• Journal of Electrochemical Science and Technology
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• v.4 no.3
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• pp.102-107
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• 2013

The electrochemical properties of Mg-doped $LiFe_{0.48}Mn_{0.48}Mg_{0.04}PO_4$ and pure $LiFe_{0.5}Mn_{0.5}PO_4$ olivine cathodes are examined and the lattice parameters are refined by Rietveld analysis. The calculated atomic parameters from the refinement show that $Mg^{2+}$ doping has a significant effect in the olivine $LiFeMnPO_4$ structure. The unit cell volume is 297.053(2) ${\AA}^3$ for pure $LiFe_{0.5}Mn_{0.5}PO_4$ and is decreased to 296.177(1) ${\AA}^3$ for Mg-doped $LiFe_{0.48}Mn_{0.48}Mg_{0.04}PO_4$ sample. The doping of $Mg^{2+}$ cation with atomic radius smaller than $Mn^{2+}$ and $Fe^{2+}$ ion induces longer Li-O bond length in $LiO_6$ octahedra of the olivine structure. The larger interstitial sites in $LiO_6$ octahedra facilitate the lithium ion migration and also enhance the diffusion kinetics of olivine cathode material. The $LiFe_{0.48}Mn_{0.48}Mg_{0.04}PO_4$ sample with larger Li-O bond length delivers higher discharge capacities and also notably increases the rate capability of the electrode.

• Transactions on Electrical and Electronic Materials
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• v.13 no.3
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• pp.121-124
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• 2012

Olivine type $LiFePO_4$ cathode material was synthesized by solid-state reaction method including one-step heat treatment. To improve the electrochemical characteristics, graphite nanofiber (GNF) was added into $LiFePO_4$ cathode material. The structure and morphological performance of $LiFePO_4$ were investigated by X-ray diffraction (XRD); and a field emission-scanning electron microscope (FE-SEM). The synthesized $LiFePO_4$ has an olivine structure with no impurity, and the average particle size of $LiFePO_4$ is about 200~300 nm. With graphite nanofiber added, the discharge capacity increased from 113.43 mAh/g to 155.63 mAh/g at a current density of 0.1 $mA/cm^2$. The resistance was also significantly decreased by the added graphite nanofiber.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2007.11a
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• pp.303-304
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• 2007

A comparison study of carbon coating on $LiFePO_4$ was done with two different carbon sources-petroleum pitch and Ketjen black. Raman spectroscopy and transmission electron microscopy (TEM) analysis were applied to the carbon-coated $LiFePO_4$. $LiFePO_4$ which was carbon-coated with petroleum pitch showed more uniform carbon layer and ordered carbon structure. Such uniformity and ordered structure of carbon coating layer resulted in higher initial discharge capacity and better rate capability.

• Bulletin of the Korean Chemical Society
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• v.30 no.10
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• pp.2223-2226
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• 2009

Pristine and sulfur-doped (LiFe$PO_{3.98}S_{0.03}$) lithium iron phosphates were synthesized by a sol-gel method. The XRD pattern of the prepared materials suggested an orthorhombic structure with a Pnma space group and an absence of impurities. The Li/LiFe$PO_4$ or LiFe$PO_{3.98}S_{0.03}$ cells were employed for cycling studies at various temperatures (25, 50 and $60\;{^{\circ}C}$). In all cases, the Li/LiFe$PO_{3.98}S_{0.03}$ cell showed an improved performance with a stable discharge behavior of ~155 mA$hg^{-1}$. Nevertheless, pristine LiFeP$O_4$ cells presented poor discharge behavior at elevated temperatures, especially $60\;{^{\circ}C}$.

• Journal of the Mineralogical Society of Korea
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• v.26 no.1
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• pp.35-44
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• 2013

Synthetic carbon-coated olivine-like structured lithium iron phosphate ($Li^+Fe^{2+}(PO_4)^{3-}/C$) powder composites were compressed up to 35.0 GPa in the symmetrical diamond anvil cell at room temperature. Bulk modulus of $LiFePO_4/C$ was determined to be $130.1{\pm}10.3$ GPa. New peak appears at the d-spacing of 3.386 ${\AA}$ above 18 GPa, and another new one at 2.854 ${\AA}$ around 35 GPa. The crystallographic symmetry of the sample (i.e. orthorhombic) is apparently retained up to 35 GPa as no clear evidence for the phase transition into spinel structure has been observed. The pressure-induced volume change in the M1 site ($Li^+O_6$) is more significant than those in M2($Fe^{2+}O_6$) and $PO_4$ tetrahedral sites.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2008.06a
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• pp.303-303
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• 2008

