• Korean Journal of Materials Research
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• v.34 no.4
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• pp.185-193
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• 2024

In this study, NASICON-type Li_1+XGa_XTi_2-X(PO₄)₃ (x = 0.1, 0.3 and 0.4) solid-state electrolytes for all-solid-state batteries were synthesized through the sol-gel method. In addition, the influence on the ion conductivity of solid-state electrolytes when partially substituted for Ti⁴⁺ (0.61Å) site to Ga³⁺ (0.62Å) of trivalent cations was investigated. The obtained precursor was heat treated at 450 ℃, and a single crystalline phase of Li_1+XGa_XTi_2-X(PO₄)₃ systems was obtained at a calcination temperature above 650 ℃. Additionally, the calcinated powders were pelletized and sintered at temperatures from 800 ℃ to 1,000 ℃ at 100 ℃ intervals. The synthesized powder and sintered bodies of Li_1+XGa_XTi_2-X(PO₄)₃ were characterized using TG-DTA, XRD, XPS and FE-SEM. The ionic conduction properties as solid-state electrolytes were investigated by AC impedance. As a result, Li_1+XGa_XTi_2-X(PO₄)₃ was successfully produced in all cases. However, a GaPO₄ impurity was formed due to the high sintering temperatures and high Ga content. The crystallinity of Li_1+XGa_XTi_2-X(PO₄)₃ increased with the sintering temperature as evidenced by FE-SEM observations, which demonstrated that the edges of the larger cube-shaped grains become sharper with increases in the sintering temperature. In samples with high sintering temperatures at 1,000 ℃ and high Ga content above 0.3, coarsening of grains occurred. This resulted in the formation of many grain boundaries, leading to low sinterability. These two factors, the impurity and grain boundary, have an enormous impact on the properties of Li_1+XGa_XTi_2-X(PO₄)₃. The Li_1.3Ga_0.3Ti_1.7(PO₄)₃ pellet sintered at 900 ℃ was denser than those sintered at other conditions, showing the highest total ion conductivity of 7.66 × 10^-5 S/cm at room temperature. The total activation energy of Li-ion transport for the Li_1.3Ga_0.3Ti_1.7(PO₄)₃ solid-state electrolyte was estimated to be as low as 0.36 eV. Although the Li_1+XGa_XTi_2-X(PO₄)₃ sintered at 1,000 ℃ had a relatively high apparent density, it had less total ionic conductivity due to an increase in the grain-boundary resistance with coarse grains.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2006.11a
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• pp.241-242
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• 2006

In this work, the $LiFePO_4-LiCoO_2$ mixed cathode electrodes were prepared and their electrochemical performances were measured in different current density. The cell of $LiFePO_4-LiCoO_2$ observed two voltage plateau regions at 3.4 and 3.9V. The cell of $LiFePO_4-LiCoO_2$ (90:10 wt%) mixed cathode delivered a discharge capacity of ca. 139.8 mAh/g at a 0.2C rate. The capacity of the cell decreased with the current rate and a useful capacity of ca 85.7mAh/g was obtained at a 2C rate.

• Journal of IKEEE
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• v.26 no.2
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• pp.232-239
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• 2022

We analyzed the effect of post-annealing on lithium phosphate (Li₃PO₄) solid-state thin-film. Li₃PO₄ thin films were deposited by radio frequency (RF) sputtering, with subsequent annealing of the films at 200-400 ℃. SEM imaging of the sample surfaces showed no significant difference in morphology between the annealed and non-annealed samples. XRD analysis indicated that the samples consist of an amorphous-like structure. Post-annealing changes in binding energy were confirmed by XPS analysis, while the leakage current density at -6 V was measured to be about 7.15 times lower in a device that had been annealed at 400 ℃ vs a non-annealed device. It was confirmed that the leakage current decreased with increasing post-annealing temperature.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2009.11a
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• pp.133-133
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• 2009

Phospho-olivine $LiFePO_4$ and $LiTi_{0.1}Fe_{0.9}PO_4$ cathode materials were prepared by the solid-state reaction. To improve conductivity we carried out electrochemical performance of $Ti^{2+}$ doped $LiFePO_4$. The $Ti^{2+}$ doped $LiFePO_4$ started 3.36 V of flat voltage on discharge curve and showed a gentle decline in the curve compared to undoped $LiFePO_4$ without great changes of capacity. And so, we could achieve to improve electrochemical performance as reversible, cycle life. Similarly, $LiFePO_4$ doping with $Ti^{2+}$ was showed the effect of dopant which was obtained the improved discharge capacity as 140 mAh/g and good cycling performance.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2009.11a
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• pp.132-132
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• 2009

Phospho-olivine $LiFePO_4$ cathode materials were prepared by hydrothermal reaction. In this study, Multi-walled carbon nanotube (MWCNT) and Carbon black was added to enhance the electrical conductivity of $LiFePO_4$. $LiFePO_4$, $LiFePO_4$-MWCNT and $LiFePO_4$-C particles were characterized by X-ray diffraction (XRD), field emission scanning electron microscope (FE-SEM) transmission electron microscope (TEM). $LiFePO_4/SPE/Li$, $LiFePO_4$-MWCMT/SPE/Li and $LiFePO_4$-C/SPE/Li cells were characterized electrochemically by charge/discharge experiments at a constant current density of $0.1mA\;cm^{-2}$ in a range between 2.5 and 4.3 V vs. $Li/Li^+$ and cyclic voltammetry (CV).

