• Journal of the Korean Electrochemical Society
• /
• v.13 no.4
• /
• pp.246-250
• /
• 2010

In this study, nano-crystallized $Al_2O_3$ was coated on the surface of $LiFePO_4$ powders via a novel dry coating method. The influence of coated $LiFePO_4$ upon electrochemical behavior was discussed. Surface morphology characterization was achieved by transmission electron microscopy (TEM), clearly showing nano-crystallized $Al_2O_3$ on $LiFePO_4$ surfaces. Furthermore, it revealed that the $Al_2O_3$-coated $LiFePO_4$ cathode exhibited a distinct surface morphology. It was also found that the $Al_2O_3$ coating reduces capacity fading especially at high charge/discharge rates. Results from the cyclic voltammogram measurements (2.5-4.2 V) showed a significant decrease in both interfacial resistance and cathode polarization. This behavior implies that $Al_2O_3$ can prevent structural change of $LiFePO_4$ or reaction with the electrolyte on cycling. In addition, the $Al_2O_3$ coated $LiFePO_4$ compound showed highly improved area-specific impedance (ASI), an important measure of battery performance. From the correlation between these characteristics of bare and coated $LiFePO_4$, the role of $Al_2O_3$ coating played on the electrochemical performance of $LiFePO_4$ was probed.

• Korean Journal of Materials Research
• /
• v.21 no.11
• /
• pp.587-591
• /
• 2011

The effect of the precipitator (NaOH, $NH_4OH$) and the amount of the precipitator (150, 200, 250, 300 ml) on the formation of $Fe_3(PO_4)_2$, which is the precursor used for cathode material $LiFePO_4$ in Li-ion rechargeable batteries was investigated by the co-precipitation method. A pure precursor of olivine $LiFePO_4$ was successfully prepared with coprecipitation from an aqueous solution containing trivalent iron ions. The acid solution was prepared by mixing 150 ml $FeSO_4$(1M) and 100 ml $H_3PO_4$(1M). The concentration of the NaOH and $NH_4OH$ solution was 1 M. The reaction temperature (25$^{\circ}C$) and reaction time (30 min) were fixed. Nitrogen gas (500 ml/min) was flowed during the reaction to prevent oxidation of $Fe^{2+}$. Single phase $Fe_3(PO_4)_2$ was formed when 150, 200, 250 and 300 ml NaOH solutions were added and 150, 200 ml $NH_4OH$ solutions were added. However, $Fe_3(PO_4)_2$ and $NH_4FePO_4$ were formed when 250 and 300 ml $NH_4OH$ was added. The morphology of the $Fe_3(PO_4)_2$ changed according to the pH. Plate-like lenticular shaped $Fe_3(PO_4)_2$ formed in the acidic solution below pH 5 and plate-like rhombus shaped $Fe_3(PO_4)_2$ formed around pH 9. For the $NH_4OH$, the pH value after 30 min reaction was higher with the same amount of additions of NaOH and $NH_4OH$. It is believed that the formation mechanism of $Fe_3(PO_4)_2$ is quite different between NaOH and $NH_4OH$. Further investigation on this mechanism is needed. The prepared samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and the pH value was measured by pH-Meter.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
• /
• 2010.06a
• /
• pp.248-248
• /
• 2010

리튬이온 2차전지의 대체 양극 후보 물질인 $LiFePO_4$를 합성하기 위하여 출발원료로 $Li_2CO_3$, $Fe_2O_3$, $NH_4H_2PO_4$를 사용하여 볼밀 방법으로 혼합 분쇄한 후 열처리를 실시하였다. 합성 시에 3가 Fe를 2가로 환원시키기 위하여 $C_{12}H_{22}O_{11}$(흑설탕)을 출발원료와 함께 5 ~ 12 wt%로 나눠서 첨가하였다. 합성 후 XRD로 결정구조의 양질성을 확인하였고. FE-SEM으로 나노미터 크기의 구형 입자를 관찰하였다. XRF를 이용하여 3 ~ 10 wt%의 탄소 잔량을 확인하였다. 전기화학적 특성을 충 방전시험기로 평가한 결과, 8wt%의 탄소원을 첨가한 $LiFePO_4$에서 가장 좋은 수명 특성을 얻었고, 최대 145 mAh/g의 방전용량을 얻었다.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
• /
• 2009.11a
• /
• pp.133-133
• /
• 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
• /
• 2008.06a
• /
• pp.303-303
• /
• 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 the Mineralogical Society of Korea
• /
• v.26 no.1
• /
• pp.35-44
• /
• 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
• /
• 2009.11a
• /
• pp.132-132
• /
• 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).

• Bulletin of the Korean Chemical Society
• /
• v.32 no.3
• /
• pp.836-840
• /
• 2011

This study examines the effects of a carbon coating on the electrochemical performances of $LiFePO_4$. The results show that the capacity of bare $LiFePO_4$ decreased sharply, whereas the $LiFePO_4$/C shows a well maintained initial capacity. The Li ion diffusivity of the bare and carbon coated $LiFePO_4$ is calculated using cyclic voltammetry (CV) to determine the correlation between the electrochemical performance of $LiFePO_4$ and Li diffusion. The diffusion constants for $LiFePO_4$ and $LiFePO_4$/C measured from CV are $6.56{\times}10^{-16}$ and $2.48{\times}10^{-15}\;cm^2\;s^{-1}$, respectively, indicating considerable increases in diffusivity after modifications. The Li ion diffusivity (DLi) values as a function of the lithium content in the cathode are estimated by electrochemical impedance spectroscopy (EIS). The effects of the carbon coating as well as the mechanisms for the improved electrochemical performances after modification are discussed based on the diffusivity data.

• Journal of Electrochemical Science and Technology
• /
• v.4 no.3
• /
• pp.102-107
• /
• 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
• /
• v.13 no.3
• /
• pp.121-124
• /
• 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.