• Bulletin of the Korean Chemical Society
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• v.32 no.3
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• pp.921-926
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• 2011

This study investigates a root cause of the improved rate performance of $LiFePO_4$ after metal doping to Fesites. This is because the metal doped $LiFePO_4$/C maintains its initial capacity at higher C-rates than undoped one. Using $LiFePO_4$/C and doped $LiFe_{0.97}M_{0.03}PO_4$/C (M=$Al^{3+}$, $Cr^{3+}$, $Zr^{4+}$), which are synthesized by a mechanochemical process followed by one-step heat treatment, the Li content before and after chemical delithiation in the $LiFePO_4$/C and the binding energy are compared using atomic absorption spectroscopy (AAS) and X-ray photoelectron spectroscopy (XPS). The results from AAS and XPS indicate that the low Li content of the metal doped $LiFePO_4$/C after chemical delithiation is attributed to the low binding energy induced by weak Li-O interactions. The improved capacity retention of the doped $LiFePO_4$/C at high discharge rates is, therefore, achieved by relatively low binding energy between Li and O ions, which leads to fast Li diffusivity.

• 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.

• Journal of Electrochemical Science and Technology
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• v.11 no.3
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• pp.282-290
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• 2020

In this article, we report the effect of blended cathode materials on the performance of all-solid-state lithium-ion batteries (ASLBs) with oxide-based organic/inorganic hybrid electrolytes. LiFePO₄ material is good candidates as cathode material in PEO-based solid electrolytes because of their low operating potential of 3.4 V; however, LiFePO₄ suffers from low electric conductivity and low Li ion diffusion rate across the LiFePO₄/FePO₄ interface. Particularly, monoclinic Li₃V₂(PO₄)₃ (LVP) is a well-known high-power-density cathode material due to its rapid ionic diffusion properties. Therefore, the structure, cycling stability, and rate performance of the blended LiFePO₄/Li₃V₂(PO₄)₃ cathode material in ASLBs with oxidebased inorganic/organic-hybrid electrolytes are investigated by using powder X-ray diffraction analysis, field-emission scanning electron microscopy, Brunauer-Emmett-Teller sorption experiments, electrochemical impedance spectroscopy, and galvanostatic measurements.

• Journal of the Microelectronics and Packaging Society
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• v.26 no.4
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• pp.83-88
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• 2019

LiBaPO₄:Eu²⁺ phosphors with stoichiometric and nonstoichiometric compositions were prepared using a solid state reaction followed by heat treatment in reduced atmosphere, and the crystal structures and photoluminescence(PL) properties of the powders were investigated by x-ray powder diffraction and luminescence spectrometer. At 900℃, the Ba₃(PO₄)₂ phase as the intermediate phase was observed with the LiBaPO₄ phase as the main crystalline phase. Samples with a low europium concentration at 1,000℃ belonged to the trigonal structure, whereas samples with Eu²⁺ content more than 4 mol% showed monoclinic structure. In the nonstoichiometric compositions of 4 mol% Eu²⁺ and above, a single phase of Eu²⁺-doped LiBaPO₄, showing bluish green emission, was formed.

• 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.

• 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.

• Bulletin of the Korean Chemical Society
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• v.34 no.3
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• pp.851-855
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• 2013

This paper describes an environmentally friendly process for the recovery of $LiFePO_4$ cathode materials from scrap electrodes by a simple thermal treatment method. The active materials were easily separated from the aluminum substrate foil and polymeric binders were also decomposed at different temperatures ($400^{\circ}C$, $500^{\circ}C$, $600^{\circ}C$) for 30 min under nitrogen gas flow. The samples were characterized by X-ray diffraction (XRD), scanning electronic microscopy (SEM), Raman spectroscopy, Thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). The electrochemical properties of the recycled $LiFePO_4$ cathode were evaluated by galvanostatic charge and discharge modes. The specific charge/discharge capacities of the recycled $LiFePO_4$ cathode were similar to those of the original $LiFePO_4$ cathode. The $LiFePO_4$ cathode material recovered at $500^{\circ}C$ exhibits a somewhat higher capacity than those of other recovered materials at high current rates. The recycled $LiFePO_4$ cathode also showed a good cycling performance.

• Journal of the Korean Electrochemical Society
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• v.15 no.1
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• pp.27-34
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• 2012

$Li_3V_2(PO_4)_3$/carbon composite materials are synthesized from a sucrose-containing precursor. Amorphous $Li_3V_2(PO_4)_3/C$ (a-LVP/C) and crystalline $Li_3V_2(PO_4)_3/C$ (c-LVP/C) are obtained by calcining at $600^{\circ}C$ and $800^{\circ}C$, respectrively, and electrochemical performance as the negative electrode for lithium secondary batteries is compared for two samples. The a-LVP electrode shows much larger reversible capacity than c-LVP, which is ascribed to the spatial $Li^+$ channels and flexible structure of amorphous material. In addition, this electrode shows an excellent rate capability, which can be accounted for by the facilitated $Li^+$ diffusion through the defect sites. The sloping voltage profile is another advantageous feature for easy SOC (state of charge) estimation.

• 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.

• 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.