$LiMn_2O_4$는 출력특성이 좋고 가격이 저렴하지만 전해액 중에서 $Mn^{2+}$이 용출되어 나오는 것과 반복적인 충방전시 구조가 파괴되는 단점이 있어 이것을 보완하고자 $FePO_4\cdot2H_2O$를 $LiMn_2O_4$의 표면에 코팅하였다, $LiMn_2O_4$를 모재로, $FePO_4\cdot2H_2O$를 코팅재로 사용하여 $FePO_4\cdot2H_2O$의 코팅량 변화와, 열처리 온도변화에 따른 물성 변화를살펴보았다, LiOH 와 $MnO_2$의 혼합물을 $1000^{\circ}C$ 에서 소성하여 $LiMn_2O_4$를 합성하고, Fe$(NO_3)_3$ 수용액과 $NH_4H_2PO_4$ 수용액을 혼합하여 $FePO_4\cdot2H_2O$를 제조하였다, $LiMn_2O_4$에 $FePO_4\cdot2H_2O$를 1wt%, 2wt%, 3wt% 비율로 ball milling 을 통해 코팅한 후, 온도를 변화시키면서 열처리 하였다. 코팅한 물질을 XRD를 통해 구조를 분석하고 SEM을 이용하여 형상을 관찰하였다. 또한 고온에서의 $Mn^{2+}$의 용출량을 ICP로 측정하고 half-cell을 만들어 충방전 test를 통해 충방전 특성을 조사하였다. 아울러, 코팅량과 열처리 온도 등 합성변수들이 소재특성 및 전기화학적 특성에 미치는 영향을 조사하였다.

• Journal of Electrochemical Science and Technology
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• v.3 no.2
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• pp.63-67
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• 2012

We prepared various $LiNi_{0.8}Co_{0.15}Al_{0.05}O_2-LiFePO_4$ mixed-cathode electrodes by changing the content of $LiNi_{0.8}Co_{0.15}Al_{0.05}O_2$ and $LiFePO_4$ used, and we analyzed the electrochemical characteristics of the cathodes. We found that the reversible specific capacity of the cathodes increased and that the capacity retention ratios of the cathodes decreased during cycling as the content of $LiNi_{0.8}Co_{0.15}Al_{0.05}O_2$ increased. Conversely, we found that although the reversible specific capacity of the cathodes decreased because of the material composition, the cycle property of the cathodes increased when the $LiFePO_4$ content increased. We analyzed the thermal stability of the $LiNi_{0.8}Co_{0.15}Al_{0.05}O_2-LiFePO_4$ mixed-material cathodes by differential scanning calorimetry and found that it increased as the $LiFePO_4$ content increased.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.33 no.5
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• pp.167-173
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• 2023

Li₃V₂(PO₄)₃ and Li₃V₂(PO₄)₃/C composite with single phase monoclinic structure for the cathode materials are successfully synthesized by direct co-precipitation method using N₂H₄·H₂O as the reducing agent and alginic acid as the carbon source, and their electrochemical properties were compared. The particles with approximately 1~2 ㎛ size and the uniform spherical-like morphology of the narrow particle size distribution were obtained. In addition, the residual carbon can also improve the electrical conductivity. The Li₃V₂(PO₄)₃/C composite has improved initial specific discharge capacity and excellent cycle characteristics to maintain capacity stably than Li₃V₂(PO₄)₃. The results indicate that the reducing agent and carbon composite can affect the good crystallinity and electrochemical performance of the cathode materials.

• 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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• 2006.06a
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• pp.384-385
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• 2006

Olivine $LiFePO_4$ cathode materials were synthesized by hydrothermal reaction, and coated by carbon black. The powders were characterized by the X-ray diffraction. $LiFePO_4$/Li cells were characterized electrochemically by charge/discharge experiments and ac impedance spectroscopy. The result showed the discharge capacity of $LiFePO_4$/Li cell was 133 mAh/g at the first cycle, and 128 mAh/g at the 30th cycle, respectively.