the best of our knowledge, this report is the first to demonstrate this phenomenon.

• Korean Chemical Engineering Research
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• v.45 no.2
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• pp.178-182
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• 2007

Non-aqueous supercapacitors by using activated C and $LiMn_2O_4$ as an active material in a positive electrode were prepared and characterized. From the cyclic voltammetry and AC impedance analysis, the capacitive effect by electric double layer of activated carbon and the faradic effect by intercalation/deintercalation of $Li^+$ ion were observed. Increasing the ratio of $LiMn_2O_4$, specific capacitances and energy densities of supercapacitor were increased. At the ratio of 0.86:0.14 ($LiMn_2O_4:C$), the maximum specific capacitance of 17.51 Wh/L and energy density of 23.83 F/cc were obtained, which were more than twice of those for a conventional electric double layer capacitor. Even after 1,000 charge/discharge cycle, the supercapacitor by using the electrode containing 14% of activated carbon and 86% of $LiMn_2O_4$ showed 60% better specific capacitance and energy density than that by using the electrode containing 100% activated carbon.

• Bulletin of the Korean Chemical Society
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• v.35 no.5
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• pp.1516-1522
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• 2014

A series of 20 wt % $(NH_4)_2SO_4$ and 3 wt % $Al_2O_3$ surface treatments were applied to $Li[Li_{0.2}Mn_{0.54}Co_{0.13}Ni_{0.13}]O_2$ substrates. The $Li[Li_{0.2}Mn_{0.54}Co_{0.13}Ni_{0.13}]O_2$ substrates were synthesized using a co-precipitation method. Sample (a) was left pristine and variations of the 20 wt % $(NH_4)_2SO_4$ and 3 wt % $Al_2O_3$ were applied to samples (b), (c) and (d). XRD was used to verify the space group of the samples as R$\bar{3}$m. Additional morphology and particle size data were obtained using SEM imagery. The $Al_2O_3$ coating layers of sample (b) and (d) were confirmed by TEM images and EDS mapping of the SEM images. 2032-type coin cells were fabricated in a glove box in order to investigate their electrochemical properties. The cells were charged and discharged at room temperature ($25^{\circ}C$) between 2.0V and 4.8V during the first cycle. The cells were then charged and discharged between 2.0V and 4.6V in subsequent cycles. Sample (d) exhibited lower irreversible capacity loss (ICL) in the first charge-discharge cycle as compared to sample (c). Sample (d) also had a higher discharge capacity of ~250 mAh/g during the first and second charge-discharge cycles when compared with sample (c). The rate capability of the $Al_2O_3$-coated sample (b) and (d) was lower when compared with sample (a) and (c). Sample (d), coated with $Al_2O_3$ after the surface treatment with $(NH_4)_2SO_4$, showed an improvement in cycle performance as well as an enhancement of discharge capacity. The thermal stability of sample (d) was higher than that of the sample (c) as the result of DSC.

• Journal of the Korean Chemical Society
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• v.53 no.1
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• pp.42-50
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• 2009

The dielectric-spectroscopic and ac conductivity studies firstly carried out on layered manganese doped Sodium Lithium Trititanates ($Na_{1.9}Li_{0.1}Ti_3O_7$). The dependence of loss tangent (Tan$\delta$), relative permittivity ($\varepsilon_r$) and ac conductivity ($\sigma_{ac}$) in temperature range 373-723K and frequency range 100Hz-1MHz studied on doped derivatives. Various conduction mechanisms are involved during temperature range of study like electronic hopping conduction in lowest temperature region, for MSLT-1 and MSLT-2. The hindered interlayer ionic conduction exists with electronic hopping conduction for MSLT-3. The associated interlayer ionic conduction exists in mid temperature region for all doped derivatives. In highest temperature region modified interlayer ionic conduction along with the polaronic conduction, exist for MSLT-1, MSLT-2, and only modified interlayer ionic conduction for MSLT-3. The loss tangent (Tan$\delta$) in manganese-doped derivatives of layered $Na_{1.9}Li_{0.1}Ti_3O_7$ ceramic may be due to contribution of electric conduction, dipole orientation, and space charge polarization. The corresponding increase in the values of relative permittivity may be due to increase in number of dipoles in the interlayer space while the corresponding decrease in the values of relative permittivity may be due to the increase in the leakage current due to the higher doping.