• Journal of the Mineralogical Society of Korea
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• v.22 no.1
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• pp.63-72
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• 2009

Carbon-coated lithium iron phosphate ($LiFePO_4/C$) composites are synthesized by the modified mechanical activation method (modified MA process) and studied by the Rietveld structural refinement. Rietveld indices of $LiFePO_4/C$ indicate good fitting with $R_p=8.14%,\;R_{wp}=11.1%,\;R_{exp}=9.09%,\;R_B=3.88%$, and S (GofF, Goodness of fit) = 1.2, respectively. $LiFePO_4/C$ with a space group Pnma shows a = 10.3229(3)${\AA}$, b = 6.0052(2) ${\AA}$, c = 4.6939(1) ${\AA}$, and V = 290.98(1) ${\AA}^3$ in dimension, indicating good agreements with those of previous works. Synthetic powders are nano-sized ($65{\sim}90nm$) homogeneous particles with high purity. Thus the modified MA method will be an efficient process to get a high quality cathode material for commercial lithium batteries.

• Journal of Electrochemical Science and Technology
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• v.4 no.3
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• pp.113-118
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• 2013

Fluorophosphate, $Na_2MnPO_4F$ as new cathode material was synthesized by carbothermal treatment method. Prepared $Na_2MnPO_4F$ has particle size under 100 nm and residual carbon exists in surface of $Na_2MnPO_4F$. Additional carbon coating was performed in order to increase the electrochemical properties. Even capacity and overpotential were improved by carbon coating using mechanical ball milling, the reduced crystallinity limited the drastic improvement of the electrochemical properties. To solve this problem, re-heat treatment was involved to recover crystallinity and then notable improvement of electrochemical properties was obtained. Specific amount of $Li^+$ that participates in electrochemical $Li^+$ insertion / extraction reaction, was x = 1 in $Li_xNa_{2-x}MnPO_4F$ within the voltage range of 2.0 to 4.8 V. The doubled capacity by 2 electron reaction can be obtained when NMPF is charged to higher voltage over 4.8 V.

• Journal of Electrochemical Science and Technology
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• v.10 no.1
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• pp.1-13
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• 2019

Na-ion batteries are being considered as promising cost-effective energy storage devices for the future compared to Li-ion batteries owing to the crustal abundance of Na-ion. However, the large radius of the Na ion result in sluggish electrode kinetics that leads to poor electrochemical performance, which prohibits the use of these batteries in real time application. Therefore, identification and optimization of the anode, cathode, and electrolyte are essential for achieving high-performance Na-ion batteries. In this context, the current review discusses the suitable high-voltage cathode materials for Na-ion batteries. According to a recent research survey, sodium vanadium fluorophosphate (NVPF) compounds have been emphasized for use as a high-voltage Na-ion cathode material. Among the fluorophosphate groups, $Na_3V_2(PO_4)_2F_3$ exhibited the high theoretical capacity ($128mAh\;g^{-1}$) and working voltage (~3.9 V vs. $Na/Na^+$) compared to the other fluorophosphates and $Na_3V_2(PO_4)_3$. Here, we have also highlighted the classification of Fluorophosphates, NVPF composite with carbonaceous materials, the appropriate synthesis methods and how these methods can enhance the electrochemical performance. Finally, the recent developments in NVPF for the application in energy storage devices and its outlook are summarized.

• Journal of the Korean Electrochemical Society
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• v.11 no.3
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• pp.197-210
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• 2008

The cathode materials for lithium ion battery have been developed in accordance with the battery performance. $LiCoO_2$ initially adapted at lithium ion battery is going to be useful even at the charging voltage of 4.3 V by surface treatment or doping which drastically improved the performance of $LiCoO_2$. On the other hand, the complicate and multiple functions of recent electronic equipments required higher operational voltage and higher capacity than ever, which is going to be driving force for developing new cathode materials. Some of them are $LiNi_{1-x}{M_xO_2}$, $Li[Ni_{x}Mn_{y}Co_{z}]O_{2}$, $Li[{Ni}_{1/2}{Mn}_{1/2}]O_{2}$. Other new type of cathode materials having high safety is also developed to apply for HEV (hybrid electrical vehicle) and power tool applications. ${LiMn}_{2}{O}_{4}$ and $LiFePO_4$ are famous for highly stable material, which are expected to give contribution to make safer battery. In near future, the various materials having both capacity and safety will be developed by new technology, such as solid solution composite.

• Journal of the Korean Electrochemical Society
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• v.3 no.1
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• pp.44-48
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• 2000

Amorphous $V_2O_5$ cathode thin films were prepared by DC-magnetron sputtering at room temperature and the thin film rechargeable lithium batteries were fabricated with the configuration of $V_2O_5/LIPON/Li$ using sequential ex-situ thin film deposition techniques. The electrochemical characteristics of $V_2O_5$ cathode materials Prepared at 80/20 of $Ar/O_2$ ratio showed high capacity and cycling behaviors by half cell test. LIPON solid electrolytes films were prepared by RF-magnetron sputtering using the self-made $Li_3PO_4$ target in pure $N_2$ atmosphere, and it was very stable for lithium contact in the range of 1.2-4.0 V vs. Li. Metallic lithium were deposited on LIPON electrolyte by thermal evaporation methode in dry room. Vanadium oxide based full cell system showed the initial discharge capacity of $150{\mu}A/cm^2{\mu}m$ in the range of $1.2\~3.5V$.