• Journal of Sensor Science and Technology
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• v.9 no.2
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• pp.146-152
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• 2000

Lithium doped zinc oxide(ZnO:Li) films are prepared by rf magnetron sputtering on Corning 7059 glass substrate using specifically designed ZnO targets containing different amount of $Li_2CO_3$ powder as the Li doping source. The structural properties of the Li doped ZnO films are investigated by XRD, SEM and AFM. The electrical properties of the ZnO:Li films are measured for various deposition conditions, such as the substrate temperature, $O_2$/Ar gas ratio and rf power. The effects of the $Li_2CO_3$ content in target and the deposition conditions on the structural and electrical properties were studied. When ZnO:Li films were sputtered at the substrate temperature of $200^{\circ}C$, $O_2$/Ar gas ratio of 100% and rf power of 100W with a target containing less than 1wt% content of $Li_2CO_3$, showed good surface morphology, strong c-axis orientation and high resistivity of more than $10^8{\Omega}cm$.

• Journal of the Korean Electrochemical Society
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• v.15 no.3
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• pp.190-197
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• 2012

We employed the vinyl ethylene carbonate (VEC) as an electrolyte additive and investigated the effect of the electrolyte additive on the electrochemical performance in hybrid capacitor. The activated carbon was adopted as cathode material, and the $Li_4Ti_5O_{12}$ oxide was used as anode material. The electrolyte was prepared with the $LiPF_6$ salt in the mixed solvent of ethylene carbonate (EC), dimethyl carbonate (DMC), and ethyl methyl carbonate(EMC). We evaluated the electrochemical performance of the hybrid capacitor with increasing the amount of the VEC electrolyte additive, which is known as the remover of oxygen functional group and the stabilizer of the electrode by reducing the surface of electrode, and obtained the superior performance data especially at the addition of the VEC electrolyte additive of around 0.7 vol%. On the contrary, the addition of the VEC more than 0.7 vol% in the electrolyte leads to the degradation in electrochemical performance of hybrid capacitor, suggesting the increase of the side reaction from the excessive VEC additive. X-ray photoelectron spectroscopy (XPS) revealed that the addition of the VEC suppressed the formation of LiF component, which is known as the insulator, on the surface of electrode. The optimized addition of VEC exhibited the improved capacity retention around 82.7% whereas the bare capacitors without VEC additive showed the 43.2% of capacity retention after 2500 cycling test.

• Journal of the Korean Electrochemical Society
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• v.10 no.1
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• pp.48-51
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• 2007

In order to investigate the effects of particle size and specific surface area(BET area) of spinel powder, $LiMn_2O_4$ were synthesized using metal oxide precursor by co-precipitation method(CoP) and solid state reaction (SSR) .X-ray diffraction(XRD) patterns revealed that the both prepared powder has a well developed spinel structure with Fd3m space group. The $LiMn_2O_4$ prepared by co-precipitation showed spherical morphology with narrow size distribution. However, the $LiMn_2O_4$ prepared by solid state reaction showed relatively smaller particles with irregular shape. The measured BET areas of the powers are $0.8m^2g^{-1}$ (CoP) and $3.6m^2g^{-1}$(SSR). The electrochemical performance of the Prepared $LiMn_2O_4$ powders was evaluated using coin type cells(CR2032) at elevated temperature ($55^{\circ}C$). The $LiMn_2O_4$ prepared by co-precipitation showed the better cycling performance(82.3%capacity retention at $50^{th}$ cycle) than that of the $LiMn_2O_4$(68.3%) prepared by solid state reaction at elevated temperature.